INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY ISSN X

Transcription

1 ISSN X ANNUAL REPORT 2013 INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY Dorodna 16, Warszawa, Poland phone: , fax: INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY

2 ANNUAL REPORT 2013 INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY

3 EDITORS Prof. Jacek Michalik, Ph.D., D.Sc. Wiktor Smułek, Ph.D. Ewa Godlewska-Para, M.Sc. Copyright by the Institute of Nuclear Chemistry and Technology, Warszawa 2014 All rights reserved

4 CONTENTS GENERAL INFORMATION 7 MANAGEMENT OF THE INSTITUTE 9 MANAGING STAFF OF THE INSTITUTE 9 HEADS OF THE INCT DEPARTMENTS 9 SCIENTIFIC COUNCIL ( ) 9 ORGANIZATION SCHEME 11 SCIENTIFIC STAFF 12 PROFESSORS 12 SENIOR SCIENTISTS (Ph.D.) 12 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 15 ONE-ELECTRON OXIDATION AND REDUCTION OF 3-METHYLQUINOXALIN-2-ONE K. Skotnicki, K. Bobrowski, J. De la Fuente, A. Cañete 17 FREE RADICAL OXIDATION OF NICOTINE: A PULSE RADIOLYSIS STUDY K. Kosno, M. Celuch, J. Mirkowski, I. Janik, D. Pogocki 19 RADIATION EFFECTS IN SORPTION MATERIALS WITH Ag + CATIONS EPR STUDY A. Bugaj, J. Sadło, M. Sterniczuk, G. Strzelczak, J. Michalik 21 RADIATION-INDUCED CURING OF EPOXY RESINS AND ITS NANOCARBON COMPOSITES G. Przybytniak, A. Nowicki, K. Mirkowski 23 PREPARATION OF THE FILMS BASED ON STARCH-PVA SYSTEM. PRELIMINARY STUDIES OF THE GAMMA IRRADIATION EFFECTS K. Cieśla, A. Abramowska, M. Buczkowski, P. Tchórzewski, A. Nowicki, J. Boguski 25 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 29 SYNTHESIS, PHYSICOCHEMICAL AND BIOLOGICAL EVALUATION OF NOVEL TECHNETIUM-99m LABELLED LAPATINIB AS A POTENTIAL TUMOUR IMAGING AGENT E. Gniazdowska, P. Koźmiński, L. Fuks, K. Bańkowski, W. Łuniewski, L. Królicki 31 CYCLOTRON PRODUCTION OF 99m Tc. SEPARATION OF 99m Tc FROM 100 Mo TARGET M. Gumiela, E. Gniazdowska, A. Bilewicz 34 THE STRUCTURES OF BISMUTH(III) COMPLEXES WITH TROPOLONE K. Łyczko, M. Łyczko, K. Woźniak, M. Stachowicz 35 SILVER IMPREGNATED NANOPARTICLES OF TITANIUM DIOXIDE AS 211 At CARRIERS E. Leszczuk, M. Łyczko, A. Piotrowska, A. Bilewicz, J. Choiński, J. Jastrzębski, A. Stolarz, A. Trzcińska, K. Szkliniarz, W. Zipper, B. Wąs 37 NANOTITANATE AS A NEW SORBENT FOR 137 Cs SEPARATION FROM RADIACTIVE WASTE B. Filipowicz, S. Krajewski, M. Łyczko, M. Pruszyński, A. Bilewicz 39 SORPTION OF AMERICIUM(III) IONS ON THE BENTONITE OF THE VOLCLAY TYPE A. Oszczak, L. Fuks, A. Gładysz-Płaska, M. Majdan 42 THE STUDY OF SORPTION OF COBALT IONS ON THE RED CLAY AND ZEOLITES G. Zakrzewska-Kołtuniewicz, A. Miśkiewicz, W. Olszewska, B. Sartowska 45 ANALYSIS OF THE POSSIBILITY OF URANIUM SUPPLY FROM DOMESTIC RESOURCES G. Zakrzewska-Kołtuniewicz, K. Kiegiel, D. Gajda, A. Miśkiewicz, P. Biełuszka, K. Frąckiewicz, I. Herdzik-Koniecko, B. Zielińska, A. Jaworska, K. Szczygłów, A. Abramowska, W. Olszewska, M. Harasimowicz, R. Dybczyński, H. Polkowska-Motrenko, B. Danko, Z. Samczyński, E. Chajduk, J. Chwastowska, I. Bartosiewicz, J. Dudek, S. Wołkowicz, J.B. Miecznik 48 STUDIES ON LEACHING COPPER ORES AND FLOTATION WASTES D. Wawszczak, A. Deptuła, W. Łada, T. Smoliński, T. Olczak, M. Brykała, P. Wojtowicz, M. Rogowski, M. Miłkowska 52

5 CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY 55 REAL-TIME PCR ANALYSIS OF EXPRESSION OF DNA DAMAGE RESPONSIVE GENES AS A BIOMARKER FOR BIOLOGICAL DOSIMETRY K. Brzóska, I. Buraczewska, I. Grądzka, B. Sochanowicz, T. Iwaneńko, M. Wojewódzka, G. Wójciuk, T. Stępkowski, M. Kruszewski 57 OPTIMIZING THE METAFER IMAGE ACQUISITION AND ANALYSIS SYSTEM FOR ESTIMATION OF DNA DOUBLE STRAND BREAK INDUCTION BY MEANS OF γ-h2ax FOCI ASSAY A. Lankoff, K. Sikorska, I. Buraczewska, I. Wasyk, T. Bartłomiejczyk, T. Iwaneńko, S. Sommer, I. Szumiel, M. Wojewódzka, K. Wójciuk, M. Kruszewski 58 QUICK SCAN OF DICENTRIC CHROMOSOMES FOR EVALUATION OF THE ABSORBED DOSE S. Sommer, I. Buraczewska, K. Sikorska, I. Wasyk, T. Bartłomiejczyk, A. Lankoff, M. Wojewódzka, M. Kruszewski 59 THE EFFECT OF SUPPLEMENTATION WITH CONJUGATED LINOLEIC ACID (CLA) ON Akt1 KINASE PHOSPHORYLATION IN X-IRRADIATED HT-29 CELLS I. Grądzka, I. Buraczewska, K. Sikorska, B. Sochanowicz, I. Szumiel, K. Wójciuk, G. Wójciuk 60 LABORATORY OF NUCLEAR ANALYTICAL METHODS 63 RADIOLYTIC REMOVAL OF SELECTED PHARMACEUTICALS AND BISPHENOL A FROM WATERS AND WASTES A. Bojanowska-Czajka, S. Borowiecka, M. Trojanowicz 64 DETERMINATION OF URANIUM IN FLOW-INJECTION SYSTEM WITH SPECTROPHOTOMETRIC DETECTION K. Kołacińska, M. Trojanowicz 67 LABORATORY OF MATERIAL RESEARCH 71 STRUCTURAL STUDIES IN Li(I) ION COORDINATION CHEMISTRY W. Starosta, J. Leciejewicz 72 FORMATION OF THE SURFACE LAYER WITH IMPROVED TRIBOLOGICAL PROPERTIES ON AUSTENITIC STAINLESS STEEL BY ALLOYING WITH REE USING HIGH INTENSITY PULSED PLASMA BEAMS B. Sartowska, M. Barlak, L. Waliś, J. Senatorski, W. Starosta 76 TECHNOLOGY, PRODUCTION AND CHRONOLOGY OF RED WINDOW GLASS IN THE MEDIEVAL PERIOD REDISCOVERY OF A LOST TECHNOLOGY J.J. Kunicki-Goldfinger, I.C. Freestone, I. McDonald, J.A. Hobot, H. Gilderdale-Scott, T. Ayers 78 POLLUTION CONTROL TECHNOLOGIES LABORATORY 79 PRELIMINARY MODELLING STUDY OF NO x REMOVAL FROM OIL-FIRED OFF-GAS UNDER ELECTRON BEAM IRRADIATION Y. Sun, A.G. Chmielewski, H. Nichipor, S. Bułka, Z. Zimek, E. Zwolińska 81 ANALYSIS OF THE CONSTRUCTION POSSIBILITY OF A LARGE ELECTRON BEAM FLUE GAS TREATMENT PLANT A. Pawelec, S. Witman-Zając 82 STABLE ISOTOPE LABORATORY 85 DETERMINATION OF SULPHUR ISOTOPIC COMPOSITION OF FOOD PRODUCTS R. Wierzchnicki, K. Malec-Czechowska 86 NEW APPROACH OF THE ISOTOPIC METHOD FOR JUICE AUTHENTICITY CONTROL R. Wierzchnicki, K. Malec-Czechowska 87 LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES 89 RECALIBRATION OF DOSIMETER FILMS CTA A. Korzeniowska-Sobczuk, A. Sterniczuk, M. Karlińska 90 LABORATORY FOR DETECTION OF IRRADIATED FOOD 93 STABILITY OF THE EPR SIGNAL PRODUCED BY IONIZING RADIATION IN DRIED FRUITS G.P. Guzik, W. Stachowicz 95

6 QUANTITY AND QUALITY OF MINERAL FRACTION IN THERMOLUMINESCENCE METHOD FOR THE DETECTION OF IRRADIATION IN ALIMENTARY ARTICLES W. Stachowicz, G. Liśkiewicz 96 LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS 99 DIAGNOSTICS OF BIOGAS INSTALLATION BY GAMMA RADIATION A. Jakowiuk, Ł. Modzelewski, J. Palige, E. Kowalska, J. Pieńkos 100 PUBLICATIONS IN ARTICLES 102 BOOKS 107 CHAPTERS IN BOOKS 107 THE INCT PUBLICATIONS 108 CONFERENCE PROCEEDINGS 109 CONFERENCE ABSTRACTS 110 SUPPLEMENT LIST OF THE PUBLICATIONS IN NUKLEONIKA 128 POSTĘPY TECHNIKI JĄDROWEJ 134 INTERVIEWS IN THE INCT PATENTS AND PATENT APPLICATIONS IN PATENTS 138 PATENT APPLICATIONS 138 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN Ph.D. THESES IN EDUCATION 143 Ph.D. PROGRAMME IN CHEMISTRY 143 TRAINING OF STUDENTS 143 RESEARCH PROJECTS AND CONTRACTS 145 RESEARCH PROJECTS GRANTED BY THE NATIONAL SCIENCE CENTRE IN DEVELOPMENT PROJECTS GRANTED BY THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT IN INNOTECH PROJECTS GRANTED BY THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT IN APPLIED RESEARCH PROGRAMME OF THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT IN INTERNATIONAL PROJECTS CO-FUNDED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN STRATEGIC PROJECT TECHNOLOGIES SUPPORTING DEVELOPMENT OF SAFE NUCLEAR POWER ENGINEERING 147 STRATEGIC PROJECT ADVANCED TECHNOLOGIES FOR GAINING ENERGY 147

7 IAEA RESEARCH CONTRACTS IN IAEA TECHNICAL AND REGIONAL CONTRACTS IN PROJECTS WITHIN THE FRAME OF EUROPEAN UNION FRAME PROGRAMMES IN EUROPEAN REGIONAL DEVELOPMENT FUND: BALTIC SEA REGION PROGRAMME 149 OTHER INTERNATIONAL RESEARCH PROGRAMMES IN STRUCTURAL FUNDS: OPERATIONAL PROGRAMME INNOVATIVE ECONOMY 149 LIST OF VISITORS TO THE INCT IN THE INCT SEMINARS IN LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN LECTURES 153 SEMINARS 154 AWARDS IN INDEX OF THE AUTHORS 158

8 GENERAL INFORMATION 7 GENERAL INFORMATION Poland decided to start a national nuclear energy programme 55 years ago and the Institute 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 Division, located at Warsaw Żerań, which became the interdisciplinary Institute of Nuclear Chemistry and Technology (INCT) in 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 the pulse radiolysis method. With its nine electron accelerators in operation and with the 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 with six electron accelerators: for radiation sterilization of medical devices and transplantation grafts; for radiation modification of polymers; for removal of SO 2 and NO x from flue gases; for food hygiene. The electron beam flue gas treatment in the EPS Pomorzany with the accelerators power over 1 MW is the biggest radiation processing facility ever built. The Institute represents the Polish Government in the Euroatom Fuel Supply Agency, in Fuel Supply Working Group of Global Nuclear Energy Partnership and in Radioactive Waste Management Committee of the Nuclear Energy Agency (Organisation for Economic Co-operation and Development). The INCT Scientific Council has the 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 2013 eight Ph.D. thesis was defended. 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 Collaborating Centre in Radiation Technology and Industrial Dosimetry. The INCT is editor of the scientific journal Nukleonika ( and the scientific-information journal Postępy Techniki Jądrowej. In 2013, the Evaluation Committee of Scientific Units in the Ministry of Science and Higher Education conferred the INCT cathegory A. The collaboration agreement between French Atomic Energy Commission (CEA) and the Institute concerning the chemical aspects of nuclear power was signed in December The consortium agreement with Électricité de France (EDF Polska SA) made possible to prepare NCBR joint grant proposal Integrated radioprotection system for nuclear buildings. The INCT has carried out several projects in the programme Innovative Economy PO IG, granted on the basis of high evaluation of the Institute s achievements: Analysis of the possibilities of uranium extraction from domestic resources (in cooperation with the Polish Geological Institute NRI); 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.

9 8 GENERAL INFORMATION The INCT is the leading institute in Poland regarding the implementation of nuclear energy related EU projects. Its expertise and infrastructure was the basis for participation in FP7-EURATOM grants: 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 radiological casualties; ASGARD: Advanced fuels for generation IV reactors: reprocessing and dissolution; RENEB: Realizing the European Network in Biodosimetry; NEWLANCER: New MS linking for an advanced cohesion in Euratom research; ARCADIA: Assessment of regional capabilities for new reactors development through an integrated approach; EAGLE: Enhancing education, training and communication processes for informed behaviors and decision-making related to ionizing radiation risks; PLATENSO: Building a platform for enhanced societal research related to nuclear energy in Central and Eastern Europe; SACSESS: Safety of actinide separation processes; TALISMAN: Transnational access to large infrastructure for a safe management of actinide. In 2013, the INCT scientists published 55 papers in scientific journals registered in the Philadelphia list, among them 36 papers in journals with an impact factor (IF) higher than 1.0. Two scientific books and 11 chapters were written by the INCT research workers. The following annual awards of the INCT Director-General for the best publications and application achievements in 2013 were granted: first degree team award to Jacek Palige, Katarzyna Wawryniuk, Otton Roubinek, Agata Urbaniak, Henryk Burliński, Andrzej G. Chmielewski for the application achievements elaboration of the project of mobile membrane installation for enrichment of biogas in methane; second degree team award to Andrzej Pawelec, Sylwia Witman-Zając, Janusz Licki, Andrzej G. Chmielewski for the application achievements realization of the project Studies of the technology of purification of flue gases with electron beam method on a pilot scale ; second degree team award to Grażyna Zakrzewska-Kołtuniewicz, Agnieszka Miśkiewicz, Marian Harasimowicz for a series of four articles concerning the removal of harmful impurities from waters and sewages with membrane technology; third degree team award to Janusz Kraś, Cezary Nobis, Tadeusz Bilka, Mirosław Gurniak, Mariusz Wieczorek, Grażyna Giers, Natalia Pawlik for the application achievements implementation of new measurement methods related to the tightness of installations and industrial pipelines; third degree individual award of Director of the Institute of Nuclear Chemistry and Technology to Yongxia Sun for a series of works concerning the removal of volatile organic compounds from gases emitted to the atmosphere third degree team award of Director of the Institute of Nuclear Chemistry and Technology to Agnieszka Majkowska-Pilip, Marek Pruszyński, Barbara Bartoś, Aleksander Bilewicz for a series of three articles concerning the application of radionuclides of scandium to the diagnosis and radionuclide theraphy. In 2013, the research teams in the INCT were involved in the organization of 12 scientific meetings.

10 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 Zbigniew Zimek, Ph.D. Centre for Radiochemistry and Nuclear Chemistry Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc. Centre for Radiobiology and Biological Dosimetry Prof. Marcin Kruszewski, Ph.D., D.Sc. Laboratory of Nuclear Control Systems and Methods Jacek Palige, Ph.D. Laboratory of Material Research Wojciech Starosta, Ph.D. Laboratory of Nuclear Analytical Methods Halina Polkowska-Motrenko, Ph.D., D.Sc, professor in INCT Stable Isotope Laboratory Ryszard Wierzchnicki, Ph.D. Pollution Control Technologies Laboratory Andrzej Pawelec, Ph.D. Laboratory for Detection of Irradiated Food Wacław Stachowicz, Ph.D. Laboratory for Measurements of Technological Doses Anna Korzeniowska-Sobczuk, M.Sc. SCIENTIFIC COUNCIL ( ) 1. Prof. Grzegorz Bartosz, Ph.D., D.Sc. University of Łódź 2. Prof. Aleksander Bilewicz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 3. Prof. Krzysztof Bobrowski, Ph.D., D.Sc. (Vice-chairman) Institute of Nuclear Chemistry and Technology 4. Marcin Brykała, Ph.D. Institute of Nuclear Chemistry and Technology 5. Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 6. Andrzej Chwas, M.Sc. Ministry of Economy 7. Jadwiga Chwastowska, Ph.D., D.Sc., professor in INCT Institute of Nuclear Chemistry and Technology 8. Krystyna Cieśla, Ph.D., D.Sc., professor in INCT Institute of Nuclear Chemistry and Technology

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

12 MANAGEMENT OF THE INSTITUTE 11 ORGANIZATION SCHEME DIRECTOR Scientific Council Accountant General Deputy Director of Finances Deputy Director of Maintenance and Marketing Deputy Director for Research and Development Laboratory of Nuclear Analytical Methods Centre for Radiation Research and Technology Stable Isotope Laboratory Centre for Radiobiology and Biological Dosimetry Pollution Control Technologies Laboratory 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

13 12 SCIENTIFIC STAFF SCIENTIFIC STAFF PROFESSORS 1. Bilewicz Aleksander radiochemistry, inorganic chemistry 2. Bobrowski Krzysztof radiation chemistry, photochemistry, biophysics 3. Chmielewski Andrzej G. chemical and process engineering, nuclear chemical engineering, isotope chemistry 4. Chwastowska Jadwiga, professor in INCT analytical chemistry 5. Cieśla Krystyna, professor in INCT physical chemistry 6. Dobrowolski Jan spectroscopy and molecular modelling 7. Dybczyński Rajmund analytical chemistry 8. Grigoriew Helena, professor in INCT solid state physics, diffraction research of non-crystalline matter 9. Grodkowski Jan, professor in INCT radiation chemistry 10. Kruszewski Marcin radiobiology 11. Lankoff Anna, professor in INCT biology 13. Michalik Jacek radiation chemistry, surface chemistry, radical chemistry 14. Migdał Wojciech, professor in INCT chemistry, science of commodies 15. Ostyk-Narbutt Jerzy radiochemistry, coordination chemistry 16. Pawlukojć Andrzej, professor in INCT chemistry 17. Pogocki Dariusz, professor in INCT radiation chemistry, pulse radiolysis 18. Polkowska-Motrenko Halina, professor in INCT analytical chemistry 19. Przybytniak Grażyna, professor in INCT radiation chemistry 20. Siekierski Sławomir physical chemistry, inorganic chemistry 21. Szumiel Irena cellular radiobiology 22. Trojanowicz Marek analytical chemistry 23. Zagórski Zbigniew physical chemistry, radiation chemistry, electrochemistry 12. Leciejewicz Janusz Tadeusz crystallography, solid state physics, material science 24. Zakrzewska-Kołtuniewicz Grażyna, professor in INCT process and chemical engineering SENIOR SCIENTISTS (Ph.D.) 1. Bartłomiejczyk Teresa biology 5. Brzóska Kamil biochemistry 2. Bojanowska-Czajka Anna chemistry 6. Buczkowski Marek physics 3. Borowik Krzysztof chemistry 7. Chajduk Ewelina chemistry 4. Brykała Marcin chemistry 8. Danilczuk Marek chemistry

14 SCIENTIFIC STAFF Deptuła Andrzej chemistry 31. Męczyńska-Wielgosz Sylwia chemistry 10. Dobrowolski Andrzej chemistry 32. Mirkowski Jacek nuclear and medical electronics 11. Dudek Jakub chemistry 33. Miśkiewicz Agnieszka chemistry Fuks Leon chemistry Głuszewski Wojciech chemistry Gniazdowska Ewa chemistry Grądzka Iwona biology Harasimowicz Marian technical nuclear physics, theory of elementary particles Nowicki Andrzej organic chemistry and technology, high-temperature technology Ostrowski Stanisław chemistry Palige Jacek metallurgy Pawelec Andrzej chemical engineering Pruszyński Marek chemistry 17. Herdzik-Koniecko Irena chemistry 39. Ptaszek Sylwia chemical engineering 18. Kciuk Gabriel chemistry 40. Rafalski Andrzej radiation chemistry 19. Kiegiel Katarzyna chemistry 41. Roubinek Otton chemistry 20. Kierzek Joachim physics 42. Sadło Jarosław chemistry 21. Kocia Rafał chemistry 43. Samczyński Zbigniew analytical chemistry 22. Kornacka Ewa chemistry 44. Sartowska Bożena material engineering 23. Koźmiński Przemysław chemistry 45. Skwara Witold analytical chemistry 24. Krajewski Seweryn chemistry 46. Sochanowicz Barbara biology 25. Kunicki-Goldfinger Jerzy conservator/restorer of art 47. Sommer Sylwester radiobiology, cytogenetics 26. Latek Stanisław nuclear physics 48. Stachowicz Wacław radiation chemistry, EPR spectroscopy 27. Lewandowska-Siwkiewicz Hanna chemistry 49. Starosta Wojciech chemistry 28. Łyczko Krzysztof chemistry 50. Sterniczuk Macin chemistry 29. Łyczko Monika chemistry 51. Strzelczak Grażyna radiation chemistry 30. Majkowska-Pilip Agnieszka chemistry 52. Sun Yongxia chemistry

15 14 SCIENTIFIC STAFF 53. Szreder Tomasz chemistry 59. Wiśniowski Paweł radiation chemistry, photochemistry, biophysics 54. Waliś Lech material science, material engineering 60. Wojewódzka Maria radiobiology 55. Walo Marta chemistry 61. Wójciuk Grzegorz chemistry 56. Warchoł Stanisław solid state physics 62. Wójciuk Karolina chemistry Wawszczak Danuta chemistry Wierzchnicki Ryszard chemical engineering 63. Zimek Zbigniew electronics, accelerator techniques, radiation processing

16 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, stop-flow experimental set-up, 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, pilot facility for radiation sterilization, polymer modification and food product processing.

17 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 functioning. That is the best example of capability and great potential of concentrated equipment, methods and staff working towards application of innovative radiation technology.

18 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY ONE-ELECTRON OXIDATION AND REDUCTION OF 3-METHYLQUINOXALIN-2-ONE Konrad Skotnicki, Krzysztof Bobrowski, Julio De la Fuente 1/, Alvaro Cañete 2/ 1/ Universidad de Chile, Santiago de Chile, Chile 2/ Pontificia Universidad Católica de Chile, Chile 17 Quinoxalin-2-ones are the class of compounds showing a variety of pharmacological properties, such as antimicrobial [1], antiviral [2], anti-inflammatory [3], antithrombotic [4, 5], anticancer [6-9] activity. A key factor decisive about their biological activity is a substitution at the carbon-3 in the pyrazine ring and at the carbons 6 and 7 in the benzene ring in a primary quinoxalin-2-one structure (Chart 1). Nearly all biologically active derivatives are substituted in these specific positions. Chart 1. Structural formula of quinoxalin-2-one. The structure activity relationship (SAR) studies have revealed that quinoxalin-2-ones derivatives bound to proteins receptors are generally located close to the adenosine triphosphate (ATP) binding pocket [6, 10], e.g. in cyclin-dependent kinases (Cdk). The fact that these compounds are bound in the very specific position in proteins may have serious consequences in their interactions with either amino acid residues or radicals derived from them. Certain amino acid residues tyrosine (Tyr), tryptophan (Trp), and cysteine (Cys) are particularly vulnerable to oxidation. Therefore, the radical cations derived from quinoxalin-2-ones can modify these amino acids which are reasonably good electron donors and can be oxidized to tyrosyl (TyrO ), tryptophyl (Trp ), and thiyl (Cys ) radicals, respectively. On the other hand, these radicals are reasonably good electron acceptors and can act potentially as oxidants. Reactive oxygen and nitrogen species (ROS and RNS) are produced in excess during the oxidative and nitrosative stress in living organisms. ROS and RNS can react with various biological targets (proteins, DNA, lipids), the most important of them being proteins and peptides because of their high concentration in cells [11]. In principle, oxidation and reduction processes in proteins can occur everywhere and involve the protein backbone, amino acid residues and also intercalated molecules (e.g. quinoxalin-2-ones). The primary steps leading to these modifications are extremely fast, consist of one electron loss and very often a subsequent one electron capture, resulting in creation of very reactive transients (radicals and radical ions) which are responsible for secondary re- Fig.1. Transient absorption spectra obtained by OH attack on 3-methylquinoxalin-2-one recorded 4 μs ( ), 80 μs ( ), 300 μs ( ) and 800 μs ( ) after the pulse in the N 2 O-saturated 0.1 mm 3-methylquinoxalin-2-one, at ph 8. Insets: kinetics traces of formation and decay recorded at 370 and 460 nm.

19 18 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY actions. For these reasons it is important to characterize spectral properties of transients derived from quinoxalin-2-ones (those derived from amino acids are mostly known) and to measure kinetic parameters of the primary and secondary reactions involving quinoxalin-2-ones and amino acid residues. These reactions lead to production of various free radicals, including those derived either from amino acids or quinoxalin-2-ones. after the pulse are characterized by two distinct absorption maxima located at λ = 370 and 460 nm (Fig.1). The first one is stable within 1.5 ms time domain. Complementry steady-state γ-radiolysis experiments revealed that this absorption is stable and is associated with a stable reaction product. The second-order rate constants k Q+OH were determined from the kinetic traces at 370 and 460 nm in pseudo first-order conditions and were found Fig.2. Transient absorption spectra obtained by e solv attack on 3-methylquinoxalin-2-one recorded 2 μs ( ), 10 μs ( ), 20 μs ( ), 40 μs ( ) and 100 μs ( ) after the pulse in the Ar-saturated 0.1 mm 3-methylquinoxalin-2-one, at ph 8. Insets: kinetics traces of formation and decay recorded at 370 and 430 nm. Radical oxidation and reduction of 3-methylquinoxalin-2-one and kinetics of its reactions with hydroxyl radicals ( OH) and solvated electrons (e aq ), respectively, were studied by pulse radiolysis technique coupled with the time-resolved UV/Vis spectrophotometric detection system. Reactions were studied in aqueous solutions saturated either with N 2 O or argon. Pulse radiolysis studies in N 2 O-saturated aqueous solution at ph 8 has been performed in order to check whether 3-methylquinoxalin-2-one is able to scavenge OH radicals. OH-induced oxidation generally leads to one-electron oxidation products. However, it is well known, that the formation of OH adducts is another possible reaction pathway. Transient absorption spectra observed 4 μs H N O H e solv N O H + to be equal to k 370 = 4.6 ± M 1 s 1 and k 460 = 4.4 ± M 1 s 1. Reaction with e aq has been performed in Ar-saturated aqueous solution containing tert-butanol at ph 8. One-electron reduction of 3-methylquinoxalin-2-one leads to the formation of at least two products, with the respective absorption maxima at λ = 370 and 430 nm (Fig.2). The second- -order rate constant k Q+e was determined from the kinetic traces at 720 nm (absorption maximum of solvated electron absorption in water) in pseudo first-order conditions and was found to be equal to k 720 = 2.8 ± M 1 s 1. Additional experiments performed in different ph values and with similar compounds allow to assume that one-electron reduction results in the for- N C N - C N H Scheme 1. A proposed mechanism for one-electron reduction of 3-methylquinoxalin-2-one. H N O

20 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 19 mation of a radical anion followed by a rapid protonation to a neutral protonated radical. Proposed reaction mechanism is presented in Scheme 1. Obtained results indicated that quinoxalin-2- -ones are able to scavenge OH radicals with high rate constants (k = M 1 s 1 ) which is a very promising result for their possible medical use. One-electron reductions leads to the formation of radical anion and protonated radical with a rate constant close to a diffusion control (k = M 1 s 1 ). Further studies concerning interactions of quinoxalin-2-ones with amino acids will be performed. References [1]. Ajani O.O. et al.: Bioorg. Med. Chem., 18(1), (2010). [2]. Xu B.L. et al.: Bioorg. Med. Chem., 17(7), (2009). [3]. El-Sabbagh O.I. et al.: Med. Chem. Res., 18(9), (2009). [4]. Ries U.J. et al.: Bioorg. Med. Chem. Lett., 13(14), (2003). [5]. Willardsen J.A. et al.: J. Med. Chem., 47(16), (2004). [6]. Hirai H. et al.: Invest. New Drugs, 29(4), (2011). [7]. Kotb E.R. et al.: Phosphorus, Sulfur Silicon Relat. Elem., 182(5), (2007). [8]. Lawrence D.S., Copper J.E., Smith C.D.: J. Med. Chem., 44(4), (2001). [9]. Yuan H.Y. et al.: Med. Chem. Res., 18(8), (2009). [10]. Mori Y. et al.: Chem. Pharm. Bull., 56(5), (2008). [11]. Dean R.T. et al.: Free Radical Biol. Med., 11(2), (1991). FREE RADICAL OXIDATION OF NICOTINE: A PULSE RADIOLYSIS STUDY Katarzyna Kosno, Monika Celuch, Jacek Mirkowski, Ireneusz Janik, Dariusz Pogocki Nicotine (3-(1-methyl-2-pyrrolidinyl)pyridine) is a commonly known natural alkaloid present mainly in tobacco plants and is characterized by a stimulant action. It interacts with the nicotinic acetylcholine receptors and cause the release of many neurotransmitters responsible for mood (e.g. noradrenaline, serotonin and dopamine). This is the main reason of its strong addictive power. However, nicotinic stimulation has also positive effects as it is used in the therapy of some neurodegenerative disorders and diseases [1]. Because of its antioxidative properties, nicotine has the potential to be widely used as a free radical scavenger. It can be used to protect nerve cells in some major neurodegenerative disorders and diseases such as Alzheimer s and Parkinson s diseases, Tourette s syndrome or schizophrenia. Neurodegeneration associated with these diseases is accompanied by an extensive oxidative stress, caused by the imbalance in the production of reactive oxygen species and the biological system s inability to detoxify them. Nervous tissue is continuously exposed to the presence of toxic oxygen radicals beyond a threshold for proper antioxidant neutralization. Nicotine can easily pass through the blood-brain barrier and prevent this destructive radical action thanks to its antioxidative properties. There are some evidence that nicotine can react with the most dangerous OH radical producing neutral or less aggressive radical products [2]. However, it has not been confirmed so far and more data about the mechanism of nicotine radical processes should be obtained. The knowledge about the reactions kinetic is also important, because the rate of nicotine radical reactions need to be high enough to exclude competitive reactions. Nicotine molecule is made of two rings: aromatic pyridine and aliphatic pyrrolidine with chiral carbon C2 atom (Fig.1). The OH radical reacts through a variety of reaction mechanisms, including direct electron transfer, hydrogen abstraction, and addition to unsaturated bonds. In case of nicotine every three pathways are possible N Considering the electron density and favourable energetic effect, substitution occurs mainly at the meta position, the most probable product of hydrogen abstraction is radical located at a chiral carbon and the cation radical is formed at pyrrolidine nitrogen. However, nicotine is a weak base with a pk a1 of 8.02 (pk a2 = 3.12) in aqueous solution at 25 o C [3] and the protonation state has the influence on its radical reactions. According to DFT calculations, protonation of pyrrolidine nitrogen increases the dissociation enthalpy of the C2 -H bond. Some reaction pathways can be even blocked in acidic solutions. The main experimental technique used to study the radical oxidation of nicotine was pulse radiolysis coupled with a time-resolved UV/Vis detection system, which enables to study molecular processes close to or even beyond the diffusion controlled reaction limit. Experiments were performed with the LAE 10 [4] (Institute of Nuclear Chemistry and Technology) and Titan Beta Model TBS-8/16-1 [5] (Notre Dame Radiation Laboratory) linear accelerators. Analysis was done in the broad range of ph giving data for protonated and unprotonated forms of nicotine. Using pyridine 2' 3' N 1' Fig.1. Structural formula of nicotine. 4' 5' CH 3 6'

21 20 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY A B C D Fig.2. Reaction scheme for the oxidation of nicotine by azide radical. and N-methylpyrrolidine as nicotine model compounds enabled to divide radical reactions into occurring with aromatic and aliphatic part of the molecule. In order to check if nicotine oxidation can proceed with single-electron transfer, its reaction with azide radical has been studied. Azide radical is a strong one-electron oxidant and it can be readily prepared radiolytically by OH oxidation of azide anions in aqueous solution (Fig.2A,B). It exhibits moderate absorption only in the UV range with a sharp maximum at 274 nm. Reaction of one-electron oxidation can only occur with the aliphatic nitrogen (Fig.2C). Azide radical will not react with aromatic ring, because according to data obtained by Schuler, the rate of its reaction with pyridine is lower than M 1 s 1 [6]. Although there are no reports that azide radicals reacts by hydrogen abstraction, theoretically in favourable reaction conditions there is such a possibility (Fig.2D). The bond dissociation energy for a bond between hydrogen atom and asymmetric car- 1.3x10 4 5x10 5 k (Nic + N3. ) = 5.23 x 107 M -1 s -1 4x10 5 G ε [m 2 /J] 1.0x x x10 3 k app (s -1 ) 3x10 5 2x10 5 1x [Nic] (10-3 mol dm -3 ) 2.5x mm Nic + 10 mm NaN 3 ph 10 ph λ [nm] Fig.3. Transient absorption spectra recorded 10 μs after the electron pulse in N 2 O-saturated, 10 mm aqueous solution of NaN 3 containing 1 mm nicotine recorded at ph 10 and 5.6. Inset: rate constant determined from the pseudo first-order growths of the 330 nm signals generated in 0.1 M NaN 3, N 2 O-saturated, aqueous solution at ph 10 as a function of nicotine concentration.

22 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 21 bon in nicotine molecule is about 25 kj/mol lower than the N-H bond dissociation energy in hydrazoic acid. The reaction of nicotine with azide radical was studied for two protonation states of the pyrrolidinyl nitrogen. Transients obtained in the reaction of unprotonated nicotine at ph 10 gave spectrum with one distinct absorption band with λ max = 330 nm and a broad absorption band with λ max ca. 460 nm, both growing with the same rate (Fig.3). It is very similar to the spectrum obtained for nicotine reaction with hydroxyl radicals, what may suggest that we also observe here mainly radical at chiral carbon. For the protonated aliphatic nitrogen at ph 5.6, the absorption at 330 nm is almost 20 times lower and we observed a weak band at A B Fig.4. Mechanism of the azide radical reaction with tryptophan and N-methylpyrrolidine. 280 nm, which can be assigned to azide radicals. This indicates that azide radical does not react with protonated form of nicotine, because the electron transfer is blocked. Hydrogen abstraction from chiral carbon is also inhibited because of the higher C* H bond dissociation energy than in unprotonated form. The reaction with the unprotonated form is second order with a rate constant of M 1 s 1. To confirm that azide radical can oxidize the pyrrolidinyl nitrogen, we studied its reaction with N-methylpyrrolidine in the presence of tryptophan. Tryptophan is a natural amino acid existing in proteins. Its reaction with azide radical is well known (Fig.4A). It proceeds with electron transfer and generates radicals absorbing at 320 and 520 nm with high extinction coefficients. The rate of this reaction at ph 11.4 is M 1 s 1. Azide radical should react with N-methylpyrrolidine also by electron transfer (Fig.4B). After the pyrrolidinyl nitrogen protonation this way of reaction is blocked. N-methylpyrrolidine has a pk a of 10.46, so the experiments were done at ph 11.4, where there is about 90% of the unprotonated form. The kinetic studies of the 520 nm absorbance changes have been done using a competition method. N-methylpyrrolidine will compete with tryptophan and react with azide radicals, what causes a decrease in the absorbance with increasing alkaloid concentration. The rate constant for the reaction of N-methylpyrrolidine with azide radical was determined to be M 1 s 1. Such a low reaction rate suggest that the electron transfer will have a minor contribution to the mechanism of nicotine reaction with azide radical. Obtained results indicate that azide radical, although is a well-known one-electron oxidant, in energetically favourable conditions it can also abstract hydrogen atoms. References [1]. Pogocki D., Ruman T., Danilczuk M., Danilczuk M., Celuch M., Wałajtys-Rode E.: Eur. J. Pharm., 563, (2007). [2]. Wang S.-L., Wang M., Sun X.-Y., Li W., Ni Y.: Spectrosc. Spect. Anal., 23, (2003). [3]. CRC Handbook of Chemistry and Physics on CD-ROM. CRC Press, [4]. Bobrowski K.: Nukleonika, 50, 3, (2005). [5]. Hug G.L., Wang Y., Schöneich Ch., Jiang P.-Y., Fessenden R.W.: Radiat. Phys. Chem., 54, (1999). [6]. Schuler R.H., Alfassi Z.B.: J. Phys. Chem., 89, (1985). RADIATION EFFECTS IN SORPTION MATERIALS WITH Ag + CATIONS EPR STUDY Anna Bugaj, Jarosław Sadło, Marcin Sterniczuk, Grażyna Strzelczak, Jacek Michalik Removal of radionuclides from aqueous nuclear wastes is a challenging task for the management of waste disposal. Sorbents containing radionuclides are exposed to high level of radiation dose which generates changes in sorbent structure. It is expected that new sorption materials will be not only effective and highly selective but also resistant to radiation for very long time [1-3]. In this report we present the studies on paramagnetic species formed in γ-irradiated saponite and crystalline sitinakite (Fig.1) containing exchangeable Ag + cations. Saponite is a layered clay

23 22 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY mineral belonging to smectite group composed of polyhedral sheets with Si 4+ in tetrahedral sites and Al 3+ and/or Mg 2+ in octahedral ones. The structure of sitinakite [molecular formula Na 2 Ti 2 O 3 (SiO 4 ) 2H 2 O] is similar to commercially available synthetic titanosilicate IONSIV * IE-911. Both materials are successfully used for sorption of radionuclides from Fukushima radioactive wastewaters. A B Fig.2. EPR spectra at 130 K of γ-irradiated sitinakite: (a) dehydrated sample with Na + cations, (b) hydrated sample with Ag + cations, (c) dehydrated sample with Ag + cations. Fig.1. Crystal structure of saponite (A) and sitinakite (B). Electron paramagnetic resonance (EPR) spectroscopy is very useful tool for characterization of paramagnetic species like radicals and paramagnetic atoms or cations generated by radiation in sorbent materials. Fission product radioisotopes can get into reactor primary cooling system as a result of zirconium cladding damage. Silver 110m Ag together with 60 Co, 137 Cs and others belongs to long-lived radioisotopes which for safety reasons should be removed from cooling water. Sorption on microporous materials like zeolites or clays is usually used for that purpose. For model studies of radiation changes of metal valence state by EPR we use silver as an exchangeable cation. Both silver isotopes 107 Ag and 109 Ag have nuclear spin ½ and large magnetic moments which usually makes possible to identify paramagnetic silver species like silver atoms, cations and clusters produced by radiation. Saponite and sitinakite samples after degassing on vacuum line at room temperature or dehydrating at 120 o C were irradiated at 77 K with dose of 10 kgy in Co-60 source. EPR spectra were measured using EPR Bruker X-band ESP 300 spectrometer in the temperature range K. In all cases samples before irradiation did not show any EPR signals. The EPR spectra of γ-irradiated sitinakite measured at 130 K are presented in Fig.2. Dehydrated Na-sitinakite shows strong anisotropic singlet T with orthorhombic symmetry of g-factor: g 1 = 2.003, g 2 = and g 3 = (Fig.2a). Hydrated Na-sitinakite sample shows the same signal. Similar EPR signal was recorded in TiO 2 colloids and was assigned to the hole trapped on the colloidal surface Ti 4+ O 2 Ti 4+ O * [4]. In Ag-sitinakite both in hydrated and dehydrated form, signal T is also recorded but then is accompanied by strong signals of paramagnetic silver species. In hydrated Ag-sitinakite the most pronounced signal is anisotropic doublet with g = 2.039, g II = 2.242, A = 3.2 mt, A II = 4.0 mt (Fig.2b). Doublet with similar g-factors and hyperfine splitting values was earlier observed after irradiation of hydrated zeolite A and was assigned to Ag 2+ divalent cation [5]. In dehydrated Ag-sitinakite perpendicular component of Ag 2+ signal shows additional splittings which indicate the overlapping of Ag 2+ EPR line with unknown signal (Fig.2c). We speculate that three lines labelled x with splitting ~10 mt belongs to the same signal but at this moment we are unable to identify its origin. Doublet H with hyperfine splitting equal ~50 mt present in all spectra in Fig.2 represents hydrogen atoms trapped in spectrosil tubings. Figure 3 shows the EPR spectra of γ-irradiated samples of hydrated saponite synthetized in NIMS, Tsukuba, Japan. The exchangeable cations were introduced into gel before synthesis. In Na-saponite (Fig.3a) three major lines W, Y, Z showing asymmetric shape and additional splitting represent unidentified radiation-induced paramagnetic defects in clay layers. Moreover, in the

24 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 23 sample with exchanged Ag + ions (Fig.3b) appears a weak doublet with hyperfine splitting 64 mt. It represents silver atoms Ag 0. In saponite sample Fig.3. EPR spectrum at 160 K of γ-irradiated hydrated saponite with: (a) Na + ; (b) Na + and Ag + ; (c) Na +, Ag + and Cs +. containing Na +, Ag + and Cs + cations (Fig.3c) the Ag 0 lines clearly shows additional splittings labelled 1, 2, 3 and 4. They are not only due to the different hyperfine splittings of 107 Ag 0 and 109 Ag 0 because then only two lines should be observed at high magnetic field and two ones at low field. In conrast both field regions show four lines which indicates that Ag 0 atoms are stabilized at two different sites. Further experiments will be carried out to specify direct locations of silver trapping sites. This information is crucial to speculate about stability of 110m Ag cations in saponite clays. The research described herein was supported by the National Centre for Research and Development, Poland in the framework of the strategic research project Technologies supporting development of safe nuclear power engineering task 8 Study of processes occurring under regular operation of water circulation systems in nuclear power plants with suggested actions aimed at upgrade of nuclear safety. References [1]. Cabrera C., Gabaldón C., Marzal P.: J. Chem. Technol. Biotechnol., 80(4), (2005). [2]. Allard T., Calas G.: Appl. Clay Sci., 43(2), (2009). [3]. Anthony R.G. et al.: Ind. Eng. Chem. Res., 33(11), (1994). [4]. Micic O.I. et al.: J. Phys. Chem., 97(28), (1993). [5]. Sadlo J., Wasowicz T., Michalik J.: Radiat. Phys. Chem., 45(6), (1995). RADIATON-INDUCED CURING OF EPOXY RESINS AND ITS NANOCARBON COMPOSITES Grażyna Przybytniak, Andrzej Nowicki, Krzysztof Mirkowski (2) (1) Scheme 1. Formulae of DGEBA (1) and cationic initiator used for radiation-induced curing Rhodorsil 2074 (IPB) (2). Recently published papers have reported that curing of epoxy resins might be supported by ionizing radiation and that such a treatment provides materials with high glass transition temperatures. Although flexural strength of radiation cured epoxy resin is comparable to thermally cured ones, other mechanical parameters are more advantageous. Enhanced toughness and unusual long-term stability make the resins usable under harsh/degradable conditions for many years. In order to obtain good quality material usually a photoinitiator at a concentration of 1% or more is required. The final product shows better features than the resins based on polyamine hardeners [1-3]. In our studies primary objective was to estimate if radiation technique might be applied for the high performance ionizing radiation curable nanocarbon composites based on thermoset. Such products are interesting from the practical point of view as they can be applied in automobile, aircraft and aerospace industry [4]. The work was focused on the studies related to radiation curing of epoxy resins based on diglycidyl ether of bisphenol A (DGEBA) in the presence of cationic photoinitiator Rhodorsil in the form of [4(1-methylethyl)phenyl][4-methylphenyl]iodonium tetrakis(pentafluorophenyl)borate salt [5] (Scheme 1). Carbon nanotubes (CNT) in the form of suspension in epoxy resin were obtained from NA- NOMATERIALS (Warszawa, Poland). Graphene oxide (GO) was synthesized by Hummer s method at the Institute of Electronic Materials Technology (ITME, Poland), whereas the reduced form of the material (RGO) was obtained at the Institute of Nuclear Chemistry and Technology (INCT) as a suspension in dichloromethane (CH 2 Cl 2 ). The ini-

25 24 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY tiator was dissolved in DGEBA at o C in an ultrasonic bath. In the same way carbon based nanofilers were dispersed in the resins. For irradiation, an Elektronika accelerator generating 10 MeV electron beam (EB) was applied at an average dose rate of 3 kgy/min, whereas gamma irradiation was performed in a Gamma Chamber 5000 (GC 5000) at a dose rate of 6.4 or 3.2 kgy/h using appropriate screens. In the GC 5000 expected effects related to absorption of Figure 3 shows the progress of temperature increase for the radiation-initiated curing of epoxy resin and its nanocomposites in the presence of cationic initiator Rhodorsil. The profiles of temperature variations related to the radiation-initiated polymerization are presented for several systems. Fig.1. Thermal effects for the selected materials placed in a Gamma Chamber 5000 at a dose rate of 6.4 kgy/h. radiation energy by the walls were observed. In order to estimated these consequences, the thermal measurements were conducted for the chamber unloaded and loaded with water or epoxy resin free from initiator (Fig.1). The diagrams indicate that even after 6 h temperature in the loaded chamber is less than 45 o C and has not reached equilibrium yet. On the basis of these results it was assumed that ionizing radiation effects predominantly initiate cross-linking in the presence of the initiator at the first stage. The conclusion confirms thermogram recorded by the DSC method showing intensive thermal curing of the system only above 170 o C (Fig.2). Fig.2. Thermogram of DGEBA in the presence of 1% initiator, heating rate 5 o C/min. Fig.3. Temperature changes in the DGEBA-based resin during radiation-induced curing: a without IPB; b 1% IPB; c, d 1% IPB; e 0.5% IPB; f 0.25% IPB; g 0.25% IPB, 0.1% CNT; h 0.25% IPB, 0.1% GO; i 0.5% RGO, 1% IPB. b irradiated EB; a, c-i irradiated in a Gamma Chamber a, c irradiation at 6.4 kgy/h; d-i irradiation at 3.2 kgy/h. For all specimens, except this one comprising RGO ( i peak), the rapid temperature increase has been confirmed for irradiation lasting less than 60 min, i.e. when temperature in the chamber loaded with the materials free from initiator does not reach 30 o C. This reflects an accumulation of the radical centres generated in the presence of the initiator at the first stage of the process. When their population achieves an appropriate level a rapid combination of radicals gives strong exothermic effect which initially intensifies curing but upon depletion of the initiator goes out with decreasing amount of the active centres. Radiation energy has to initiate thermal curing which requires about 170 o C (Fig.2), as just above this temperature thermal effect prevails over radiation-induced phenomena. Worth noting that in spite of various dose rates and initiator concentrations maximum temperature of exothermic curing is above 200 o C for all comprising IPB systems irradiated in the GC High temperature of polymerization is an unfavourable phenomenon as in such a case significant thermal stress is created within the matrix. For the bulk specimens, the effects can result in cracking and subsequently destruction of the material. For the same concentration of the initiator (1% b, c and d profiles), the thermal changes depend predominantly on the method of irradiation. Induction time is very short for exposure to an electron beam (a few minutes) and much longer for gamma irradiation. In the second case the maximum temperature is achieved after 30 and 45 min at 6.4 kgy/h (3.2 kgy) and 3.2 kgy/h (2.4 kgy), respectively. These discrepancies arise from various phenomena standing behind electron beam and gamma-ray irradiations. In the former case, the temperature does not reach value high enough to begin thermal curing thus polymerization is completely radiation-dependent. Such a course of the processes results from generation in situ a suf-

26 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 25 ficient population of intermediates due to the high dose rate what causes fast exhaustion of the initiator combined with decay of radicals. Therefore, the system cannot be thermally cured, contrary to gamma-initiated processes. The presence of graphene derivatives extends the induction time of exothermic polymerization, particularly in the case of RGO, what can results from adsorption of the part of initiator by the developed surface of the filler. On the other hand, carbon nanotubes that have not oxygen containing functional groups do not reveal such phenomena. Therefore, it seems that access to polar substituents in GO and RGO facilitates binding of the initiator to the carbon nanostructures what delays curing of the resin. On the basis of the studies it was found that the temperature profiles recorded during radiation curing of epoxy resins in the presence of cationic photoinitiators and selected carbon nanofillers were determined by the type of radiation and its dose rate, the concentration of initiator and the nature of nanofillers. The induction time of polymerization is even twice longer for graphene based composites than for non-filled matrix due to limiting access to the initiator absorbed on the surface of dispersed phase. The work was financially supported by the International Atomic Energy Agency (IAEA) CRP contract No and the Ministry of Science and Higher Education, Poland project ID References [1]. Degrand H., Cazaux F., Coqueret X., Defoort B., Boursereau F., Larnac G.: Radiat. Phys. Chem., 68, 5, (2003). [2]. Alessia S., Parlato A., Dispenza C., De Maria M., Spadaro G.: Radiat. Phys. Chem., 76, 8-9, (2007). [3]. Alessi S., Dispenza C., Fuochi P.G., Corda U., Lavalle M., Spadaro G.: Radiat. Phys. Chem., 76, 8-9, (2007). [4]. Sui G., Zhang Z-G., Liang Z-Y., Chen Ch.-Q.: Mater. Sci. Eng. A, 342, (2003). [5]. Rhodorsil photo initiator 2074 Material Safety Data Sheet. RHODIA Inc. SILICONES (USA). PREPARATION OF THE FILMS BASED ON STARCH-PVA SYSTEM. PRELIMINARY STUDIES OF THE GAMMA IRRADIATION EFFECTS Krystyna Cieśla, Anna Abramowska, Marek Buczkowski, Paweł Tchórzewski, Andrzej Nowicki, Jacek Boguski The increasing problem of the non-degradable plastic waste induces the interest in substitution of traditional packaging by the biodegradable materials. Preparation of the films in the mixed systems composed of variety of natural polymers (polysaccharides or proteins) as well as containing polysaccharide artificial biodegradable polymer seems to be one of the abilities to obtain better and more friendly for the environment packaging material. Starch is an abundant and cheap biopolymer with a good film forming ability and therefore it appears to be an appropriate source for preparation of the cheap biodegradable packaging [1-3]. In purpose to improve mechanical and barrier properties of starch films various modification methods are applied for the starch substrate as well as blending starch with the other natural or artificial biodegradable polymer. PVA (polyvinyl alcohol) can be used for packaging purposes, and is known to be the appropriate polymer for blending with starch [3]. The potential application for packing of the products subjected to radiation decontamination and the possibility of radiation modification of its structure and properties makes interesting to examine the effect of ionizing radiation on biodegradable polymer [4]. Our previous results have already shown that using the irradiated starch enables to obtain films with better functional properties as compared to those prepared basing on the native starch [1, 2]. Accordingly, our present studies were focused on the elaboration of method for preparation of the biodegradable films based on starch and PVA and examination of the effect of gamma irradiation on the properties of the obtained materials. Four PVAs (products of Sigma and of Alfa Aesar) characterized by various molecular masses (M w ; PVA1: , PVA2: 90000, PVA3: 60000, and PVA4: ) as well as two cornstarches SC1 (by Sigma) and SC2 (by Cerestar) and two potato starches S8 (Sigma product) and S7 (commercial, local market) were selected for the films preparation. Moreover, the starches SC1 d and S8 d degraded by the way of irradiation with a dose of 10 kgy (in purpose to reduce their viscosity [1, 5]) were prepared and applied. Films were prepared by the solution casting method after addition of glycerol as a plasticizer at a level of 0, 20 and 30% (in relation to the starch-pva mass). The films were dried, peeled from the substrate and conditioned during couple of days at a relative humidity of 43% before testing. Irradiations were carried out with Co-60 gamma radiation in vacuum or in air at ambient temperature in a Gamma Chamber 5000 placed in the Centre for Radiation Research and Technology, INCT. Irradiations of the PVA films were conducted with a dose of 100 kgy and irradiation of the the starch and starch-pva were carried out using a dose of 25 kgy. Mechanical tests were carried out using an Inström testing machine [2]. The average values of tensile strength and elongation at break were calculated on the basis of 6-8 measurements performed for each composition. For evaluation of

27 26 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY Table 1. The average values of tensile strength and elongation at break determined for the PVA films, non-irradiated and irradiated with gamma rays in the absence of oxygen. Films were conditioned at a temperature of ca. 35 o C. PVA PVA1 PVA2 PVA3 PVA4 Glycerol content [wt.%] tensile strength [MPa] Dose 0 kgy elongation at break [%] tensile strength [MPa] Dose 100 kgy elongation at break [%] hydrophilic/hydrophobic properties the capability for water uptake and the wetting angle for water were measured using an instrument constructed in the Laboratory of Material Research, INCT and the method described in [2]. In purpose to evaluate the polymer degradation/crosslinking degree gel content in the starch containing films was determined after heating in water [1, 6]. At the beginning, the experimental conditions enabling preparation of PVA and starch films were optimized using all the substrates. Then, optimization of the conditions for preparation of the starch-pva films was conducted. The film compositions were based on PVA : starch ratio 1:1. Two sets of syntheses were carried out. Solubilization of PVAs and preparation of starch gels appear to be the crucial step in the films synthesis. Moreover, phase separation was observed in the starch-pva films. Therefore, temperature and time of the PVA solvation and of the starch gelatinization were adapted, as well as the amount of plastificator and conditions applied for its addition. Glycerol was introduced into the film forming solution before the starch gelatinization or prior to casting. The difficulties arise in obtaining homogeneous starch films based on the native starches in regard to the high viscosity of the gels formed at the intermediate step of the syntheses. Accordingly, application of the starches degraded on the way of irradiation were expected to be advantageous [1, 5]. Our present experiments have shown that the films prepared using the starch irradiated with a 10 kgy dose reveal better properties as compared to the films prepared basing on the non-irradiated starch. In result of the optimization the experimental procedure homogeneous starch-pva films were finally obtained. Basing on these results the PVA1 and cornstarch SC1 d (pre-irradiated) were selected for the further more advanced experiments. Flexible PVA films and stiff starch films were obtained. Elasticity of PVA film was lower when M w of the substrate was higher (Table 1). The lowest tensile strength values were determined for the films based on the PVA4 characterized by the lowest M w. Increase in elasticity and decrease in tensile strength were connected with an increase in the glycerol content in the films. All the PVA and starch films shown limited hydrophilicity (PVA contact angle ca. 70 o ). In the majority of cases the hydrophilicity of PVA films was higher when M w was smaller and when plastificator content was higher (for example the water uptake determined after 11 days for PVA1 films containing 0, 20 and 30% of glycerol was equal to 28.07, and 27.89, respectively, as compared to the values of 36.72, and found for PVA4). Hydrophilicity (shown by the contact angle data) decreases during storage of the films. A contact angle determined for the films containing native starches and 30% of glycerol varied in the range o. The films obtained basing on Table 2. The average values of tensile strength and elongation at break determined for the selected starch-pva films, non-irradiated and irradiated with gamma rays in oxygen free atmosphere. The first set of experiments. All the films contain 30% of glycerol introduced into the final solution. The samples were conditioned at 20 o C. Composition Dose 0 kgy Dose 25 kgy tensile strength [MPa] elongation at break [%] tensile strength [MPa] elongation at break [%] PVA3 + SC PVA3 + SC PVA1 + SC1 d

28 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 27 the pre-irradiated specimens reach higher contact angle value (till 90 o ) as compared to those obtained using the non-irradiated starches. Starch-PVA films were characterized by the relatively good mechanical properties (Tables 2 and 3). The values of the wetting angle of the starch-pva films (77-88 o, Table 4) were generally higher as compared to those of pure PVA films (ca. 70 o ). However, the water uptake by those films (Table 4) were higher as compared to the PVA films. For example, the water uptake of the blends of PVA1 with various starches (20% of glycerol) were in the range of % as compared to 30.78% determined for the pure PVA1 under similar conditions. Mechanical data (Table 1) obtained for the PVA films prepared without glycerol addition or using 20% of glycerol suggest that the application of gamma radiation might result in an increase in tensile strength, in particular in the case of PVAs with a low molecular mass (PVA4 and PVA3). A negligible differences were noticed in the case of the films containing 30% of glycerol. In the cases of the PVA with the high molecular mass a small decrease in tensile strength was noticed and the higher decrease was observed when the samples contained a higher amount of glycerol. In all the cases of the irradiated films a decrease in elongation at break value occurs as compared to the non- -irradiated films. None particular differences were found in the contact angle data determined for the non-irradiated and the irradiated films. However, the moisture uptake was somewhat higher in the majority of the irradiated films. Table 3. The average values of tensile strength and elongation at break determined for the selected starch-pva films (30% of glycerol; obtained in the frame of the second set of experiments), non-irradiated and irradiated with gamma rays in oxygen free atmosphere and in air. Composition tensile strength [MPa] Dose 0 kgy Dose 25 kgy, oxygen absence Dose 25 kgy, air elongation at break [%] tensile strength [MPa] elongation at break [%] tensile strength [MPa] elongation at break [%] a) PVA2 + SC1 d a) PVA1 + SC1 d b) PVA1 + SC1 d c) 14.0 c) a) Glycerol introduced prior to casting. b) Glycerol introduced before starch gelatinization. c) Measurements carried out after one month. The effect of irradiation on the mechanical properties of the starch-pva films depends on their composition and the conditions applied during synthesis and irradiation. Therefore, none particular differences, a decrease in tensile strength with a simultaneous increase in elasticity as well as decrease in elasticity with negligible effect on strength were found after irradiation (Tables 2 and 3). Degree of radiation effect differs after irradiation of the same sample in air and in oxygen free atmosphere, although the directions of the changes are the same. This result suggest that degradation of the material is the prevailing process taking place in air. The increase in the films homogeneity after irradiation might be concluded basing on the SEM observation (Fig.1) and the smaller dispersion of the mechanical results. Hydrophilicity of the majority of the starch- -PVA films has increased after irradiation (Tables 4 and 5). However, in some cases these properties became unchanged or even decreases. Table 4. Wetting angle, moisture uptake at 20 o C after two weeks and gel fraction determined for the selected starch-pva films (non-irradiated and irradiated in the oxygen absence (25 kgy). PVA type Starch sample Glycerol content [%] Dose [kgy] Gel fraction [%] % of the gel fraction of the initial film Moisture uptake [%] Wetting angle [ o ] PVA3 SC PVA3 SC PVA3 SC PVA3 SC PVA3 SC PVA3 SC PVA3 SC PVA3 SC PVA1 SC1 d PVA1 SC1 d PVA1 SC1 d PVA1 SC1 d

29 28 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY A 1000 x B Fig.1. The exemplar images of the starch-pva films (SC1 d -PVA1, 30% of glycerol): A initial, B irradiated in vacuum with a dose of 25 kgy. Decrease in the gel fraction content was found after irradiation in the majority of the samples (Tables 4 and 5) showing the occurring degradation processes. However, the degree of this decrease differs in the cases of particular samples. Moreover, it seems to be in some cases insignificant, or at least lower than can be expected after particpation might be even more important than that of degradation. None particular effect of irradiation on mechanical properties found in some cases suggests that the materials based on the examined system, properly prepared, might appear appropriate for packing products predicted for radiation decontamination. Table 5. Moisture uptake at 4 o C after 48 h and gel fraction determined for the starch-pva films (30% of glycerol; the second experiment), non-irradiated and irradiated using a dose of 25 kgy. Composition Dose [kgy] Gel fraction [%] % of the gel fraction of the initial film Moisture uptake [%] a) PVA2 + SC1 d a) PVA2 + SC1 d 25 c) a) PVA2 + SC1 d 25 d) a) PVA1 + SC1 d a) PVA2 + SC1 d 25 c) a) PVA2 + SC1 d 25 d) b) PVA1 + SC1 d b) PVA2 + SC1 d 25 c) b) PVA2 + SC1 d 25 d) a) Glycerol introduced prior to casting. b) Glycerol introduced before starch gelatinization. c) In oxygen absence. d) In air. irradiation performed using a dose of 25 kgy. For example, it reach the value ca. 75% in the case of PVA1-SC1 d (pre-irradiated starch, 30% of glycerol) of that obtained for the initial sample (Tables 4 and 5), while the value of ca. 30% was found under the same conditions for the SC1 d pure starch. This result suggests that crosslinking accompanies degradation in these systems. The last conclusion was supported by thermogravimetry. These preliminary results show the increase in the compatibility of the components in the PVA- -starch-glycerol systems taking place under gamma radiation. The effect of irradiation depends on the sample composition and on the applied conditions. Degradation was found to be the prevailing process taking place in the majority of the films. However, it can be supposed that crosslinking occurs simultaneously with degradation and in some cases its The work was sponsored in the frame of the International Atomic Energy Agency (IAEA) research contract No (CRP F2206). References [1]. Cieśla K.: Przekształcenia struktury nadcząsteczkowej w polimerach naturalnych inicjowane promieniowaniem jonizującym (Transformation of supramolecular structure initialized in natural polymers by gamma irradiation). Institute of Nuclear Chemistry and Technology, Warszawa 2009, 223 p. (in Polish). [2]. Cieśla K., Nowicki A, Buczkowski M.: Nukleonika, 55, 2, (2010). [3]. Tang X., Alavi S.: Carbohydr. Polym., 85, 1-16 (2011). [4]. Ryzhkova, Jarzak U., Schäffer A., Bämer M., Swiderek P.: Carbohydr. Polym., 83, 608 (2011). [5]. Cieśla K.: J. Therm. Anal. Calorim., 74, (2003). [6]. Cieśla K., Eliasson A-C.: Acta Aliment., 36(1), (2007).

30 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY Chemical issues of nuclear power and radiopharmaceutical chemistry the two top 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 The research projects of the Centre were financed from the National Centre for Research and Development (NCBR), the National Science Centre (NCN), the European Comission (FP7 Euratom, Fission), from the national Operational Programme Innovative Economy (PO IG), and also as the Institute s statutory research. The teams of three Centre laboratories (Radiochemical Separation Methods, Membrane Processes and Technologies, and Sol-Gel Technology) continued their studies on radioactive waste management, and on special nuclear materials. In this respect, the Sol-Gel team continued the execution of the European Collaborative Project ASGARD, contributing to the development of new types of MOX nuclear fuels based on uranium oxides and carbides. The work was accompanied by statutory research on the synthesis of another potential nuclear fuel, mixed thorium-uranium dioxide in the form of microspheres. The Separation team started their research on modifying solvent extraction systems for i-sanex process, in the frame of the new European Collaborative Project SACSESS (Safety of actinide separation processes). Studies on actinide complexes with a new hydrophilic, polyheterocyclic-n-dentate ligand in solvent extraction systems have been commenced. A few Centre teams continued their research in the frame of workpackage related to the management of spent nuclear fuel and radioactive wastes a part of the NCBR strategic project on the development of safe nuclear energy in Poland. Various aspects were studied, related to the management and storage of spent nuclear fuel and radioactive wastes formed in the course of exploitation of nuclear power plants, with a special emphasis on Polish nuclear industry. Within another NCBR project and statutory research, novel methods were examined for the separation of radionuclides and heavy metal ions, based on hybrid processes (membrane filtration combined with sorption or complex formation, and micellar-enhanced ultrafiltration), as the basis for further technologies for radioactive waste management. In 2013, we completed the execution of a number of research projects in the matter: (i) the national project related to the possibilities of supplying uranium from indigenous resources, financed from PO IG, and coordinated by the member of our team; (ii) the Euratom FP7 project IPPA, aimed at the creation of a safe arena for the exchange of opinions and public acceptation of the problems of radioactive waste disposal; and (iii) the other Euratom FP7 project NEWLANCER, aimed at enhancing the participation of Polish teams in the research programmes of Euratom. As the result of the first project, Polish uranium resources have been evaluated and efficient methods adapted for extracting uranium from low-grade ores, secondary raw materials and industrial by-products. The other two projects allowed to establish strong international cooperation in the field of radioactive waste management and various aspects of waste disposal including public acceptance and involvement in decision-making. Within these projects several national and international meetings involving partner institution from Poland and cooperating European organizations were organized by the Centre. Research on radiopharmaceutical chemistry (Laboratory of Radiopharmaceuticals Synthesis and Studies) were focused on obtaining and studying novel potential radiopharmaceuticals, both diagnostic and therapeutic, by labelling either novel biomolecules (e.g. derivatives of tacrine and substance P) with 99m Tc, 68 Ga, or nanobodies with 225 Ac and 212 Pb. Other studies were directed at labelling peptide vectors (e.g. substance P) with alpha emitters ( 223 Ra, 225 Ac and 211 At) via nanoparticles of functionalized zeolite, titanium dioxide and core shell Au 2 S-Au ones. Also microspheres of yttrium-90 oxide (synthesized at the Laboratory of Sol-Gel Tech-

31 nology) were further tested as potential radiopharmaceuticals for anticancer therapy by radioembolization. Apart from the Institute statutory research, the studies on radiopharmaceutical chemistry were funded from eight NCN and NCBR projects, some of them under international cooperation. Three members of the Centre staff have defended their PhD theses, and one PhD student got Fulbright fellowship to work in radiopharmaceutical chemistry for 6 months at one of leading USA laboratories. Further medals (at international exhibitions) and some other prizes have been awarded to the Centre staff members. The international and national scientific cooperation of the Centre was successfully continued and enhanced. The new bi- and multilateral R&D projects make the Centre team a desired partner not only on the national scale but also in the European research area.

32 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY SYNTHESIS, PHYSICOCHEMICAL AND BIOLOGICAL EVALUATION OF NOVEL TECHNETIUM-99m LABELLED LAPATINIB AS A POTENTIAL TUMOUR IMAGING AGENT Ewa Gniazdowska, Przemysław Koźmiński, Leon Fuks, Krzysztof Bańkowski 1/, Wojciech Łuniewski 1/, Leszek Królicki 2/ 1/ Pharmaceutical Research Institute, Warszawa, Poland 2/ Nuclear Medicine Department, Medical University of Warsaw, Warszawa, Poland A O S O H N O O HO S O N HN N O HO S O Cl O F 31 ethyl)-amine; 2,2,2 -nitrilotriethanethiol) and a monodentate isocyanide species CN-BFCA (bifunctional coupling agent, isocyanobutyric acid succinimidyl ester) previously coupled with lapatinib molecule. The tetradentate NS 3 ligand was prepared by reaction of tris(2-chloroethyl)amine hydrochloride with potassium thioacetate followed by reduction with LiAlH 4 [2]. The aliphatic linker CN-BFCA was synthesized according to the procedure described in [3]. The coupling reaction of the isocyanide linker CN-BFCA with the lapatinib molecule (Scheme 1) was performed according to the procedure described in [4]. Crude product was purified on a semi-preparative HPLC column (system 1), alkalized and lyophilized, yield 35%. MS: m/z: calcd ; found [M+H + ], [M+Na + ]. B N S 99m Tc S S CN Fig.1. Lapatinib molecule (A) and 99m Tc-labelled lapatinib using the 4+1 approach (B). O Lapatinib (NS 3 ) 99m Tc(CN-BFCA-Lapatinib) One of the most important radiopharmaceuticals which selectively distribute within given tissues or organs, are formed by coordination compounds with diagnostic/therapeutic radiometal firmly attached to selected biologically active molecule. Lapatinib ditosylate (Fig.1A) is an anticancer drug used for treatment of solid tumours such as breast or lung cancer, because it exhibits high affinity towards Her-2 receptors [1]. It is expected, that lapatinib labelled with technetium-99m may also serve as a diagnostic receptor radiopharmaceutical for patients suffering from breast cancer of the Her-2 type. The aim of this work was to synthesize conjugate containing technetium-99m complex of the 4+1 type and lapatinib as the biologically active IR: (KBr plates), cm 1 : 2153 (C N), 1814, 1785, 1729 (succinimidyl ester). The (NS 3 ) 99m Tc(CN-lapatinib) conjugate was synthesized in n.c.a. scale in two-step procedure according to [4] (Scheme 2). The NS 3 molecule coordinates the 99m Tc(III) cation and leaves the fifth coordination site available for one monodentate isocyanide ligand CN-lapatinib. N N C N O O N O O O + S O H N O HN N Cl O F C N O S O O N O HN N Cl O F + H O O O Scheme 1. Coupling reaction of CN-BFCA with lapatinib. EDTA-kit 99m TcO - 99m 4 Tc-EDTA room temp. 70 o C, 30 min 20 min Scheme 2. Two-step synthesis of (NS 3 ) 99m Tc(CN-lapatinib) conjugate in n.c.a. scale. molecule (Fig.1B) and to determine physicochemical and biological properties of the conjugate important from the radiopharmaceutical point of view. The conjugate (NS 3 ) 99m Tc(CN-lapatinib) consists of 99m Tc(III) cation coordinated by the tetradentate NS 3 tripodal chelator (tris(2-mercapto- The reaction progress was checked by TLC (thin layer chromatography) and HPLC (high performance liquid chromatography; system 2) methods. The radiochemical yield of the synthesized conjugate was higher than 97%. Conditions of HPLC systems were the following: NS 3, CN-lapatinib, MeOH (NS 3 ) 99m Tc(CN-lapatinib) System 1: Phenomenex Jupiter Proteo semi-preparative column (4 μm, 90 Å, 250 x 10 mm), UV/Vis detector (220 nm); elution conditions: solvent A water with 0.1% TFA (v/v), solvent B acetonitrile with 0.1% TFA (v/v); gradient 0-20 min 20 to 80% solvent B, min 80% solvent B; 2 ml/min. System 2: Phenomenex Jupiter Proteo analytical column (4 μm, 90 Å, 250 x 4.6 mm), gamma radia-

33 32 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY tion detector; elution conditions: solvent A water with 0.1% TFA (v/v), solvent B acetonitrile with 0.1% TFA (v/v); gradient 0-20 min 20 to 80% solvent B, min 80% solvent B; 1 ml/min. TLC analyses were performed using Merck 60 F 254 aluminum sheets. All radioactive substances were placed on the strip, developed with appropriate solutions and dried. Distribution of radioactivity on the strip was determined using a home- -made automatic TLC analyser SC-05 (INCT). The synthesized conjugate was characterized by determination of the logarithm of its partition coefficient, log P, in the n-octanol/pbs (ph 7.40) system. Stability of the isolated conjugate was investigated both as a function of time (HPLC) and in challenge experiments (in the presence of excess of histidine or cysteine), as well as in rat serum. The biological properties of the conjugate were characterized in vitro by investigations of the conjugate affinity to Her-2 receptor using cell line SKOV-3 and in vivo by the biodistribution studies. The conjugate (NS 3 ) 99m Tc(CN-lapatinib) is formed with high yield and purity (Fig.2). The small peaks recorded at R T = 3.4 and 7.9 min correspond cpm (NS 3) 99m Tc(CN-lapatinib) R T = 18.5 min min Fig.2. HPLC chromatogram of the reaction mixture (performed in system 2) after completion of the synthesis of the (NS 3 ) 99m Tc(CN-lapatinib) conjugate. to the intermediate complexes 99m Tc-EDTA/mannitol and 99m Tc(NS 3 ), respectively. The determined lipophilicity value of the conjugate was found to be 1.24 ± 0.04 (n = 3). The studied conjugate exhibited high stability. After 24 h of incubation in 10 mm histidine or cysteine solution and in rat serum the obtained HPLC chromatograms have shown mainly the existence of one radioactive species in the solution, with the retention time characteristic for the studied conjugate. Biological studies were performed using the SKOV-3 cell line. The cells were maintained in McCOY S 5A Medium (Modified), containing 2 mm of L-glutamine, 10% of fetal bovine serum and supplemented with 0.1 IU/ml penicillin and 0.1 mg/ml streptomycin. Cells were cultured at 37 o C in a humidified incubator under an atmosphere containing 5% of CO 2. The cells were subcultured once a week. Affinity studies were performed on 6-well plates (SARSTEDT) in McCOY S 5A Medium which contained approximately 4 x 10 5 adherent cells in % ID m TcO4 99m Tc-EDTA Fig.3. Cell binding of (NS 3 ) 99m Tc(CN-lapatinib) conjugate in comparison with other 99m Tc species. Cell binding levels are expressed as the percentage of added doses (% ID). each well. Cell count was determined using hemocytometer and microscope. Preliminary affinity studies were performed by incubating SKOV-3 cells together with the studied conjugate, as well as with other 99m Tc-species, namely with 99m TcO 4, 99m Tc-EDTA/mannitol and 99m Tc(NS 3 ). After 45 min of incubation the binding was stopped, the solution from above the cells was quantitatively separated and the cells were washed three times with cold PBS, ph 7.4 (in order to eliminate unbound radioactivity). Then, the cells were solubilized with 1 M NaOH and activity of solution from above the cells and that of solubilized cells was measured in the gamma counter. Affinity of the conjugate was A B % Specific Bound [nm] B/F 3 2,5 2 1,5 1 0,5 0 1,2 1,0 0,8 0,6 0,4 0,2 0,0 B max = 2.4 nm Fig.4. (A) The saturation curve for (NS 3 ) 99m Tc(CN-lapatinib). The specifically bound radioligand is plotted as a function of increasing concentrations of (NS 3 ) 99m Tc(CN-lapatinib). (B) Scatchard plot. 99m Tc(NS 3) (NS 3) 99m Tc(CN-lapatinib) concentration of (NS 3) 99m Tc(CN-lapatinib) [nm] K d = 3,5 nm 0,00 0,50 1,00 1,50 2,00 2,50 3,00 B [nm]

34 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 33 calculated as the ratio of activity bound by cells to the sum of activity bound by cells and that which remained in the solution above the cells (Fig.3). Binding of the (NS 3 ) 99m Tc(CN-lapatinib) conjugate to Her-2 receptor of SKOV-3 cells was found to be saturable and specific in the predominant degree (Fig.4A). The non-specific binding determined in the presence of 0.1 μm solution of lapatinib accounts in general for about 0.3% of specific binding. The B max value was found to be 2.4 ± 0.3 nm (n = 3), which corresponds to the approximate number of binding sites per cell. The dissociation constant, K d, usually used to describe the affinity of the conjugate to its receptor (Fig.4B), was found to be 3.5 ± 0.4 nm (n = 3). The low value of K d indicates high affinity of the studied conjugate. In a competitive binding experiment the unlabelled lapatinib molecules inhibited binding of (NS 3 ) 99m Tc(CN-lapatinib) and the inhibitory concentration of 50% (IC 50 ) obtained for lapatinib was % Specific Bound ,E-11 1,E-10 1,E-09 1,E-08 1,E-07 1,E-06 1,E-05 1,E-04 1,E-03 log [M] Fig.5. Displacement of (NS 3 ) 99m Tc(CN-lapatinib) by increasing concentration of unlabelled lapatinib. found to be 41.2 ± 0.4 nm (Fig.5). This value also confirms satisfactorily high affinity of (NS 3 ) 99m Tc (CN-lapatinib) conjugate to Her-2 receptors in the SKOV-3 cells. Table. Biodistribution studies of (NS 3 ) 99m Tc(CN-lapatinib) conjugate in BALB/c mice at 30 and 60 min p.i. (n = 6, % ID/g ± SD). Uptake in organ, percentage Organ of injected dose per g tissue [% ID/g ± SD] Heart 0.10 ± ± 0.04 Kidneys 3.28 ± ± 0.6 Liver 4.89 ± ± 0.8 Lungs 0.77 ± ± 0.09 Spleen 0.44 ± ± 0.02 Blood 0.99 ± ± 0.02 Thyroid 0.94 ± ± 0.02 Biodistribution studies of (NS 3 ) 99m Tc(CN-lapatinib) conjugate (Table, Fig.6) were performed on normal 3 months old male BALB/c mice (of weight %ID/g Heart Kidneys Liver 30 min after injection 60 min after injection Fig.6. Biodistribution studies of (NS 3 ) 99m Tc(CN-lapatinib) in BALB/c mice after 30 and 60 min p.i. between 23 and 28 g, n = 12), according to the relevant national regulations. The mice were injected via tail vein with MBq in μl of aqueous solution of (NS 3 ) 99m Tc(CN-lapatinib) and sacrificed at 30 and 60 min after injection of conjugate. Then, tissues were dissected, washed free of blood and weighed. Associated radioactivity was counted using gamma counter. The accumulated radioactivity in the tissue of organs was calculated as the percentage of injected dose per gram (% ID/g) of tissue, as well as the percentage of injected dose per gram of blood. The standard source of 99m Tc was also measured simultaneously with the samples in order to perform the decay correction. The presented data show similar uptake of (NS 3 ) 99m Tc(CN-lapatinib) conjugate in liver (4-5% ID/g) and in kidney (3-5% ID/g). It points out to the clearance of the conjugate through the renal and through the hepatic route in the comparable degree. The uptake in other organs remained on the level < 1% ID/g. (NS 3 ) 99m Tc(CN-lapatinib) conjugate is formed with high yield and presents high stability in solutions containing competitive cysteine/histidine ligands. The biological in vitro and in vivo studies of the conjugate showed its high affinity to Her-2 receptor and the clearance through the renal and hepatic route in comparable degree. To conclude, (NS 3 ) 99m Tc(CN-lapatinib) conjugate may be considered a promising diagnostic radiopharmaceutical for patients suffering from breast cancer of Her-2 type. The work was carried out within the grant No. N R (National Centre for Research and Development, Poland). References [1]. Burris H.A. et al.: Oncologist, 9, (2004). [2]. Spies H., Glaser M., Pietzsch H.-J., Hahn F.E., Luegger T.: Inorg. Chim. Acta, 240, (1995). [3]. Kuenstler J.-U., Veerenda B., Figueroa S.D., Sieckman G.L., Rold T.L., Hoffman T.J., Smith C.J., Pietzsch H.-J.: Bioconjugate Chem., 18, (2007). [4]. Seifert S., Kuenstler J.-U., Schiller E., Pietzsch H.-J., Pawelke B., Bergmann R., Spies H.: Bioconjugate Chem., 15, (2004). Lungs Spleen Blood Thyroid

35 34 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY CYCLOTRON PRODUCTION OF 99m Tc. SEPARATION OF 99m Tc FROM 100 Mo TARGET Magdalena Gumiela, Ewa Gniazdowska, Aleksander Bilewicz Every day about diagnosis procedures using 99m Tc-radiopharmaceuticals are performed rendering this the most widely used radioisotope in nuclear imaging. 99m Tc is commonly easy available from 99 Mo /99m Tc generators. 99 Mo (the mother nuclide, t 1/2 = 66 h) is produced via either thermal neutron irradiation of natural Mo in the reaction 98 Mo(n,γ) 99 Mo or thermal fission of highly enriched 235 U (HEU) in the reaction 235 U(n,f) 99 Mo. Usually, the operation period of research reactors used for the production of 99 Mo is about years. Most reactors used for the preparation of 99 Mo have already reached this age, or they will reach it in the near future. Therefore, there is still growing interest in exploring alternative cyclotron production of 99m Tc using 100 Mo(p,2n) 99m Tc reaction, the method proposed first by Beaver and suitable for use in novel modes of 99m Tc production. Separation of technetium from irradiated molybdenum may be carried out using either wet or dry chemical processes. Wet separation techniques require dissolving of the metallic target under oxidative conditions and then separation of pertechnetate can be achieved using one of many strategies, e.g. liquid-liquid extraction [3], ion-exchange chromatography [4], aqueous biphasic extraction chromatography using ABEC resin [5] and electrochemistry [6]. The aim of our studies was to elaborate a simple and fast method for separation of microquantities of pertechnetate from macroquantities of molybdate anions in the process of cyclotron production of 99m Tc. The schematic diagram of proposed methods is presented in Fig.1. Fig.1. Scheme of the separation process of 99m Tc from 100 Mo. Hupf nearly 40 years ago [1]. In other way, some amounts of 99 Mo suitable for the production of 99 Mo/ 99m Tc generators can be obtained in the nuclear reaction 100 Mo(p,pn) 99 Mo [2]. The significant advantage of the direct production of 99m Tc using cyclotrons is the less nuclear waste production compared to the fission product method of 99 Mo production. On the other hand, due to the relatively short half-life of 99m Tc, the method of direct 99m Tc production can be applied only in hospitals near cyclotron centres. Natural molybdenum consists of several isotopes including 92 Mo, 94 Mo, 95 Mo, 96 Mo, 97 Mo, 98 Mo and 100 Mo. During proton bombardment of natural Mo, depending on proton energy, several reaction channels may be present and, apart from 99m Tc, various isotopes of technetium, such as 96 Tc, 95 Tc and 94 Tc, can be produced. Therefore, the application of molybdenum target enriched with 100 Mo (97.46%) is needed. However, the natural abundance of 100 Mo is only 9.63%. High cost associated with the isotopic enrichment of 100 Mo from natural molybdenum makes necessary to investigate the recycling of the 100 Mo target material. So, there is a real necessity to develop separation technologies Our studies were carried out using natural molybdenum powder. We utilized formation of insoluble yellow ammonium molybdenum phosphate (AMP) in the reaction of ammonium phosphate with molybdate anions, which takes place according to the formula: (NH 4 ) 3 PO 4 3H 2 O + 12MoO H + (NH 4 ) 3 P(Mo 3 O 10 ) 4 + 5H 2 O In the first step, metallic molybdenum target was dissolved in 3.5 M HNO 3. Next, triammonium phosphate and ammonium nitrate were added, and AMP was precipitated in the form of yellow solid. We have optimized four parameters of the process: the concentration of NH 4 NO 3 and of (NH 4 ) 3 PO 4 3H 2 O, temperature and the time of precipitation. The increase in the concentration of ammonium nitrate results in lower solubility of AMP precipitate. In M ammonium nitrate solution the solubility of AMP is nearly twice less than in the case when the precipitation was carried out in the absence of ammonium nitrate. We have also found that the concentration of (NH 4 ) 3 PO 4 3H 2 O does not influence the AMP solubility, and no excess of triammonium phosphate is needed. In the next steps, we analysed the influence of tem-

36 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 35 Fig.2. Concentration of Mo in solution as a function of time and temperature of precipitation process. perature and time on the precipitation process (Fig.2). Precipitation process was tested at various temperature (40, 60 and 80 o C) and time periods (15 min-1 h). The lowest concentration of Mo in the solution, equal to about 370 μg/ml, was reached in the reaction mixture heated at 80 o C. As one can see in Fig.2, the concentration of Mo in the reaction mixture only slightly depends on the time of sample heating. Based on the performed experiments, the following optimal conditions for the separation of microamounts of 99m Tc from Mo target have been selected: 25 mg of metallic Mo target is dissolved in 0.5 ml of 3.5 M HNO 3, next 400 μl 0.44 M of (NH 4 ) 3 PO 4 and 100 μl 3 M of NH 4 NO 3 is added. The process should be carried out at 80 o C for 30 min. The precipitate can be separated by filtration or centrifugation. Finally, we also studied the possibility of 99m Tc coprecipitation with AMP. After separation process, under conditions presented above, we found in the filtrate solution 99.6% of the total 99m Tc activity. Basically, it means that 99m Tc does not coprecipitate with AMP. This proposed process is promising and allows for fast separation of Mo macroamounts from the solution without coprecipitation of 99m Tc. After optimization of the precipitation conditions, the lowest concentration of MoO 4 2 was only 0.37 mg/ml. The final solution will be conducted through a column containing one of the Zr-based sorbents. References [1]. Beaver J., Hupf H.: J. Nucl. Med., 12, (1971). [2]. Almeida G.L., Helus F.: Radiochem. Radioanal. Lett., 28, 205 (1977). [3]. Dallali N., Ghanbari M., Yamini Y., Fateh B., Agrawal Y.K.: Indian J. Chem. A, 46A, (2007). [4]. Chattopadhyay S., Das S.S., Das M.K., Goomer N.C.: Appl. Radiat. Isot., 66, 12, (2008). [5]. Rogers R.D., Bond A.H., Griffin S.T., Horwitz E.P.: Solvent Extr. Ion Exch., 14, (1996). [6]. Chakravarty R., Dash A., Venkatesh M.: Nucl. Med. Biol., 37, (2010). THE STRUCTURES OF BISMUTH(III) COMPLEXES WITH TROPOLONE Krzysztof Łyczko, Monika Łyczko, Krzysztof Woźniak 1/, Marcin Stachowicz 1/ 1/ Department of Chemistry, University of Warsaw, Warszawa, Poland Tropolone (2-hydroxy-2,4,6-cycloheptatriene-1- -one), abbreviated as Htrop, is an aromatic compound with a seven-membered carbon ring. It contains two neighbouring functional groups (carbonyl and hydroxyl) which make possible its coordination to various metal ions. The tropolonate anion (trop ) is a bidentate oxygen donor ligand forming a five-membered chelate ring upon complexation. In the 1960s the bismuth(iii)-tropolonato complexes, such as [Bi(trop) 2 Cl] [1], Bi(trop) 3 and Na[Bi(trop) 4 ] [2], were synthesized for the first time. In 1995, the preparation and characterization of new bismuth(iii) compounds with tropolone and its derivatives were presented. Among them, the structures of only nitratobis(tropolonato)bismuth(iii) and aquabis(4,5-benzotropolonato)bismuth(iii) nitrate were published [3]. However, they are not available in the Cambridge Structural Database. We have previously reported the formation of three polymeric lead(ii)-tropolonato complexes [Pb(trop)(CF 3 SO 3 )(H 2 O)] n, [Pb 3 (trop) 4 (ClO 4 ) 2 ] n, [Pb 2 (trop) 2 (NO 3 ) 2 (CH 3 OH)] n and one dimeric compound [Pb(trop) 2 ] 2, which depends on the ph of solution and the counterion [4]. Bismuth compounds have been extensively studied in respect of their antibacterial properties and possible usage in cancer therapy [3, 5-8]. Based on our work concerning of lead(ii)-tropolonato complexes [4], we decided to investigate the effect of counterion and ph of the solution on the formation of bismuth(iii)-tropolonato compounds. The reaction of tropolone with Bi(CF 3 SO 3 ) 3, Bi(ClO 4 ) 3 and Bi(NO 3 ) 3 in methanol solution in the molar ratios 1:2 and 1:3 led to the formation of three different bismuth(iii) complexes: one dimeric and two polymeric. The structures of the [Bi(trop) 2 (CF 3 SO 3 )] 2 (1), [Bi 2 (trop) 4 (ClO 4 ) 2 ] n (2) and [Bi 2 (trop) 4 (NO 3 ) 2 ] n (3) compounds were determined by single crystal X-ray diffraction (Figs.1-3). A simple tris(tropolonato)bismuth(iii) complex, Bi(trop) 3 (4), was obtained from bismuth(iii) acetate salt. In the crystal structure of 1 two Bi(trop) 2 (CF 3 SO 3 ) entities are held together in dimeric units (Fig.1). Compounds 2 and 3 have polymeric structures with the Bi 2 (trop) 4 (ClO 4 ) 2 and Bi 2 (trop) 4 (NO 3 ) 2 fragments, respectively, repeated in the polymeric chains (Figs.2-3). Each bismuth(iii) ion in the compounds 1-3 is chelated by two tropolonato ligands. It is obvious that the counterions (triflate, perchlorate and nitrate) play an important role in the formation of the studied compounds, through entering their structures. Contrary to the complex 1 which has the bismuth centres of the same kind, the complexes 2 and 3

37 36 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY Fig.1. The structure of [Bi(trop) 2 (CF 3 SO 3 )] 2 (1). Selected bond lengths, distances [Å] and angles [ o ]: Bi(1) O(2) 2.279(3), Bi(1) O(1) 2.231(3), Bi(1) O(12) 2.266(3), Bi(1) O(11) 2.164(3), Bi(1) O(3) 2.870(3), Bi(1) O(4) 2.862(3), Bi(1) O(1 ) 2.657(3), O(1) Bi(1) O(2) 70.31(9), O(11) Bi(1) O(12) 72.19(10). The non-hydrogen atoms are shown as the 50% probability ellipsoids. comprise two coordinatively different types of Bi atoms. In all the complexes studied, the tropolonate ions chelate the bismuth(iii) ions in an anisobidentate manner, with one shorter and one longer Bi O bond. The lengths of the chelating Bi O bonds are within the range Å. In addition, some tropolonato ligands are also bridging to one (in 1-3) or two (in 2 and 3) neighbouring bismuth(iii) ions. In the studied structures, the bridging Bi O (trop) distances are longer than the chelating Bi O (trop) bonds, and vary in the range Å. The bond distances between Fig.2. The structure of [Bi 2 (trop) 4 (ClO 4 ) 2 ] n (2). Selected bond lengths [Å] and angles [ o ]: Bi(1) O(1) 2.304(3), Bi(1) O(2) 2.226(3), Bi(1) O(11) 2.306(3), Bi(1) O(12) 2.176(3), Bi(1) O(4) 2.823(4), Bi(1) O(8 ) 2.776(3), Bi(1) O(21) 2.740(3), Bi(1) O(32) 2.896(3), Bi(2) O(21) 2.299(3), Bi(2) O(22) 2.179(3), Bi(2) O(31) 2.242(3), Bi(2) O(32) 2.193(3), Bi(2) O(1) 2.753(3), Bi(2) O(2 ) 2.870(3), Bi(2) O(11 ) 2.894(4), Bi(2) O(7 ) 2.880(4), O(1) Bi(1) O(2) 69.32(12), O(11) Bi(1) O(12) 71.59(12), O(21) Bi(2) O(22) 70.63(12), O(31) Bi(2) O(32) 71.29(11). The atoms are shown as the 50% probability ellipsoids. Hydrogen atoms are omitted. Fig.3. The structure of [Bi 2 (trop) 4 (NO 3 ) 2 ] n (3). Selected bond lengths [Å] and angles [ o ]: Bi(1) O(1) 2.360(2), Bi(1) O(2) 2.309(2), Bi(1) O(11) 2.269(2), Bi(1) O(12) 2.189(2), Bi(1) O(3) 2.652(2), Bi(1) O(4) 2.746(2), Bi(1) O(6 ) 2.776(2), Bi(1) O(21) 2.901(2), Bi(1) O(32) 2.630(2), Bi(2) O(21) 2.205(2), Bi(2) O(22) 2.250(2), Bi(2) O(31) 2.248(2), Bi(2) O(32) 2.376(2), Bi(2) O(6) 2.909(2), Bi(2) O(7) 2.658(2), Bi(2) O(1) 2.651(2), Bi(2) O(2 ) 2.960(2), Bi(2) O(11 ) 2.875(2), O(1) Bi(1) O(2) 67.48(5), O(11) Bi(1) O(12) 72.01(6), O(21) Bi(2) O(22) 71.26(6), O(31) Bi(2) O(32) 67.52(6). The atoms are shown as the 50% probability ellipsoids. Hydrogen atoms are omitted. the metal ions and oxygen atoms of counterions (CF 3 SO 3, ClO 4 and NO 3 ), changing in the range Å, are similar to the bridging Bi O (trop) contacts in respect to distance. The shortest distances of those type (2.652 and Å) are found in 3 for nitrate ions. Moreover, some perchlorate and nitrate ions act as bridges between two neighbouring metal atoms within the same polymeric chain. All these bismuth-oxygen distances are much shorter than the calculated sum of van der Waals radii of bismuth and oxygen atoms, 3.59 Å [9]. The studied complexes demonstrate various total coordination numbers of bismuth(iii) ions: from 7 in [Bi(trop) 2 (CF 3 SO 3 )] 2, 8 in [Bi 2 (trop) 4 (ClO 4 ) 2 ] n, to 9 in [Bi 2 (trop) 4 (NO 3 ) 2 ] n. The structure of the homoleptic complex 4 was modelled by quantum-mechanical calculations at the DFT/B3LYP level of theory, using Gaussian program [10], because we failed in obtaining single crystals suitable for crystallographic measurements. The optimized geometry shows that the bismuth(iii) ion is six-coordinated with three shorter (2.220 Å) and three longer (2.400 Å) Bi O bond lengths (Fig.4). The arrangement of these six oxygen atoms around the metal centre forms strongly distorted octahedron (or distorted triangle antiprism) with the bismuth(iii) ion placed almost on the surface built up of three O atoms [O(2), O(4) and O(6)] (Fig.4B). The 6s 2 lone electron pairs on the bismuth(iii) ions seem to be stereochemically active in all complexes studied. The presence of distinct empty volumes around the metal ions is the evidence for

38 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 37 A B Fig.4. The calculated molecular structure of tris(tropolonato)bismuth(iii), Bi(trop) 3 (4), in two projections: (A) top view and (B) side view. the stereochemically active 6s 2 lone pair in the compounds 1 and 4 [11]. In turn, the observed pattern in 2 and 3, with a few adjacent shorter and a few adjacent longer Bi O distances, can also indicate the active character of this lone electron pair [11]. The formation of studied complexes, similarly as in the case of lead(ii)-tropolonato compounds [4], depends on ph of the solution. The ph of methanolic solutions of salts originating from strong acids (Bi(CF 3 SO 3 ) 3, Bi(ClO 4 ) 3 and Bi(NO 3 ) 3 ) was much lower (~0 or less) than that (ph > 5) of Bi(CH 3 CO 2 ) 3 the salt of weak acid. Addition of tropolone to very acidic solutions, as for the first three salts, results in the formation of polymeric or dimeric compounds. At higher ph, as for the case of bismuth(iii) acetate, the precipitation of simple tris(tropolonato)bismuth(iii) has been observed. Very low ph impedes the formation of the Bi(trop) 3 moiety and favours the dimerization and polymerization processes. References [1]. Muetterties E.L., Wright C.M.: J. Am. Chem. Soc., 86, (1964). [2]. Muetterties E.L., Roesky H., Wright C.M.: J. Am. Chem. Soc., 88, (1966). [3]. Diemer R., Keppler B.K., Dittes U., Nuber B., Seifried V., Opferkuch W.: Chem. Ber., 128, (1995). [4]. Lyczko K., Starosta W., Persson I.: Inorg. Chem., 46, (2007). [5]. Dittes U., Vogel E., Keppler B.K.: Coord. Chem. Rev., 163, (1997). [6]. Briand G.G., Burford N.: Chem. Rev., 99, (1999). [7]. Imam S.K.: Int. J. Radiat. Oncol. Biol. Phys., 51, (2001). [8]. Su F-M., Beaumier P., Axworthy D., Atcher R., Fritzberg A.: Nucl. Med. Biol., 32, (2005). [9]. Mantina M., Chamberlin A.C., Valero R., Cramer C.J., Truhlar D.G.: J. Phys. Chem. A, 113, (2009). [10]. Frisch M.J. et al.: Gaussian 09, revision C.01. Gaussian, Inc., Wallingford CT, USA [11]. Shimoni-Livny L., Glusker J.P., Bock Ch.W.: Inorg. Chem., 37, (1998). SILVER IMPREGNATED NANOPARTICLES OF TITANIUM DIOXIDE AS 211 At CARRIERS Edyta Leszczuk, Monika Łyczko, Agata Piotrowska, Aleksander Bilewicz, Jarosław Choiński 1/, Jerzy Jastrzębski 1/, Anna Stolarz 1/, Agnieszka Trzcińska 1/, Katarzyna Szkliniarz 2/, Wiktor Zipper 2/, Bogdan Wąs 3/ 1/ Heavy Ion Laboratory, University of Warsaw, Warszawa, Poland 2/ University of Silesia, Katowice, Poland 3/ The Henryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, Poland 211 At is one of the most prospective alpha emitters studied so far for cancer therapy. It is produced in the 209 Bi(α,2n) 211 At reaction in cyclotrons. Its half- -life of 7.2 h is sufficient for separation, labelling, quality control, shipment and medical application. It decays by double branch pathway with the mean alpha energy of 6.7 MeV. From chemical point of view, astatine as a heavy halogen has similar properties to other members of the group, but it also exhibits some metallic character. Therefore, its bonds with aromatic and aliphatic moieties are much weaker than those of iodine [1]. Thus, the labelling of peptides or antibodies with 211 At is a big challenge. Moreover, bioconjugates labelled with 211 At are usually unstable under physiological conditions, which limits the use of astatinated radiophamaceuticals. We propose a new type of 211 At carriers, based on TiO 2 nanoparticles modified with metallic silver. The nanoparticles are nanoscale materials (at least one dimensions below 100 nm). They exhibit some useful properties, e.g. ultra-small size, high specific surface area, high ion exchange properties, possibility of attaching organic compounds to the sur-

39 38 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY face. Moreover, the surface of TiO 2 nanoparticles can be modified with silver easily. This feature can be used during the labelling of the carrier with astatine, which has high affinity toward metallic silver [2]. TiO 2 nanoparticles modified with sliver (TiO 2 / Ag) were synthesized according to the procedure described by Kang et al. [3]. The bare nanoparticles were added to 0.01 M AgNO 3 solution, then stirred for 30 min at room temperature. The product was carefully washed with distilled water. The loaded nanoparticles were shaken with solutions of ammonia (25%) and glucose (0.1 M). The adsorbed silver cations were reduced in commonly known reaction silver mirror (Tollens reaction). The colour of the particles changed from white to dark brownish grey. The modified nanoparticles were washed with distilled water and ethanol, then dried at 100 o C. The obtained nanoparticles differing in size (6-100 nm) and in the amount of adsorbed silver, were then labelled with 211 At. The labelling of TiO 2 /Ag nanoparticles with 211 At was performed in phosphate buffer (ph 7.4). 2 ml PBS with 211 At (~0.1 MBq/ml) was added to 5 mg TiO 2 /Ag nanoparticles, and the mixture was shaken for 1 h. The radiolabelled nanoparticles A Fig.1. The leakage of 211 At from TiO 2 /Ag nanoparticles of different diameter in various solutions after 1 h. were separated from the solution by ultracentrifugation ( rpm). In all experiments the distribution coefficient of 211 At exceeded 10 4 cm 3 /g. The stability of 211 At-labelled nanoparticles was assessed by adding the material (~3 mg) to physiological salt solution (0.9% NaCl), 0.02 M PBS buffer, M cysteine, M glutathione and human serum (2 ml each). The labelled nanoparticles were incubated from 1 to 14 h at room temperature, except of human serum which was additionally heated to 37 o C. After 1 h, the leakage of 211 At was less than 6% in all samples (Fig.1). Prolonged incubation of radiolabelled nanoparticles, caused slight increase in 211 At leakage, e.g. 7.8% of 211 At activity was detected in human serum after 14 h. We observed that TiO 2 /Ag nanoparticles tend to agglomerate in aqueous media. In order to stabilize them in the dispersed form, the particles were coated with polyethylene glycol (PEG). Methoxyl silane functionalized PEG was used, because it can be easily attached to the surface of metal oxide nanoparticles via the reaction of hydroxyl groups with trimethoxyl silane. The aim of the surface modification was not only to hamper the agglomeration process, but also to make the nanoparticles more resistant to protein adsorption and to enhance their biocompatibility [4]. Thermal gravimetric analysis (TGA) confirmed that the TiO 2 /Ag nanoparticles had been successfully covered with PEG molecules. The images of TiO 2 /Ag nanoparticles observed under transmission electron microscope (TEM) are shown in Fig.2. B Fig.2. TEM images of bare TiO 2 /Ag nanoparticles (A) and TiO 2 /Ag nanoparticles covered with PEG (B). Afterwards, the samples of TiO 2 /Ag nanoparticles covered with PEG molecules were examined for labelling with 211 At. The results were similar to those obtained for uncoated TiO 2 /Ag nanoparticles. Also in this case the distribution coefficients were high (>10 4 cm 3 /g). The stability of radiolabelled Fig.3. The leakage of 211 At from labelled TiO 2 /Ag nanoparticles covered with PEG of different diameter in various solutions after 1 h.

40 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 39 nanoparticles covered with PEG was tested in the same solutions as above. No significant leakage of 211 At was detected in any of the samples after 1 h (Fig.3). The highest release of 211 At (ca. 6%) was detected in human serum. At the longest incubation time (14 h) the slightly higher leakage of 211 At (< 8%) was detected. In conclusion, the new type of nanoparticles was successfully synthesized and tested. Both types of nanoparticles, TiO 2 /Ag and TiO 2 /Ag covered with PEG, exhibited high affinity for 211 At and high stability in human serum. Therefore, they are good astatine carriers that can be used in nuclear medicine. Further experiments will focus on the modification of TiO 2 /Ag nanoparticles by attaching a tumour seeking agent. The stability, cell affinity and radiotoxicity studies with these new nanoparticles will be carried out. References [1]. Vaidyanathan G., Zalutsky M.R.: Curr. Radiopharm., 3, (2008). [2]. Johnson G.L., Leininger R.F., Segrè E.: J. Chem. Phys., 17, 1-10 (1949). [3]. Kang J., Sohn Y.: J. Mater. Sci., 47, (2012). [4]. Eck W., Craig G., Sigdel A., Ritter G., Old L.J., Tang L., Brennan M.F., Allen P.J., Mason M.D.: ACS Nano, 2, (2008). NANOTITANATE AS A NEW SORBENT FOR 137 Cs SEPARATION FROM RADIOACTIVE WASTE Barbara Filipowicz, Seweryn Krajewski, Monika Łyczko, Marek Pruszyński, Aleksander Bilewicz Radionuclides of 134 Cs and 137 Cs with the half-lives of 2 and 30 years, respectively, belong to the main long-lived fission products of 235 U. These radionuclides undergo radioactive decay with the emission of beta particles and relatively strong gamma radiation. Caesium salts, the most common form of the element easily dissolved in water, which causes a serious hazard if an accident appears with a nuclear reactor. Caesium radionuclides leaked into the environment make a serious threat to the A health of present and future generations. Therefore, serious attention has been paid to the removal and separation of radiocaesium, especially 137 Cs, from nuclear waste. Various approaches and technologies such as coprecipitation and ion exchange have been developed for the separation and immobilization of radioactive aqueous wastes generated at different stages of nuclear fuel cycle. Common ion exchange resins are not sufficiently efficient for radiocaesium B C D Fig.1. SEM images of: (A) nanotubes, (B) nanofibers, (C) nanoribbons, (D) nanowires.

41 40 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY A B Sorption % Sorption % nantubes 10 nanofibers Time[min] Time[min] C D Sorption% Sorption % nanoribbons 10 nanowires Time[min] Time[min] Fig.2. Sorption percentages of caesium on: (A) nanotubes, (B) nanofibers, (C) nanoribbons, (D) nanowires, as a function of time. sorption from the waste. On the other hand, many inorganic and composite sorbents, such as insoluble ferrocyanides [1], zeolites [2], ammonium heteropolyacid salts [3], titanium dioxide [4] and sodium titanates [5], have been systematically studied for separation of 137 Cs from nuclear wastewater and safe disposal of the exchanged cations. The advantage of these materials is their ability to withstand intense radiation and elevated temperature in addition to their high selectivity for Cs + ions. Nanostructures of titanates play an important role in the process of binding inorganic cations, including radionuclides, because of their good sorption properties. The advantage of some layered nanotitanates is the collapse of their structure, which occurs during the ion exchange, and results in tight immobilization of targeted cations in the interlayer, thus in irreversible ion exchange [6, 7]. Therefore, the aim of our work was to examine various nanostructured titanates as sorbents for caesium radionuclides. To prepare nanotitanates we used the method of hydrothermal synthesis (in autoclave). We have obtained four different forms of nanotitanates. The formation mechanism is complex and not clear. Both, the method used and conditions of the synthesis play the key role in obtaining the forms of interest. The morphology of various titanate forms is shown in Fig.1. The structures displayed an aggregated shape with heterogeneous morphological distribution of diverse polyhedral forms and particles diameter that oscillated between nm. Hydrothermal reaction of TiO 2 (in the form of anatase) with a concentrated NaOH solution at 140 o C resulted formation of nanotubes (Fig.1A). Contrary, amorphous TiO 2 under the same conditions formed nanofibers (Fig.1B). Amorphous TiO 2 was also used as a substrate to produce nanoribbons (Fig.1C), when the synthesis was performed with NaOH solution at 200 o C, whereas nanowires (Fig.1D) were obtained in KOH solution. The morphology and elemental composition of the corresponding nanostructures were characterized by SEM (scanning electron microscopy) and TEM (transmission electron microscopy) with EELS (electron energy-loss spectroscopy). The structure and the degree of conversion of the substrate were determined by XRD (X-ray diffraction) spectra. The specific surface area and porosity were measured by the BET method. Table. The K d values of 137 Cs on nanotitanate and amorphous TiO 2 in 0.1 M solution of NaNO 3. Nanostructure K 137 d Cs (0.1 M NaNO 3 ) Nanotubes 4 x 10 2 Nanowires 2 x 10 2 Nanofibers 3 x 10 2 Nanoribbons 1 x 10 2 TiO 2 amorphous 1 x 10 2

42 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 41 The sorption studies of 137 Cs radionuclide were conducted on the all synthesized nanotitanates. The distribution coefficients (K d ) were determined in 0.1 M NaNO 3. The results are shown in Table. Presumably, similarly as in the case of ferrocyanides and zeolites, Cs + sorption can occur inside the nanotubes, where cations are dehydrated and the selectivity of adsorption depends on the energy of hydration. The inner sorption of Cs + is relatively easy, since the energy of hydration for the Cs + is rather small. This conclusion was also supported by the slow kinetics Cs + the sorption on the nanotubes, which suggest Cs + diffusion into the interior. Kinetics of ion exchange is one of the most important characteristics in defining the efficiency of the sorbent. Na-titanate nanostructures revealed high and fast initial sorption of 137 Cs +, followed by apparent saturation, that was especially visible in the case of nanowires and nanotubes (Fig.2). This can be explained by the fast initial sorption on the surface of the nanostructure, and a slower ion exchange inside the nanopores. Sorption of 137 Cs + ions on four forms of titanate nanostructures with different size and morphology (nanotubes, nanowires, nanoribbons and nanofibers) was examined also at different concentrations of NaNO 3 or KNO 3 ( M). As shown in Fig.3, a linear dependence of log K d on log Na + and log K + confirms ion exchange mechanism of sorption. Again, nanotubes and nanowires structures had the highest values of sorption towards A log(kd) B log(kd) 4,5 4,0 3,5 3,0 2,5 2,0 1,5-3,5-3,0-2,5-2,0-1,5-1,0-0,5 4,5 4,0 3,5 3,0 2,5 2,0 log[na + ] nanotubes nanowires nanoribbons nanofibers 1,5-3,5-3,0-2,5-2,0-1,5-1,0-0,5 log[k + ] nanotubes nanowires nanoribbons nanofibers Fig.3. Effect of concentration of: (A) sodium and (B) potassium ions on the sorption of 137 Cs +. log(kd) 3,0 2,5 2, Fig.4. Effect of ph on the caesium sorption on titanate nanostructures. 137 Cs + ions, probably due to their higher surface area compared to other nanostructures. The K d values for 137 Cs + ions slowly decreased with increasing the NaNO 3 or KNO 3 concentrations due to the competition and blocking of active sites on the nanostructures surface. As predicted, the K d values for K + are smaller in relation to the values for Na +, what is related to the larger size of the K + cation, and thus the greater competition with a 137 Cs +. The effect of ph on 137 Cs sorption was studied in the ph range of The results are shown in Fig.4. The observed dependence of log K d on ph above ph 9 seems rather unusual for sorption of inorganic cations on oxide sorbents, where the increase in ph is usually followed by a simultaneous increase in the K d values. In the case of nanostructures the highest sorption of 137 Cs was reached at ph 7-9, and at higher ph the K d decreased. Leaching experiments in NaNO 3 solutions showed that the release of 137 Cs from titanate nanotubes was negligible. This proves irreversible sorption and suggests that the exchange of Na + for Cs + may result in the change of sorbent structure. The presented results show that nanotitanates, in particular nanotubes, efficiently absorb radiocaesium from aqueous solutions, which makes them a prospective material for disposal of nuclear waste. The work has been carried out within the strategic research project Technologies for the development of safe nuclear power engineering (No. SP/J/4/ /11). References [1]. Avramenko V., Bratskaya S., Zheleznov V.: J. Nucl. Sci. Technol., 48, (2011). [2]. Lonin A.Yu., Krasnopyorova A.P.: Probl. Atom. Sci. Tech., 3, (2009). [3]. Murthy G.S., Sivaiah M.V., Kumar S.S.: J. Radioanal. Nucl. Chem., 260, (2004). [4]. Bilewicz A., Dybczyński R., Narbutt J.: J. Radioanal. Nucl. Chem., Articles, 148, (1991). [5]. Mishra S.P., Dubey S.S., Tiwari D.: J. Radioanal. Nucl. Chem., 261, 457 (2004). [6]. Li N., Zhang L., Chen Y., Fang M., Zhang J., Wang H.: Adv. Funct. Mater., 22, (2012). [7]. Yang D.J., Sarina S., Zhu H.Y., Liu H.W., Zheng Z.F., Xie M.X., Smith S.V., Komarneni S.: Angew. Chem. Int. Edit., 50, (2011). ph nanotubes nanofibers nanoribbons nanowires

43 42 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY SORPTION OF AMERICIUM(III) IONS ON THE BENTONITE OF THE VOLCLAY TYPE Agata Oszczak, Leon Fuks, Agnieszka Gładysz-Płaska 1/, Marek Majdan 1/ 1/ Faculty of Chemistry, Maria Curie-Skłodowska University, Lublin, Poland Element Storage of radioactive wastes requires various protective barriers against leaching of the stored radionuclides: metal canisters (tanks), buffers made of adsorbent of metal ions, and often the surrounding rocks. On the other hand, humidity from the outside may penetrate the storage tanks. Various biopolymers and naturally occurring inorganic adsorbents were examined as inexpensive and abundant materials able to slow down to a significant degree the velocity of migration of the radionuclides, e.g. [1, 2]. Volclay MX80 bentonite, aluminum silicate clay formed from volcanic ash, was intensively studied for the last 20 years as a compact barrier for nuclear waste repositories [3], and it has been found suitable for this purpose. Studies performed in the frame of the strategic project Technologies supporting development of safe nuclear power engineering task 4 Development of spent nuclear fuel and radioactive waste management techniques and technologies concerned bentonite easily available in Poland, which has been tested as potential buffer in the National Radioactive Waste Repository in Różan (Poland), and also as a sorbent for removing of radionuclides potentially contaminating water, in particular drawn in the water supply of the Institute of Nuclear Chemistry and Technology (INCT). The present work was devoted to the study of this bentonite as adsorbent of trivalent ions of americium-241. This radionuclide is the only actinide element which has been used in the household in smoke detectors. These sensors use 241 Am in the form of dioxide as the source of radiation that ionizes air [4], because this alpha emitter in combination with beryllium forms an efficient neutron source owing to the large cross-section of beryllium-9 for the (α,n) nuclear reaction [5]. Americium-241 is also used as a portable source of both gamma rays and alpha particles applied in some medical and industrial uses. The 60-keV gamma-ray emissions from 241 Am in these sources can be used for indirect analysis of materials in radiography and X-ray fluorescence spectroscopy, as well as for quality control and nuclear densometers. Because of that, americium-241 is a significant component of radioactive wastes and it is important test efficient barriers for the 241 Am containing repositories. To check the possibility of application of the bentonite sorbent as the engineering barrier, samples of the granular Volclay bentonite were gamma-irradiated in the cobalt bomb at the INCT with the dose of 100 kgy. Some main properties of the irradiated bentonite, among them sorption, were compared with these of the non-irradiated material. Prior to the studies, the commercial Volclay bentonite (P.W. Structum Ltd, Lublin, Poland) in the granular form was converted to its sodium form (assigned as Na-Vc) by equilibrating 5 g of raw bentonite with 100 ml of 1 mol/dm 3 aqueous solution of NaCl. Chemical composition of the Na-Vc is presented in Table 1. Similarity in the composition of the irradiated material with that of the non-irradiated one suggests that no decomposition occurs upon gamma radiation. Porosity of sorbents and their surface size are the fundamental factors for sorption processes of the toxic and/or radioactive metals [6]. Therefore, in separate studies we determined these properties of Na-Vc. They are summarized in Table 2. Powder X-ray diffraction studies reveal that Na-Vc is the material of layered structure, both in natural and in the irradiated materials (Fig.1). Remarkable shift, however, of the small 2θ angle Table 1. Chemical composition of the Volclay bentonite used in the studies (ED XRF energy dispersive X-ray fluorescence) major components. Concentration [%] Concentration [ppm] Element non-irradiated irradiated non-irradiated irradiated Al 11.1 ± ± 1.5 Mn ± ± Mg 1.4 ± ± 0.2 Sr ± ± 88.3 Na 1.2 ± ± 0.4 Ba ± ± Si 29.8 ± ± 3.5 V 96.5 ± ± 17.0 Fe 4.4 ± ± 0.7 Zn 99. ± ± 19.1 K 1.3 ± ± 0.1 Pb 32.7 ± ± 5.1 Ca 0.38 ± ± 0.13 Cu 50.0 ± ± 4.6 Rb 55.0 ± ± 9.7 Ce 84.5 ± ± 13.4

44 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 43 Table 2. Main physicochemical properties of the Volclay bentonite applied in the presented work [7]. Property Value Apparent powder density [g/cm 3 ] 1.31 Particle diameter [mm] 0.1 BET surface [m 2 /g] Micropore surface [m 2 /g] Total volume of the pores [cm 3 /g] Volume of the micropores [cm 3 /g] Mean diameter of the pores [Å] The only significant difference in the concentrations of sodium cations may be explained by the supposed presence of the excess of these cations used for the conversion of the bentonite to its sodium form. Post-decontamination liquids were simulated by dissolving 21 g of citric acid in 100 ml of water to obtain 1 M solution prior to americium-241 addition. Sorption of americium(iii) was studied as a function of contact time, initial ph and mass of the sorbent, respectively. Except the experiments on the time necessary for reaching the equilibrium, all examinations were made in parallel: with normal Na-Vc and with the irradiated material. The latter seems to be of interest because of its possible application as the engineered barrier in radioactive waste repositories. As it can be seen from Fig.2, adsorption of Am 3+ comprises two stages: a primary rapidly increasing phase and a secondary phase, of slower increment. At the first 1 h, Am 3+ removal from the aqueous Lin (Counts) Fig.1. Powder X-ray diffraction plots of the Na-bentonite; the upper plot corresponds to the natural material, the lower to the gamma-irradiated one. peak from to deg suggests a decrease in the distance between the layers, from to Å, which occures upon the irradiation. The potable water was collected in the INCT. Content of different ions in the water is presented in Table 3 together with the WHO quality standards. Content of all main cations and anions present in the drinkable water and in the water shaken with the bentonite sample indicates that the sorbent is both chemically and mechanically stable. Table 3. Content of ions [mg/dm 3 ] in the potable water samples. Fresh water solutions was observed in the rapid stage, while from 1 to 6 h, the adsorption increase was slow. It reached an equilibrium at about 4 h of shaking Content of ion [mg/dm 3 ] Na + K + Mg 2+ Ca 2+ Fe 3+ Zn 2+ Cu 2+ F Cl 2 NO 3 SO ± ± ± ± Theta - Scale ± ± ± ± ± ± ± 11.6 Agitated water* WHO [8] > > > 0.2 > 3 > 2 > 1.5 > 250 > 50** > 500 * 2 h agitation of 10 ml of water with 30 mg of the non-irradiated material. ** Total nitrogen.

45 44 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY with the efficiency of about 99.7%. We may assume that initially, the uptake can be attributed to the concentration gradient of Am 3+ and to the Fig.2. Effect of time on Am(III) sorption on Na-bentonite. greater number of available binding sites. In the second stage of the Am 3+ intake, the active bonding sites of the sorbent are to a great extent occupied by Am 3+, which reduces the number of the remaining active sites [9]. Bentonite clay has a very strong negative ionic charge. This negative charge attracts species of the opposite, positive charge, not only heavy/radioactive metals, but also toxins, harmful bacteria, dyes and various pathogens [10]. Thus the acidity of the solution is an important factor that must be considered during sorption studies due to the protonation and deprotonation properties of the sorbent surface. The effect of ph on Am(III) removal was studied in the ph range from 2.0 to 10.0 for an adsorbent dose of about 3.5 g L 1. The results presented in Fig.3 clarify that at ph < 5, the removal of Am(III) is lower due to the competition between hydroxonium ions (H 3 O + ) with the metal cations for the adsorption sites of bentonite. In weakly acidic (ph = 5-7) and basic (ph = 7-10) solutions, various hydrolysed polymeric species of Am(III) may appear in the relative proportions depending on the ph and the total americum concentration. It may be concluded from the plot in Fig.3 that H 3 O + and OH ions in relatively small concentrations do not significantly compete with americium for the bentonite Fig.3. Effect of ph on sorption of Am(III) by bentonite. Fig.4. Effect of the sorbent mass on sorption of Am(III) by Na-bentonite. binding sites, thus only small increase in the sorption percentage is observed. The dependence of Am(III) sorption on ratio of the adsorbent mass : decontaminated solution volume was studied by varying the amount of the the sorbent from 0.1 to 2 g L 1, keeping other parameters (ph and contact time) constant. Figure 4 shows the Am(III) sorption capacity for Na-Vc and it can be seen as expected that the sorption capacity improved with increasing dose, indicating the greater availability of the adsorption sites. Around 99% of Am(III) was removed when 1 g of the sorbent was put in the solution. After reaching this dose, the plateau in the sorption percent values is observed even with further addition of the adsorbent. An attempt to revitalize of the Am(III)-loaded Na-Vc was done by shaking the material at room temperature with different types of desorbing agents, i.e M NaCl, 0.01 M NaNO 3, 0.01 M Na 3 PO 4, 0.01 Na 2 CO 3, 0.01 M Na 2 SO 4, or 1 M CaCl 2 in potable water collected at the INCT. Samples of drinking water of different acidities were also tested. The results presented in Fig.5 show that the percentage of Am(III) desorption with all agents studied does not exceed 0.1%. Experiments with potable water of the ph in the range of 2.5 to 10.5 also show for strong binding of Am(III) by Na-Vc. No more than 0.4% of the adsorbed radioactivity has been removed from the material. So, in the combination with strong affinity toward water, Na-Vc may be proposed as a potential material for protecting barriers in radioactive waste tanks in waste repositories. We thank Dr. T. Szreder (INCT) for irradiating the bentonite samples, Dr. J. Dudek (INCT) for carrying out the ICP-MS analyses of the bentonite and Mr. K. Kulisa (INCT) for analyses of the samples of water. The work was supported by the National Centre for Research and Development, Poland in the frame of the strategic project Technologies supporting development of safe nuclear power engineering task 4 Development of spent nuclear fuel and radioactive waste management techniques and technologies (No. SP/J/4/ /11).

46 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 45 A B Fig.5. Desorption of Am(III) from Na-Vc: (A) by different aqueous solution, (B) effect of ph on the desorption by potable water collected at the INCT. References [1]. Combined methods for liquid radioactive waste treatment. Final report of a coordinated research project IAEA, 2003, 250 p. Report IAEA-TEC- -DOC [2]. Wold S.: Sorption of prioritized elements on montmorillonite colloids and their potential to transport radionuclides. Svensk Kärnbränslehantering AB, 2010, 40 p. Report SKB-TR [3]. Use of inorganic sorbents for treatment of liquid radioactive waste and backfill of underground repositories. IAEA, 1992, 183 p. Report IAEA-TEC-DOC-675. [4]. Smoke detectors and americium-241 fact sheet. [5]. Americium-241/Beryllium. uk/legacy/resources/americium-beryllium.pdf. [6]. Pusch R.: Clay Miner., 27, (1992) [7]. Gładysz-Płaska A., Majdan M.: Adsorpcja La(III), Eu(III) i Lu(III) na bentonicie naturalnym (Sorption of La(III), Eu(III) and Lu(III) on the natural bentonite). Materiały konferencyjne: Nauka i Przemysł metody spektroskopowe w praktyce, nowe wyzwania i możliwości, , Maria Curie-Skłodowska University, Lublin, Poland, pp (in Polish). [8]. Guidelines for drinking-water quality. Third edition, incorporating first and second addenda. Volume 1. World Health Organization (WHO), Geneva gdwq3rev/en/. [9]. Sag Y., Aktay Y.: Process Biochem., 36, (2000). [10]. Bentonite clay to remove toxic heavy metals, clear diaper rashes, stop stinky feet and more. naturalnews.com/036972_bentonite_clay_heavy_ metals_detox.html#. THE STUDY OF SORPTION OF COBALT IONS ON THE RED CLAY AND ZEOLITES Grażyna Zakrzewska-Kołtuniewicz, Agnieszka Miśkiewicz, Wioleta Olszewska, Bożena Sartowska The removal of hazardous heavy metals from aqueous streams represents a significant environmental challenge. Cobalt is classified as heavy metal that can cause serious environmental contamination if present at high enough concentration. The agriculture, mining, electronics, metallurgical, and pigment/paint industries are the principal sources of excessive release of cobalt in waste streams. Zeolites are proven ion exchange materials where the indigenous (typically sodium) charge balancing cations are not fixed rigidly to the hydrated aluminosilicate framework and are readily exchanged with cations in solutions [1]. Zeolites were previously applied for water and wastewater treatment [2] as well as for radioactive waste processing [3, 4]. Clay based adsorbents have also emerged as promising adsorbents for wastewater treatment [5]. Clays possess certain properties which make them an ultimate choice for adsorption process such as low cost, high availability, and environmentally friendly material. Consequently, clays can substitute expensive activated carbon as well as low-performing biosorbents [6, 7]. The clays can be used either in their natural form or modified with some chemical agents, depending on the target pollutants [6]. Red clay is one such material that is abundantly available and not expensive, so it can also be considered as an adsorbent like other clay materials. Sorption properties of red clay and different types of clay materials have been extensively investigated for the purpose of Brilliant Green dye removal from aqueous solutions [8]. Red clay was also used for sorption of transition metals [9] as well as such radioactive elements as Cs-134, Sr-85 and Zn-65 [10]. In the present work red clay and zeolite 5A were used for cobalt ions removal from aqueous solutions with further perspective of using them for the treatment of radioactive solutions. The idea is to use these materials just as a adsorbents of radioactive species or as binding material in ultrafiltration/sorption hybrid process for radioactive wastes processing. Characteristics of red clay (Pałęga mining) with particle size lower than 0.1 mm is collected in Table 1. Zeolite 5A (POCH, ACROS OR-

47 46 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY A B Fig.1. Kinetics of sorption of cobalt ions on: (A) red clay ph = 6, [Co 2+ ] 0 = 5 mg/l, [Co 2+ ]/[sorbent] = 1/2000; (B) zeolite 5A ph = 7, [Co 2+ ] 0 = 100 mg/l, [Co 2+ ]/[sorbent] = 1/20; sorption efficiency, ο sorption capacity (q). GANIC) used in current studies was in the form of powder with particle size lower than 50 μm. In the first stage, sorption kinetic studies were performed. Furthermore, the effect of ph, ionic Table 1. Characteristics of red clay. Mineralogical composition mineral content [%] Illite Kaolinite 6-12 Chlorite 3-5 Quartz Hematite 3-6 Chemical composition SiO Al 2 O Fe 2 O MgO 2.38 K 2 O 2.68 CaO 0.4 TiO MnO 0.09 strength as well as the ratio of the reagents on the efficiency of cobalt ions removal was examined in order to select the optimal process parameters. Kinetic experiments with red clay, carried out with reagent ratio ([Co 2+ ]/[sorbent]) equal to A 1/1000, and at ph = 6 showed that sorption efficiency of cobalt ions exceeded 80% just after few minutes of the phases contact (Fig.1A). Even higher sorption efficiency, nearly 90%, was observed in the case of using zeolite 5A as a sorbent of cobalt ions. In this experiment lower excess of sorbent was applied, namely 1/20, ph was held at the level of 7. However, in the case of zeolite, the equilibrium of sorption of cobalt ions was obtained only after 10 days of process, what is shown in Fig.1B. Generally, zeolite 5A showed ca. 100-times higher sorption capacity than red clay. Table 2. Sorption efficiency and sorption capacity of two sorbents for different reagent ratio ([Co 2+ ]/[sorbent]). Experiments conditions: red clay ph = 7, [Co 2+ ] 0 = 5 mg/l, t eq = 0.5 h; zeolite 5Å ph = 7, [Co 2+ ] 0 =100 mg/l, t eq = 264 h. Reagent Sorption efficiency [%] q [mg/g] ratio red clay zeolite 5A red clay zeolite 5A 1/ / / / Sorption ability of red clay as well as zeolite 5A was dependent on ph. As showed in the experiments, the best conditions of binding Co 2+ by both sorbents was at ph = 7 (Fig.2). The studies performed also showed that the most effective reagent ratio was 1/2000 and 1/20 for red clay and zeolite 5A, respectively. Experi- B Fig.2. Effect of ph on the sorption efficiency of cobalt ions on: (A) red clay [Co 2+ ] 0 = 5 mg/l, [Co 2+ ]/[sorbent] = 1/2000, t eq = 0.5 h; (B) zeolite 5A [Co 2+ ] 0 = 100 mg/l, [Co 2+ ]/[sorbent] = 1/20, t eq = 264 h.

48 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 47 A B Fig.3. Effect of salinity on the sorption efficiency of cobalt ions on: (A) red clay [Co 2+ ] 0 = 5 mg/l, [Co 2+ ]/[sorbent] = 1/2000, ph = 7, t eq = 0.5 h; (B) zeolite 5A [Co 2+ ] 0 = 100 mg/l, [Co 2+ ]/[sorbent] = 1/10, ph = 7, t eq = 23 h. mental data showing the relation between sorption efficiency and the amount of sorbents are collected in Table 2. Finally, the effect of the salinity on the sorption abilities of chosen sorbents was determined. As can be seen from Fig.3, increasing salinity of the solution resulted in a decrease in the ability of cobalt ions binding by the sorbents. The reduction of sorption efficiency was more significant for the red clay than for the zeolite 5A. Thus, addition of potassium nitrate at the concentration equal to 10 mmol/l to the feed solution in the presence of red clay resulted in a decrease in the sorption efficiency from 80% to less than 20%, while for zeolite the same salinity of the solution caused a modest reduction of sorption efficiency: from 43 to 35%. In order to verify the applicability of a hybrid process for the removal of cobalt ions from the aqueous solutions, the ultrafiltration/sorption process in dead-end mode was performed. This experiment has been conducted using filtration cell (Amicon) with polyethersulphone membrane (Millipore Corporation, NMWL ). Model solution of cobalt ions of 1 mg/l concentration with an appropriate amount of the sorbent was filtered through the membrane. The UF installation worked under 0.3 MPa pressure. The samples of filtrate were collected for analysis every 15 min. The experiment showed high retention of cobalt ions using the hybrid ultrafiltration/sorption process (Fig.4). A Fig.4. Retention of cobalt ions during filtration of the suspension of the red clay and cobalt chloride, using Amicon cell with polyethersulphone membrane; cut-off = 10 kda, p = 0.3 MPar, [Co 2+ ] 0 = 1 mg/l, [Co 2+ ]/[sorbent] = 1/4000, ph = 7, t eq = 0.5 h. After filtration, the whole amount of the prepared solution (1 dm 3 ), which took about 1 h, the membrane was removed from the filtration cell, dried and observed through the scanning electron microscope (DSM 942, Zeiss). The sample images of the membrane surface and deposit collected on the membrane are presented in Fig.5. As can be observed, clay deposit covers the membrane surface non-uniformly, and the surface of the deposit particle has a rough structure. The results show that the sorption ability of the red clay and zeolite 5A are satisfactory. Proper se- B Fig.5. SEM images of: (A) membrane used in ultrafiltration experiment of filtration of the red clay suspension; (B) deposit accumulated on the membrane during filtration experiment.

49 48 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY lection of process conditions allows adsorption of cobalt ions with an efficiency greater than 95%. Moreover, by the use of sorption/ultrafiltration hybrid process it is possible to remove cobalt ions from water solution with high efficiency. The research was done in the scope of the strategic research project Technologies supporting development of safe nuclear power engineering stage 6 of research task 4 Development of spent nuclear fuel and radioactive waste management techniques and technologies. References [1]. Breck D.W.: Zeolites molecular sieves: structure, chemistry and use. New Wiley and Sons, New York 1974, pp [2]. Wang S., Peng Y.: Chem. Eng. J., 156, (2010). [3]. Sharygin L.M., Muromskii A.Y.: Radiochemistry, 46, 2, (2004). [4]. Çiçek E., Cojocaru C., Zakrzewska-Trznadel G., Harasimowicz M., Miskiewicz A.: Environ. Technol., 33, 1, (2012). [5]. Auta M., Hameed B.H.: Chem. Eng. J., , (2012). [6]. Nassar M.M., El-Geundi M.S., Al-Wahbi A.A.: Desalin. Water Treat., 44, (2012). [7]. Nandi B.K., Goswami A., Purkait M.K.: J. Hazard. Mater., 161, (2009). [8]. Rehman M.S.U., Munir M., Ashfaq M., Rashid N., Nazar M.F., Danish M., Han J.: Chem. Eng. J., 228, (2013). [9]. Takematsu N.: JOSJ (Journal of the Oceanographical Society of Japan), 35, 1, (1979). [10]. Twining J.R., Payne T.E., Itakura T.: J. Environ. Radioact., 71, (2004). ANALYSIS OF THE POSSIBILITY OF URANIUM SUPPLY FROM DOMESTIC RESOURCES Grażyna Zakrzewska-Kołtuniewicz, Katarzyna Kiegiel, Dorota Gajda, Agnieszka Miśkiewicz, Paweł Biełuszka, Kinga Frąckiewicz, Irena Herdzik-Koniecko, Barbara Zielińska, Agnieszka Jaworska, Katarzyna Szczygłów, Anna Abramowska, Wioleta Olszewska, Marian Harasimowicz, Rajmund Dybczyński, Halina Polkowska-Motrenko, Bożena Danko, Zbigniew Samczyński, Ewelina Chajduk, Jadwiga Chwastowska, Iwona Bartosiewicz, Jakub Dudek, Stanisław Wołkowicz 1/, Jerzy B. Miecznik 1/ 1/ Polish Geological Institute National Research Institute, Warszawa, Poland One of the objectives of the Polish Nuclear Power Programme [1] is the assessment of domestic uranium deposits as a potential source of uranium for Polish nuclear reactors. Presently, mining of Polish low-grade uranium ores appears uneconomic [2]. However, studies on the prospects of recovery of uranium from domestic resources are in progress, keeping in mind the inevitable growing uranium demand and perspectives of the global uranium market. The most perspective deposits are in the Lower Ordovician Dictyonema shale of Podlasie Depression (North-Eastern Poland) with uranium concentration of ppm and the Lower and Middle Triassic rocks of the central part of Peribaltic Syneclise, where concentrations reach even 1.5% U (recent analysis of archive samples). The main objectives of this research were: to assess the possibility of exploitation of uranium resources in Poland, and to work out methods of uranium extraction from the ores for production of yellow cake U 3 O 8. The characteristics of the material originating from uranium ores vary significantly from deposit to deposit. The effect of ore mineralogy and mineral liberation on the leaching behaviour of uranium is not well defined. The procedure of uranium extraction must be designed to fit specific characteristics of the ore; however the general scheme of the process is similar for most of the ore materials. The basic steps of processing of uranium ores are: crushing and grinding, leaching, solid-liquid separation, ion exchange or solvent extraction, and finally precipitation of final product yellow cake U 3 O 8 [3]. The solid-liquid extraction is a very important stage in the technology of uranium production from the uranium ores. In the present work at the beginning of the extraction process, uranium was leached from the ground ore by using sulphuric acid or carbonate (CO 3 2 ) solutions [4, 5]. In comparison with acid processing, alkaline leaching had the advantage of being selective for uranium. The metals associated with uranium in the ores were also present in acidic post-leaching solutions. In the case of alkaline leaching process only three or two metallic components of the ores were detected: U, Mo and V (dictyonemic shales) or U and small amounts of V (sandstones) (Fig.1). The post- -leaching solutions were separated from the leached ore by filtering and washing and then concentrated and purified using solvent extraction or ion exchange chromatography [6]. The helical membrane contactor equipped with rotating part, applied for uranium recovery from uranium ores, was proposed. In this method leaching uranium ores combined with solid-liquid separation by filtration in one membrane apparatus can be carried out [7]. Series of experiments were performed using helical contactor for the purpose of testing the leaching uranium and other valuable metals from uranium ores. The process parameters varied according to the experimental plan were as follows: the velocity of the feed flow (in the range from 0.67 to 1.33 L/min) and rotation frequency of the inner cylinder (in the range from 0 to 2500 rpm).

50 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 49 Fig.1. Minimal and maximal value of efficiencies of leaching of metals from sandstones deriving from Perbaltic Syneclise (various deposits) under different process conditions: (A) 10% H 2 SO 4, MnO 2, 60 o C, 1 h; (B) 10% HCl, 30% H 2 O 2, 60 o C, 1 h; (C) 8% NaOH/18% Na 2 CO 3, 30% H 2 O 2, 60 o C, 1 h; (D) 5% Na 2 CO 3 /NaHCO 3, KMnO 4, 60 o C, 1 h. Results of experiments are presented in Fig.2. It can be noticed that by increasing flow velocity the efficiency of uranium leaching can be enlarged but Fig.2. Comparison of the uranium leaching efficiency depending on feed flow velocity and velocity of the rotor in the helical membrane contactor. the influence of the speed of the rotor is rather insignificant. Efficiency of uranium leaching obtained with acentric membrane contactor was comparable with those obtained by leaching in a stationary reactor with mixing. The concentration of other associated metals like vanadium, molybdenum or lanthanides was measured in the permeate. The metals were recovered together with uranium when acidic leaching was applied. The advantage of using the membrane contactor is a possibility of combining two processes in one apparatus: leaching and separation of solid phase from post-leaching solutions. Such an approach results in reduction of total cost of operation with no consequences to the separation efficiency. Uranium could be recovered from post-leaching solutions by using solvent extraction followed by stripping to aqueous phase. The extracting agents, like for example tributylphosphate (TBP), di(2-ethylhexyl)phosphoric acid (DEHPA), trioctylphosphine oxide (TOPO), triethylamine (TEA), tri-n-octylamine (TnOA), and other reagents, were tested with the model uranium solutions [8]. The Fig.3. Extraction and re-extraction efficiencies of metals from: (A) acidic and (B) alkaline post-leaching solution.

51 50 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY mixture of DEHPA and TBP was found as a good extractant for uranium and the studies of extraction of uranium from ore-leaching liquors (sulphuric and carbonate) were carried out. The use a different reagents as strip solutions for uranium in organic phase was also investigated. The results are presented in Fig.3. The technique of membrane extraction with application of the contactors with co-current flow of aqueous and organic phases was also examined as an alternative to traditional methods of extraction [9]. Preliminary tests of membrane resistivity and determination of extraction efficiency were carried out for model uranium solutions. DEHPA was found to be the most favourable for the membrane extraction process. Then the experiments of extraction/re-extraction with real post-leaching eluents eluents Feed solution A U R R B R OH OH HO HO Fig.4. The structure of calix[6]arene. R OH HO R solutions were proceeded and the high value of recovery of uranium (96%), thorium (81%) and ytterbium (67%) was obtained. The possibility of application of calixarenes (Fig.4) as selective extracting agents for uranium were also considered. The calix[6]arenes act as very R Other accompanying metals Fig.5. Set of two columns with: (A) strongly basic anion exchanger (DOWEX1 X8), (B) strongly acidic cation exchanger (DOWEX50 WX8). good uranophiles in separation processes [10]. They may be useful for extracting UO 2 2+ from solutions after leaching of uranium ores, sea water, radioac- Ln Fig.6. Elution of metals from columns with: (A) anion exchanger, (B) and (C) cation exchanger; 1 feed solution, 2 eluent 0.15 M H 2 SO 4, 3 eluent 1 M H 2 SO 4, 4 eluent 1 M H 2 SO 4, 5 eluent H 2 O, 6 eluent 2 M HCl, 7 eluent 4 M HNO 3.

52 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 51 Table. The precipitation of uranium salts precursors of U 3 O 8. Precipitated uranium compound (NH 4 ) 2 U 2 O 7 UO 4 H 2 O Concentration of uranyl ions [mg/ml] C H2SO4 Temperature [ o C]/time [h] Yield [%] M 40 o C/4 h M 40 o C/4 h M 40 o C/4 h M 40 o C/7 h M 60 o C/4 h M 40 o C/4 h M 60 o C/4 h M 60 o C/4 h M 60 o C/4 h M 90 o C/4 h 99 tive waste or contaminated soil. Application of such extracting agents enables the use of 10 to 100 times lower ligand concentrations necessary to reach an assumed extraction yield than with the other existing extractants. The purification of uranium from accompanying metals could be also achieved by the ion exchange chromatography [6]. Two following columns, one by one, were adapted for purification of acidic post- -leaching solution. First column was filled with strongly basic anion exchanger (DOWEX1 X8), and the second with strongly acidic cation exchanger (DOWEX50 WX8) (Fig.5). Feed solution was introduced into the first column (Fig.6A). This column did not adsorb cations, which are eluted to the second column (Fig.6B,C). The combination of different eluents allowed to obtain pure fractions of valuable metals. Uranium complexes were adsorbed on the anion exchanger and next they were eluted with 1 M (one molar) sulphuric acid. Behaviour of U and some other metals, when feed solution was poured into the columns is shown in Fig.6. The precipitation of ammonium diuranate or uranium peroxide forms is the most crucial step in the production of uranium oxide. This is followed by calcination step forming triuranium octoxide (U 3 O 8 ). The study of the precipitation was carried out for the model uranium solution. The influence of concentration of sulphuric acid, temperature and concentration of uranyl ion in the solution were examined. The representative results are presented in Table. The present project allowed preparing the set of methods and technologies that will be ready for subsequent implementation in the nuclear fuel production to extract uranium from the ores and other sources. On the basis of these results, the process design of pilot-scale installation was prepared [11]. The project was completed with technical and economic analysis [12]. References [1]. Program Polskiej Energetyki Jądrowej (Polish Nuclear Power Programme). Ministerstwo Gospodarki, Pełnomocnik Rządu ds. Polskiej Energetyki Jądrowej, Warszawa, grudzień 2010 (in Polish). [2]. Miecznik J.B., Strzelecki R., Wolkowicz S.: Prz. Geol., 59, 10, (2011), in Polish. [3]. Edwards C.R, Oliver A.J.: JOM, (2000). [4]. Zakrzewska-Trznadel G., Kiegiel K., Frąckiewicz K., Gajda D., Chajduk E., Bartosiewicz I., Chwastowska J., Wołkowicz S., Miecznik J.B., Strzelecki R.: Studies on the leaching of uranium from lower Triassic Peribaltic sandstones. In: INCT Annual Report Institute of Nuclear Chemistry and Technology, Warszawa 2012, pp [5]. Frackiewicz K., Kiegiel K., Herdzik-Konecko I., Chajduk E., Zakrzewska-Trznadel G., Wolkowicz S., Chwastowska J., Bartosiewicz I.: Nukleonika, 58, 4, (2012). [6]. Zakrzewska G., Gajda D., Dybczyński R., Samczyński Z., Herdzik I., Chajduk E., Danko B.: The study on the separation of uranium from associated metals in the post-leaching solution by ion-exchange process. In: INCT Annual Report Institute of Nuclear Chemistry and Technology, Warszawa 2013, pp [7]. Zakrzewska-Trznadel G., Jaworska-Sobczuk A., Miśkiewicz A., Łada W., Dłuska E., Wroński S.: Method of obtaining and separation of valuable metallic elements, specifically from low grade uranium ores and radioactive liquid wastes. European Patent Application No [8]. Kiegiel K., Zielińska B., Biełuszka P., Zakrzewska- -Trznadel G., Chajduk E., Wołkowicz S., Miecznik J.B.: Solvent extraction of uranium from post-leaching solutions. In: INCT Annual Report Institute of Nuclear Chemistry and Technology, Warszawa 2013, pp [9]. Biełuszka P., Zakrzewska G., Chajduk E., Dudek J.: J. Radioanal. Nucl. Chem., 299, 1, (2014). [10]. Kiegiel K., Steczek L., Zakrzewska-Trznadel G.: J. Chem., Article ID , 16 p. (2013), org/ /2013/ [11]. Pochopień H., Szyndler K.: Projekt procesowy instalacji pozyskiwania uranu z rud uranowych (The process design of pilot-scale installation for uranium recovery from uranium ores). Centrum Projektowe Polimex- -Mostostal, Gliwice 2013 (in Polish). [12]. Sprawozdanie Tom II. Zadania 5-7. Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych POIG /09 (Report: Analysis of the possibility of uranium supply from domestic resources POIG /09. Vol. II. Tasks 5-7). Konsorcjum: Instytut Chemii i Techniki Jądrowej i Państwowy Instytut Geologiczny Państwowy Instytut Badawczy, Warszawa 2013 (in Polish).

53 52 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY STUDIES ON LEACHING COPPER ORES AND FLOTATION WASTES Danuta Wawszczak, Andrzej Deptuła, Wiesława Łada, Tomasz Smoliński, Tadeusz Olczak, Marcin Brykała, Patryk Wojtowicz, Marcin Rogowski, Magdalena Miłkowska Table 1. The content of important elements in copper ores and copper flotation wastes [ppm] (ICP-MS analysis). Elements Waste 1 Copper concentrate Waste 3 Waste Gilów KGHM 1 Waste Gilów 2 Ba Co Cu Eu Fe La Mn Mo Ni Th U V Zn PBK In the era of expanding nuclear energy new solutions are increasingly sought for uranium extraction from unconventional sources, including phosphate rocks, flotation tailings from copper production, wastes from phosphoric acid production, and even sea water [1-3]. Studies on uranium leaching from copper ores and tailings were carried out at the Institute of Nuclear Chemistry and Technology (INCT). Significant deposits of copper ores exist in Poland. Large amounts of flotation wastes are produced in the process of extraction from the ores. Many other valuable metals accompany copper in the ores and flotation wastes. Flotation tailings Table 2. The leaching results for samples roasted, unroasted, and treated with the oxidant (AC method). Material (initial uranium content) Waste 1 (14.7 ppm) Copper concentrate (12.9 ppm) Waste 3 (15.5 ppm) Waste Gilów (7.3 ppm) Concd. H 2 SO 4 Uranium content samples treated samples roasted samples unroasted with the oxidant MnO 2 [ppm] [%] [ppm] [%] [ppm] [%] 96% % % % % ~100 72% ~100 48% % % % % % % % % %

54 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 53 from the enrichment process of copper ore are estimated as about 90% of the amount of the ore processed. The uranium content in the ore from the copper mine Sieroszowice Lubin is about 60 ppm (the copper content 2%) [4]. Production of copper in the basin Lubin-Sieroszowice in 2009 was about 569 kilotons. It is estimated that the U [ppm] unroasted roasted roasted +MnO2 four types of flotation wastes (Gilów, Waste 3, Gilów 2, Waste 1). Using ICP-MS (inductively coupled plasma mass spectrometry) analysis, the content of individual elements in the examined samples was determined. It has been found that uranium content in the materials studied varies from 4.5 to 27 ppm. The other elements that have Cooper Concentrate - 96% H2SO4 Waste 3-96% H2SO4 Cooper Concentrate - 72% H2SO4 Waste 3-72% H2SO4 Fig.1. Recovery of uranium from samples of copper concentrate and Waste 3 using AC method, under various conditions. U % recovery unroasted roasted roasted +MnO2 amount of uranium discharged in Poland to landfill waste is about 1700 tons per year. The main goal of the present work was the analysis of uranium content in a series of indigenous copper ores and wastes, and the elaboration of procedures for uranium recovery from the raw materials. The study involved two types of ore (KGHM 1 and PBK), copper concentrate, and been determined in these materials are: Cu (4-5% in ores and % in the waste), Ag, Re, Mo, lanthanides, Ni, V, etc. (Table 1). The process of digestion and leaching of uranium ores and flotation wastes was carried out by two methods. The acid-cure (AC) method consisted in direct action of concentrated sulphuric acid (H 2 SO 4 ) on the sample. After 5 h, the sample Table 3. Uranium leaching from the indicated samples (WR method). Material (initial uranium content) Waste 1 (14.7 ppm) Copper concentrate (12.9 ppm) Waste 3 (15.5 ppm) Waste Gilów (7.3 ppm) Uranium content Concd. H 2 SO 4 samples roasted samples unroasted [ppm] [%] [ppm] [%] 40% % % % % % % % % ~100 20% % % % % % %

55 54 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY was leached with H 2 O, either at room temperature (RT) or at 70 o C for 5 h, and then filtered. This method was also applied to samples pre-calcined at 900 o C for 2 h and to the samples with addition of 2% MnO 2 as oxidant [5, 6]. The second method, WR, consisted in digestion of the sample for 5 h with sulphuric acid of various concentrations (40, 20, 10 and 5%) at boiling temperatures [7]. The influence of grinding the samples on leaching efficiency, and on the kinetics of leaching was also studied. The optimum leaching conditions have been found. The concentrations of uranium in the final solutions were generally less than 15 ppm. The leaching solutions contained also the other metals. Table 2 presents the leaching results (AC method) for samples roasted, unroasted, and also treated with the oxidant (MnO 2 ), and selected results have been presented more clearly in Fig.1. The data show that the highest leaching yields of uranium (> 70%) were obtained for samples roasted and treated with MnO 2, but only for copper concentrate they approached to 100%. The results of uranium leaching using the WR process are shown in Table 3. A U % recovery Concentration of sulfuric acid % 100 B Concentration of sulfuric acid % >1 mm 0,5<d<1mm 0,5<d<0,2mm d<0,2mm U % recovery Fig.2. Influence of grains sizes for uranium leaching from two samples: KGHM ore (A) and Waste Gilów (B). The influence of grinding the samples on uranium leaching is shown in Fig.2. In the case of KGHM ore, the effect of grinding on uranium leaching was not significant because for many fractions the efficiency close to 100% was reached. For the Waste Gilów such high yields were observed only for the fraction mm. For evaluation of the two leaching methods tested, AC and WR, the following parameters were studied: type of material (ore or waste), concentration of sulphuric acid, sulphuric acid with a 2% oxidizing agent, additional pre-calcination step, leaching time, grinding of initial material. In conclusion, the AC method is definitely better than the WR one for the recovery of uranium. The highest yields, nearly 100% leaching, have been found for samples initially calcined, and samples treated with oxidizing agent, MnO 2. Simultaneous liquid-liquid extraction of uranium and other metals from the leaching solutions is under study. In our opinion, only such a combined procedure could be cost-effective for the recovery of uranium together with the accompanying elements. The studies were supported from the Operational Programme Innovative Economy (PO IG) project Analysis of the possibility of uranium supply from domestic resources, No. POIG /09. References [1]. Afolabi A.S., Muzenda E., Sigwadi R.: Effect of reagent parameters on recovery of South Africa uranium ore. Proceedings of the 3rd International Conference on Uranium 40th Annual Hydrometallurgy Meeting, August 2010, Saskatoon, Saskatchewan, Canada, Vol.1, p [2]. Habashi F.: Uranium from phosphate rock. An update. Proceedings of the 3rd International Conference on Uranium 40th Annual Hydrometallurgy Meeting, August 2010, Saskatoon, Saskatchewan, Canada, Vol.1, p [3]. Prasser H.M.: Are the sources of uranium big enough for the nuclear energy industry? Nuclear energy in Poland: Opportunity or necessity? October 2008, Warszawa, Poland. [4]. Ostrowski M., Skłodowska A.: Małe bakterie wielka miedź (The small bacteria great copper). SCI-ART, Warszawa 1996 (in Polish). [5]. Brejnak E., Pinkas K.: Badania technologiczne nad przerobem łupków dictyonemowych w skali laboratoryjnej (Technology research on the processing of dictyonema shale on a laboratory scale). Instytut Badań Jądrowych, Opracowanie wewnętrzne nr 170/Ch-IV/75 (in Polish). [6]. Brejnak E., Pinkas K., Deptułowa D.: Badania technologiczne nad przerobem łupków dictyonemowych w skali laboratoryjnej. Prace uzupełniające (Technology research on the processing of dictyonema shale on a laboratory scale. Supplementary work). Instytut Badań Jądrowych, Opracowanie wewnętrzne nr 171/Ch-IV/75 (in Polish). [7]. Szymańska D.: Opracowanie optymalnych parametrów otrzymywania koncentratu torowego z rudy toronośnej H (Development of optimal parameters for obtaining concentrated thorium from ore H ). Instytut Badań Jądrowych, Opracowanie wewnętrzne nr 45/Ch-IV/67 (in Polish).

56 CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY Studies carried out in 2013 concentrated on the validation, adaptation and implementation of various biodosimetric methods in the frame of the strategic research project Technologies supporting development of safe nuclear power engineering from the National Centre for Research and Development (SP/J/6/ /11), as well as in the Development of multiparameter»triage«test to assess population exposure to ionising radiation funded in the frame of the Operational Programme Innovative Economy (POIG /09). The latter is suported by the European Union Structural Funds and the Ministry of Regional Development (Poland). A package of procedures is being developed and a strategy is prepared of proceeding in the case of a large-scale radiation event. Quick estimation of radiation dose and allotment of casualties into groups of risk will allow an effective and efficient rescue operation. The set of documents and manuals will be transferred to subjects connected with the nuclear industry, and in particular, to the responsible authorities for the nuclear safety and the protection, the national defence, the administration and internal matters and environmental protections. The Centre also participates in the Coordination Action project RENEB founded within the 7th EU Framework Programme EURATOM Fission. The project is aimed at establishing a sustainable European network in biological dosimetry involving 23 organizations from 16 EU countries. Their competence has been identified by a survey carried out in The project will significantly improve the response capabilities in the case of a large-scale radiological emergency. An operational network has been created, based on coordination of the existing reliable and proven methods in biological dosimetry. This will guarantee the highest efficiency in processing and scoring of biological samples for fast, reliable results implemented in the EU emergency management. We take part in WP1, WP3 and WP4 of the RENEB project. Besides dicentric assay, micronuclei assay and histone γ-h2ax assay, which are implemented and calibrated in the Centre, other two methods of biological dosimetry are being introduced in the frame of RENEB: PCC and FISH-translocation assay. The Institute of Nuclear Chemistry and Technology (INCT) is the leader organization of Task 4.1 of WP4 Infrastructure, transport, linking to first responders, disaster management units and is the only Polish partner of the project. We participated in the MULTIBIODOSE project ( FP7-SECURITY SEC ) which continued until April It was a Capability project funded within the 7th EU Framework Programme under Theme 10 SECURITY and aimed at preparing multi-disciplinary biodosimetric tools to manage high scale radiological casualties. The participation involved cooperation with other European laboratories, exchange of samples and microscopic preparations in order to unify the procedures and training. The results of the cooperation are summarized in a booklet Guidance for using MULIBIODOSE tools in emergencies. Our contributions to the RENEB and MULTIBIODOSE, as well as two other projects (POIG /09 and SP/J/6/ /11) were presented at several conferences in Poland and abroad, mostly concerning biodosimetric problems. Results of minimum cell number determination were shown for evaluation of dicentric chromosome frequency after blood cell exposure to a range of X-ray doses. The study has been aimed at speeding up the radiation dose estimation within a reasonable error margin in the case of a large-scale radiation event. Related experiments concerned the use of expression level of chosen genes implicated in the cellular and/or systemic response to ionizing radiation as biomarker of individual exposure. Amelioration of the cytometric analysis of the histone γ-h2ax, an acknowledged marker of DNA double strand break, was another goal. An important research topic for the last few years has been the oxidative stress, its molecular and cellular mechanisms in mammalian cells exposed to ionizing radiation and/or nano-

57 materials. In particular, differentiation of Lund human mesencephalon (LUHMES) cells to a dopaminergic neuron-like phenotype was examined and found that it leads to a decrease in expression of the mitochondrial PGAM5 phosphatase. Studies of the cellular response to ionizing radiation with a special emphasis on the molecular mechanisms of the oxidative stress are continued: the role of pirin protein and the signalling pathway NRF2/KEAP1 in relation to apoptosis (grant IUVENTUS PLUS funded by the Ministry of Science and Higher Education, Poland, No. IP ). In cooperation with the Jena University we have previously found that the X-irradiated colon cancer HT-29 cells become markedly radiosensitized in result of culture in a conjugated linoleic acid (CLA)-complemented medium. This points to interaction between the nuclear and plasma membrane signalling systems in the X-irradiated cell. The recent experiments demonstrated an X-ray (+/- CLA) induced differential activation of the nuclear and cytoplasmic kinase Akt1. The localization-dependent activity reflects the balance between pro-survival and pro-death signalling and this apparently may be modified by CLA.

58 CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY REAL-TIME PCR ANALYSIS OF EXPRESSION OF DNA DAMAGE RESPONSIVE GENES AS A BIOMARKER FOR BIOLOGICAL DOSIMETRY 57 Kamil Brzóska, Iwona Buraczewska, Iwona Grądzka, Barbara Sochanowicz, Teresa Iwaneńko, Maria Wojewódzka, Grzegorz Wójciuk, Tomasz Stępkowski, Marcin Kruszewski In a large-scale radiologic accidents, fast identification of radiation-exposed individuals is crucial for triage and optimal medical management. Current biological dosimetry methods are inadequate for the task, mainly because of their low throughput resulting from the time-consuming procedures and requirement for highly trained and experienced personnel. Our objective is to develop simple and fast bioassays for biological dosimetry based on molecular biomarkers such as gene expression signatures. To this end, we analysed the literature data concerning gene expression changes in the blood cells following irradiation. Based on the available literature (e.g. [1-3]), the following genes were chosen as the most promising biomarkers of radiation exposure: GADD45A, CDKN1A, BBC3, BAX, GDF15, DDB2, MDM2, ATF3, PLK3, SESN2, BCL2. To further analyse the expression patterns of the selected genes in irradiated blood we performed the experiments outlined as described below. Blood samples were collected from three healthy donors with informed consent from all subjects. A total of 15 ml of blood was collected from each donor into heparin vacutainer tubes. Each sample was aliquoted into three tubes (one tube per dose group) and irradiated with a single dose of X-rays. X-irradiation was carried out at 37 o C, with the use of a Smart200 (Yxlon) defectoscope operating at 200 kv and 4.5 ma, with 3 mm Al filtration, at a dose rate of 1.14 Gy/min. Following irradiation, each tube of blood corresponding to a single dose, was divided into four tubes (1 ml of the whole blood per tube), one tube for each time point. RPMI 1640 medium (Sigma) was Fig.2. Fold changes in gene expression in the whole blood at four time points after X-irradiation with 0.6 or 2 Gy. Each point represents a different donor. Fig.1. Schematic representation of the experimental schedule. added to each tube at a 2:1 ratio with the whole blood. The samples were incubated at 37 o C in a humidified incubator with 5% CO 2 for either 6, 12, 24, 48 h. The experimental schedule is shown in Fig.1. Total RNA was extracted from samples using the RiboPure-Blood Kit (Ambion); 500 ng of total RNA was converted to cdna in a 20 μl reaction volume using the High Capacity cdna Reverse Transcription Kit (Life Technologies). Further, cdna was diluted to 100 μl with de-ionized, nuclease-free H 2 O. Real-time PCR was performed in a 20 μl reaction mixture containing 5 μl of diluted cdna, 4 μl of de-ionized, nuclease-free H 2 O, 10 μl of TaqMan Gene Expression Master Mix (Life Technologies) and 1 μl of TaqMan Gene Expression Assay (Life Technologies). All reactions were run in duplicate. PCR amplification was carried out using a 7500 Real-Time PCR System (Life Technologies) with an initial 10-min step at 95 o C followed by 40 cycles of 95 o C for 15 s and 60 o C for 1 min. Relative gene expression was calculated using the ΔΔCt method with ITFG1 and DPM1 as reference controls. Changes in the mrna levels in the whole blood after X-irradiation for each of the genes studied have shown that mrna levels of genes such as GADD45A (cf. Fig.2), CDKN1A, BBC3, BAX, GDF15, DDB2 are significantly elevated even 48 h after irradiation, which allows for correct identification of irradiated samples. In most cases fold changes after 0.6 and 2 Gy are very similar, which precludes distinction between samples irradiated with different doses of radiation. There is a substantial variability in fold changes between donors especially at longer times after irradiation. The mrna levels of MDM2, ATF3, PLK3, SESN2, BCL2 show only slight changes (less than two-fold in most cases) after irradiation which, together with substantial variability among donors, preclude

59 58 CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY their usefulness as a molecular biomarkers in biological dosimetry. These preliminary data indicate that analysis of expression of selected genes in the whole blood samples may be useful for fast identification of the irradiated individuals and therefore, may constitute a promising molecular biomarker for radiation biodosimetry. Nevertheless, further research is needed to establish a reliable, gene expression- -based test for biological dosimetry. References [1]. Paul S., Barker C.A., Turner H.C., McLane A., Wolden S.L., Amundson S.A.: Radiat. Res., 175, (2011). [2]. Joiner M.C., Thomas R.A., Grever W.E., Smolinski J.M., Divine G.W., Konski A.A., Auner G.W., Tucker J.D.: Radiother. Oncol., 101, (2011). [3]. Budworth H., Snijders A.M., Marchetti F., Mannion B., Bhatnagar S., Kwoh E., Tan Y., Wang S.X., Blakely W.F., Coleman M., Peterson L., Wyrobek A.J.: PLoS ONE, 7, e48619 (2012). OPTIMIZING THE METAFER IMAGE ACQUISITION AND ANALYSIS SYSTEM FOR ESTIMATION OF DNA DOUBLE STRAND BREAK INDUCTION BY MEANS OF γ-h2ax FOCI ASSAY Anna Lankoff, Katarzyna Sikorska, Iwona Buraczewska, Iwona Wasyk, Teresa Bartłomiejczyk, Teresa Iwaneńko, Sylwester Sommer, Irena Szumiel, Maria Wojewódzka, Karolina Wójciuk, Marcin Kruszewski The detection, visualization and enumeration of γ-h2ax foci allow the assessment of DNA double strand breaks and DNA repair in cells exposed to chemical, biological and physical factors. γ-h2ax assay has been used as a biodosimeter for radiation exposure, drug development, as well as a biomarker of radiosensitivity, aging, cancer and chronic inflammation (e.g. [1]). Despite the documented advantages of the γ-h2ax assay, there is a considerable variation between laboratories regarding foci formation in the same cell lines and exposure conditions. Automatic or semiautomatic systems substantially increase the productivity of the foci counting analysis and are free of the unavoidable operator subjectivity. However, it was shown that the number of foci may be markedly affected by the automated quantification method and parameters [2]. Since no criteria and recommendations have been developed to justify the choice of particular parameter values, we investigated the effect of various cell selection and object features/spot counting parameters on the number of scored cells and the slope of the γ-h2ax foci dose-response curve, using the training data files generated by the Metafer system (Metasystems, Germany). Since no criteria and recommendations have been developed to justify the choice of an appropriate protocol for the γ-h2ax assay, we evaluated the influence of different settings of automated image acquisition and analysis system (classifiers) on the number of scored cells and the slope of the γ-h2ax foci dose-response curve. Peripheral blood samples were collected from 34 healthy donors (20 females and 14 males, average age 44 ± 12 yrs) into heparinized (10-20 U/ml) Greiner bio-one tubes. None of the donors was previously exposed to radiation. Venous whole blood was processed according to four protocols and irradiated at room temperature with 250 kv X-rays at a dose rate of 1.14 Gy/min with the doses 0, 0.2, 0.4, 0.6, 0.8, 1, 1.5, 2, 3, 4 Gy (Xylon International Smart 200-E irradiator, Xylon, San Jose, USA). Isolation of lymphocytes and microscopic slide preparation was according to standard protocols. Images of individual cells with γ-h2ax foci were recorded as a training data files with an automated image acquisition and analysis system Metafer. These files were used to test 10 different classifiers varying in parameters dealing with automated cell selection (minimum object area, maximum object area, maximum concavity depth, maximum aspect ratio and CS object threshold %) and object features/spot counting (minimum and maximum intensity of a spot, mean relative object area, minimum spot distance, maximum spot distance). Statistical analysis of the obtained data was performed using Statistica 7.1 software (StatSoft. Inc., Tulsa, USA). The data were expressed as mean ± standard deviation (SD). To compare the frequencies of γ-h2ax foci in individual experiments as well as in pooled results, two-way analysis of variance followed by post-hoc Tukey s test was performed. Significant differences were defined at p < The dose-response curves were fitted to a linear model: y = αd + C where: y the yield of γ-h2ax foci, D the dose. The coefficients C and α were calculated with the method of iteratively reweighted least squares for curve fitting. The mean numbers of γ-h2ax foci per cell and deviation of the variance for each point of the dose-response curves were calculated to test the distribution of γ-h2ax foci among the analysed lymphocytes according to the Poisson s law. The number of γ-h2ax foci obtained by applying various classifiers was used to construct the dose-response curves. Two such curves (out of 10) are presented in Fig. They illustrate the influence of different settings of automated image acquisition and analysis system on the number of scored cells and the slope of the γ-h2ax foci dose-re-

60 CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY 59 γ-h2ax foci per cell γ-h2ax foci per cell Dose [Gy] Dose [Gy] Fig. Example of the influence of various parameters of automated image acquisition and analysis on the slope of dose- -response calibration curves for γ-h2ax foci. The same training data file generated by the Metafer were used for testing 10 classifiers. Results are shown for two of them. γ-h2ax foci induction was analysed after irradiation with the doses indicated followed by 30 min incubation at 37 o C. sponse curve. The lowest and highest slope values are shown, for classifiers 3 and 10, respectively. These results indicate that the combination of cell selection and spot counting parameters have a significant impact on the number of scored cells and the slope of dose-response curve for γ-h2ax foci. References [1]. Rothkamm K., Horn S.: Ann. Ist. Super. Sanita, 45, (2009). [2]. Qvarnström O.F., Simonsson M., Johansson K.A., Nyman J., Turesson I.: Radiother. Oncol., 72, (2004). QUICK SCAN OF DICENTRIC CHROMOSOMES FOR EVALUATION OF THE ABSORBED DOSE Sylwester Sommer, Iwona Buraczewska, Katarzyna Sikorska, Iwona Wasyk, Teresa Bartłomiejczyk, Anna Lankoff, Maria Wojewódzka, Marcin Kruszewski In the event of a large-scale radiological emergency, biodosimetry tools will be essential that can provide timely assessment of radiation exposure to the general population and enable the identification of those individuals exposed who should receive medical treatment. A number of biodosimetric tools are potentially available, but they must be adapted and tested for a large-scale emergency scenario. These methods differ in their specificity and sensitivity to radiation, the stability of the signal and speed of performance. A large-scale radiological emergency can take different forms. Based on the emergency scenario, different biodosimetric tools should be applied. The dicentric chromosome assay is considered to be the best and most reliable ( gold-standard ) assay for accurately estimating unknown radiological doses to individuals following radiological or nuclear accidents [1]. The assay is labour-intensive and time-consuming. In a mass-casualty scenario, this assay is not well suited for providing timely dose estimates due to its time- and expertise-intensive nature. There are two ways to increase triage-quality biological dosimetry throughput: increasing the number of trained personnel capable of conducting the DCA, evaluating alternative biodosimetry approaches. The latter case is a new scoring technique (termed QuickScan, i.e. quick scan of dicentric chromosomes). It has been accepted as an alternative rapid-scoring approach [1-3] that could be of value in the triage and management of people at risk for the acute radiation syndrome [3]. Fig. Frequencies of dicentric chromosomes determined in varying cell numbers. Standard deviation indicated.

61 60 CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY To investigate how the number of metaphase spreads influences dose prediction accuracy in our hands, numbers of dicentrics were analysed in 20, 30, 50 and 100 cells (depending on the dose) in order to find the lowest number of cells enabling to reconstruct the dose properly. In the range of high doses, 2-4 Gy of acute irradiation, even 20 cells were enough to reconstruct the doses properly with the confidence interval sufficient for triage analysis (cf. Fig.). On the other hand, even 100 scored cells may not be enough to recognize whether the person was irradiated with a very low dose. References [1]. Flegal F.N., Devantier Y., McNamee J.P., Wilkins R.C.: Health Phys., 98, (2010). [2]. Flegal F.N., Devantier Y., Marro L., Wilkins R.C.: Health Phys., 102, (2012). [3]. Romm H., Wilkins R.C., Coleman C.N., Lillis-Hearne P.K., Pellmar T.C., Livingston G.K., Awa A.A., Jenkins M.S., Yoshida M.A., Oestreicher U., Prasanna P.G.: Radiat. Res., 175, (2011). THE EFFECT OF SUPPLEMENTATION WITH CONJUGATED LINOLEIC ACID (CLA) ON Akt1 KINASE PHOSPHORYLATION IN X-IRRADIATED HT-29 CELLS Iwona Grądzka, Iwona Buraczewska, Katarzyna Sikorska, Barbara Sochanowicz, Irena Szumiel, Karolina Wójciuk, Grzegorz Wójciuk Conjugated linoleic acids (CLA) are natural components of human diet. The most abundant isomer, cis-9,trans-11 CLA (c9,t11-cla) exhibits strong antitumour activity, and therefore its usefulness as an adjuvant in radiotherapy of cancer is worth considering. Previously, we have shown that c9,t11-cla sensitized human colon cancer HT-29 cells to X-radiation [1]. The 24-hour supplementation with the CLA isomer (70 μm) did not affect the cell cycle progression or expression of DNA-repair-related genes. Nevertheless, it caused disturbances in the rejoining of X-ray inflicted double strand breaks (DSBs), as shown by pulse-field gel electrophoresis. The transient increase in DSB levels during repair in CLA-supplemented cells was reflected in DNA repair foci number (histone γ-h2ax), immunocytochemically monitored, and in chromatid fragmentation frequencies, measured by premature chromosome condensation. The cell growth inhibition was strengthened by c9,t11-cla but, interestingly, higher chromosome aberration frequencies were not observed. The delay in DSB rejoining was associated with a diminished activation of DNA-dependent protein kinase (DNA-PK) a key enzyme of the non- -homologous DNA end joining (NHEJ). At the same time, the nuclear accumulation of epidermal growth factor receptor (EGFR), known to activate DNA-PK under ionizing radiation-induced stress, was restrained. DNA-PK is also involved in Akt1 (protein kinase B) activation in response to ionizing radiation-inflicted DNA damage (reviewed in [2]). Activation proceeds through phosphorylation of serine (Ser473). Akt1 forms nuclear foci and colocalizes with DNA-PK at DSBs. Akt1 knockout mice resemble the DNA-PK deficiency radiosensitivity phenotype, with increased apoptosis in re- A B Fig. Time course of Akt1 phosphorylation after X-irradiation. (A) Western blots of Akt1 and pakt1 (Ser473) in nuclei of HT-29 cells, control or CLA-supplemented, X-irradiated (5 Gy) and incubated for intervals indicated. (B) normalized to control Akt1 content (left) and ratio of the phosphorylated to total Akt1 (right).

62 CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY 61 sponse to DNA damage, supporting the notion that DNA-PK/Akt1 pathway has a marked impact on cell survival after DNA damage. The above results suggest that apart from the role in DSB repair, DNA-PK is the source of anti-apoptotic signalling pathway and CLA treatment prevents this function. Therefore, the effect of c9,t11-cla on Akt1 activation was examined. HT-29 cells were incubated with CLA-supplemented or non-supplemented medium as described in [1] and the extent of Akt1 phosphorylation and Akt1 level were determined with specific antibodies by Western blotting in the nuclear and cytoplasmic fractions of HT-29 cells after X-irradiation with 2 Gy X-rays. X-irradiation induced a pronounced increase in phosphorylation of the nuclear Akt1 with a maximum at 20 min after irradiation, whereas phosphorylation of the cytoplasmic Akt1 was much smaller but more stable. Further, the ratio of Akt1 pser473 to unphosphorylated Akt1 was determined in the nuclear fraction. Figure presents the Western blots from a representative experiment. It can be seen that X-irradiation induced a pronounced phosphorylation of the nuclear Akt1 in the absence of CLA supplementation, whereas CLA considerably decreased the Akt1 pser473 content. This effect corresponded with the previously observed lowered DNA-PK activity after X-irradiation of CLA-supplemented cells as compared to the non-supplemented ones [1]. This observation explains the decreased survival of X-irradiated CLA-supplemented cells as compared to the non-supplemented ones in spite of the absence of increase in the chromosomal damage that is usually observed in the case of impaired DNA-PK activity. It also shows that the signalling function of DNA-PK may be affected by composition of the plasma membrane lipids, obviously resulting in a disturbed function of EGFR. Direct measurement of apoptosis should provide a firm basis for this conclusion. References [1]. Grądzka I., Sochanowicz B., Brzóska K., Wójciuk G., Sommer S., Wojewódzka M., Gasińska A., Degen C., Jahreis G., Szumiel I.: Biochim. Biophys. Acta, 1830, (2013). [2]. Toker A.: Trends Biochem. Sci., 33, (2008).

63 LABORATORY OF NUCLEAR ANALYTICAL METHODS The Laboratory of Nuclear Analytical Methods was created in 2009 on the basis of the former Department of Analytical Chemistry. 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 other laboratories of the INCT and provides analytical services for them as well as for the 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-ray counting. In 2013, the research projects carried out in the Laboratory were concerned with the chemical aspects of nuclear power, and nuclear and related analytical techniques for environment protection. In 2013, the Laboratory participated, together with the Centre for Radiochemistry and Nuclear Chemistry, in Operational Programme Innovative Economy (PO IG) project Analysis of the possibilities of uranium supply from domestic resources. The Laboratory participated also in the strategic research project from the National Centre for Research and Development (NCBR), Poland Technologies supporting development of safe nuclear power enegineering. The Laboratory is a member of consortium MODAS consisting of eight leading Polish universities and scientific institutes. Within the scope of the MODAS project, the Laboratory has prepared four new environmental candidate reference materials for their certification for the contents of a possibly great number of trace elements. The materials in question are: Bottom Sediment, Herring Tissue, Cormorant Tissue and Cod Tissue. In 2013, the Laboratory of Nuclear Analytical Methods conducted two proficiency tests (PT). The PT on the determination of H-3, Am-241, Ra-226 and Pu-239 in water, food and environmental samples was conducted on the request of National Atomic Energy Agency, Poland for laboratories forming radiation monitoring network in Poland. Proficiency testing scheme PLANTS 13: Determination of As, Cd, Cr, Cu, Hg, Pb, Se and Zn in dry edible mushroom powder (Suillus bovinus) was provided for laboratories analysing food and environmental samples. All proficiency tests are provided following requirements of ISO/IEC 17043:2010 and IUPAC International Harmonized Protocol (2006).

64 64 LABORATORY OF NUCLEAR ANALYTICAL METHODS RADIOLYTIC REMOVAL OF SELECTED PHARMACEUTICALS AND BISPHENOL A FROM WATERS AND WASTES Anna Bojanowska-Czajka, Sylwia Borowiecka 1/, Marek Trojanowicz 1/ Faculty of Chemistry, University of Warsaw, Warszawa, Poland Increasing presence of human and veterinary pharmaceuticals in the natural environment is since many years a common environmental problem. This concerns not only wastes of various origin and surface waters [1, 2], but also drinking water which is produced in conventional water treatment plants for communal use [3, 4]. A limited efficiency of waters and wastes conventional treatment is well illustrated by data published about the removal of a large group of popular pharmaceuticals and hormones in Spain [2]. As it is shown by histogram in Fig.1, among 20 different examined species occurring in wastes at levels from ng/l to μg/l, only five of them were completely decomposed, and not found in the effluent for treatment plant. The research studies dealing with that problem are carried out currently in several areas. Their three main fields include development of new analytical methods for efficient monitoring of the presence of pharmaceutical residues in environmental samples, toxicological studies on the interaction of residual pharmaceuticals with human and animal organisms, and studies on the development of new and more efficient methods of their removal from waters and wastes. Concerning analytical methods, the most powerful for simultaneous determinations at trace and ultra-trace levels are high-performance separation methods hyphenated with mass spectrometry [5], but also flow analysis methods [6], and sensors [7] are being developed mostly for screening purposes and simple use by the end users. Toxicological studies in this area are mostly focused on the combined interactions with living organisms of a large number of pharmaceuticals, which are present in the environment at trace level [8]. The most advanced studies on the development of new methods of efficient decomposition of pharmaceuticals residues in environment involve especially different advanced oxidation processes, based on radical reactions in aqueous media [9]. Surprisingly, even in this relatively recent review there is no mention on the application of ionizing radiation as especially effective method of decomposition of pharmaceutical residues. There are hundreds of papers published in the last three decades on the application of ionizing radiation for decomposition of organic pollutants in aqueous phase dealing with different groups of compounds. In the last decade an increasing amount of such applications concerns decomposition of pharmaceutical residues in waters and wastes. Very recent papers published in the last two years deal, e.g. with a commonly used analgestic and antipyretic drug paracetamol [10], salicylic and methyl substituted salicylic acids [11], popular non-steroidal anti-inflammatory drugs such as ketoprofen [12, 13], diclofenac [13-16], and ibuprofen [13, 17, 18]. Also radiolytic degradation using gamma irradiation was reported recently for X-ray contrast medium diatriazoate [19], and several other commonly used drugs in wastewater [13]. In the majority of publications, the conducted studies were focused on the elucidation of mechanism of radical reactions of the examined species with products of water radiolysis, and the determination of optimum conditions for decomposition of target compounds at mg/l concentration levels. For compounds examined in this study, e.g. for diclofenac it was level from 30 [14] to 296 [16] mg/l, for ibuprofen from 28 to 59 mg/l [17], while for carbendazim 1.2 mg/l [17]. On the other hand, the highest levels of ibuprofen found in surface water reach 1 μg/l [3], and in wastes 4.2 μg/l [2]. Then, for diclofenac, the data collect- Fig.1. Histogram showing maximum concentrations [ng/l] of selected pharmaceuticals and hormones found in influents and effluents from the sewage treatment plants in Catalonia, in Spain [2].

65 LABORATORY OF NUCLEAR ANALYTICAL METHODS ed from 16 countries in effluents from wastewater treatment plants the determined values were up to 1.8 μg/l, and in surface waters up to 0.3 μg/l [20]. The same values for carbendazim were 3.2 and 0.5 μg/l, respectively [20]. Those data show values, which are several orders of magnitude lower than the concentrations examined in the above-mentioned studies on radiolytic decomposition of those pharmaceuticals. In this study three pharmaceuticals occurring as water pollutants were examined (diclofenac, ibuprofen, and carbendazim), and also one common industrial organic pollutant bisphenol A. In the coarse of this study the examined standard solutions and environmental samples were gamma-irradiated using a 60 Co source Gamma Chamber with a dose-rate of 8.0 kgy/h. The reversed-phase HPLC analyses of irradiated samples were carried out using a Shimadzu chromatograph with a diode array UV/Vis detector, a Luna ODS2, 5 μm mm analytical column and a guard column from Phenomenex (Torrance, CA, USA). For simultaneous monitoring of concentrations of target species and products of decomposition, two HPLC procedures with UV detection have been developed, for which example of recorded chromatograms are shown in Fig.2. In both methods the base-line separation can be achieved for all analytes, however, in method B the total analysis time to get the elution of all the determined species was about 60 min, while in method A 12 min. The HPLC determinations with UV detection at μg/l concentration level require an initial Fig.2. Comparison of HPLC chromatograms for standard mixtures of determined analytes obtained with two developed methods of isocratic elution. A Eluent composition: 40% 0.2 M formic acid, 60% acetonitrile, ph 4.0; injection 4 mg/l each analyte (method A). B Eluent composition: 50% 0.6 mm KH 2 PO 4, 30% acetonitrile, 20% methanol, ph 4.0; injection 2 mg/l each analyte (method B). In both cases: flow-rate 1 ml/min, detection UV at 220 nm. A B Carbamazepine Bisphenol A Diclofenac 65 Fig.3. Comparison of the application of two developed HPLC methods in the determination of investigated analytes in river water samples. A chromatograms (3 repetitions) obtained with method A for river water sample from the Vistula river, collected before treatment plant with marked retention times for determined analytes. B chromatograms of river water with added 10 μg/l concentration of each analyte, obtained with method B for sample prior to the irradiation (1), after gamma irradiation with a dose of 100 (2) and 250 Gy (3). preconcentration of analytes, which in this study was carried out using the solid-phase extraction (SPE) method employing commercial resin Oasis HLB (Waters) with a sorbent bed of 60 mg for each analysis run. In optimized conditions analytes were preconcentrated 250 times, with the use of 500 ml initial sample volume with ph adjusted to 8.0, and elution with 2 ml of methanol. Example chromatograms obtained with two developed HPLC methods in determination of the examined species in natural river water samples from the Vistula river are shown in Fig.3. A satisfactory reproducibility of determinations shown in recordings using method A, indicate that the level of target analytes in the example river water samples is below the limits of detection (LOD), which was evaluated as 0.03, 0.06, 0.11 and 0.14 μg/l for carbamazepine, bisphenol A, diclofenac and ibuprofen, respectively. The drawback of HPLC method A is a large signal obtained for matrix components of natural waters, which are simultaneously with analytes retained and eluted in the preconcentration step (Fig.3A). This effect is less important when method B is employed (Fig.3B), although in this case LODs values are about one order of magnitude poorer. The investigations of efficiency of radiolytic decomposition reported already in the literature for ibuprofen [13, 17, 18], and carbamazepine [13], were broadened in this work by examination of the effect of ph of the irradiated solutions. At A B Ibuprofen 1 2 3

66 66 LABORATORY OF NUCLEAR ANALYTICAL METHODS an initial concentration of both compounds 10 mg/l, the ph effect for ibuprofen is observed only at doses kgy, where irradiated compound is only partly decomposed (Fig.4A). In the case of more resistant towards radiation carbamazepine (Fig.3B), the decomposition process in the whole range of employed doses is about 20% less efficient than in neutral or acidic media (Fig.4B). A samples and hospital effluent (Fig.6). In both cases the monitored samples were irradiated after spiking them with 10 μg/l each analyte. The obtained results confirm that especially the decomposition of carbamazepine and bisphenol A requires much larger irradiation doses in the case of hospital effluent than river water samples. In the case of bisphenol A the application of 100 Gy absorbed dose allows the decomposition of 95% in river water, while 70% only in hospital effluent. For carbamazepine those yields were 90 and 37%, respectively. A B B Fig.4. Illustration of the effect of ph of gamma-irradiated solutions of pharmaceuticals (10 mg/l each) on the yield of radiolytic decomposition in aerated solutions at different irradiation dose: A ibuprofen, B carbamazepine. As it is shown by chromatograms in Fig.5, for the irradiation of the hospital effluent with added 10 μg/l each analyte, up to 0.5 kgy irradiation dose was used. One can see, that only in the case of diclofenac and ibuprofen it was sufficient the complete decomposition was observed at 0.25 kgy. A comparison of the effect of matrix of the irradiated solution on the yield of decomposition of the examined compounds is illustrated by signal changes in recorded chromatograms for river water Carbamazepine Bisphenol A Diclofenac Ibuprofen Fig.5. HPLC chromatograms recorded for the sample of wastewater from a hospital spiked with 10 μg/l each analyte prior to gamma irradiation (1), after irradiation with doze 100 (2), 250 (3) and 500 Gy (4) Fig.6. Comparison of the yield of gamma irradiation of the investigated compounds at different irradiation doses in various water matrices for samples spiked with 10 μg/l concentration each: A river water sample from the Vistula river, B effluent from a hospital. Results of this study firmly show a very essential impact of matrix composition of irradiated natural samples on the yield of decomposition of pharmaceutical residues at their examined level, close to real occurring ones in environmental samples. The observed complete decomposition at an absorbed dose level of about 1 kgy indicate that this AOP process may be a competitive method for the decomposition of pharmaceutical residues from waters and wastes compared to methods routinely used nowadays. References [1]. Nikolaou A., Meric S., Fatta D.: Anal. Bioanal. Chem., 387, (2007). [2]. Pedrouzo M., Borrull F., Pocurull E., Marce R.M.: Water Air Soil Poll., 217, (2011). [3]. Mompelat S., Le Bot B., Thomas O.: Environ. Int., 35, (2009). [4]. Kleywegt S., Pileggi V., Yang P., Hao C., Zhao X., Rocks C., Thach S., Cheung P., Whitehead B.: Sci. Total Environ., 409, (2011).

67 LABORATORY OF NUCLEAR ANALYTICAL METHODS [5]. Pitarch E., Portoles T., Marin J.M., Ibanez M., Albarran F., Hernandez F.: Anal. Bioanal. Chem., 397, (2010). [6]. Trojanowicz M.: Talanta, 96, 3-10 (2012). [7]. Rodriguez-Mozaz S., Lopez de Alda M., Barcelo D.: Anal. Bioanal. Chem., 386, (2006). [8]. Fent K., Weston A.A., Caminda D.: Aquat. Toxicol., 76, (2006). [9]. Klavariotti M., Mantzavinos D., Kassinos D.: Environ. Int., 35, (2009). [10]. Szabo L., Toth T., Homlok R., Takacs E., Wojnarovits L.: Radiat. Phys. Chem., 81, (2012). [11]. Ayatollahi S., Kalnina D., Song W., Turks M., Cooper W.J.: Radiat. Phys. Chem., 92, (2013). [12]. Illes E., Takacs E., Dombi A., Gajda-Schranz, Gonter K., Wojnarovits L.: Radiat. Phys. Chem., 81, (2012). [13]. Kimura A., Osawa M., Taguchi M.: Radiat. Phys. Chem., 81, (2012). 67 [14]. Homolok R., Takacs E., Wojnarovits L.: Chemosphere, 85, (2011). [15]. Trojanowicz M., Bojanowska-Czajka A., Kciuk G., Bobrowski K., Gumela M., Koc A., Nałęcz-Jawecki G., Torun M., Ozbay D.S.: Eur. Water, 39, (2012). [16]. Yu H., Nie E., Xu J., Yan S., Cooper W.J., Song W.: Water Res., 47, (2013). [17]. Zheng B.G., Zheng Z., Zhang J.B., Luo X.Z., Wang J.Q., Liu Q., Wang L.H., Desalination, 276, (2011). [18]. Illes E., Takacs E., Dombi A., Gajda-Schranz K., Racz G., Gonter K., Wojnarivits L.: Sci. Total Environ., 447, (2013). [19]. Velo-Gala I., Lopez-Penalver J.J., Sanchz-Polo M., Rivera-Utrilla J.: Chem. Eng. J., , (2012). [20]. Zhang Y., Geissen S., Gal C.: Chemosphere, 73, (2008). DETERMINATION OF URANIUM IN FLOW-INJECTION SYSTEM WITH SPECTROPHOTOMETRIC DETECTION Kamila Kołacińska, Marek Trojanowicz Flow analysis is considered as a very efficient way of carrying out numerous analytical determinations with different detections and on-line sample treatment processes. The essential feature of the flow analysis is the possibility of mechanization of numerous on-line processes and automation of all analytical procedures, which means a full control over the fluid flow, its volumes, flow rates, timing and detection conditions. This improves the efficiency of measurements, provides a good reproducibility of results and also minimizes the human error influence by mechanization of all the performed processes. The development of the flow analysis laboratory methods began with the research conducted by Skeggs in the 1950s, who introduced the air segmentation of liquid in analytical systems designed to study body fluids (SFA segmented flow analysis) [1]. A significant technological progress of the method came through inventing the flow injection analysis (FIA) [2]. The operational principle of FIA technique is based on recording the transient signal in detector, which corresponds to the analyte concentration in the injected sample. A FIA measuring system consists of a pumping device, which provides flow of a liquid, a tubing manifold, an injection valve with an injection loop to load a sample into system and also a detector. After the sample is injected into a flowing carrier stream, it moves downstream and mixes with an introduced reagent in a reactor coil to produce a detectable form by a chemical reaction. In a more complex FIA setups there are also different modules for on-line sample processing incorporated into the flow system. A sequential injection analysis (SIA) is considered to be a new generation of FIA method, which compared to FIA, can be regarded as a more flexible because it introduces flow reversal; the change of the flow direction is programmed and usually controlled by a computer [3]. The flow methods in chemical analysis have been developed for over 50 years and also numerous others highly specialized systems were invented. This includes MCFIA multi-commuted flow injection analysis [4], MSFIA multi-syringe flow injection analysis [5], MPFS s multi-pumping flow system [6] and the most recent option LOV Lab-on-Valve systems [7]. Currently, flow analysis has a solid place among other methods of modern analytical chemistry [8, 9], and is widely applied to the chemical analysis of environmental samples as well as geological, industrial or clinical ones. The implementation of this technique for the determination of radionuclides is a relatively new field of applications; although the first approach of using FIA in radioanalysis was reported for measuring vanadate by passage sample through column with radioisotope of silver [10]. The applications of flow analysis to the determination of radionuclides for different purposes have been developed for more than 20 years, which were already a subject of several reviews [11-14]. A choice of a detection type depends primarily on the nature of the sample analysed and analytes to be determined. Generally, for radiochemical analysis few kinds of detectors are used, only, such as radiometric, mass spectrometric and also spectrophotometric. In recent decade several papers were published on the application of flow-injection methods for the determination of uranium [15-29]. Methods which were based on the use of spectrophotometric detection [15-22], or amperometric one [23] allow the determination of total content of uranium in analysed samples. The application of inductively coupled plasma mass spectrometry (ICP-MS) can be used in the determination of particular isotopes such as 234 U [24], 236 U [25] and 238 U [26-29], or isotope ratio 235 U/ 238 U [27]. Regarding the construction of flow systems, a typical FIA systems are most often used [15, 20-24, 26-28].

68 68 LABORATORY OF NUCLEAR ANALYTICAL METHODS Fig.1. Schematic diagram of MSFIA-LOV system used for determination of uranium. Very recently, a design of SIA system was reported for simultaneous determination of 236 U, 237 Np, and Pu isotopes in sea water [25]. Several attempts can be found in the literature on design of MSFIA systems [16, 17], recently also employing a more complex construction of rotary injection valves LOV with built-in a mini-column for extraction, preconcentration and separation of analytes [18, 19, 29]. Most commonly in flow injection systems for the determination of uranium is spectrophotometric detection based on the formation of coloured complexes of UO 2 2+ cation with Arsenazo III [15-20], and also such ligands as Chromazurol S [21] and Chlorphosphonazo III [22]. With the use of Arsenazo III, limits of detection for different configurations of flow system are in a wide range form 40 mg/l [16] down to even 5.9 ng/l [19], at a well optimized preconcentration procedure. For on-line trace U(VI) preconcentration, various types of sorbents are employed, including commercially available extraction chromatography resins TRU-Spec [17, 20, 27], UTEVA [18, 19, 24, 25, 29], TEVA [28], strong anion exchanger Amberlite IRA-402 [20], and also, e.g. a laboratory-made styrene-divinylbenzene copolymer modified with dodecylamidoxime [22]. In this study, initiated recently in the Institute of Nuclear Chemistry and Technology (INCT), a commercial MSFIA-LOV system from Sciware Systems (Bunyola, Spain) was employed, which was already used in the determination of uranium in environmental samples with spectrophotometric detection [18]. The configuration of flow system is shown schematically in Fig.1. The spectrophotometric detection was based on the formation of UO 2 2+ complex with Arsenazo III (2,2 -(1,8-dihydroxy-3,6-disulfonapthylene-2,7-bisazo)bisbenzenearsonic acid), whose structure is shown in Fig.2. The maximum of absorption of U(VI) complex with Arsenazo is at 651 nm, and molar absorption coefficient M 1 cm 1 [30]. Taking into account this absorption maximum, as a source of light in MSFIA-LOV system, seven different light emitting diodes (LED) were examined with the emission maxima from 650 to 660 nm. As the optimum one, the LED type L-53SRC/F from Kingbright (Issum, Germany) was employed, with an emission maximum at 655 nm (Fig.3). Spectrophotometric measurements were carried out with Fig.2. Structure of UO 2 2+ complex with Arsenazo III. Fig.3. Emission spectrum of light emitting diode L-53SRC/F from Kingbright company used as a source of radiation in the MSFIA-LOV system for determination of uranium.

69 LABORATORY OF NUCLEAR ANALYTICAL METHODS 69 Table. Sequence of operation in flow-injection determination of uranium in MSFIA-LOV system. No. Process Reagent Volume [ml] Flow rate [ml/min] 1 Column conditioning 3 M HNO Sample loading U(VI) in 3 M HNO M HCl Elution of interferences 4 5 M HCl Elution of uranium 0.01 M HCl Complex forming 0.001% Arsenazo III Washing the flow system H 2 O a 100 cm long waveguide capillary cell (LWCC) from World Precision Instruments (Saracota, USA), and with a CCD detector type USB 2000 from Ocean Optics (Dunedin, USA). Arsenazo III forms also stable complexes with Th, Zr, Cd, Zn, Ca and can be used for spectrophotometric determination of those elements. The selectivity of spectrophotometric determination of U(VI) can be achieved by the application of suitable masking reagents, as it was shown in the simultaneous determination of U and Th in FIA system [21], or by the use of the above-mentioned selective sorbents. In this work, for this purpose the extraction resin UTEVA from Triskem (Bruz, France) was used. By the use of diamyl amylphosphonate as extrahent, this resin allows selective retention of U(VI) and tetravalent actinides as neutral nitrato complexs [31]. The resin (30 mg) was packed into mini-column of LOV injection valve, and all stages of analytical procedure were 1,4 carried out according to the programme shown in Table. For spectrophotometric detection, 0.001% Arsenazo III solution in 0.7 M chloroacetic acid 0.1 M sodium chloroacetate buffer of ph 2.0 was used. In the initial experiments 1 μg/l to 1 mg/l of U(VI) solutions in 3 M HNO 3 were injected. Example of the signals recorded in FIA system are shown in Fig.4. This recording shows that for 1 ml of the injected sample volume, the whole measurement of 1 sample takes about 3 min, which indicates a very efficient way of conducting analytical determination in such a system. The obtained detectability at this initial stage of the work, is far from satisfactory, the whole measuring procedure requires further optimization in order to improve detection level, examination of completeness of retention and elution of the analyte from the sorbent bed. In further steps also selectivity of retention/elution process will be examined in flow injection conditions employed, and eventually adjusted by the modification of the whole procedure. The developed method will be also examined in the determination of total uranium content in environmental samples. The work was financed by the National Centre for Research and Development, Poland in the frame of the strategic research project Technologies supporting development of safe nuclear power engineering task 8 Study of processes occurring under regular operation of water circulation systems in nuclear power plants with suggested actions aimed at upgrade of nuclear safety ppb 1, ppb Abs [a.u.] 0,8 0,6 0,4 0 ppb 1 ppb 10 ppb 0, Fig.4. Example of flow-injection signals obtained in the MSFIA-LOV system for injection of uranium solutions at different concentrations. Time [s] References [1]. Skeggs L.J.: Am. J. Clin. Pathol., 28, (1975). [2]. Ruzicka J., Hansen E.H.: Anal. Chim. Acta, 78, (1975). [3]. Ruzicka J., Marshall G.D.: Anal. Chim. Acta, 237, (1990). [4]. Reis B.F., Gine M.F., Zagatto E.A.G., Lima J.L.F.C., Lapa R.A.: Anal. Chim. Acta, 293, (1994). [5]. Cerdá V., Estela J.M., Forteza R., Cladera A., Becerra E., Altimira P., Sitjar P.: Talanta, 50, (1999). [6]. Lapa R.A.S., Lima J.L.F.C., Reis B.F., Santos J.L.M., Zagatto E.A.G.: Anal. Chim. Acta, 466, (2002).

70 70 LABORATORY OF NUCLEAR ANALYTICAL METHODS [7]. Ruzicka J.: Analyst, 125, (2000). [8]. Advances in flow analysis. Ed. M. Trojanowicz. Wiley-VCH, Weinheim [9]. Westmeier W., Siemon K.: J. Environ. Radioact., 117, (2013). [10]. Grudpan K., Nacapricha D.: Anal. Chim. Acta, 246, (1991). [11]. Grate J.W., Egorov O.B.: Automated radiochemical separation, analysis and sensing. In: Handbook of radioactivity analysis. 2nd ed. Ed. M. L Annunziata. Elsevier Science, USA 2003, pp [12]. U M., Tölgyessy J.: J. Radioanal. Nucl. Chem., 191, (1995). [13]. Grate J.W., Egorov O.B., O Hara J.M., DeVol T.A.: Chem. Rev., 108, (2008). [14]. Fajardo Y., Avivar J., Ferrer L., Gómez E., Casas M., Cerdà V.: Trends Anal. Chem., 29, (2010). [15]. De Sousa A.S.F., Ferreira E.M.M., Cassella R.J.: Anal. Chim. Acta, 620, (2008). [16]. Guzmán Mar J.L., López Mertínez L., López de Alba P.L., Ornelas Soto N., Cerdá V.: J. Radioanal. Nucl. Chem., 281, (2009). [17]. Avivar J., Ferrer L., Casas M., Cerdá V.: Anal. Bioanal. Chem., 397, (2010). [18]. Avivar J., Ferrer L., Casas M., Cerdà V.: Talanta, 84, (2011). [19]. Avivar J., Ferrer L., Casas M., Cerdá V.: Anal. Bioanal. Chem., 400, (2011). [20]. Nisa Q., Ali A., Haleem Khan M.: J. Radioanal. Nucl. Chem., 295, (2013). [21]. Hirano Y., Ogawa Y., Oguma K.: Anal. Sci., 19, (2003). [22]. Oguma K., Suzuki T., Saito K.: Talanta, 84, (2011). [23]. Aguiar M.A.S., Marquez K.S.G., Gutz I.G.R.: Electroanalysis, 12, (2000). [24]. Godoy M.L.D.P., Godoy J.M., Kowsmann R., dos Santos G.M., Petinatti da Cruz R.: J. Environ. Radioact., 88, (2006). [25]. Qiao J., Hou X., Steier P., Golser R.: Anal. Chem., 85, (2013). [26]. Truscott J.B., Bromley L., Jones P., Evans E.H., Turner J., Fairman B.: J. Anal. At. Spectrom., 14, (1999). [27]. Benkhedda K., Epov V.N., Evans R.D.: Anal. Bioanal. Chem., 381, (2005). [28]. Schaumlöffel D., Giusti P., Zoriy M.V., Pickhardt C., Szpunar J., Łobiński R., Becker J.S.: J. Anal. At. Spectrom., 20, (2005). [29]. Avivar J., Ferrer L., Casas M., Cerda V.: J. Anal. At. Spectrom., 27, (2012). [30]. Golmohammadi H., Rashidi A., Safadri S.J.: Chem. Chem. Technol., 6, (2012). [31]. Horwitz E.P., Dietz M.L., Chiarizia R., Gatrone R.C., Esslin A.M., Bane R.W., Graczyk D.: Anal. Chim. Acta, 266, (1992).

71 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 (nanomof) using particle track membranes as template, modification of surface layer of engineering materials by implantation of lanthanide elements and nitrogen atoms using high intensity pulsed plasma beam (HIPPB), 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 (MOF) are of great interest due to their potential applications for gas storage, gas separation, catalysis, sensors, etc. Despite many achievements in the field, new rational and effective methods for assembling coordination polymers with a specific or desired structure are still awaited. Our interests are focused on the light s block metals coordination polymers with ligands showing carboxylic group and/or hetero-ring nitrogen functionality. In the last year the crystal structures of four new lithium coordination polymers with azine carboxylate ligands have been solved and published. High intensity pulsed plasma beam technique has been applied for AISI 316L austenitic stainless steels surface layer modification. The results of implantation of Ce, La or Ce+La elements to the surface layer and their influence on wear resistance improvement of AISI 316L are reported in details in this Annual Report. Since 1989, systematic studies of works of art, historical, archaeological objects and their fragments have been conducted. Results of these studies have enabled authenticity verification, information on the technology and techniques that were used by a given master and indication of the optimum conservation techniques that should be used during restoration and conservation work of a given object. The main objective of the study is characterization and identification of pigments and grounds in the 15th-17th century paintings from South-Eastern Poland collected at the Orthodox Art Department at the Castle Museum of Łańcut, Museum of Folk Architecture in Sanok, National Museum in Lvov and from so-named Gdańsk school. Together with commonly occurring pigments, such as vermilion (cinnabar), red lead, red iron oxide, orpiment, yellow ochre, lead white, chalk, gypsum, anhydrite and copper-containing green, one unusual material was identified lead tin yellow. Elemental analysis, especially trace elements analysis, carried out for lead white and earth pigments, allows establishing chemical patterns or finger prints, which are characteristic of specific artistic workshops. Extensive research aimed at determining precise details on the painting techniques applied, as well as the age, origin and authenticity of the objects examined has brought the results that could be a basis for future restoration of the paintings. The SEM-EDXA (scanning electron microscopy with energy dispersive X-ray analysis), TEM (transmission electron microscopy) and LA-ICP-MS (laser ablation inductively coupled plasma mass spectrometry) analytical techniques have been used to characterize and investigate the technologies of the red window glass in the medieval period. The study reported on the next pages confirms the presence of Cu nanoparticles. The results enabled identification of two structural categories of red glass sheet.

72 72 LABORATORY OF MATERIAL RESEARCH STRUCTURAL STUDIES IN Li(I) ION COORDINATION CHEMISTRY Wojciech Starosta, Janusz Leciejewicz Like diazine carboxylate, diazole and triazole carboxylate ligands have a number of multifunctional potential coordination sites involving hetero-ring N and carboxylate O atoms. They are accessible to metal ions and as such can be coordinated as mono-, bi- and tetradentate and act as linkers providing multibridging modes generating different types of coordination polymers. Recent results of our studies are briefly summarized below: Among 22 new structures determined in course of this project only three have been observed to be built of discrete molecules. The latest example is represented by the structure of a complex with pyrazole-4-carboxylate and water ligands [1]. Dinuclear moiety in which two Li ions and two ligand molecules related by an inversion centre has been observed as a structural unit in 12 complexes studied in the course of the present project. This unit has been observed to exist either as a separate dimeric molecule or as a building unit of polymeric structures. An example is provided by the structure of a Li complex with triazole carboxylate ligand. A discrete centrosymmetric dimeric molecule constitutes the structural building unit of a complex with 1,2,3-triazole monocarboxylate and water ligands [2], while centrosymmetric dinuclear moieties bridged by carboxylate O atoms form the polymeric structure of a complex with pyrazole-3,5-dicarboxylate and water ligands [3]. The molecular pattern observed in the structure of a Li complex with 5,6-dimethylpyrazine-2,3- -dicarboxylate and water ligands composed of molecular ribbons in which Li ions are bridged by both N,O bonding sites [4] has been earlier found in the structures of four Li complexes with pyrazine-2,3-dicarboxylate and water ligands [5, 6]. In the structure of one of them nitrato groups bridge the ribbons giving rise to a three- -dimensional framework [6]. In all the above structures an intra-molecular short hydrogen bond between carbonyl and carboxylato O atoms is operating; in all Li ions show trigonal bipyramidal coordination environment. PART 19. Triaqua(pyrazole-4-carboxylato-κN 1 )- -lithium The orthorhombic structure of the title compound is composed of discrete mononuclear molecules in which Li 1+ is coordinated by the non-protonated hetero-ring N atom of the ligand molecule and three aqua O atoms at the apices of distorted tetrahedron. The observed Li O and Li N bond distances and bond angles reveal usual values. The carboxylic group is deprotonated. It makes a dihedral angle of 10.7(2) o with the almost planar [r.m.s (1) Å] pyrazole ring. Bond distances and bond angles within the latter are close to those observed in the structure of the parent acid. Complex Fig.1. The molecule of the title compound with atom labelling scheme and 50% probability displacement elipsoids. molecules form layers parallel to the unit cell ac plane (Fig.1) and are stacked along the b axis (Fig.2). Coordinated water molecules are active as donors and acceptors in an extended hydrogen bond system in which carboxylate O atoms are as acceptors. The protonated hetero-ring N atom as a donor and a carboxylate O atom as an acceptor are also observed. Fig.2. A single molecular layer viewed along the [010] direction.

73 LABORATORY OF MATERIAL RESEARCH PART 20. Di-μ-aqua-bis([aqua(5-carboxylato- -1H-1,2,3-triazole-4-carboxylic acid-κ 2 N 3,O 4 ) lithium The triclinic unit cell of the title compound comprises two Li(C 4 H 2 N 3 O 4 )(H 2 O) 2 molecules related by an inversion centre to form a dimeric moiety in which two Li ions are bridged by an aqua 73 Fig.3. A dinuclear molecule of the title compound with 50% probability displacement ellipsoids. Symmetry code: (i) -x+1, -y+1, -z+1. O atom donated by each molecule (Fig.3). The coordination of the Li ion is distorted square pyramidal: carboxylate O1, hetero-ring N1, aqua O6 and O5 i atoms constitute its base [r.m.s (2) Å], the Li1 ion is (2) Å out of it, the aqua O5 i is at the apex. Li-O and Li-N bond distances are usual. The ligand triazole ring is almost planar [r.m.s (1) Å]. The carboxylate C6/O1/O2 and C7/O3/O4 groups make with it dihedral angles of 2.0(1) o and 5.5(1) o, respectively. The Fourier map indicates clearly that the O2 atom is protonated and acts as a donor in a fairly short intra- -molecular hydrogen bond of 2.538(2) Å to the O3 atom as an acceptor. The C7/O3/O4 carboxylic group remains deprotonated and coordination inactive. The bond distances and bond angles within the triazole ring do not differ from those reported in the structures of other complexes. The dimers form molecular sheets (Fig.4) in which they interact via an extensive hydrogen bond network; coordinated water molecules are as donors a hetero- -ring N atom and carboxylate O atoms as acceptors. PART 21. catena-poly[[diaquabis(μ 3-5-carboxylato-1H-pyrazole-3-carboxylic acid-κ 3 O 3 :O 3 ;O 5 ) dilithium(i)] monohydrate] The structural unit of the title complex is a centrosymmetric dinuclear moiety composed of two Li ions bridged by two bidentate carboxylato O atoms, each donated by a symmetry related ligand (Fig.5). The ligand acts in μ 3 bridging mode since apart from the bidentate O1 atom, the O4 atom of its second carboxylate group is chelated to a Li vi ion in the adjacent dimer. In this way a Li ion is coordinated by the bridging O1 and O1 ii atoms, the O4 i from the adjacent dimer and an aqua O5 atom resulting in a distorted tetrahedral geometry. The Li O bond distances which fall in the range between 1.930(2) Å and 1.980(3) Å are typical of Li complexes with carboxylate and water ligands. The pyrazole ring is planar with r.m.s. of (1) Å; the carboxylate group C6/O1/O2 and C7/O3/O4 make with it dihedral angles of 2.4(1) o and 5.5(1) o, respectively. The carboxylate O2 atom is chelating inactive, the O3 remains protonated and participates as a donor in the short hydrogen bond of 2.516(2) Å to O2 vi in an adjacent dimer. Bond distances and bond angles within the pyrazole ring do not differ from those reported in the structure of the parent acid. The plane of the Li,O1,Li ii,o1 ii dimer core makes a dihedral angle of 36.1 o with the ligand plane. The dimeric units linked by carboxylate O4 atoms form polymeric Fig.4. The packing of the dinuclear molecules with hydrogen bonds shown as dashed lines.

74 74 LABORATORY OF MATERIAL RESEARCH Fig.5. A fragment of the molecular ribbon showing dinuclear building unit of the title compound with atom labelling scheme and 50% displacement ellipsoids. Symmetry code: (i) x, y-1, z+1; (ii) -x+1, -y, -z+1. ribbons along [011] crystal direction. A solvate water molecule O6 with 50% site occupancy is present in the asymmetric cell resulting in one molecule per a dimer. Moreover, this water molecule shows 0.5/0.5 positional disorder. The ribbons are held together by a system of hydrogen bonds involving coordinated and crystal water molecules, the carboxylate groups and pyrazole N ring atoms resulting in a three-dimensional architecture (Fig.6). Fig.6. The packing of molecular ribbons viewed along their propagation direction. PART 22. catena-poly[[aqualithium(i)]-μ-3-carboxy-5,6-dimethylpyrazine-2-carboxylatoκ 4 O 2,N 1 :O 3,N 4 ] The asymmetric unit of the title compound contains two Li(I) ions and two coordinated to them water molecules, all located on the rotation twofold axis, a Li(I) ion, two ligand molecules and a coordinated to water molecule. Two water coordinated Li(I) ions located on the rotation twofold axis are bridged by a ligand via its both N,O bonding sites form type 1 molecular ribbon. The type 2 molecular ribbon is built of units composed of a water coordinated Li(I) cation and a ligand which also uses its both N,O bonding sites (Fig.7). Both ligands act in μ 2 bridging mode. All three Li(I) cations show slightly distorted trigonal bipyramidal coordination geometry. The Li11 cation is situated in the equatorial plane composed of O11, O11 ii and O13 atoms; N11 and N11 ii atoms are in the apical positions. The Li12 coordination is formed by O13, O13 iii and O16 atoms, N14 and N14 iii atoms are at the apices; the Li12 is also coplanar with the equatorial plane. On the other hand, the Li21 cation is (2) Å out of the equatorial plane formed by O21, O21 i and O25 atoms; N22 i and N21 i are at the apices. The Li-O and Li-N bond distances fall in the range observed in the structures of other Li complexes with diazine carboxylate ligands. Methyl carbon and pyrazine ring atoms in both ligands are coplanar with r.m.s. of

75 LABORATORY OF MATERIAL RESEARCH 75 Fig.7. Structural units of the title complex with atom labelling scheme and 50% probability displacement ellipsoids. Symmetry code: (i) -x, y, -z+3/2; (ii) -x, y, -z+1/2; (iii) x, -y, z+1/2. propagate in [001] direction (Fig.8). The planes of ribbon 1 and ribbon 2 pairs are inclined 91.1(1) o each to the other. They are held together by a system of hydrogen bonds in which water molecules Fig.8. The packing of molecular ribbons viewed along the [001] direction (1) Å in the ligand 1 and (2) Å in the ligand 2. The carboxylic groups C17/O11/O12 and C18/O13/O14 form with the ligand 1 ring dihedral angles of 6.1(1) o and 10.9(1) o, respectively. The dihedral angles between ligand 2 and carboxyl groups C27/O21/O22 and C28/O23/O24 are 1.2(10) o and 9.0(1) o, respectively. In both ligands the second carboxyl O atoms remain protonated and act as donors in the short intramolecular hydrogen bonds with bond distances of 2.378(2) Å and 2.369(2) Å. Two ribbons of the same type form pairs which act as donors and carboxyl O atoms are as acceptors giving rise to a three-dimensional molecular framework. References [1]. Starosta W., Leciejewicz J.: Acta Crystallogr., E69, m438 (2013).

76 76 LABORATORY OF MATERIAL RESEARCH [2]. Starosta W., Leciejewicz J.: Acta Crystallogr., E69, m515-m516 (2013). [3]. Starosta W., Leciejewicz J.: Acta Crystallogr., E69, m593-m594 (2013). [4]. Starosta W., Leciejewicz J.: Acta Crystallogr., E69, m655-m656 (2013). [5]. Starosta W., Leciejewicz J.: Acta Crystallogr., E67, m1133-m1134 (2011). [6]. Starosta W., Leciejewicz J.: Acta Crystallogr., E69, m62 (2013). FORMATION OF THE SURFACE LAYER WITH IMPROVED TRIBOLOGICAL PROPERTIES ON AUSTENITIC STAINLESS STEEL BY ALLOYING WITH REE USING HIGH INTENSITY PULSED PLASMA BEAMS Bożena Sartowska, Marek Barlak 1/, Lech Waliś, Jan Senatorski 2/, Wojciech Starosta 1/ National Centre for Nuclear Research, Otwock-Świerk, Poland 2/ Institute of Precision Mechanics, Warszawa, Poland Modification of the surfaces of technical materials is applied to change their surface properties. Austenitic stainless steels are used in numerous industrial applications, mainly due to their corrosion resistance in different environments, for example: nuclear and petrochemical industries and chemical processing. But poor tribological and mechanical properties of austenitic stainless steels limited their applications. Improvement of the wear resistance of austenitic stainless steels without loss of corrosion resistance can be achieved using different surface treatment, for example: enrichment of the surface layer with reactive elements or re-solidification techniques using laser, electron or ion beams. Rapid solidification process is useful to obtain very fine structure with uniform properties [1-4]. It is also well known that high oxygen affinity elements such as Y, Ce, La, Er and other rare earth elements (REE) added to steels in small amounts can improve their resistance for wear and mechanical properties [5, 6]. 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 [7-9], sol-gel coating [9] or using plasma beams [10]. Austenitic stainless steel AISI 316L (Cr 16.3 wt.%, Ni 11.5 wt.%, Mo 2.0 wt.%, Mn 1.3 wt.% and Fe balance) was used as the substrate for investigations. As the REE sources, cerium or lanthanum or mischmetal (MM) with a composition: Ce 65.3 wt.%, La 34.0 wt.% and balance of Fe, Mg, and Pr were used. REE were incorporated into one surface of steel samples using high intensity pulsed plasma beams HIPPB ( W/cm 2 ). The plasma pulses were generated in a rod plasma injector (RPI) with its own name IBIS described with details in [11]. The pulse energy was high enough for melting the surface layer of the material. Heating and cooling processes were of non-equilibrium type. Samples were irradiated with 3 pulses with an energy density of 3.0 J/cm 2, in PID (pulsed implantation doping), DPE (deposition by pulse erosion) and mixed modes with titanium rods coated with Ce, La or mischmetal tips as electrodes and nitrogen as the working gas. Samples of initial and modified materials were characterized by: scanning electron microscopy (SEM) DSM 942 (Zeiss, Germany), energy dispersive X-ray spectrometry (EDS) Quantax 400 (Bruker, Germany), grazing angle X-ray diffraction (GXRD) diffractometer D8 Advanced (Bruker, Germany). Wear resistance measurements were carried out using the Amsler method. After the modification process, the initial grain boundaries (Fig.1A) almost disappeared. Features typical of the melted and rapidly solidified material of the mixed deposit-substrate forms can be seen (Fig.1B-D). Atomic concentrations of REE incorporated into specimens were in the range of at.%. GXRD spectra for initial and modified material analysis confirm the presence of FCC phase austenitic structure with Fm-3m symmetry. Austenitic peaks (111) present in the spectra of modified materials are shifted towards bigger angles, what means that lattice parameters were decreased (Fig.2). Austenite lattice parameters calculated using the computer program Topas3 are presented A B C D Fig.1. Surface morphology of AISI 316L samples of initial (A) and modified material up to 1.1 at.% REE: (B) Ce, (C) La, (D) Ce+La.

77 LABORATORY OF MATERIAL RESEARCH L 316L+Ce 316L+La 3000 Intensity (counts) , , , ,5 2 Theta (deg) Fig.2. Details of (111) peak analysis obtained for the surface layer of initial and modified with HIPPB with a single REE incorporation. in Table. Austenite lattice parameters decreased significantly as a result of remelting and rapid solidification of the surface layer. Table. Lattice parameter of austenitic structure identified in the initial and modified surface layer. Material Lattice parameter [A] Lattice parameter change [%] 316L L+Ce L+La L+REE HIPPB modified AISI 316L steel reveals smaller value of linear wear and this means higher wear resistance as compared with the initial material (Fig.3). Final value of the linear wear were of about 80% lower for the samples modified with HIPPB with a single REE incorporation and about 60% for the samples modified with HIPPB with Ce + La incorporation as compared with the initial material. Results obtained from GXRD investigations and wear tests showed an interesting fact. Practically no differences were observed in the results between alloying AISI 316L steel with Ce or La. Differences between alloying using MM or a single REE were observed. MM consists not only of 65% Ce + 34% La, it is a mixture of other elements. These elements can be accepted as impurities with an unknown role in modification processes. Conclusions are the following: Austenitic phases (FCC) were identified in the modified surface layer with decreased lattice parameters as compared with the initial material. Modified surface layers showed improvement of the tribological properties as compared with the initial material. The present authors suppose that improvement of the tribological properties of the modified surfaces is connected with the fine grains formation and enrichment of grain boundaries with REE. References [1]. Piekoszewski J., Werner Z., Szymczyk W.: Vacuum, 63, (2001). [2]. Pereira A. et al.: Thin Solid Films, , (2004). [3]. Sartowska B. et al.: Plasma Process. Polym., 4, S314-S318 (2007). [4]. Wang, X., Lei M.K., Zhang J.S.: Surf. Coat. Technol., 201, (2007). [5]. Cheng X.H., Xie C.Z.: Wear, 254, (2003). [6]. Liu H., Yan M.F., Wu D.L.: J. Mater. Process. Technol., 210, (2010). [7]. Abreu C.M., Cristobal M.J., Novoa X.R.: Surf. Coat. Technol., 158, 1, (2002). [8]. Cleugh D. et al.: Surf. Coat. Technol., , (2001). [9]. Riffard F. et al.: Appl. Surf. Sci., 199, (2002). [10]. Piekoszewski J. et al.: Surf. Coat. Technol., 206, (2011). [11]. Werner Z., Piekoszewski J., Szymczyk W.: Vacuum, 63, (2001) L 316L+Ce 316L+La 316L+REE Linear wear (um) Sliding distance (m) Fig.3. Linear wear of initial material and modified up to at.% REE concentration.

78 78 LABORATORY OF MATERIAL RESEARCH TECHNOLOGY, PRODUCTION AND CHRONOLOGY OF RED WINDOW GLASS IN THE MEDIEVAL PERIOD REDISCOVERY OF A LOST TECHNOLOGY Jerzy J. Kunicki-Goldfinger, Ian C. Freestone 1/, Iain McDonald 2/, Jan A. Hobot 3/, Heather Gilderdale-Scott 4/, Tim Ayers 4/ 1/ Institute of Archaeology, UCL, London, United Kingdom 2/ School of Earth and Ocean Sciences, Cardiff University, Cardiff, United Kingdom 3/ Electron Microscopy Unit, School of Medicine, Cardiff University, Cardiff, United Kingdom 4/ Department of History of Art, University of York, Heslington, United Kingdom SEM-EDXA (scanning electron microscope with energy dispersive X-ray analysis) of 132 examples of medieval red window glass reveals the presence of around 1% copper oxide in all cases. SEM and TEM (transmission electron microscopy) of selected samples confirm the presence of Cu nanoparticles. Two structural categories of red glass sheet are identified. Sheets comprising a single layer of red glass from a few tens to around 300 μm thick overlying a supporting substrate of white glass, with or without a protective cover of white glass, are typically found from the 14th century onwards. However, in the 12th-14th century England, France and Spain, and perhaps elsewhere, typical red glass sheets have a complex microstructure comprising multiple coloured striae about 1 μm thick in a white background. SEM-EDXA, TEM and LA-ICP-MS (laser ablation inductively coupled plasma mass spectrometry) have been used to characterize and investigate the technologies of the two types in detail. The single-layered glasses were produced using an approach analogous to that of copper red glass in the modern period, where a red glass is flashed onto a colourless base. In contrast, the multi-layered glasses were formed by the incomplete mixing of an oxidized high-cu and a reduced low-cu glass. The red colour forms due to the diffusion of oxidized copper into the reduced glass and the nucleation and growth of metallic copper during heat-treatment. This represents a previously unrecognized medieval glass technology, where red was created by mixing two weakly coloured glasses, a complex, arcane and mysterious procedure which must have reinforced the exclusivity of the craft. The occurrence of the technique has implications for dating windows and the identification of glass which has been inserted in early restorations and repairs, for the trade in coloured glass and for the transfer of glassmaking technologies in medieval times. This provides a link between stained glass window technology of the high medieval period and the glass-colouring practices of the late first millennium CE [1]. References [1]. Kunicki-Goldfinger J.J., Freestone I.C., MacDonald I., Hobot J.A., Gilderdale-Scott H., Ayers T.: J. Archaeol. Sci., 41(1), (2014).

79 POLLUTION CONTROL TECHNOLOGIES LABORATORY Research activities of the Pollution Control Technologies Laboratory concern the concepts and application of methods of process engineering to the environmental area. In particular, we participate in research on the application of electron accelerators 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 of both basic and applicable research. Among them, the most important research fields are: development of electron beam flue gas treatment (EBFGT) technology, support of industrial implementation of EBFGT process, 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; UV pulsed fluorescent SO2 analysers Model 40 and chemiluminescent NO/NO x analysers with molybdenum converter Model 10 A/R, manufactured by Thermo Electron Corporation (USA); gas chromatograph GC-17A with a mass spectrometer GCMS-QP5050, manufactured by Shimadzu Corporation (Japan); portable gas analyser type Lancom II, manufactured by Land Combustion (UK) (NOx, SO 2, CO, O 2, etc.). The following projects were realized in 2013 in the Laboratory: Attracting investments in plasma-based air and water cleaning technologies PlasTEP+ (international project co-financed by ERDF). The project is continuation of the previous one Dissemination and fostering of plasma-based technological innovation for environment protection in Baltic Sea Region PlasTEP. Design basis for an industrial scale EBFGT facility (project realized for Saudi ARAMCO, Saudi Arabia). Feasibility study of large scale EBFGT facility (project realized for Saudi ARAMCO, Saudi Arabia). The Laboratory is open for 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); EB Tech Co., Ltd. (Republic of 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 (Denmark); Uppsala University, The Ångström Laboratory (Sweden);

80 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).

81 POLLUTION CONTROL TECHNOLOGIES LABORATORY PRELIMINARY MODELLING STUDY OF NO x REMOVAL FROM OIL-FIRED OFF-GAS UNDER ELECTRON BEAM IRRADIATION Yongxia Sun, Andrzej G. Chmielewski, Henrietta Nichipor 1/, Sylwester Bułka, Zbigniew Zimek, Ewa Zwolińska 1/ Joint Institute for Power and Nuclear Research Sosny, National Academy of Sciences of Belarus, Minsk, Belarus 81 NO x is still one of the most important air pollutants to be controlled. It is expected that by 2020 the emissions from international shipping around Europe are forcasted to exceed the emissions of these pollutants from all other sources in the European Union (EU). Although NO x removal from off-gases was widely studied, most of them were focused on NO x emission control from off-gases generated from power plants, chemical industry and car engine. Fewer investigations were conducted on NO x emission from diesel engine of cargo ship. Heavy fuel oil (HFO) is the main fuel used in the diesel engine of the ship with a high sulphur content up to 4.0 wt.% [1]. In this work we theoretically studied NO x removal from oil-fired off-gas under electron beam (EB) irradiation with the aid of computer simulation. The computer simulation of NO x removal in oil-fired off-gas under EB irradiation was carried out by using the computer code KINETIC and GEAR method. 200 reactions involving 55 species were considered for 700 ppm SO 2 + (74.3% N % O % H 2 O) + NO x (200 ppm, 1500 ppm). Five main groups of reactions were included, the rate constants of reactions were mostly taken from the literatures [2-4]. The units of rate constant are 1/s, m 3 /mole s and m 6 /mole 2 s for first-, second and third-order reactions, respectively. When fast electrons from electron beams are absorbed in the carrier gas, they cause ionization and excitation process of the nitrogen, oxygen and H 2 O molecules in the carrier gas. Primary species and secondary electrons are formed. The secondary electrons are fast thermalized within 1 ns in air at a 1 bar pressure. The G-values (molecules/100 ev) of main primary species are simplified as follows [4]: 4.43N N 2 * N( 2 D) N( 2 P) N N N e (1) 5.377O O 2 * O( 1 D) + 2.8O (O*) O O e (2) 7.33H 2 O 0.51H O( 3 P) OH H (H 2 O + ) (H 2+ ) (OH + ) (H + ) (O + ) + 3.3e (3) The generation of active species under the electron beam is described in [4]: dni = Gn Dx (4) i iρ dt where: n i concentration of the i-th component [mole/m 3 ], G ni radiation yield of the i-th component of the gas [mole/j], x i mole fraction of the i-th component, Ḋ dose rate [J/(kg s)], ρ gas density [kg/m 3 ]. Kinetics of chemical reactions of species formed during gas irradiation with molecules of the gas medium and with one another is described by differential equations: n dni (n) = ni ki nk (5) dt n k= 1 For given initial concentrations: n i (0) = n i0 (6) where: n i concentration of the i-th component [mole/m 3 (n) ], k i rate constant for n-order chemical reaction between the i-th and the k-th components of gas, n k concentration of the k-th component, n i0 initial concentration of the i-th component. Removal efficiency of NOx 10% 8% 6% 4% 2% 0% 70 C 90 C Inlet gas temperature 200ppm 1500ppm Fig.1. Calculation results of NO x removal from oil-fired off-gases under EB irradiation. Calculations were made at 8.8 kgy absorbed dose with two different temperatures, 70 and 90 o C, respectively: 700 ppm SO 2 + (74.3% N % O % H 2 O) + NO x (200 and 1500 ppm, respectively). Calculation results of NO x removal from oil-fired off-gas under EB irradiation at the absorbed dose of 8.8 kgy are presented in Fig.1, and the corresponding experimental results are presented in Fig.2 [5]. It is seen that NO x removal efficiency is slightly improved with increasing temperature. The key reactions are listed below: Removal efficiency of NOx 25% 20% 15% 10% 5% 0% 70 C 90 C Inlet gas temperature 200ppm 1500ppm Fig.2. Experimental results of NO x removal from oil-fired off-gases under EB irradiation.

82 82 POLLUTION CONTROL TECHNOLOGIES LABORATORY N + NO = O + N 2 (R1) O 2 + 2NO = 2NO 2 (R2) O + NO = NO 2 (R3) NO + O 4 = NO 3 + O 2 (R4) OH + NO + M = HNO 2 (R5) NO 2 + OH + M = HNO 3 + M (M is the third body in the reaction system) (R6) HO 2 + NO = OH + NO 2 (R7) NO 2 + O = O 2 + NO (R8) The oxidation-reduction cycle between NO 2 and NO is toward the oxidation path. Comparing calculation results with experimental results, we drew the following conclusions: Removal efficiency of NOx is increased with increasing temperature. Removal efficiency of NOx is decreased with increasing initial inlet concentration of NO x. At 8.8 kgy of the absorbed dose less than about 1% NO x was removed from flue gas for 1500 ppm a high inlet concentration of NO x without ammonia added. References [1]. Basfar A.A. et al.: Fuel, 87, 8-9, (2008). [2]. Albritton D.L.: At. Data Nucl. Data, 22, (1978). [3]. [4]. Mätzing H.: Advances in chemical physics.vol. LXXX. John Wiley & Sons, Inc., New Jersey 1991, pp [5]. Chmielewski A.G. et al.: Radiat. Phys. Chem., 81, 8, (2012). ANALYSIS OF THE CONSTRUCTION POSSIBILITY OF A LARGE ELECTRON BEAM FLUE GAS TREATMENT PLANT Andrzej Pawelec, Sylwia Witman-Zając Electron beam flue gas treatment (EBFGT) process was invented in Japan in the 1970s. At the beginning, the process was elaborated for SO 2 removal from ore sintering plants, however soon the possibility of simultaneous removal of both of SO 2 and NO x was observed. During the next twenty years processes of the intensive development were undertaken resulting in the construction of three industrial EBFGT plants at Chengdu and Hangzhou Power Plants (China) and the Pomorzany Power Plant in Szczecin (Poland). All of the plants were designed for treatment up to Nm 3 /h of flue gas that corresponds to a rather small (up to 100 MW th ) energy generation unit. In the recent years a new phase of EBFGT technology development began. New implementation of the technology in the TPP Sviloza in Svishtov (Bulgaria) was undertaken. The plant was planned to purify up to Nm 3 /h of flue gas from coal fired boilers, that is twice more than the existing EBFGT plant. However, nowadays, the most important direction of technology development is the application of EBFGT technology for treatment of flue gas from heavy fuel oil combustion. This application is dedicated to Middle East countries using liquid fuels as the main source of energy. Laboratory and pilot research on this topic were performed with satisfactory results. Dependences of SO 2 and NO x removal efficiency on main process parameters as well as process optimization were elaborated. With regard to the experiences gathered during construction and exploitation of the Pomorzany industrial EBFGT facility, the technology is ready for design and construction of industrial plant to be applied for liquid fuel fired boilers. However, in the most cases large energy generation units are applied and previously constructed electron beam flue gas treatment facilities are too small for practical application. Therefore, analysis of the possibility of application of EBFGT technology for large energy generation units was undertaken. For the purpose of the elaboration, a Nm 3 /h flue gas flow rate unit was selected as a basic unit for large plant application. A typical composition and parameters of flue gas for heavy fuel oil fired boilers were assumed. Oxygen content was assumed to be 3.2% vol., humidity 12.6% vol. and a temperature of 360 o C. Pollutants concentrations were taken respectively: SO ppmv, NO x 240 ppmv and dust 170 mg/nm 3. Required removal rates according to Saudi Arabian standards were 45% removal of SO 2 for general rules (82% for special industrial zones) and 22% removal of NO x. For the purpose of technology demonstration 90% of SO 2 removal and 50% of NO x removal were assumed. Typical construction of the EBFGT plant may be used in this case. Raw flue gas from boilers shall be directed to a gas conditioning unit in order to decrease its temperature and increase humidity. The gas out coming from the oil fired boilers has too high temperature to be properly cooled down in one stage by water evaporation. Therefore, two- -stage gas conditioning unit composed of heat exchanger and spray cooler shall be applied. In the next step ammonia shall be injected into flue gas. Ammonia shall be stored in the liquid form in pressurized tanks and added to the flue gas upstream reactors. Such a prepared gas is directed to the reaction unit, which is the main unit of the EBFGT plant. Reaction unit is composed of such parts as reactors, accelerators, radiation shielding, cooling and ventilation system, etc. In this unit flue gas is being irradiated by electron beam from accelerators that initiate chemical reactions leading to SO 2 and NO x conversion into ammonium sulphate and ammonium nitrate. Due to reliability of the EBFGT plant, at least two parallel reaction chambers shall be constructed. The by-product a mixture of ammonium salts formed in the process of SO 2 and NO x removal shall be collected and shipped to a receiver. According to experiences from other EBFGT installations, electrostatic pre-

83 POLLUTION CONTROL TECHNOLOGIES LABORATORY 83 Fig. Conceptual scheme of a large-scale EBFGT facility. cipitator is the most appropriate apparatus for by-product collection. The purified flue gas is released to atmosphere. In order to compensate pressure drop in the plant, auxiliary fan shall be installed upstream the stack. The conceptual scheme of a large-scale EBFGT installation is presented in Fig. As most of the equipment is used in conventional flue gas treatment technologies, selection of the reliable, high power electron accelerators is crucial for the large-scale EBFGT facility construction. However, nowadays intensive development of electron accelerators is observed and 1 MW, 1.5 MeV accelerators may be offered by the manufacturers. Application of four pieces of such equipment for irradiation of two independent reactors (double stage irradiation system) makes the construction of Nm 3 /h unit feasible. The performed analysis showed that the construction of Nm 3 /h electron beam flue gas treatment unit for SO 2 and NO x removal from flue gas emitted during combustion of heavy fuel oil is fully feasible from the technical point of view. Assumed removal efficiencies 90% for SO 2 and 50% for NO x can be achieved by the use of EBFGT facility. The Nm 3 /h EBFGT facility may be constructed as a basic unit for the treatment of flue gas from large combustion plants. For larger amounts of flue gas, this unit may be multiplied.

84 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: plus mass spectrometer DELTA (FinniganMAT, Germany); elemental analyser Flash 1112NC (ThermoFinnigan, Italy); GasBench II (ThermoQuest, Germany); H/Device (ThermoQuest, Germany); gas chromatograph (Shimadzu, Japan); gas chromatograph with a mass spectrometer (Shimadzu, Japan); 14 liquid scintillation counter (for C and tritium environmental samples) Guardian (Wallac-Oy, Finland); portable gas analyser (N2O, CO 2, CH 4, H 2 S), (Nanosens, Poland). Research staff of the Laboratory is involved in the following projects: The study of the influence of the environmental factors on the isotopic compositions of dairy products, 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 undertake 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 Rolno-Spożywczych, 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), Joint Research Centre (Ispra, Italy).

85 86 STABLE ISOTOPE LABORATORY DETERMINATION OF SULPHUR ISOTOPIC COMPOSITION OF FOOD PRODUCTS Ryszard Wierzchnicki, Kazimiera Malec-Czechowska Sulphur is one of the popular elements in living organisms: C, H, N, P, O, S. In food product sulphur isotopic composition δ 34 S is strongly influenced by its origin: geology of the region, feed diet of animal, fertilization of plant, climate and closeness to the sea. Typically δ 34 S values of the food samples ranged from -2 to +12. The variation in δ 34 S values observed within a single region could be due to the different production systems (conventional and organic). Rich products into sulphur mostly contain proteins: meat, poultry, eggs, dairy product, cabbage, fish, legumes, cauliflower, broccoli, garlic and onion (Table 1). Table 1. Proteins concentration in food products. Food products The protein content in the dry matter [%] Legumes 40 Vegetable 3 Fruit 1 Meat 20 Milk 5 Fish 15 Sulphur have a four stable isotopes: 32 S (95.02 at.%), 34 S (4.21 at.%), 33 S (0.75 at.%), 36 S (0.02 at.%) and three radioisotopes: 31 S (3.2 s), 35 S (87.1 day), 37 S (5.04 min half-life). Sulphur in chemical composition occur in on few oxidation steps. Bacterial reduction of sulphate (sulphur cycle) to sulphide. For sulphur is the lack of the enrichment effect in the nutritional cycle (chain). Our interest in the study of sulphur isotopic compostition it is a result of differentiation δ 34 S in the environment (Table 2) and possibility of applying this parameter to food origin control. Aim of this study is to explore this isotopic parameter for differentiate of food origin, method of production and food composition in the field of food authenticity control. The following instruments were used in sulphur isotopic measurements: isotope ratio mass spectrometer DELTA plus, FinniganMAT (Bremen, Germany); elemental analyser Flash 1112NC, Thermo- Finnigan (Italy); Parr Bomb oxidation, Parr Instrument Company (Illinois, USA); ConFloIII interface for EA and IRMS connecting, Finnigan, (Bremen, Germany). Basic problem which we have with sulphur isotopic measurement is a low content of sulphur in organic matter. For extraction sulphur from organic samples without isotopic effects we can use the method of Parr Bomb oxidation. The mass of the samples is connected with sulphur content in the sample. For sample powder 2 mg and 3-5 drops Table 2. Examples of isotopic variability of sulphur in environmental samples. δ 34 S [ ] Environment marine: - marine sediments atmosferic sulphate Environment terrestrial: - fossil fuels soil plants meat milk fish vegetable 0 6 of bidestilled water for one pill is used. Every sample should be prepared two times two pills. After burning the samples a special chemical procedure for BaSO 4 preparation from the produced SO 2 dissolved in water is used. Finally the sulphur can be precipitated as BaSO 4 using a 10% BaCl 2 solution. To obtain BaSO 4 for sulphur isotopic measurements by the use elemental analyser- -isotope ratio mass spectrometer (EA-IRMS). For sulphur isotopic measurements with EA-IRMS we use a special procedure of food samples conversion to BaSO 4 (Fig.). The elemental analyser for sulphur measurements is specially equipped with: teflon tubes (connection), GC column and special quartz reactor for sulphur. Samples and references materials are loaded into an autosampler AS200 on elemental analyser Flash Mass of sulphur in the measured materials should be 30 μg per sample or more. To rich protein product the mass of samples should be mg; for pure protein the mass of samples can be 3-5 mg (for casein 5 mg). Sulphur isotope ratio is expresed using conventional notation: Rsp δcdt S δ CDT S/ S = [ ] R CDT where: R sp measured isotopic ratio between abundance of isotope 34 S and isotope 32 S in sample, R CDT isotopic ratio between abundance of isotope 34 S and isotope 32 S in international standard CDT (Canyon Diablo Troilite) actual in use standard VCDT (Vienna Canyon Diablo Troilite) with R CDT = Reference materials for sulphur isotopic measurements were the following: barium sulphate NBS-127, barium sulphate IAEA-SO-5 (IAEA), silver sulphide IAEA-S-1 (IAEA).

86 STABLE ISOTOPE LABORATORY Pills preparation Burning pills in Parr Bomb NH 4OH addition (pink to yellow) Filtration H 2O ml HCl (yellow to red) HCl 2ml Boiling 5 ml BaCl 2 Filtration Washing and roasting at 800 o C (overnight) filters with sediment Fig. The steps of chemical treatment for BaSO 4 preparation. For improve oxidation condition to every weighted sample the V 2 O 5 (1:1 or more) is added. Typically the standard deviation for measurements was ± 0.3 Problems with sulphur measurements in food samples are the following: 87 low concentration of sulphur in food, high memory effect of measurements connected with the SO 2 reactivity, high concentration of carbon in food sample. The first stage of the project was concerning an implementation of method of sulphur isotopic measurement and two methods of sample preparation. A further approach in our study will be testing the possibility to discriminating different methods of food production and different regions of its origin. Stable isotope ratios of sulphur of food product can be used as a good indicator of geographical origin of meat [1], milk [2] and other products [3]. The sulphur isotope composition is a good supplementary isotopic parameter for carbon and nitrogen isotopic composition in food origin control. This study was supported by the Ministry of Science and Higher Education, Poland in the frame of statutory work. References [1]. Boner M., Förstel H.: Anal. Bioanal. Chem., 378, 2, (2004). [2]. Molkentin J., Giesemann A.: Anal. Bioanal. Chem., 388(1), (2007). [3]. Rossmann A.: Food Rev. Int., 17(3), (2001). NEW APPROACH OF THE ISOTOPIC METHOD FOR JUICE AUTHENTICITY CONTROL Ryszard Wierzchnicki, Kazimiera Malec-Czechowska The subject of our study was the authenticity of fruit juice originated from the Polish market. Nowadays in Europe, origin and authenticity is probably one of the most important characteristic features of food. This is connected with economic politics of European Commission in agriculture sector (Table 1). Adulteration is as an addition of Table 1. Standard methods accepted by the European Union for juice authenticity control. undeclared addition of sugar/pectin, undeclared addition of water, undeclared addition of organic acids, undeclared addition of vitamin C, undeclared addition of flavour compounds. Important limitation of the application of isotopic method for food authenticity control is the Method Fraction Technique Isotope ratio CEN (ENV 12140) sucrose IRMS a) 13 C/ 12 C AOAC method ethanol (from fermentation) SNIF-NMR b) (D/H) I, (D/H) II, R CEN (ENV 12141) water IRMS 18 O/ 16 O CEN (ENV 12142) water IRMS 2 H/ 1 H AOAC method ethanol (from fermentation) IRMS 13 C/ 12 C CEN (ENV 13075) pulp IRMS 13 C/ 12 C a) IRMS isotope ratio mass spectrometry. b) SNIF-NMR site specific natural isotope fractionation determined by nuclear magnetic resonance. the artificial (prohibited) components to natural products, a cheaper product put into a place expensive one and mislabelling of products. Fruit juice can be adulterated by: lack of database of stable isotope composition in juice of different origin. Stable Isotope Laboratory of the Institute of Nuclear Chemistry and Technology (INCT) since many years is carring out a

87 88 STABLE ISOTOPE LABORATORY Table 2. Multielement analysis for the control of juice origin. Element Ratio Material Provenance of isotopic effects Instrument for measurements Hydrogen 2 H/ 1 H water precipitation geographical altitude H/Device IRMS a) Oxygen 18 O/ 16 O water precipitation geographical altitude GasBench IRMS Nitrogen 15 N/ 14 N solid fertilizer (organic or synthetic) EA IRMS Carbon 13 C/ 12 C solid C3, CAM, C4 metabolism EA IRMS Hydrogen 2 H/ 1 H solid precipitation, climate Py b) IRMS Oxygen 18 O/ 16 O solid precipitation, climate Py IRMS Sulphur 34 S/ 32 S solid fertilizer, distance to the sea, bacterial processes EA IRMS, ICP-MS c) Strontium 87 Sr/ 86 Sr solid geology, geographical origin regional factor TIMS, ICP-MS d) a) IRMS isotope ratio mass spectrometry. b) Py pyrolise. c) ICP-MS inductively coupled plasma mass spectrometry. d) TIMS thermal ionization mass spectrometry. study of isotopic composition of food by IRMS method (Table 2) implementation and by database for some food from the Polish market. These instruments were used in the multielement method in control of fruit juices: GasBench II (GB) for oxygen in water; H/Device (HD) for hydrogen in water; elemental analyser (EA) for organic C, N, S; plus mass spectrometer DELTA with dual inlet system (IRMS); HPLC preparative + multicollector; Parr Bomb for sulphur from organic product preparation. An actual problem encountered in the area of fruit juice authentication is in the detection of undeclared sugar added to a juice. The sugar can be added in the form of a beet or cane sucrose or as a high fructose corn syrup (HFCS). Other important topic in fruit juice analysis is the detection of adulteration by L-ascorbic acid. For this reason, the method of internal standard with malic acid Internal carbon isotopes of acids: malic, citric and ascorbic, can be used to detect the addition of synthetic organic acids. Ratios between bulk sugars and individual acids by IRMS, to detect sugars or acid addition [3] can be applied. Specific stable isotope analysis (CSIA) of juice by the use of a gas chromatograph or a liquid chromatograph connected with combustion and mass spectrometer: GC-C-IRMS and LC-C-IRMS can be applied. We look for a rapid and precise method for juice authenticity control. Most isotope techniques require the use of the database of isotopic composition or original fruits as a reference for comparison with the composition of analysed product. The database can be substituted by the isotope analysis of an internal standard. The application of internal component reduces measurement errors which is depending on the isotope variability of raw materials. In our study, no clear conclusions were Table 3. Carbon isotopic composition of juice components and some artificial juice components for multicomponent method of juice control. Juice components Apple Strawberry Black currant Commercial product Sugars -26.5, beet HFCS -9.7 Malic acid -24.5, Citric acid -25.5, / Ascorbic acid -26.0, , -12 was proposed [1]. Carbon stable isotope ratio δ 13 C analysis to multicomponent method for juice authenticity control is applicable. We try to use different method of comparison of isotopic composition between components of juice: sugars and acids (Table 3). Minimal sample preparation, rapid separation and good recovery support for these procedures is a promising for the sugars and acids isotope composition determination in fruits. Trends in isotopic analyses of juice are the following: Insoluble solids (pulp) of the whole fruit can be used as internal standard [2]. possible with a still limited number of samples investigated. This research work was supported by the Ministry of Science and Higher Education, Poland under grant No /2010. References [1]. Jamin E., Martin F., Santamaria-Fernandez R., Lees M.: J. Agric. Food Chem., 53, (2005). [2]. Figueira R., Venturini Filho W.G., Ducatti C., Nogueira A.M.P. : Ciênc. Tecnol. Aliment., 31, 3, (2011). [3]. Tremblay P., Paquin R.: J. Agric. Food Chem., 55, (2007).

88 LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES The 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 ( 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 Issledovatel and a Gamma Chamber The sources were calibrated in April 2009 and in March 2012, respectively, according to NPL (National Physical Laboratory, Teddington, UK) primary standard. The uncertainty of the dose rate was estimated to be 2.9 and 3.1% (U, k = 2).

89 90 LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES RECALIBRATION OF DOSIMETER FILMS CTA Anna Korzeniowska-Sobczuk, Aneta Sterniczuk, Magdalena Karlińska The average thickness [mm] 0,155 0,150 0,145 0,140 0,135 0,130 0,125 0,120 A CTA film dosimeter, so it is advisable to redo recalibration the dosimeter. the LMTD having accreditation of the Polish Centre for Accreditation in accordance with the requirements of PN-EN ISO/EIC 17025:2005 [4] imposed on the LMTD implementation of improvement activities, preventive as well as quality control tests. The implementation of this subject allows for comprehensive requirements according to a previous experimental data and archival film samples after irradiation of the CTA film dosimeter which will allow to trace the changes in the long term. Absorbance Ao 0,155 0,150 0,145 0,140 0,135 0,130 0,125 0,120 B 0, Sample number Fig.1. The physicochemical parameters of the dosimeter films CTA. The responses of most films used in routine dosimetry are usually influenced by the environmental conditions such as temperature during irradiation, dose rate and post-irradiation storage [1]. Many problems may be encountered in the routine dosimetry for radiation processing applications, because the conditions in irradiation facilities may differ considerably from the conditions in which dosimeter films were calibrated. These differences may lead to expected systematic errors in dose estimation. The advantage of the CTA film is its linear response to the dose and the dose-independent post-irradiation signal change. However, its low sensitivity to ionizing radiation restricts its use to high and very high doses [2]. Implementation issues related to research the CTA film dosimeter results from the need to continually monitor the quality of services provided [3]. In the Laboratory for Measurments of Technological Doses (LMTD) of the Institute of Nuclear Chemistry and Technology (INCT) is the accreditation method for measuring the absorbed dose based 0, Sample number Table. Change of the parameters of the CTA dosimetric film with time after irradiation (post-effects). Dose [kgy] Time after irradiation 30 min 24 h 7 days 30 days 6 months A A 0 A A 0 % A A 0 % A A 0 % A A 0 % Parameters of calibration curves Y=0.0064X Y=0.0067X Y=0.0069X Y=0.0070X Y=0.0079X R2 = R2 = R2 = R2 = R2 = on a CTA film dosimeter. CTA dosimeter, production Fujifilm, was purchased in 2005 and then made the first calibration purchased batch with this dosimeter. Currently, the LMTD owns approximately 40% of the originally purchased amount of the The film dosimeters CTA was irradiated with 10-MeV electron beams from an industrial 10-kW linear accelerator radiation in the range of kgy dose (accelerator Elektronika 10/10) and the gamma radiation kgy in the gamma field of a reference 60 Co source Issledovatel (~0.5 kgy/h) having the dose rate traceable to a primary standard maintained by the National Physical Laboratory NPL (Teddington, UK). In the experiments the film dosimeters CTA were used, with an optical signal detection. The absorbance was measured by using a JASCO-V650 spectrophotometer UV/Vis (λ max = 280 nm). The wavelength and absorbance scales were checked before each experiment by a calibrated reference standard.

90 LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES 91 In 2013, the first stage of the study was to verify the physicochemical parameters of unexposed film and comparison with the data contained on the score sheet dosimeter (after the first calibration). A comparison of the absorbance, A 0, and an average thickness of 60 samples revealed no radiation of the CTA film (Fig.1). Absorbance A A 0 0,30 0,25 0,20 0,15 0,10 0,05 0,00 y = 0,0064x - 0,0053 R 2 = 0,9915 y = 0,0062x + 0,0073 R 2 = 0,9939 y = 0,0063x + 0,0053 R 2 = 0,9854 y = 0,0056x + 0,0182 R 2 = 0, Dose [kgy] Fig.2. Summary of calibration curves for CTA films made in different years from the date of purchase of the film. Parameters determined for the calibration curves take into account the changes in absorbance (post- -effects) after 30 min, 24 h, 7 and 30 days, 3 and 6 months after the irradiation. Details are presented in Table. Compilation of all annual calibrations, 30 min after irradiation, taking into account also the aging of the CTA film is presented in Fig.2. On the basis of these results the following conclusions can be drawn (scientific and practical applications): The absorbance of unexposed film CTA increases during storage, this factor should be taken into account when determining the dosimetric signal for each sample. Differences in thickness within one series (spool) CTA film are negligible. Answer the CTA film dosimetry test is linear in the full range of doses and increased with storage time after irradiation. Using the CTA dosimeter as the transfer dosimeter should take into account the passage of time between irradiation and spectrophotometric measurement. Adapting the measuring points to the calibration curve, in many cases R2 > References [1]. McLaughlin W.L., Boyed A.W., Chadwick K.H., McDonald J.C., Miller A.: Dosimetry for Radiation Processing. Taylor & Francis, Ltd., London 1989, 251 p. [2]. Peimel-Stuglik Z., Fabisiak S.: Appl. Radiat. Isot., 66, (2008). [3]. ISO/ASTM Standard , Standard practice for use of cellulose aceteate dosimetry system. [4]. PN-EN ISO/IAC 17025:2005. Ogólne wymagania dotyczące kompetencji laboratoriów badawczych i wzorcujących (General requirements for the competence of testing and calibration laboratories).

91 LABORATORY FOR DETECTION OF IRRADIATED FOOD Laboratory for Detection of Irradiated Food was created at the Institute of Nuclear Chemistry and Technology in 1994 and, after adoption of the quality assurance system received the accreditation certificate in Certificate is issued by the Polish Centre of Accreditation. From that time, the Laboratory has the status of the accredited R&D unit authorized to analyse various food samples whether irradiated. Every four years the accreditation certificate is renewed after passing positively by the Laboratory the PCA expert audit. Present accreditation certificate was received in 2010 and is valid until Professional and experienced staff of the Laboratory works on the improvement and development of detection methods to make them more sensitive and suitable for the identification of radiation treatment in enlarged assortment of food products. Currently, the Laboratory offers analytical service to domestic and foreign customers having potential to detect radiation treatment in many kinds of food with the use of standardized and adequate analytical methods. Scope of Accreditation, the integral part of accreditation certificate, offers to the customers five methods suitable for the detection of radiation treatment in almost all assortments of food. During the last 11 years more than 2700 food samples were examined and classified successfully as irradiated or unirradiated. Currently, a lot of complex samples including herbal pharmaceuticals, diet supplement and food extracts delivered by our customers for examination are analysed every month. The Laboratory is equipped with modern instrumentation which allowed to implement and validate the following detection methods: method for the detection of irradiated food containing bone with the use of electron paramagnetic spectroscopy (EPR/ESR) based on analytical procedure offered by the CEN European standard EN-1786; method for the detection of irradiated food containing cellulose with the use of EPR spectroscopy based on analytical procedure given by the CEN European standard EN-1787; method for the detection of irradiated food containing crystalline sugars with EPR spectroscopy based on analytical procedures given by the CEN European standard EN-13708; method for the detection of irradiated food from which silicate minerals can be isolated using a thermoluminescence (TL) reader and based on analytical procedures recommended by the CEN European standard EN-1788; method for the detection of irradiated food using a photostimulated luminescence (PSL) reader and based on analytical procedures recommended by the CEN European standard EN The application of five standardized and validated detection methods addressed to specified groups of foods validated in the Laboratory guarantees an accurate analysis and classification of every one food sample delivered to the Laboratory for testing. Presently, the Laboratory is engaged in the implementation of modified and/or new analytical and measuring procedures suitable for the detection of irradiation in complex food articles which typically contain low concentration of irradiated ingredient admixed to unirradiated product which appears in abundance. Typical groups of products controlled in the Laboratory.

92 It has been found that modification of mineral isolation procedure, the control of mineral yields separated from food and the evaluation of the effectiveness of luminescence from isolated mineral are the ways to the improvement of detection ability of the methods used. In total, 261 food samples of very different kind were examined in The samples were delivered from several domestic and foreign firms in Germany, Italy, Denmark, Switzerland, Great Britain, Russia, China. The assortment of samples examined comprises spices, fermented rice, mushrooms, teas, herbal pharmaceuticals, diet supplements, food extracts. Twenty three samples (9.2%) of the total number of samples were found irradiated. The majority of samples, i.e. 225 (86%), were examined by the thermoluminescence (TL) method while PSL based analytical procedures was applied 36 times (14%). On 19th June 2012, the Laboratory was nominated by the Ministry of Health the country reference laboratory in the field of the detection of irradiated food in Poland. As such, the Laboratory organized in 2013 an interlaboratory TL proficiency test to establish the detection limit for the examination of complex samples containing low concentration (1-5%) of irradiated component.

93 LABORATORY FOR DETECTION OF IRRADIATED FOOD 95 STABILITY OF THE EPR SIGNAL PRODUCED BY IONIZING RADIATION IN DRIED FRUITS Grzegorz P. Guzik, Wacław Stachowicz The standard method for the detection of irradiation in dried fruits EN-13708:2003 issued by the CEN (European Committee for Standardization) in Brussels in 2002 [1] is currently widely used for irradiation control of raisins, dates, figs, mangos, papaya, etc. in Europe and over the world. The method is based on the identification of a specific EPR (electron paramagnetic resonance) signal in irradiated food articles which is never observed in dried fruits not exposed to the action of ionizing radiation. It is suggested that this signal originates from free radicals produced by ionizing radiation in crystalline domains of dried fruits [2]. The efforts were undertaken to identify these radicals [3, 4]. The important feature of any EPR signal which is used for the detection of irradiation is its stability at room temperature. The EPR signal recorded in irradiated fruits is stable several months after irradiation, but decays slowly during prolonged storage. Dried fruits belong to this assortment of food commodities which are allowed to be stored safely for a relatively long time. In order to ascertain the reliability of the identification of the EPR signal observed in radiation treated dried fruits during their storage for several months the model experiments have been performed. The following fruits purchased in the market were chosen: cranberry, papaya, pineapple, date, fig, rowan berry, banana and raisins. The fruits were divided into three parts each irradiated with 0 kgy different dose of 60 Co gamma rays: 0.5, 1 and 3 kgy, respectively. The adapted doses correspond to technological doses as announced to be used for radiation disinfestation and pasteurization of dried fruits. After radiation treatment, the samples were stored at room temperature with the access of air. The EPR measurements were conducted with each of the samples after one day, and subsequently after 30, 90, 180 and 360 days of storage. All measurements were done with the samples handled similarly under the same EPR spectrometer settings and operational conditions. The recorded EPR signals were doubly integrated within the same range of magnetic field 7 mt. The scans were centred at g = The integrated signal areas are in proportion to the overall signal intensity. The EPR signals of raisins unirradiated and irradiated with 0.5, 1 and 3 kgy are shown as an example in Fig.1. The upper record represents the EPR spectrum of unirradiated raisins. A weak, not specific signal is seen which is easily distinguished from multicomponent signals typical for irradiated samples (shown below). Such weak, so-called native EPR signals appear in some of irradiated fruits and originate from stable paramagnetic impurities or trace components present. The integrated EPR signal areas related to irradiated samples and measured as a function of prolonged storage time were used to construct the kinetic decay curves for each of the sample. x kgy x kgy x 1.3 A 3 kgy A B x 1 Fig.2. Decay of the EPR signal intensity in dried fruits (dates, raisins, rowan berries and cranberries) during one year of storage. The result refers to the samples irradiated with 3 kgy of 60 Co gamma rays. B Magnetic fi eld [G] Fig.1. EPR signal of dried raisins irradiated with 0.5, 1 and 3 kgy of 60 Co gamma rays. The upper graph refers to unirradiated sample. The numbers in the right denote to the attenuation of the recorded signals. In Fig.2, the time-dependent decay curves of the EPR signals intensity recorded with the samples of dried dates, raisins, rowan berries and cranberries are presented. The decrease of the EPR signal intensity does not fit to a classic first- or second-order kinetics. The decay process of radicals in dried fruits exposed to ionizing radiation

94 96 LABORATORY FOR DETECTION OF IRRADIATED FOOD can be divided at least in two phases. The first easily distinguished phase of radical decay lasting about 50 days proceeds relatively fast, resulting in the decrease of initial EPR signal intensity by about 30%. The annihilation of less temperature resistant shallow radical traps might be responsible. The second phase of temperature-dependent radical decay in dried fruits treated with ionizing radiation is markedly slower. The EPR measurements have been done between the 50th day of storage to one year (360 days). Although the recording time was ca. 6 times longer than in the first phase, the decreases of the EPR signal intensity did not exceed 20%. It is clear that at this stage thermal annihilation of radical traps is less effective. In general, the radiation-induced radical decay in eight kinds of dried fruits studied was found similar. It means that in all fruits two described phases of radical decay can be distinguished. However, distinct individual differences do appear between some of them which are seen in Fig.2 and in the Table. The highest stability of radiation-induced EPR signal after one year of storage at room temperature was found in cranberry resulting in 88.2% survival of EPR signal what means that it decreased by 11.8% only. The lowest stability, in turn, was demonstrated by raisins resulting in 43.2% survival of the EPR signal and the decrease of the EPR signal intensity by 56.8%. The general conclusion drawn from the above experiments is that the stability of the EPR signals utilized for the detection of radiation treatment in dried fruits according to EN European standard is high and facilitates the reliable detection of radiation treatment in any kind of dried fruits after one year of storage at room temperature with free access of air oxygen to the product. It is concluded from the analysis of the decay curves after 200 days of storage (Fig.2) that the Table. Decrease of the EPR signal intensity in dried fruits irradiated with 3 kgy of 60 Co gamma rays after 360 days of storage. Dried fruit Decrease of the EPR signal intensity [%] Intensity of remaining EPR signal [%] Cranberry Papaya Pineapple Date Fig Rowan berry Banana Raisin decrease of the signal by storing dried fruits much longer than for one year (two or more years) will not influence negatively on the detection of radiation treatment in this product. As to our knowledge, long-lasting kinetic studies on the stability of radiation-induced radicals in food had not been performed so far. From the practical point of view the obtained results can be useful for the control of food reserves and for accidental dosimetry. References [1]. EN-13708:2001 Foodstuffs Detection of irradiated food containing crystalline sugar by ESR spectroscopy. European Committee for Standardization (CEN), Brussels. [2]. Raffi J., Angel J.P.: Radiat. Phys. Chem., 34, (1989). [3]. Guzik G., Stachowicz W., Michalik J.: Nukleonika, 57, 4, (2012). [4]. Guzik G., Stachowicz W.: Nukleonika, 58, 3, (2013). QUANTITY AND QUALITY OF MINERAL FRACTION IN THERMOLUMINESCENCE METHOD FOR THE DETECTION OF IRRADIATION IN ALIMENTARY ARTICLES Wacław Stachowicz, Grażyna Liśkiewicz Thermoluminescence (TL) is a method successfully used for the detection of irradiation in different alimentary articles from which crystalline minerals can be isolated. Dried spices and herbs belong to this group, while those imported from tropical countries are usually highly contaminated with microorganisms, parasites and pests being often dried in the opened air. For that reason, these products undergo disinfection processing. A very effective method for the neutralization of biological contaminates in food is radiation pasteurization with gamma rays or beams of accelerated electrons. Aromatic spices and herbs undergoing this processing do not lose their aroma or flavour as it is the case by applying the elevated temperature or pressure, for example. Presently dried spices, herbs and seasonings belong to this category of food products which are treated quite frequently with ionizing radiation. Thermoluminescence method for the detection of irradiated spices and herbs is currently adapted for the identification of radiation treatment in very different food assortments containing only negligible flavour admixtures of spices as souses, cheese or dinner compositions. The method is also successfully used for the detection of irradiated components in diet supplements and herbal pharmaceuticals. The essential problem of the method is effective isolation of mineral fraction based on general procedure recommended in European standard

95 LABORATORY FOR DETECTION OF IRRADIATED FOOD 97 Table. Weight and temperature simulated luminescence of minerals isolated from aromatic and flavour components of alimentary articles. Product samples 100 g ± 0.2 g each Weight of isolated mineral fraction [mg] Mineral loss by heating to 500 o C [%] Chondroitin porcine Cumin seeds Eyebright powder Hawthorn extract Paprika flakes Leek flakes Paprika flowers sharp Garlic powder Apple powder Paprika flowers sharp Fermented rice Angkak Horsetail powder Garlic flakes Chondroitin bovine Chilli powder Chilli flakes Chilli needles Golden rot powder Millet powder Paprika powder Garlic flakes Ginkgo biloba extract Chilli rolls Gingko biloba extract Leek sliced Protein Erbse powder Chondroitin marine Protein Erbse powder EN-1788 [1], as discussed in our earlier study [2], and the content and quality of isolated minerals. In the proceeding study it has been shown [3] that the weight of mineral fraction isolated from different commodities (samples weighing 20 g) varied from 0.1 do 2.5 mg while the corresponding TL intensity differs from sample to sample even by the factor of 500. It has been also observed that the correlation between the weight of mineral and the intensity of thermoluminescence was not proven. The explanation lies in different geographical origin of the investigated vegetal products and consequently in a very different composition of soils in which the plants giving the products were cultivated [4]. In order to throw more light on this problem a new experimental approach has been undertaken. In addition to the weight of isolated mineral fraction before the TL measurement the weight of this fraction was determined but after heating to 500 o C. The number of 28 samples delivered to the Laboratory for Detection of Irradiated Food, INCT for testing whether irradiated was used to perform the study. The experiment delivers the information concerning the stability of mineral fraction isolated from food at elevated temperature. This kind of study has not been done, as to our knowledge, so far. The samples were organized in the Table according to the increasing loss of weight by heating (column 3). As is seen from the Table, the weight losses of the mineral fraction isolated from the most of the samples heated to 500 o C are surprisingly high, proving a low temperature stability of mineral fraction separated. The source of the thermoluminescene released from mineral constituents of food are structural imperfections in the crystalline lattice of minerals suitable traps

96 98 LABORATORY FOR DETECTION OF IRRADIATED FOOD for radiation energy during the irradiation processing. This kind of stable energy traps appear in crystalline minerals such as quartz, quartzite, feldspar defined as silicate minerals [5]. The isolation procedure of mineral fraction recommended in European Standard EN-1788 eliminates efficiently limestone and ground chalk from mineral deposit separated from organic pulp but does not eliminate amorphous loams, clay stones, shale, etc. which may appear in the form of hard, rigid particles and accompany the crystalline minerals. Amorphous components of soil contain a lot of structural water which is easily freed by heating. The heating can also stimulate the decomposition of organic constituents which are always contained in amorphous rocks appearing in mineral fraction. Both dehydration and decomposition of amorphous soil originated solid deposits separated from food can be responsible for the observed effect of significat loss of the weight of mineral fraction isolated from food. References [1]. EN-1788:2001 Foodstuffs Detection of irradiated food from which silicate minerals can be isolated. European Committee for Standardization (CEN), Brussels. [2]. Sadowska M., Stachowicz W.: Effectiveness of different procedures of mineral isolation from irradiated spices suitable for thermoluminescence detection method. In: INCT Annual Report Institute of Nuclear Chemistry and Technology, Warszawa 2012, pp [3]. Sadowska M, Stachowicz W.: Luminescence of silicate minerals and sensitivity of thermoluminescnce method for detection of food irradiation. In: INCT Annual Report Institute of Nuclear Chemistry and Technology, Warszawa 2013, pp [4]. Sanderson D.C.W., Carmichael L.A.. Naylor J.D.: Food Sci. Technol. Today, 7, (1995). [5]. Sanderson D.C.W., Slater C., Cairns V.J.: Radiat. Phys. Chem., 34, (1989).

97 LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS The main subject of the Laboratory activity in 2012 was the development of methods and apparatus, 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 industrial testing of a gamma scanner for diagnostics of industrial installations; development of measuring equipments for other Institute laboratories and centres; 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 contamination detection, 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 measurements, was constructed and tested for contamination detection in laboratory and industrial conditions. The system for attached and unattached radon 222 Rn 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 which 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.

98 100 LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS DIAGNOSTICS OF BIOGAS INSTALLATION BY GAMMA RADIATION Adrian Jakowiuk, Łukasz Modzelewski, Jacek Palige, Ewa Kowalska, Jan Pieńkos During the exploitation of industrial installations a very important task is to maintain their proper technical conditions. In the case of the emergency state it is also important to locate the place of its occurrence as soon as possible. This often involves discontinuation of the production process and interference in the structure of the installation by dismounting it [1]. Such kind of approach entails considerable financial losses. Then, it becomes deliberate to search and use such diagnostic methods that do not require interruption of the technological process and are able to give information on the actual degree of exhaustion (or pollution) of the installation elements that are examined. In solving this type of problem it seems appropriate to apply the measurement methods using ionizing radiation [2, 3]. With this radiation we can examine installation (gamma scanning) [4] and on the basis of the measurements locate the place and type of damage. Examination of such kind were designed and carried out on an average lab installation for obtaining biogas. The initial studies were performed using two radiation sources: 137 Cs (activity 550 MBq) and 60 Co (activity 300 MBq). Source and probe were placed at a distance of 90 cm from each other. The test system including the located measuring system is shown in Fig.1. Installation was tested in its middle part. For each source, have been made three runs measuring with a moving set of source-probe Fig.1. Installation for obtaining biogas. The measuring system probe-source. from the bottom up. The obtained results are shown in Fig.2. Then, the obtained values were converted to density according to the formula: Fig.2. Scan results [imp/s].

99 LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS 101 Fig.3. Scan results density [g/cm 3 ]. N0 ln N x ρ= μd where: N 0 number of pulses at the open area source-probe [imp/s], N x measured number of pulses [imp/s], μ average mass attenuation coefficient [cm 2 /g], d distance between probe and source [cm]. Assuming average mass attenuation coefficient for radiation 137 Cs as cm 2 /g and for 60 Co value cm 2 /g the average densities in the examined cross section were calculated. The densities are shown in Fig.3. From the graph, we can read with a certain approximation the current level of factor (of biomass) used in the system ( 14 cm). Also a frame surrounding the tank in the central part is visible. The obtained results of initial tests will serve as a benchmark for testing the installation of biogas plants at a later data. Installation tests will be compared with those obtained earlier and on that basis the changes in the installation can be noticed (e.g. change of level, density factor). References [1]. Charakterystyka technologiczna rafinerii ropy i gazu w Unii Europejskiej (Technological characteristics of oil and gas refineries in the European Union). Ed. M. Mihułek. Ministerstwo Środowiska, Warszawa 2003 (in Polish). [2]. Kraś J., Waliś L., Myczkowski S.: Doświadczenia z izotopowej kontroli szczelności obiektow technologicznych aspekty techniczne i ekonomiczne (Experience in isotope leak-proof control of engineering objects technical and economical aspects). In: Technika jądrowa w przemyśle, medycynie, rolnictwie i ochronie środowiska. T.2. Instytut Chemii i Techniki Jądrowej, Warszawa 2002, pp Raporty IChTJ. Seria A nr 2/2002 (in Polish). [3]. Strategia rozwoju atomistyki w Polsce (Nuclear strategy development in Poland). Rada do Spraw Atomistyki, Warszawa 2006 (in Polish). [4]. Jakowiuk A., Kowalska E., Pieńkos J., Filipiak P., Modzelewski Ł., Palige J., Kraś J.: The radiometric probes for industrial measuring systems. In: INCT Annual Report Institute of Nuclear Chemistry and Technology, Warszawa 2012, pp

100 102 PUBLICATIONS IN 2013 PUBLICATIONS IN 2013 ARTICLES 1. Arabski M., Lisowska H., Lankoff A., Davydova V.N., Drulis-Kawa Z., Augustyniak D., Yermak I.M., Molinaro A., Kaca W. The properties of chitosan complexes with smooth and rough forms of lipopolysaccharides on CHO-K1 cells. Carbohydrate Polymers, 97, (2013). 2. Baran M., Zhydachevskii Ya., Suchocki A., Reszka A., Warchoł S., Diduszko R., Pajączkowska A. Sol-gel synthesis and luminescent properties of nanocrystalline YAP:Mn. Optical Materials, 34, (2013). 3. Bartłomiejczyk T., Lankoff A., Kruszewski M., Szumiel I. Silver nanoparticles allies or adversaries? Annals of Agricultural and Environmental Medicine, 20, 1, (2013). 4. Bartoś B., Łyczko K., Kasperek A., Krajewski S., Bilewicz A. Search of ligands suitable for 212 Pb/ 212 Bi in vivo generators. Journal of Radioanalytical and Nuclear Chemistry, 295, (2013). 5. Bator G., Sobczyk L., Sawka-Dobrowolska W., Wuttke J., Pawlukojć A., Grech E., Nowicka-Scheibe J. Structural spectroscopic and theoretical studies on 3,4,7,8-tetramethyl-1,10-phenantroline complex with pictric acid. Chemical Physics, 410, (2013). 6. Białońska A., Drabent K., Filipowicz B., Siczek M. Reversible guest vapour sorption in breathing crystals of a discreate ionic binuclear Cu(I) complex. CrystEngComm, 15, (2013). 7. Blicharska M., Bartoś B., Krajewski S., Bilewicz A. Separation of fission produced 106 Ru from simulated high level nuclear wastes for production of brachytherapy sources. Journal of Radioanalytical and Nuclear Chemistry, 298, (2013). 8. Calinescu I., Chmielewski A., Ighigeanu D. E-beam SO 2 and NO x removal from flue gas in the presence of fine water droplets. Radiation Physics and Chemistry, 85, (2013). 9. Chajduk E., Bartosiewicz I., Pyszynska M., Chwastowska J., Polkowska-Motrenko H. Determination of uranium and selected elements in Polish dictyonema shales and sandstones by ICP-MS. Journal of Radioanalytical and Nuclear Chemistry, 295, (2013). 10. Dispenza C., Grimaldi N., Sabatino M.-A., Todaro S., Bulone D., Giacomazza D., Przybytniak G., Alessi S., Spadaro G. Studies of network organization and dynamics of e-beam crosslinked PVPs: From macro to nano. Radiation Physics and Chemistry, 81, (2012). 11. Filipiak P., Hug G.L., Bobrowski K., Pędziński T., Kozubek H., Marciniak B. Sensitized photooxidation of S-methylglutathione in aqueous solution: intramolecular (S O) and (S N) bonded species. The Journal of Physical Chemistry B, 117, (2013). 12. Georgantzopoulou A., Balachandran Y.L., Rosenkranz P., Dusinska M., Lankoff A., Wojewódzka M., Kruszewski M., Guignard C., Audinot J.-N., Girija S., Hoffmann L., Gutleb A.C. Ag nanoparticles: size- and surface-dependent effects on model aquatic organisms and uptake evaluation with NanoSIMS. Nanotoxicology, 7, 7, (2013).

101 PUBLICATIONS IN Głuszewski W. Napromieniowany czy promieniotwórczy? (Irradiated or radioactive?). Postępy Techniki Jądrowej, 56, 2, (2013). 14. Głuszewski W. Nowe możliwości medycyny nuklearnej w Polsce (New possibilities of the nuclear medicine in Poland). Postępy Techniki Jądrowej, 56, 4, (2013). 15. Głuszewski W. Porozumienie o współpracy między SFEN i PTN (Agreement on the cooperation between SFEN and PTN). Postępy Techniki Jądrowej, 56, 4, 9-11 (2013). 16. Głuszewski W. Techniki radiacyjne w konserwacji obiektów o znaczeniu historycznym (Radiation techniques in preservation of objects of historical importance). Postępy Techniki Jądrowej, 56, 3, (2013). 17. Głuszewski W., Zagórski Z.P., Rajkiewicz M. Efekty ochronne w radiolizie elastomerów (Protective effects in the radiolysis of elastomers). Tworzywa Sztuczne w Przemyśle, 6, (2013). 18. Głuszewski W., Zimek Z., Zagórski Z.P., Rajkiewicz M. Radiacyjna modyfikacja polimerów (Radiation modification of polymers). Tworzywa Sztuczne w Przemyśle, 1, (2013). 19. Gniazdowska E., Koźmiński P., Fuks L. Synthesis, radiochemistry and stability of the conjugates of technetium-99m complexes with Substance P. Journal of Radioanalytical and Nuclear Chemistry, 298, (2013). 20. Grądzka I., Sochanowicz B., Brzóska K., Wójciuk G., Sommer S., Wojewódzka M., Gasińska A., Degen C., Jahreis G., Szumiel I. Cis-9,trans-11-conjugated linoleic affects lipid raft composition and sensitizes human colorectal adenocarcinoma HT-29 cells to X-radiation. Biochimica et Biophysica Acta, 1830, (2013). 21. Grudny J., Kołakowski J., Kruszewski M., Szopiński J., Śliwiński P., Wiatr E., Winek J., Załęska J., Zych J., Roszkowski-Śliż K. Association of genetic dependences between lung cancer and chronic obstructive pulmonary disease. Pneumonologia i Alergologia Polska, 81, 4, (2013). 22. Houée-Levin Ch., Bobrowski K. The use of the methods of radiolysis to explore the mechanisms of free radical modifications in proteins. Journal of Proteomics, 92, (2013). 23. Iller E., Wawszczak D., Konior M., Polkowska-Motrenko H., Milczarek J.J., Górski L. Synthesis and structural investigations of gel metal oxide composites WO 3 -ZrO 2, WO 3 -TiO 2, WO 3 -ZrO 2 - -SiO 2, and their evaluation as materials for the preparation of 188 W/ 188 Re generator. Applied Radiation and Isotopes, 75, (2013). 24. Jagadeesh S., Ravi Shankar A., Kamachi Mudali U., Nowicki A., Raj B. Characterisation of pyrolitic graphite exposed to molten LiCl-KCl salt. Surface Engineering, 29, 1, (2013). 25. Kacprzak J., Kuszewski T., Lankoff A., Müller W.-U., Wójcik A., Lisowska H. Individual variations in the micronucleous assay for biological dosimetry after high dose exposure. Mutation Research/Genetic Toxicology and Environmental Mutagenesis, 756, (2013). 26. Kamiński A., Komender J., Michalik J. 50 lat bankowania i sterylizacji radiacyjnej tkanek w Polsce (50 years of banking and radiation sterilization of tissues in Poland). Postępy Techniki Jądrowej, 56, 3, (2013). 27. Kapka-Skrzypczak L., Niedźwiecka J., Skrzypczak M., Kruszewski M. Udział składników diety w modulacji procesów zapalnych (Nutrients as inflamatory state modulators). Pediatric Endocrinology, Diabetes and Metabolism, 19, 1, (2013).

102 104 PUBLICATIONS IN Kiegiel K., Starosta W., Leciejewicz J. Pyrimidine-4-carboxylic acid. Acta Crystallographica Section E, 69, o885 + [4] p. (2013), doi: /s , Kiegiel K., Steczek Ł., Zakrzewska-Trznadel G. Application of calixarenes as macrocyclic ligands for uranium(vi): A review. E-Journal of Chemistry, //dx.doi.org/ /2013/ (16 p.) (2013). 30. Kornacka E.M., Przybytniak G., Święszkowski W. The influence of crystallinity on radiation stability of UHMWPE. Radiation Physics and Chemistry, 84, (2013). 31. Krajewski S., Cydzik I., Abbas K., Bulgheroni A., Simonelli F., Holzwarth U., Bilewicz A. Cyclotron production of 44 Sc for clinical application. Radiochimica Acta, 101, (2013). 32. Kruszewski M., Grądzka I., Bartłomiejczyk T., Chwastowska J., Sommer S., Grzelak A., Zuberek M., Lankoff A., Dusińska M., Wojewódzka M. Oxidative DNA damage corresponds to the long term survival of human cells treated with silver nanoparticles. Toxicology Letters, 219, (2013). 33. Lankoff A., Arabski M., Węgierek-Ciuk A., Kruszewski M., Lisowska H., Banasik-Nowak A., Rozga-Wijas K., Wojewódzka M., Słomkowski S. Effect of surface modification of silica nanoparticles on toxicology and cellular uptake by human peripheral blood lymphocytes in vitro. Nanotoxicology, 7, 3, (2013). 34. Latek S. 20 lat współczesnej edycji Postępów Techniki Jądrowej (20 years of the new edition of Postępy Techniki Jądrowej journal). Postępy Techniki Jądrowej, 56, 3, (2013). 35. Latek S. Co dalej po IPPA? (What to do next after finishing IPPA?). Postępy Techniki Jądrowej, 56, 4, (2013). 36. Latek S. Jubileusz Postępów Techniki Jądrowej : celebracja i sprawy poważne (Jubilee of the Postępy Techniki Jądrowej : celebration and serious matters). Postępy Techniki Jądrowej, 56, 4, 2-8 (2013). 37. Latek S. Nobel za boską cząstkę (Nobel prize for the divine particle ). Postępy Techniki Jądrowej, 56, 3, 2-6 (2013). 38. Leciejewicz J. Kryptonim Absolwenci. Nabór pracowników naukowych do IBJ w roku 1955 (Code name Absolvents. Recruitment of new scientists to the Institute of Nuclear Research in the year 1955). Postępy Techniki Jądrowej, 56, 4, (2013). 39. Leciejewicz J. Reaktor EWA jako stymulator awansu naukowego pracowników IBJ na przykładzie jednego z zakładów (The EWA research reactor as a stimulator of the INR scientific promotion exemplified by one of the Institute departments). Postępy Techniki Jądrowej, 56, 2, (2013). 40. Lewandowska H. Coordination chemistry of nitrosyls and its biochemical implications. Structure and Bonding, [70] p. (2013), doi: /430_2013_ Lewandowska H. Spectroscopic characterization of nitrosyl complexes. Structure and Bonding, [51] p. (2013), doi: /430_2013_ Lisowska H., Węgierek-Ciuk A., Banasik-Nowak A., Braziewicz J., Wojewódzka M., Wójcik A., Lankoff A.

103 PUBLICATIONS IN The dose-response relationship for chromosomes and γ-h2ax foci in human peripheral blood lymphocytes: Influence of temperature during exposure and intra- and inter-individual variability of donors. International Journal of Radiation Biology, 89, 3, (2013). 43. Łuczyńska-Szymczak K., Starosta W., Drużbicki K. Solid-state DFT-assisted Raman study of titanate nanostructures. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 116, (2013). 44. Łyczko K. 1,5-Dimethyl-2-phenyl-1H-pyrazol-3(2H)-one-4,4 -(propane-2,2-diyl)bis[1,5-dimethyl-2-phenyl-1h-pyrazol-3(2h)-one] (1/1). Acta Crystallographica Section E, 69, o127-o128 + [11] p. (2013). 45. Łyczko K., Łyczko M. 2-Hydroxy-7-nitrocyclohepta-2,4,6-trien-1-one. Acta Crystallographica Section E, 69, o536 + [5] p. 46. Malec-Czechowska K., Wierzchnicki R. A study of stable isotope composition of chosen foodstuffs from the Polish market. Nukleonika, 58, 2, (2013). 47. Migdał W., Gryczka U. Radiacyjna metoda higienizacji i utrwalania żywności (Radiation method of the food products hygienization and preservation). Postępy Techniki Jądrowej, 56, 1, 8-14 (2013). 48. Mioduski T., Gumiński C., Zeng D., Voigt H. IUPAC-NIST Solubility Data Series. 94. Rare earth metal iodides and bromides in water and aqueous systems. Part 2. Bromides. Journal of Physical and Chemical Reference Data, 42, 1, (2013). 49. Miśkiewicz A., Zakrzewska-Trznadel G. Helical contractor for recovery of uranium and associated metals from uranium ores and radioactive wastes. Transations of the American Nuclear Society, 108, (2013). 50. Miśkiewicz A., Zakrzewska-Trznadel G. Investigation of hydrodynamic behaviour of membranes using radiotracer techniques. The European Physical Journal Web of Conferences, 50, 7 p. (2013), doi:10.105/epiconf/ Niesteruk A., Lewandowska H., Golub Ż., Świsłocka R., Lewandowski W. Zainteresujmy się rokitnikiem. Preparaty z rokitnika zwyczajnego (Hippophae rhumnoides L.) jako dodatki do żywności oraz ocena ich rynku w Polsce (Let us have interest in Hippophae rhumnoides as an addition to food and their evaluation on the market in Poland). Kosmos Problemy Nauk Biologicznych, 62, 4, (2013). 52. Pignalosa D., Lee R., Hartel C., Sommer S., Nikoghosyan A., Debus J., Ritter S., Durante M. Chromosome inversions in lymphocytes of prostate cancer patients treated with X-rays and carbon ions. Radiotherapy and Oncology, 109, (2013). 53. Piotrowska A., Leszczuk E., Brucherfseifer F., Morgenstern A., Bilewicz A. Functionalized NaA nanozeolites labeled with 224,225 Ra for targeted alpha therapy. Journal of Nanoparticles Research, 15, 11, 11 p. (2013), doi: /s Połosak M., Piotrowska A., Krajewski S., Bilewicz A. Stability of 47 Sc-complexes with acylic polyamino-polycarboxylate ligands. Journal of Radioanalytical and Nuclear Chemistry, 295, (2013). 55. Rewerski B., Mielnicki S., Bartosiewicz I., Polkowska-Motrenko H., Skłodowska A. Uranium post-mining wastes as a potential reverse source of uranium for nuclear energy plants. Physicochemical Problems of Mineral Processing, 1, 5-11 (2013). 56. Romm H., Ainsbury E., Barnard S., Barrios L., Barquinero J.F., Beinke C., Deperas M., Gregoire E., Koivistoinen A., Lindholm C., Moquet J., Oestreicher U., Puig R., Rothkamm K., Sommer S., Thierens H., Vandersickel V., Vral A., Wójcik A. Automatic scoring of dicentric chromosomes as a tool in large scale radiation accidents. Mutation Research/Genetic Toxicology and Environmental Mutagenesis, 756, (2013).

104 106 PUBLICATIONS IN Romm H., Ainsbury E., Barnard S., Barrios L., Barquinero J.F., Deperas M., Gregoire E., Koivistoinen A., Lindholm C., Moquet J., Oestreicher U., Puig R., Rothkamm K., Sommer S., Thierens H., Vandersickel V., Vral A., Wójcik A. Automatic scoring of dicentric chromosomes as a tool in large scale radiation accidents. Mutation Research/Genetic Toxicology and Environmental Mutagenesis, 756, (2013). 58. Sartowska B., Starosta W., Apel P., Orelovitch O., Blonskaya I. Polymeric track etched membranes application for advanced porous structures formation. Acta Physica Polonica A, 123, 5, (2013). 59. Sartowska B., Waliś L., Starosta W., Barlak M., Pochrybniak C., Kowalska E. Enrichment of AISI 316L steel surface layer with rare earth elements using ion beams. Acta Physica Polonica A, 123, 5, (2013). 60. Shkrob I.A., Marin T.W., Hatcher J.L., Cook A.R., Szreder T., Wishart J.F. Radiation stability of cations in ionic liquids. 2. Improved radiation resistance through charge delocalization in 1-benzylpyridinium. The Journal of Physical Chemistry B, 117, (2013). 61. Skowron K., Olszewska H., Paluszak Z., Zimek Z., Kałuska I., Skowron K.J. Radiation hygienization of cattle and swine slurry with high energy electron beam. Radiation Physics and Chemistry, 87, (2013). 62. Sobczyk L., Pawlukojć A., Grech E., Huczyński A., Brzeziński B. Extremely different structures and vibrational spectra of tetramethylpyrazine nitrate dihydrate in solid and solutions. Journal of Molecular Structure, 1037, (2013). 63. Stachowicz W. Identyfikacja napromieniowania produktów spożywczych w IChTJ (Identification of the irradiated food products in the INCT). Postępy Techniki Jądrowej, 56, 2, (2013). 64. Starosta W., Leciejewicz J. catena-poly[[aqualithium(i)]-μ-3-carboxy-5,6-dimethylpyrazine-2-carboxylato-κ 4 O 2,N 1 :O 3,N 4 ]. Acta Crystallographica Section E, 69, m655-m656 + [8] p. (2013), doi: /s , Starosta W., Leciejewicz J. catena-poly[[diaquabis(μ 3-5-carboxylato-1H-pyrazole-3-carboxylic acid-κ 3 O 3 :O 3 ;O 5 )dilithium(i)] monohydrate]. Acta Crystallographica Section E, 69, m593-m594 + [5] p. (2013), doi: /s , Starosta W., Leciejewicz J. Di-μ-aqua-bis[aqua(5-carboxylato-1H-1,2,3-triazole-4-carboxylic acid-κ 2 N 3,O 4 )lithium]. Acta Crystallographica Section E, 69, m515-m516 + [5] p. (2013), doi: /s , Starosta W., Leciejewicz J. Poly[(μ 4-3-carboxypyrazine-2-carboxylato)(μ 4 -nitrato)dilithium]. Acta Crystallographica Section E, 69, m62 + [7] p. (2013). 68. Starosta W., Leciejewicz J. Triaqua(pyrazole-4-carboxylato-κN 1 )-lithium. Acta Crystallographica Section E, 69, m438 + [5] p. (2013). 69. Starosta W., Leciejewicz J., Kiegiel K. Tetraaqua(pyridine-4,6-dicarboxylato-κ 2 N 1,O 6 )magnesium monohydrate. Acta Crystallographica Section E, 69, m189 + [5] p. 70. Strzelczak G., Sterniczuk M., Sadło J., Kowalska M., Michalik J. EPR study of γ-irradiated feather keratin and human fingernails concerning retrospective dose assessment. Nukleonika, 58, 4, (2013). 71. Sun Y., Chmielewski A.G., Bułka S., Zimek Z. Toluene and 4-chlorotoluene decomposition in air mixture in electron beam generated non-thermal plasma reactor and their by-products identification.

105 PUBLICATIONS IN Surface & Coatings Technology, 234, (2013). 72. Trojanowicz M., Koc M. Recent developments in methods for analysis of perfluorinated persistent pollutants. Microchimica Acta, 180, (2013), doi: /s z. 73. Tymiński Z., Miśta E., Kalbarczyk P. Pomiary radionuklidów kosmogenicznych w meteorycie z Oslo i interpretacja wyników (The Oslo meteorite research for cosmogenic radionuclides and the interpretation of the results). Acta Societaris Metheoriticae Polonorum, 4, (2013). 74. Walo M., Przybytniak G., Akkas Kavakh P., Güven O. Radiation-induced graft polymerization of N-vinylpyrrolidone onto segmented polyurethane based on isophorone diisocyanate. Radiation Physics and Chemistry, 84, (2013). 75. Walo M., Przybytniak G., Sadło J. Radiation-induced radicals in aliphatic poly(ester urethane)s studied by EPR spectroscopy. Journal of Molecular Structure, 1036, (2013). 76. Zakrzewska G., Biełuszka P., Chajduk E., Wołkowicz S. Recovery of uranium(vi) from water solutions by membrane extraction. Advanced Materials Research, 704, (2013). 77. Zakrzewska-Trznadel G. Advances in membrane technologies for the treatment of liquid radioactive waste. Desalination, 321, (2013). 78. Zalewska E., Rabiński M., Latek S. Jubileusz 20-lecia nowej edycji PTJ (Jubilee of the Postępy Techniki Jądrowej new edition). Postępy Techniki Jądrowej, 56, 3, (2013). BOOKS 1. Guidelines for the development, validation and routine control of industrial radiation processes. M. Bailey, B. Croonenborghs, I.M. Kałuska, A. Kovacs, K. Mechta, A. Miller, J. Mittendorfer, I.V. Moise, A. Safrany, P. Sharpe, Z. Zimek (eds.). IAEA Radiation Technology Series no. 4. IAEA, Vienna 2013, 129 p. 2. Sun Y. Degradation of air pollutants in non-thermal plasma generated by electron beam experimental and technological study. Institute of Nuclear Chemistry and Technology, Warszawa 2013, 75 p. CHAPTERS IN BOOKS Chmielewska D.K. Ionizing radiation as a tool for silver nanoclusters formation. In: Radiation synthesis of materials and compounds. B.I. Kharisov, O.V. Kharissova, U. Ortiz Mendez (eds.). CRC Taylor & Francis Group, Press Boca Raton 2013, pp Cieśla K. Radiation modification of the functional and structural properties of the biodegradable and edible films prepared using starch, starch-surfactant and starch-lipid system. In: Report of the first RCM on application of radiation technology in development of advanced packaging materials for food products, 22 to 26 April 2013, Vienna. Working material. IAEA, Vienna 2013, pp Dybczyński R.S., Polkowska-Motrenko H. Certyfikowane materiały odniesienia w analizie śladowej (Certified reference materials for trace analysis). In: Analiza śladowa. Zastosowania. Pod red. I. Baranowskiej. Wydawnictwo Malamut, Warszawa 2013, pp

106 108 PUBLICATIONS IN Nowicki A., Przybytniak G., Mirkowski K. Radiacyjne sieciowanie żywic epoksydowych z napełniaczami nanowęglowymi (Radiation crosslinking of epoxy resins containing carbon nanofillers). In: Modyfikacja polimerów. Stan i perspektywy w roku Praca zbiorowa pod red. R. Stellera i D. Żuchowskiej. Wydawnictwo TEMPO s.c., Wrocław 2013, pp Samczyński Z. Minimalizacja wpływu pierwiastków towarzyszących na oznaczanie uranu metodą spektrofotometrii UV/VIS z zastosowaniem arsenazo III (Minimization of influence of accompanying elements on the determination of uranium by spectrophotometry UV/VIS using arsenazo III). In: Nauka i przemysł metody spektroskopowe w praktyce, nowe wyzwania i możliwości. Praca zbiorowa pod red. Z. Hubickiego. Wydawnictwo UMCS, Lublin 2013, pp Zakrzewska-Trznadel G. Membrane for the isotopes separation. In: Encyclopedia of membranes. E. Drioli and L. Giorno (eds.). Springer Verlag, Berlin-Heidelberg 2013, [3] p. DOI: /SpringerReference_ Zakrzewska-Trznadel G. Membrane in nuclear science and technology. In: Encyclopedia of membranes. E. Drioli and L. Giorno (eds.). Springer Verlag, Berlin-Heidelberg 2013, [2] p. DOI: /SpringerReference_ Zakrzewska-Trznadel G. Membranes in nuclear waste treatment. In: Encyclopedia of membranes. E. Drioli and L. Giorno (eds.). Springer Verlag, Berlin-Heidelberg 2013, [2] p. DOI: /SpringerReference_ Zakrzewska-Trznadel G. Nuclear waste processing by pressure driven membrane processes. In: Encyclopedia of membranes. E. Drioli and L. Giorno (eds.). Springer Verlag, Berlin-Heidelberg 2013, [2] p. DOI: /SpringerReference_ Zakrzewska-Trznadel G. Nuclear waste processing by supported liquid membranes. In: Encyclopedia of membranes. E. Drioli and L. Giorno (eds.). Springer Verlag, Berlin-Heidelberg 2013, [5] p. DOI: /SpringerReference_ Zakrzewska-Trznadel G. Nuclear waste processing by thermal processes. In: Encyclopedia of membranes. E. Drioli and L. Giorno (eds.). Springer Verlag, Berlin-Heidelberg 2013, [4] p. DOI: /SpringerReference_ THE INCT PUBLICATIONS INCT Annual Report Institute of Nuclear Chemistry and Technology, Warszawa 2013, 164 p. Sun Y. Degradation of air pollutants in non-thermal plasma generated by electron beam. Experimental and theoretical study. Institute of Nuclear Chemistry and Technology, Warszawa 2013, 75 p. Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych (Analysis of the possibility of uranium supply from domestic resources). Instytut Chemii i Techniki Jądrowej, Warszawa 2013, 30 p. Recommendations for broader and sustainable participation of New Member States in H2020. Institute of Nuclear Chemistry and Technology, Warszawa 2013, 67 p. Chajduk E., Polkowska-Motrenko H., Pyszynska M., Skwara W., Dudek J., Szaniawska E. Badanie biegłości ROŚLINY 12 oznaczanie zawartości As, Cd, Cr, Cu, Hg, Pb, Se i Zn w grzybach suszonych (Leccinum scabrum) (Proficiency test PLANTS 12 determination As, Cd, Cr, Cu, Hg, Pb, Se and Zn in dry mushroom powder (Leccinum scabrum)). Instytut Chemii i Techniki Jądrowej, Warszawa Raporty IChTJ. Seria B nr 1/2013, 32 p.

107 PUBLICATIONS IN 2013 CONFERENCE PROCEEDINGS Biełuszka P., Zakrzewska-Trznadel G. The use of the membrane contractor for extraction of uranium(vi) from aqueous solutions. CYSENI 2013, 10th International Conference of Young Scientists on Energy Issues, Kaunas, Lithuania, Conference proceedings, VII-423-VII Chmielewski A.G., Palige J., Urbaniak A., Zalewski M.K., Roubinek O., Dobrowolski A., Wawryniuk K. Wzbogacanie biogazu ze składowiska odpadów komunalnych i miejskiej oczyszczalni ścieków w metan w procesie membranowym (Methane enrichment of biogas from municipal waste landfill and wastewater treatment plant in membrane process). XI Konferencja Dla miasta i środowiska problemy unieszkodliwiania odpadów, Warszawa, Poland, Materiały konferencyjne, [6] p. 3. Chmielewski A.G., Pawelec A., Witman-Zając S. Możliwości zastosowanie radiacyjnej technologii oczyszczania spalin w praktyce przemysłowej (Possibilities of EBFGT technology application in industrial practice). XI Konferencja Dla miasta i środowiska problemy unieszkodliwiania odpadów, Warszawa, Poland, Materiały konferencyjne, [4] p. 4. Chmielewski A.G., Pawelec A., Witman-Zając S., Dobrowolski A. Plazmowe metody oczyszczania gazów odlotowych (Plasma-based methods of flue gas treatment). XI Konferencja Dla miasta i środowiska problemy unieszkodliwiania odpadów, Warszawa, Poland, Materiały konferencyjne, [6] p. 5. Dybczyński R., Polkowska-Motrenko H., Samczyński Z. History, achievements and present time of production of CRMs for inorganic trace analysis in Poland. 1st International Scientific Conference: Reference Materials in Measurement and Technology, Ekaterinburg, Russia, Conference proceedings, pp Głuszewski W., Zimek Z. Radiacyjna modyfikacja materiałów opakowaniowych (Radiation modification of packaging materials). Wpływ promieniowania jonizującego na wybrane biodegradowalne materiały opakowaniowe. Materiały sympozjum naukowego 9 kwietnia 2013 r. Red. nauk. H. Kubera. Uniwersytet Ekonomiczny w Poznaniu, Poznań 2013, pp Głuszewski W., Zimek Z., Cieśla K. Badania radiolizy materiałów opakowaniowych (Studies of the radiolysis of packaging materials). Wpływ promieniowania jonizującego na wybrane biodegradowalne materiały opakowaniowe. Materiały sympozjum naukowego 9 kwietnia 2013 r. Red. nauk. H. Kubera. Uniwersytet Ekonomiczny w Poznaniu, Poznań 2013, pp Sartowska B. Technologies supporting development of safe nuclear power engineering the strategic research project in Poland. Proceedings of the 19th International QUENCH Workshop, Karlsruhe Institute of Technology, , 16 p. (CD edition). 9. Starosta W., Sartowska B., Barlak M., Waliś L., Michalik J. Modification of the zirconium alloys surface layer with yttrium by ion implantation and plasma pulse techniques. Proceedings of the 19th International QUENCH Workshop, Karlsruhe Institute of Technology, , 18 p. (CD edition). 10. Trojanowicz M., Gumiela M., Koc A., Bojanowska-Czajka A., Kciuk G., Bobrowski K., Nałęcz-Jawecki G. Radiolytic decomposition of pharmaceutical residues of diclofenac analytical, toxicological and pulse radiolysis studies. Proceedings of the International Conference on Environmental Pollution and Remediation, Toronto, Canada, Paper no. 30, 8 p. 11. Zakrzewska-Trznadel G., Kiegiel K., Abramowska A., Zielińska B., Biełuszka P., Steczek Ł., Chajduk E., Wołkowicz S. Recovery of uranium from post-leaching solutions by solvent extraction: state of the art and new technological possibilities. Proceedings of the Nuclear 2013: The 5th Annual International Conference on Sustainable Development through Nuclear Research and Education, Pitesti, Romania, Book of abstract, pp

108 110 PUBLICATIONS IN 2013 CONFERENCE ABSTRACTS Abramowska A., Kiegiel K., Gajda D., Szczygłów K., Zakrzewska-Trznadel G., Chajduk E., Wołkowicz S. Otrzymywanie czystego tlenku uranu do produkcji paliwa jądrowego z krajowych zasobów rud uranowych (Obtaining of pure uranium oxide to produce nuclear fuel from domestic resources of uranium ores). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, P1. Abramowska A., Kiegiel K., Zakrzewska G., Samczyński Z., Skwara W. Precypitacja prekursorów oktatlenku triuranu do produkcji paliwa jądrowego (Precipitation of precursors of triuranium octa-oxide for nuclear power engineering). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium naukowe w ramach projektu POIG /09, Warszawa, Poland, Streszczenia referatów, p. 17. Antoniak M., Chmielewska D. Silver micro- and nanoparticle embedded in cellulose matrix with UV and ionizing radiation. ChemSession 13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, Streszczenia, p. 47. Barnard S., Ainsbury E.A., Al-hafidh J., Hadjidekova V., Hristova R., Lindholm C., Monteiro Gil O., Moquet J., Moreno M., Rößler U., Thierens H., Vandevoorde C., Vral A., Wojewódzka M., Rothkamm K. The 1st gamma-h2ax biodosimetry intercomparison exercise of the developing European Biodosimetry Network RENEB. The Join International Symposium on EPR Dosimetry and Dating and the International Conference on Biological Dosimetry, Leiden, The Netherlands, Abstracts of lectures and poster presentations, p Bartłomiejczyk T., Grądzka I., Kruszewski M. Promieniouczulający wpływ nanocząstek srebra na ludzkie komórki nowotworowe A549 i HepG2 (Silver nanoparticles as radiation sensitizers in human cancer cell lines: A549 and HepG2). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p. 76. Bartosiewicz I., Chajduk E., Chwastowska J., Dudek J., Pyszynska M., Polkowska-Motrenko H. Oznaczanie całkowitych zawartości oraz analiza specjacyjna uranu i pierwiastków towarzyszących w polskich rudach z Obniżenia Podlaskiego i Syneklizy Perybałtyckiej (Determination of the whole content and speciation analysis of uranium and accompanying elements in the Polish ores from the Podlasie depresion and the Peribaltic synecline). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium naukowe w ramach projektu POIG /09, Warszawa, Poland, Streszczenia referatów, p. 10. Bartosiewicz I., Chwastowska J., Polkowska-Motrenko H. Badanie składu i wpływu na środowisko pouranowych odpadów kopalnianych w bloku Karkonosko-Izerskim (Studies of the composition and influence on the environment from uranium mining impurities in the Karkonosko-Izerski block). 56. Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i Techników Przemysłu Chemicznego, Siedlce, Poland, Materiały zjazdowe, pp Bartosiewicz I., Chwastowska J., Polkowska-Motrenko H. Oznaczanie uranu i wybranych metali techniką spektrometrii mas z jonizacją w plazmie indukcyjnie sprzężonej (ICP-MS) w materiałach roślinnych (Determination of uranium and selected metals in plant materials by ICP-MS). Ogólnopolska konferencja naukowa: Jakość w chemii analitycznej, Mory k/warszawy, Poland, , p. 36. Bartosiewicz I., Skwara W., Dudek J., Chwastowska J., Polkowska-Motrenko H. Badanie specjacji pierwiastków śladowych występujących w łupkach dictyonemowych i piaskowcach (Speciation of trace elements in dictyonema shales and sandstones). XXII Poznańskie Konwersatorium Analityczne Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków, Poznań, Poland, , p. 43.

109 PUBLICATIONS IN Biełuszka P., Zakrzewska G. Symulacja wielostopniowego układu do ekstrakcji uranu z rudy uranowej ekstrakcja ciało stałe-ciecz w kontraktorach membranowych (Simulation of multistage system for the extraction of uranium from uranium ore-solvent extraction in membrane contractors). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium naukowe w ramach projektu POIG /09, Warszawa, Poland, Streszczenia referatów, p. 13. Biełuszka P., Zakrzewska G., Chajduk E. Ekstrakcja ciecz-ciecz uranu w kontraktorach membranowych (Solvent extraction of uranium with membrane contractors). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium naukowe w ramach projektu POIG /09, Warszawa, Poland, Streszczenia referatów, p. 15. Biełuszka P., Zakrzewska-Trznadel G. Ekstrakcja ciecz-ciecz uranu(vi) w układzie z kontaktorem membranowym (Liquid-liquid extraction of uranium(vi) in the system with a membrane contactor). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, K2. Biełuszka P., Zakrzewska-Trznadel G. The study on liquid-liquid extraction of uranium(vi) in the system with the membrane contractor. Proceedings of the 2nd International Conference on Methods and Materials for Separation Processes, Świeradów Zdrój, Poland, , [1] p. Biełuszka P., Zakrzewska G., Harasimowicz M. Koncepcja hybrydowego układu do usuwania uranu z kwasu fosforowego (Conception of hybrid system for the removal of uranium from phosphoric acid). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium naukowe w ramach projektu POIG /09, Warszawa, Poland, Streszczenia referatów, p. 19. Bobrowski K. Pulse radiolysis: a tool for investigating radical processes in biological molecules. COST Action CM1201 Biomimetic Radical Chemistry 2nd MC Meeting & 1st Annual Scientific Meeting, Bologna, Italy, , p Bobrowski K. Reactions of OH radicals with 2 -deoxyguanosine derivatives: infuence of substituents. 1st WG2 Meeting of the COST Action CM1201 Biomimetic Chemistry, Athens, Greece, Abstract book, p. 24. Bobrowski K., Filipiak P., Hug G.L., Marciniak B., Pędziński T., Pogocki D., Schöneich C. Neighboring group participation during oxidation of peptides containing sulfur amino acids. 28th Miller Conference on Radiation Chemistry, Dead Sea, Israel, , p. 44. Boguski J., Przybytniak G., Łyczko K. Kryteria oceny radiacyjnego i termicznego starzenia kabli (Assessment criteria of radiation and thermal aging of cables). Konferencja naukowo-techniczna: Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, , p. 13. Bojanowska-Czajka A., Kołacińska K., Trojanowicz M. Application of flow analytical methods for determination of radionuclides in cooling water and wastes from nuclear plants. 5th Asia-Pacific Symposium on Radiochemistry, APSORC 13, Kanazawa, Japan, , p Brykała M., Deptuła A., Rogowski M. Synteza uranowych prekursorów paliw węglikowych i azotkowych za pomocą kompleksowej metody zol-żel (CSGP) (Synthesis of precursors of uranium carbides and nitrides fuels by complex sol-gel process (CSGP)). Konferencja naukowo-techniczna: Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, , p. 20. Brykała M., Deptuła A., Rogowski M., Łada W., Olczak T. Process IChTJ method for preparation of spherical particles of ceramic nuclear fuels.

110 112 PUBLICATIONS IN th Conference under auspices of E-MRS: Composites and Ceramic Materials Technology, Application and Testing, Białowieża, Poland, Book of abstracts, p. 27. Brykała M., Deptuła A., Rogowski M., Olczak T., Łada W., Smoliński T., Wawszczak D., Wojtowicz P. Synteza za pomocą kompleksowej metody zol-żel (CSGP) stablizowanego ditlenku cyrkonu jako potencjalnej matrycy inertnej do transmutacji aktynowców (Synthesis by complex sol-gel process (CSGP) of stabilized zirconium dioxide as potential materials to inert matrices to transmutation of actinides). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, P3. Brykała M., Deptuła A., Rogowski M., Olczak T., Łada W., Smoliński T., Wawszczak D., Wojtowicz P. Synteza ziaren ditlenku uranu dotowanych tlenkiem neodymu za pomocą kompleksowej metody zol-żel (CSGP) (Synthesis of uranium dioxide microspheres doped by neodynium oxide by complex sol-gel process (CSGP)). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, K4. Brykała M., Deptuła A., Walczak R., Rogowski M., Olczak T., Łada W., Smoliński T., Wawszczak D. Immobilizacja aktynowców mniejszościowych w matrycach inertnych otrzymanych za pomocą metody CSGP (Immobilization of minor actinides in inert matrix prepared by the CSGP method). ChemSession 13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, Streszczenia, p. 60. Brykała M., Rogowski M., Deptuła A., Olczak T., Łada W., Smoliński T., Wawszczak D., Wojtowicz P. Synteza węglika uranu za pomocą kompleksowej metody zol-żel (CSGP) (Synthesis of uranium carbide by complex sol-gel process (CSGP)). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, K34. Brykała M., Rogowski M., Deptuła A., Wawszczak D., Łada W., Smoliński T. Badania nad otrzymywaniem węglika uranu i azotku uranu za pomocą CSGP (Research on the preparation of uranium carbide and uranium nitride by CSGP). ChemSession 13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, Streszczenia, p Brzóska K., Kruszewski M. Gene expression signatures in blood as a biomarker for biological dosimetry. XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p. 36. Brzóska K., Stępkowski T., Kruszewski M. Regulation of pirin expression as a mechanism enabling cross-talk between NRF2 and other transcription factors. 13th Young Scientists Forum, Saint Petersburg, Russia, Book of abstracts, p. 44. Brzóska K., Stępkowski T., Kruszewski M. Regulation of pirin expression as a mechanism enabling cross-talk between NRF2 and other transcription factors. FEBS Journal, 280, Suppl. 1, 218 (2013). Brzóska K., Wojewódzka M., Stępkowski T., Kruszewski M. Real-time PCR analysis of expression of DNA damage responsive genes as a biomarker for biological dosimetry. Global Conference on Radiation Topics ConRad 2013, Munich, Germany, Abstracts, [1] p. Bugaj A., Sadło J., Sterniczuk M., Strzelczak G., Michalik J. Centra paramagnetyczne generowane radiacyjnie w sitach molekularnych typu TiAlMCM badania z wykorzystaniem techniki EPR (Paramagnetic centers generated by irradiation in molecular sieves TiAlMCM type EPR study). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p. 95. Bugaj A., Sadło J., Sterniczuk M., Strzelczak G., Michalik J. Paramagnetic centres generated radioanalytically in molecular sieves TiAlMCM type EPR study.

111 PUBLICATIONS IN Porous and Powder Materials Symposium and Exhibition PPM 2013, Cesme Izmir, Turkey, , p Bugaj A., Sadło J., Sterniczuk M., Strzelczak G., Michalik J. Radiacyjnie generowane centra paramagnetyczne w sitach molekularnych typu TiAlMCM badania EPR (Radiation generated paramagnetic centers in molecular sieves TiAlMCM type EPR study). ChemSession 13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, Streszczenia, p. 63. Bugaj A., Sadło J., Sterniczuk M., Strzelczak G., Michalik J. Radiation generated paramagnetic centres in molecular sieves TiAlMCM type EPR study. 6th European Young Investigator Conference, Słubice, Poland, Book of abstracts, p. 52. Celuch M., Mirkowski J., Bojanowska-Czajka A., Kulisa K., Kisała J., Pogocki D. Wolnorodnikowa degradacja wybranych pestycydów (Free radical degradation of some pesticides). XVII Mikrosympozjum: Kinetyczne Metody Badania Mechanizmów Reakcji w Roztworach, Poznań, Poland, , P-37. Celuch M., Skotnicki K., Bobrowski K., Masłowska A., Kisała J., Pogocki D. Wydajność chemoradiacyjna wodorku w roztworach wodnych w obecności nanocząstek tlenku cyrkonu (Yield of hydrogen in the aqueous solutions in the presence of zirconium oxide nanoparticles). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p. 68. Chajduk E., Bartosiewicz I., Pyszynska M., Chwastowska J., Polkowska-Motrenko H. Analiza złóż uranonośnych z Obniżenia Podlaskiego i syneklizy perybałtyckiej metodą ICP-MS (Analysis of Polish dictyonema shales and sandstones by ICP-MS). XXII Poznańskie Konwersatorium Analityczne Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków, Poznań, Poland, , p. 41. Chajduk E., Danko B., Pańczyk E., Dudek J., Skłodowska A., Polkowska-Motrenko H. Complementary application of ICP MS and INAA in microanalysis of elemental composition of historical samples. XVII EuroAnalysis: Analytical Chemistry for Human Well-Being and Sustainable Development, Warsaw, Poland, Book of abstracts, p Chajduk E., Dudek J., Polkowska-Motrenko H. Program Rośliny Wnioski z dziesięciu lat badań (PT scheme Plants lessons from the decade of experience). Ogólnopolska konferencja naukowa: Jakość w chemii analitycznej, Mory k/warszawy, Poland, , p. 37. Chajduk E., Polkowska-Motrenko H., Bilewicz A. Novel radiochemical separation of arsenic from selenium for 72 Se/ 72 As generator. 5th Asia-Pacific Symposium on Radiochemistry, APSORC 13, Kanazawa, Japan, , p Chajduk E., Witman-Zając S., Polkowska-Motrenko H. Determination of low level 99 Tc in the primary coolant water by ICP-MS. Analysis of potential interferences. 5th Asia-Pacific Symposium on Radiochemistry, APSORC 13, Kanazawa, Japan, , p Chajduk E., Zuba M., Skwara W., Dudek J., Polkowska-Motrenko H. Sorpcja 226 Ra na jonitach z wytrąconych MnO 2 i jego oznaczanie w próbkach środowiskowych za pomocą ICP-MS (Sorption of 226 Ra on ionites from precipitated MnO 2 and its determination with ICP-MS). XVIII Konferencja: Zastosowanie metod AAS, ICP-OES i ICP-MS w analizie środowiskowej, Kraków, Poland, , p. 45. Chmielewska D., Sartowska B. Silver micro- and nanoparticle embedded in cellulose matrix with UV and ionizing radiation. 17th International Meeting on Radiation Processing, Shanghai, China, , p Chmielewski A.G. Chemia w energetyce jądrowej polska perspektywa (Chemistry for nuclear power Polish perspective). 56. Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i Techników Przemysłu Chemicznego, Siedlce, Poland, Materiały zjazdowe, p. 96. Chmielewski A.G. Działania IChTJ na rzecz Polskiego Programu Energetyki Jądrowej (Activity of the INCT for the Polish Nuclear Power Programme).

112 114 PUBLICATIONS IN Konferencja naukowo-techniczna: Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, , pp Chmielewski A.G. Radiation processing for rich and poor, experts and beginners. 17th International Meeting on Radiation Processing, Shanghai, China, , p Chmielewski A.G. Radiation processing technology now & in the future. 17th International Meeting on Radiation Processing, Shanghai, China, , p Chmielewski A.G., Pawelec A., Licki J., Sun Y., Zimek Z. New horizons for electron beam flue gas treatment technology applications. 17th International Meeting on Radiation Processing, Shanghai, China, , pp Chmielewski A.G., Sartowska B., Jakowiuk A., Ptaszek S., Modzelewski Ł., Sommer S. Analiza potencjału polskich firm pod kątem możliwości wykonywania dostaw systemów dozymetrycznych dla bezpiecznej eksploatacji elektrowni jądrowej (Analysis of potential of the Polish firms concerning the supply of dosimetric systems for sale operation of a nuclear power plant). Konferencja naukowo-techniczna: Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, , p. 25. Cieśla K. Modification of the structure and the functional properties of the starch based films by radiation treatment and addition of lipids/surfactant. 4th International Conference on Biodegradable Polymers and Suistance Composites BIOPOL-2013, Rome, Italy, , [2] p. Cieśla K., Nowicki A., Buczkowski M., Sartowska B., Łyczko K. Modification of the structure and the functional properties of the biodegradable films based on starch by radiation treatment and addition of lipids/surfactants. 3rd International Conference on Multifunctional, Hybrid and Nanomaterials, Sorrento, Italy, , [1] p. [A ]. Cieśla K., Rahier H., Łyczko K. The influence of gamma irradiation on the physico-chemical properties of the complexes formed by potato starch with cetyl-trimethyl ammonium bromide. 3rd International Polysaccharide Conference: Polysaccharides and polysaccharide-derived products, from basic science to applications, Nice, France, Book of abstracts, p Deptuła A., Brykała M., Rogowski M., Olczak T., Łada W., Wawszczak D., Smoliński T. Badania nad otrzymywaniem spiekalnego ditlenku uranu za pomocą kompleksowej metody zol-żel (CSGP) (Studies on the preparation of sinterable uranium dioxide by complex sol-gel process (CSGP)). Konferencja naukowo-techniczna: Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, , p. 28. Deptuła A., Wawszczak D., Łada W., Miłkowska M., Brykała M., Olczak T., Chmielewski A.G., Laskowska R., Gorzałczyński J. Analiza możliwości pozyskiwania uranu z krajowych zasobów rud miedzionośnych i odpadów poflotacyjnych (Analysis of the possibilities of obtaining uranium from domestic resources of copper ores and post-flotation wastes). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium naukowe w ramach projektu POIG /09, Warszawa, Poland, Streszczenia referatów, p. 20. Dybczyński R.S. 50 years of adventures with neutron activation analysis with the special emphasis on radiochemical separations. 5th Asia-Pacific Symposium on Radiochemistry, APSORC 13, Kanazawa, Japan, , p. 2. Dybczyński R.S. Dlaczego neutronowa analiza aktywacyjna (NAA) jest tak potrzebna w procesie zapewnienia jakości w nieorganicznej analizie śladowej? (Why neutron activation analysis (NAA) is so needed in the process of quality assurance in inorganic trace analysis?). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, W1.

113 PUBLICATIONS IN Dybczyński R.S. Temperatura trochę lekceważony parametr w chromatografii jonowymiennej i chromatografii jonowej (Temperature a little neglected parameter in ion exchange and ion chromatography). 3. Konferencja Naukowa Monitoring i Analiza Wody. Chromatograficzne metody oznaczania substancji o charakterze jonowym, Toruń, Poland, , p. 17. Dybczyński R., Polkowska-Motrenko H., Samczyński Z. Historia, osiągnięcia, teraźniejszość i przyszłość wytwarzania certyfikowanych materiałów odniesienia dla nieorganicznej analizy śladowej w Polsce i problem zapewnienia jakości (History, achievements, present and future of production of CRMs for inorganic trace analysis in Poland and problems of quality assurance). Ogólnopolska konferencja naukowa: Jakość w chemii analitycznej, Mory k/warszawy, Poland, , p. 7. Filipiak P., Hug G.L., Bobrowski K., Pędziński T., Kozubek H., Marciniak B. Sensitized photooxidation of S-methylglutathione in aqueous solution. Intramolecular (S O) and (S N) bonded species. 28th Miller Conference on Radiation Chemistry, Dead Sea, Israel, , p. 76. Filipowicz B. Badania nad wykorzystaniem nanomateriałów tytanianowych do separacji produktów rozszczepienia uranu (Research on the use of titanate nanomaterials to the separation of uranium fission products). Konferencja naukowo-techniczna: Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, , p. 31. Filipowicz B. Porównanie sorpcji 137 Cs na nanostrukturach TiO 2 -ZrO 2 i TiO 2 (Comparison of sorption of 137 Cs in the TiO 2 -ZrO 2 and TiO 2 nanostructures). ChemSession 13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, Streszczenia, p. 82. Filipowicz B., Krajewski S., Bilewicz A. Nanostruktury tytanianowe jako nowe sorbenty wykorzystywane do separacji Cs + i Sr 2+ z odpadów promieniotwórczych (Titanate nanostructures as new sorbents used for separation of Cs + and Sr 2+ from radioactive waste). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, P10. Gajda D., Danko B., Zakrzewska-Trznadel G., Kiegiel K., Chajduk E., Bartosiewicz I., Samczyński Z. The study of sandstone rocks as a potential source of uranium from domestic deposits. European Nuclear Young Generation Forum, Stockholm, Sweden, , [2] p., qymactg0liazxee9f6p-3cshnzys3tlmno. Gajda D., Zakrzewska G., Danko B., Samczyński Z., Dybczyński R., Chajduk E., Bartosiewicz I. Wydzielanie uranu i metali towarzyszących z roztworu po ługowaniu rud uranowych z wykorzystaniem wymieniaczy jonowych typu Dowex (Separation of uranium and accompanying metals from a solution after leaching of uranium ores with the use of ion exchangers of Dowex type). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium naukowe w ramach projektu POIG /09, Warszawa, Poland, Streszczenia referatów, p. 16. Gajda D., Zakrzewska G., Kiegiel K., Frąckiewicz K., Szczygłów K., Chajduk E., Bartosiewicz I., Herdzik-Koniecko I. Ługowanie uranu i innych pierwiastków towarzyszących z piaskowców Syneklizy Perybałtyckiej oraz łupków dictyonemowych Obniżenia Podlaskiego (Leaching of uranium and other accompanying elements from sandstones of the Peribaltic synecline and dictyonema shales from the Podlasie depression). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium naukowe w ramach projektu POIG /09, Warszawa, Poland, Streszczenia referatów, p. 11. Gajda D., Zakrzewska-Trznadel G., Kiegiel K., Danko B., Chajduk E., Bartosiewicz I. Oddzielenie związków uranu od metali towarzyszących z roztworów otrzymanych po ługowaniu piaskowców pochodzących z polskich złóż, metodą chromatografii jonowymiennej (Separation of uranium compounds from accompanying metals from solutions after leaching of sandstones from the Polish deposits).

114 116 PUBLICATIONS IN ChemSession 13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, Streszczenia, p. 83. Głuszewski W., Rajkiewicz M., Zagórski Z.P. Radiacyjna modyfikacja elastomerów (Radiation modification of elastomers). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p. 91. Głuszewski W., Rajkiewicz M., Zagórski Z.P. Rola związków aromatycznych w chemii radiacyjnej elastomerów / The role of aromatic componds in radiation chemistry of elastomers. Elastomery 2013 Nauka i przemysł. XV Międzynarodowa Konferencja Naukowo-Techniczna / Elastomery 2013 Science and Industry XV International Science and Technology Conference, Warszawa, Poland, , [2] p. Głuszewski W., Rajkiewicz M., Zagórski Z.P., Kubacki R. Kompozyty elastomerowe w ochronie przed promieniowaniem jonizującym i elektromagnetycznym (Elastomers composites in the protection against ionizing and electromagnetic radiation). Konferencja naukowo-techniczna: Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, , p. 36. Głuszewski W., Tran Q.K., Cortella L. Radiacyjna konserwacja obiektów o znaczeniu historycznym (Radiation conservation of works of art). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p. 47. Głuszewski W., Zagórski Z.P., Rajkiewicz M. Protective effects in radiation modification of elastomers. 17th International Meeting on Radiation Processing, Shanghai, China, , p Gniazdowska E., Koźmiński P., Fuks L., Bańkowski K., Łuniewski W., Królicki L. In vitro and in vivo evaluation of lapatinib labeled with technetium(iii)-99m. The 20th International Symposium on Radiopharmaceutical Sciences May 2013, ICC JEJU, Jeju, Korea. Journal of Labelled Compounds and Radiopharmaceuticals, 56, Suppl. 1, S435 (2013). Graupner A., Gutzkow K.B., Collins A.R., Shaposhikov S., Štetina R., Kruszewski M., Sirota N., Jones G.D., Møller P., Koppen G., Brunborg G. An inter-laboratory calibration trial: To what extent can we compare comet results obtained in different laboratories? 10th International Comet Assay Workshop, Porto, Portugal, Book of abstracts, p. 61. Grądzka I., Sochanowicz B., Męczyńska-Wielgosz S. Promieniouczulające działania sprzężonego dienu kwasu linolowego (CLA) na komórki raka jelita, HT-29, poprzez zaburzenie sygnalizacji przeżycia (Radiosensitizing properties of conjugated linoleic acid (CLA) in HT-29 colon cancer cells, through the impairement of prosurvival signaling). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p. 43. Gryczka U., Migdał W., Chmielewska D., Buttafava A., Dondi D. Study on the radiolytic transformation of willow biomass. 17th International Meeting on Radiation Processing, Shanghai, China, , p Gumiela M., Gniazdowska E., Koźmiński P., Bilewicz A. Otrzymywanie 99m Tc na cyklotronach medycznych (Cyclotron production of 99m Tc). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, P12. Gumiela M., Gniazdowska E., Koźmiński P., Bilewicz A. Wydzielanie Tc-99m z aktywowanej w cyklotronie tarczy molibdenowej (Tc-99m separation from isotopically enriched 100 Mo via proton bombardment). II Ogólnopolska Konferencja Radiofarmaceutyczna, Łódź, Poland, , p. 43. Gumiela M., Gniazdowska E., Koźmiński P., Bilewicz A. Wydzielanie Tc-99m z aktywowanej w cyklotronie tarczy molibdenowej (Tc-99m separation from isotopically enriched 100 Mo via proton bombardment). ChemSession 13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, Streszczenia, p. 94.

115 PUBLICATIONS IN Ignasiak M.T., Scuderi D., Houée-Levin Ch., Pędziński T., Filipiak P., Rusconi F., Kciuk G., Bobrowski K., Marciniak B. Radiolytic and photolytic oxidation of methionine-containing peptides. 28th Miller Conference on Radiation Chemistry, Dead Sea, Israel, , p. 29. Jakowiuk A., Modzelewski Ł., Ptaszek S., Sartowska B. Systemy detekcji skażeń izotopami promieniotwórczymi dla obiektów jądrowych / Radioisotopes contamination detection systems for the nuclear facilities. I Międzynarodowa Konferencja Ochrony Radiologicznej, Cerna Hora, Czech Republic, , [2] p. Janowicz M., Buraczewska I., Kruszewski M., Sommer S., Wasyk I., Wojewódzka M., Lankoff A. DOSE-MATIC: a computational tool for biological dosimetry and biomonitoring. XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p. 81. Janowicz M., Buraczewska I., Kruszewski M., Sommer S., Wasyk I., Wojewódzka M., Lankoff A. DOSE-MATIC: a multiparametric computational tool for dose estimation and data analysis in biological dosimetry and biomonitoring. 40th Annual Meeting of the European Radiation Research Society, Dublin, Ireland, , W-72. Kalbarczyk P., Chajduk E., Pyszynska M., Fuks L., Polkowska-Motrenko H., Zuba M. Metody przygotowywania materiałów do badań biegłości wypracowane w Laboratorium Jądrowych Technik Analitycznych (Preparation of methods for materials to studying the proficiency elaborated in the Laboratory of Nuclear Analytical Methods). Konferencja naukowo-techniczna: Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, , p. 42. Kapka-Skrzypczak L., Brzóska K., Niedźwiecka J., Sawicki K., Czajka M., Popek S., Skrzypczak M., Kruszewski M. DNA damage and genetic polymorphisms: assessment of individual sensitivity of children environmentally exposed to pesticides. 11th International Conference on Environmental Mutagens, XI Congress of SBMCTA and IX Congress of ALAMCTA, Foz do Iguaçu, Brazil, , p Kapka-Skrzypczak L., Niedźwiecka J., Sawicki K., Cyranka M., Wasak M., Turski W.A., Kruszewski M. Susceptibility of children to environmental xenobiotics measured by cytokinesis-block MN assay. 5th International Congress of the Federation of the European Societies for Trace Elements and Minerals: Trace Elements in Avignon. Bridging Between New Advances and Public Health Issues, Avignon, France, , p Kapka-Skrzypczak L., Posobkiewicz M., Hołownia P., Niedźwiecka J., Sawicki K., Cyranka M., Kruszewski M. Assessing DNA damage in children environmentally exposed to pesticides through using the comet assay and the micronucleous test. 141st APHA Annual Meeting, Boston, USA, , [1] p. Kasperek A., Leszczuk E., Bilewicz A. Bioconjugated nanozeolites labeled with 223,224,225 Ra. The 20th International Symposium on Radiopharmaceutical Sciences May 2013, ICC JEJU, Jeju, Korea. Journal of Labelled Compounds and Radiopharmaceuticals, 56, Suppl. 1, S243 (2013). Kaźmierczak U., Banaś D., Braziewicz J., Choiński J., Czub J., Jaskóła M., Korman A., Kruszewski M., Lankoff A., Lisowska H., Malinowska A., Szefliński Z., Wojewódzka M. Validation of the Warsaw cyclotron for radiobiological research. XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p. 44. Kiegiel K., Abramowska A., Biełuszka P., Zielińska B., Chajduk E., Zakrzewska G. Ekstrakcja uranu z roztworów otrzymanych po jego ługowaniu z rud uranowych z następującą reekstrakcją do fazy wodnej (Extraction of uranium from solutions after its leaching from uranium ores followed by reextraction into the aqueous phase). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium naukowe w ramach projektu POIG /09, Warszawa, Poland, Streszczenia referatów, p. 14.

116 118 PUBLICATIONS IN Kiegiel K., Steczek Ł., Zakrzewska G. Zastosowanie kaliks[6]arenów jako makrocyklicznych ligandów kompleksujących uran (Application of calix[6]arenes as macrocyclic ligands complexing uranium). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium naukowe w ramach projektu POIG /09, Warszawa, Poland, Streszczenia referatów, p. 21. Kołacińska K. Konstrukcja optoelektronicznych detektorów dedykowanych do zastosowania w połączeniu z analizą przepływową (The construction of optoelectronic detectors dedicated to apply with flow analysis). ChemSession 13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, Streszczenia, p Kołacińska K., Koncki R. Application of optoelectric detectors in flow injection determination of ammonia using Nessler method. 18th International Conference on Flow Injection Analysis (18th ICFIA), Porto, Portugal, , p. 97. Kornacka E.M., Przybytniak G.K., Mirkowski K. Studies of interaction between inorganic and polymeric components in a hybrid system. 28th Miller Conference on Radiation Chemistry, Dead Sea, Israel, , p. 87. Kornacka E.M., Zagórski Z.P. Wpływ promieniowania jonizującego na życie na Ziemi korzyści i zagrożenia (Radiation effects of life on Earth the benefits and risks). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p. 93. Kosno K., Celuch M., Janik I., Pogocki D. Kinetyka rodnikowego utleniania nikotyny w roztworach wodnych (Kinetics of nicotine radical oxidation in aqueous solutions). XVII Mikrosympozjum: Kinetyczne metody badania mechanizmów reakcji w roztworach, Poznań, Poland, , K-8. Kosno K., Celuch M., Janik I., Pogocki D. Mechanism and kinetics of nicotine radical oxidation. 6th European Young Investigator Conference, Słubice, Poland, Book of abstracts, p. 28. Kosno K., Celuch M., Janik I., Pogocki D. Mechanism of nicotine radical reactions. 28th Miller Conference on Radiation Chemistry, Dead Sea, Israel, , p. 36. Kosno K., Celuch M., Janik I., Pogocki D. Mechanizm i kinetyka rodnikowych reakcji nikotyny (Mechanism and kinetics of nicotine radical reactions). ChemSession 13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, Streszczenia, p Kosno K., Celuch M., Janik I., Pogocki D. Radioliza impulsowa wodnych roztworów nikotyny i jej związków modelowych (Pulse radiolysis of nicotine and its model compounds aqueous solutions). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p Kowalska M., Węgierek-Ciuk A., Lisowska H., Kruszewski M., Sommer S., Wojewódzka M., Lankoff A. The uptake kinetics and genotoxic effects of silver nanoparticles in HepG2 and A549 cells. VI Polish Conference on Nanotechnology, Szczecin, Poland, , p Koźmiński P., Gniazdowska E. Ghrelin peptide labelled with technetium-99m complexes a potential diagnostic radiopharmaceuticals. The 20th International Symposium on Radiopharmaceutical Sciences May 2013, ICC JEJU, Jeju, Korea. Journal of Labelled Compounds and Radiopharmaceuticals, 56, Suppl. 1, S433 (2013) Kruszewski M., Buraczewska I., Lankoff A., Sommer S., Wójciuk K., Wójciuk G., Wojewódzka M. Dozymetria biologiczna dla potrzeb energetyki jądrowej (Biological dosimetry for nuclear power engineering).

117 PUBLICATIONS IN Konferencja naukowo-techniczna: Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, , p Kruszewski M., Dziendzikowska K., Oczkowski M., Krawczyńska A., Gromadzka-Ostrowska J., Niedźwiecka J., Sawicki K., Cyranka M., Kapka-Skrzypczak L. Biodistribution of silver nanoparticles in male Wistar rats and their possible interactions with pesticide toxicity. 5th International Congress of the Federation of the European Societies for Trace Elements and Minerals: Trace Elements in Avignon. Bridging Between New Advances and Public Health Issues, Avignon, France, , p Kruszewski M., Grądzka I., Bartłomiejczyk T., Chwastowska J., Sommer S., Grzelak A., Zuberek M., Lankoff A., Dusińska M., Wojewódzka M., Kapka-Skrzypczak L. Long term survival of human cells treated with silver nanoparticles corresponds to the formation of oxidative DNA damage. 11th International Conference on Environmental Mutagens, XI Congress of SBMCTA and IX Congress of ALAMCTA, Foz do Iguaçu, Brazil, , p Kubacki R., Brzóska K., Buraczewska I., Lankoff A., Sikorska K., Sommer S., Wojewódzka M., Kruszewski M., Wnuk M. Wysokomocowe impulsy broni elektromagnetycznej i ich skutki biologiczne (High-energy pulses of electromagnetic weapons and their biological effects). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p Kulka U., Ainsbury E.A., Atkinson M., Barquinero J.F., Bassinet C., Barrios L., Beinke C., Cucu A., Darroudi F., Fattibene P., Gil O., Gregoire E., Hadjidekova V., Haghdoost S., Herranz R., Jaworska A., Lindholm C., Mkacher R., Mört S., Fabregat N., Montoro A., Moquet J., Moreno M., Noditi M., Oestreicher U., Palitti F., Pantelias G., Popescu I., Prieto M.J., Romm H., Rothkamm K., Sabatier L., Sommer S., Terzoudi G., Testa A., Thierens H., Trompier F., Turai I., Vandersickel V., Vaz P., Voisin P., Vral A., Ugletveit F., Wieser A., Woda C., Wójcik A. RENEB Progress of the BioDose Network. 5th International MELODI Workshop, Brussels, Belgium, , [2] p Kulka U., Ainsbury E.A., Atkinson M., Barquinero J.F., Bassinet C., Barrios L., Beinke C., Cucu A., Darroudi F., Fattibene P., Gil O., Gregoire E., Hadjidekova V., Haghdoost S., Herranz R., Jaworska A., Lindholm C., Mkacher R., Mört S., Montoro A., Moquet J., Moreno M., Noditi M., Obazghi A., Oestreicher U., Palitti F., Pantelias G., Popescu I., Prieto M.J., Romm H., Rothkamm K., Sabatier L., Sommer S., Terzoudi G., Testa A., Thierens H., Trompier F., Turai I., Vandersickel V., Vaz P., Voisin P., Vral A., Ugletveit F., Wieser A., Woda C., Wójcik A. RENEB status quo of the European network of biodosimetry. 40th Annual Meeting of the European Radiation Research Society, Dublin, Ireland, , [1] p Kulka U., Ainsbury E.A., Atkinson M., Barquinero J.F., Bassinet C., Barrios L., Beinke C., Cucu A., Darroudi F., Fattibene P., Gil O., Gregoire E., Hadjidekova V., Haghdoost S., Herranz R., Jaworska A., Lindholm C., Mkacher R., Mörtl S., Montoro A., Moquet J., Moreno M., Ogbazhi A., Oestreicher U., Palitti F., Pantelias G., Popescu I., Prieto M.J., Romm H., Rothkamm K., Sabatier L., Sommer S., Terzoudi G., Testa A., Thierens H., Trompier F., Turai I., Vandersickel V., Vaz P., Voisin P., Vral A., Ugletveit F., Woda C., Wójcik A. RENEB Realizing the European network of biological dosimetry. Global Conference on Radiation Topics - ConRad 2013, Munich, Germany, Abstracts, [1] p Kunicki-Goldfinger J.J. Glass in Central Europe from late-medieval to end of pre-industrial era: A materials science approach. The 23rd International Congress on Glass, Prague, Czech Republic, Vydavatelstvi Ceske sklarske spolecnosti, Teplice 2013, p Kużelewska I., Chajduk E., Polkowska-Motrenko H. Opracowanie procedury mineralizacji mikrofalowej Apatite Concentration certyfikowanego materiału odniesienia i oznaczenie w nim śladowych zawartości metali ziem rzadkich z użyciem ICP-MS (Elaboration of mineralization microwave procedure of apatite concentration certified reference material and determination in this material trace content of rare earth elements using ICP-MS). ChemSession 13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, Streszczenia, p. 135.

118 120 PUBLICATIONS IN Leszczuk E., Piotrowska A., Bilewicz A., Morgenstern A., Bruchertseifer F. Modyfikowane polietylenoglikolem nanocząstki TiO 2 jako nośniki radionuklidów 225 Ac i 212 Pb dla celowanej radioterapii (TIO 2 nanoparticles modified with polyethylene glycol as carriers for 225 Ac and 212 Pb for targeted radiotherapy). II Ogólnopolska Konferencja Radiofarmaceutyczna, Łódź, Poland, , p Leszczuk E., Piotrowska A., Bilewicz A., Morgenstern A., Bruchertseifer F. TiO 2 nanoparticles as carries of 225 Ac/ 213 Bi in vivo generator. 8th International Symposium on Targeted Alpha Therapy, Oak Ridge, Tennessee, USA, p Lisowska H., Fortuna B., Fendrych Ż., Nowakowska J., Stankiewicz M., Węgierek-Ciuk A., Braziewicz J., Wójcik A., Lankoff A. The effect of hypothermia on the ionizing radiation-induced DNA damage and cell cycle progression in HepG2 and A549 cells. XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p Łada W., Wawszczak D., Deptuła A., Brykała M., Olczak T., Smoliński T., Wojtowicz P., Rogowski M., Miłkowska M. Badania nad ekstrakcją cieczową uranu i pierwiastków towarzyszących z roztworów po ługowaniu rud miedzianonośnych i odpadów poflotacyjnych (Solvent extraction of uranium and other elements from copper ores and flotation wastes). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, P Łada W., Wawszczak D., Deptuła A., Narbutt J., Iller E., Królicki L. Nowa technologia otrzymywania sferycznych ziaren tlenku itru dla medycyny nuklearnej (New technology for production of yttrium oxide microspheres for nuclear medicine). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, K Łuczyńska-Szymczak K., Starosta W. Badania korelacji pomiędzy właściwościami strukturalnymi nanomateriałów na bazie tytanianów a ich zdolnością sorpcyjną dla wybranych metali (Studies of the correlation between structural properties of titanate nanostructures and the sorption capacity for selected metal ions). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, K Łyczko M., Bilewicz A., Krajewski S., Wąs B., Choiński J., Jastrzębski J., Stolarz A., Chudyka J., Szkliniarz K., Zipper W. Kompleksy rodu z astatem i jodem jako potencjalne radiofarmaceutyki do alfa terapii (Complexes of rhodium with astatine and iodine as potential pharmaceuticals). II Ogólnopolska Konferencja Radiofarmaceutyczna, Łódź, Poland, , p Męczyńska-Wielgosz S., Wojewódzka M., Lankoff A., Iwaneńko T., Kruszewski M. Nanocząstki srebra hamują popromienną naprawę DNA w komórkach HepG2 (Nanoparticles of silver brake the part-irradiation repair of DNA in the HepG2 cells). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p Migdał W., Gryczka U., Bertrandt J., Nowicki T., Pytlak R. Radiation methods in decision support system for food safety. 17th International Meeting on Radiation Processing, Shanghai, China, , p Miloch J., Kciuk G., Kocia R., Rak J. Induced by solvated electrons damage to brominated single stranded oligonucleotide trimers. Central European School on Physical Organic Chemistry: From Molecule to Material Chemistry for the Future, Przesieka, Poland, , L Miśkiewicz A., Zakrzewska G., Jaworska-Sobczak A. Ługowanie uranu z rud uranowych z separacją faz w membranowym aparacie z przepływem helikoidalnym (Leaching of uranium from uranium ores with the separation of phares in a membrane apparatus with a helicoidal flow). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium naukowe w ramach projektu POIG /09, Warszawa, Poland, Streszczenia referatów, p. 12.

119 PUBLICATIONS IN Miśkiewicz A., Zakrzewska-Trznadel G., Niesłuchowska W., Harasimowicz M. Hybrid UF/sorption and MF/sorption processes using inorganic sorbents for radioactive waste treatment. 6th Membrane Conference of Visegrad Countries PERMEA 2013, Warsaw, Poland, Proceedings. J. Krzysztoforski, M. Szwast (eds.), p Modzelewski Ł., Jakowiuk A., Kowalska E., Pieńkos J., Sartowska B. Urządzenia do pomiaru promieniowania i kontroli zagrożenia radiacyjnego opracowane w Instytucie Chemii i Techniki Jadrowej. / Devices for radiation measurements and control of radiation risk developed at the Institute of Nuclear Chemistry and Technology in Warsaw. I Międzynarodowa Konferencja Ochrony Radiologicznej, Cerna Hora, Czech Republic, , [4] p Narbutt J., Ozimiński W.P., Wodyński A. Teoretyczna ocena przyczyn selektywności ligandów bis-triazynylobipirydynowych w procesie oddzielania ameryku(iii) od lantanowców metodą ekstrakcji ciecz-ciecz (Reasons of the selectivity of bis-triazinyl-bipyridine ligands in the process of solvent extraction separation of americium(iii) from lanthanides a theoretical approach). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, K Niesłuchowska W., Miśkiewicz A., Zakrzewska-Trznadel G., Kulisa K. Zastosowanie biosorbentów w procesach hybrydowych UF/sorpcja do usuwania wybranych radionuklidów z niskoaktywnych odpadów promieniotwórczych (Application of biosorbents in UF/sorption hybrid processes for removal of selected radionuclides from low-level radioactive wastes). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, P Nowicki T., Pytlak R., Waszkowski R., Zawadzki T., Migdał W., Bertrandt J. Creating and calibrating models of food-borne epidemics. Annals of Nutrition & Metabolism, 63, Suppl. 1, 1027 (2013) Nyga M., Grodkowski J., Mirkowski J., Szreder T. Generowanie rodnika utleniającego I 2 i jego reaktywność w cieczach jonowych (Generation of an oxidation radical I 2 and its reactivity in ionic liquids). XVII Mikrosympozjum: Kinetyczne Metody Badania Mechanizmów Reakcji w Roztworach, Poznań, Poland, , P Olszewska W., Kiegiel K., Gajda D., Zakrzewska G., Abramowska A., Wołkowicz S. Projekt procesowy instalacji pozyskiwania uranu z rud uranowych i analiza kosztów (Design process of the installation for obtainig uranium from uranium ores and analysis of costs). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium naukowe w ramach projektu POIG /09, Warszawa, Poland, Streszczenia referatów, p Oszczak A., Fuks L., Rejnis M. Materiały pochodzenia naturalnego jako sorbenty radionuklidów z roztworów wodnych (Materials of natural origin as sorbents for radionuclides from aqueous solutions). Konferencja naukowo-techniczna: Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, , pp Oszczak A., Fuks L., Sartowska B., Sternik D. Alginian wapnia i chitozan jako potencjalne sorbenty radionuklidów z roztworów wodnych (Calcium alginate and chitosan as potential sorbents radionuclides from aqueous solutions). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, P Oszczak A., Zakrzewska G. Fosforyty jako potencjalne źródła uranu (Phosphites as a potential source of uranium). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium naukowe w ramach projektu POIG /09, Warszawa, Poland, Streszczenia referatów, p Pędziński T., Bobrowski K., Ignasiak M., Kciuk G., Hug G.L., Lewandowska-Andralojc A., Marciniak B. 3-Carboxybenzophenone (3CB) as a new sensitizer in the photooxidation of sulfur-containing peptides in aqueous solution. Spectral, kinetic and acid-base properties of selected benzophenone derivatives.

120 122 PUBLICATIONS IN 2013 Radiolytic and photolytic oxidation of methionine-containing peptides. 28th Miller Conference on Radiation Chemistry, Dead Sea, Israel, , p Polkowska-Motrenko H., Fuks L., Kalbarczyk P., Chajduk E., Dudek J., Pyszynska M., Zuba M., Oszczak A. Metody przygotowywania materiałów do badań biegłości (PT) dotyczących oznaczania radionuklidów procedury IChTJ (Preparation of test materials for determination of radionuclides the INCT approaches). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, P Polkowska-Motrenko H., Smolik M., Danko B., Jakóbik-Kolon A. Analiza wysokiej czystości cyrkonu metodą NAA (Analysis of high purity zirconium by NAA). XXII Poznańskie Konwersatorium Analityczne Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków, Poznań, Poland, , p Przybytniak G. Fizykochemiczne i strukturalne efekty radiacyjne w polimerach (Physicochemical and structural radiation affects in polymers). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p Przybytniak G., Boguski J. Ocena starzenia kabli elektrycznych niskiego napięcia zainstalowanych w elektrowniach jądrowych (Evaluation of aging of electric cables of low voltage installed in nuclear power stations). Konferencja naukowo-techniczna: Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, , p Ptaszek S., Chmielewski A., Sartowska B., Jakowiuk A., Modzelewski Ł., Sommer S. Analiza potencjału polskich firm pod kątem możliwości wykonywania dostaw systemów ochrony radiologicznej dla bezpiecznej eksploatacji obiektów jądrowych / Potential analysis of Polish companies in terms of ability to perform radiological protection systems of supplies for the safe operation of nuclear facilities. I Międzynarodowa Konferencja Ochrony Radiologicznej, Cerna Hora, Czech Republic, , [2] p Rejnis M., Herdzik-Koniecko I., Narbutt J. Kompleksowanie produktów rozszczepienia w fazie wodnej, zapobiegające ich współekstrakcji z aktynowcami w 2. cyklu procesu GANEX (Complexation of fission products in the aqueous phase to prevent their co-extraction with the actinides in the 2nd cycle GANEX process). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, P Romm H., Ainsbury E., Barnard S., Barquinero J.F., Barrios L., Beinke C., Deperas M., Gregoire E., Kulka U., Lindholm C., Moquet J., Puig R., Oestreicher U., Rothkamm K., Sommer S., Thierens H., Vral A., Vandersickel V., Wójcik A. Validation of semi-automatic scoring of dicentric chromosomes after simulation of 3 different irradiation scenarios. Global Conference on Radiation Topics ConRad 2013, Munich, Germany, Abstracts, [1] p Romm H., Bajinskis A., Oestreicher U., Thierens H., Vral A., Rothkamm K., Ainsbury E., Benderitter M., Voisin P., Fattibene P., Lindholm C., Barrios L., Sommer S., Woda C., Scherthan H., Beinke C., Vojnovic B., Trompier F., Jaworska A., Wójcik A. MULTIBIODOSE: new development of multi-disciplinary biodosimetric tools to manage a high scale radiological casualty. 8th Future Security Security Research Conference, Berlin, Germany, , p Samczyński Z. Oznaczanie uranu metodą UV/VIS. Eliminacja wpływu jonów interferujących (Determination of uranium by means of UV/Vis. Elimination of the influence of interfering ions). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium naukowe w ramach projektu POIG /09, Warszawa, Poland, Streszczenia referatów, p Sartowska B., Barlak M., Waliś L., Starosta W., Senatorski J. Poprawa właściwości tribologicznych stali AISI 316L przez stopowanie pierwiastkami ziem rzadkich przy wykorzystaniu intensywnych impulsów plazmowych (Improvement of tribological properties of the AISI 316L steel by alloying with REE with the use of intensive plasma beams).

121 PUBLICATIONS IN Konferencja naukowo-techniczna: Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, , p Sartowska B., Barlak M., Waliś L., Starosta W., Senatorski J., Starosta W. Formation of the surface layer with improved tribological properties on austenitic stainless steel by alloying with REE using HIPPB. 6th International Conference on Solidification and Gravity, Miskolc-Lillafüred, Hungary, , p Sartowska B., Barlak M., Waliś L., Starosta W., Senatorski J. Surface layer of austenitic stainless steel formed by alloying with REE using high intense pulsed plasma beams (HIPPB). V Ogólnopolska Konferencja Naukowa Nowoczesne Technologie w Inżynierii Powierzchni, Łodź Spała, Poland, , p Sartowska B., Starosta W., Pieniążek A., Orelovitch O., Apel P. Template synthesis of nanoscale porous materials nanoscale metal-organic frameworks (MOFs). 3rd International Conference on Multifunctional, Hybrid and Nanomaterials, Sorrento, Italy, , [1] p Sartowska B., Waliś L., Pańczyk E., Dudek J., Weker W., Widawski M. Skład pierwiastkowy w mikroobszarach średniowiecznych denarów krzyżowych (Elemental composition in microareas of the mediaeval denars). XIII Konferencja: Analiza chemiczna w ochronie zabytków, Warszawa, Poland, , p Sikorska K., Buraczewska I., Wasyk I., Bartłomiejczyk T., Sommer S., Lankoff A., Wojewódzka M., Kruszewski M. Szybka analiza dicentryków w celu oszacowania dawki pochłoniętej (Rapid analysis of dicentric to estimate the absorbed dose). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p Skotnicki K. Badanie pochodnych chinoksalinonu przy użyciu radiolizy impulsowej (Studies of the quinoxaline derivatives by means of pulse radiolysis). ChemSession 13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, Streszczenia, p Skotnicki K. Badanie pochodnych chinoksalinonu przy użyciu radiolizy impulsowej (Studies of the quinoxaline derivatives by means of pulse radiolysis). XVII Mikrosympozjum: Kinetyczne Metody Badania Mechanizmów Reakcji w Roztworach, Poznań, Poland, , K Skotnicki K. Pulse radiolysis study of quinoxalin-2-one in aqueous solutions. 6th European Young Investigator Conference, Słubice, Poland, Book of abstracts, p Skotnicki K., de La Fuente J., Bobrowski K. Radioliza impulsowa pochodnych chinoksalin-2-onu (Pulse radiolysis of quinoxaline-2 derivatives). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p Smoliński T., Deptuła A., Łada W., Wawszczak D., Olczak T., Brykała M., Rogowski M., Wojtowicz P., Zaza F. Synteza perowskitu komponentu materiałów typu SYNROC z wykorzystaniem kompleksowej metody zol-żel (Synthesis of perovskite one of the component of SYNROC materials by CSGP). ChemSession 13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, Streszczenia, p Smoliński T., Deptuła A., Łada W., Wawszczak D., Olczak T., Brykała M., Wojtowicz P., Rogowski M., Zaza F. Metoda zestalania odpadów radioaktywnych w perowskicie (Method for the solidification of radioactive wastes in perovskite). Konferencja naukowo-techniczna: Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, , p Smoliński T., Deptuła A., Łada W., Wawszczak D., Olczak T., Brykała M., Wojtowicz P., Rogowski M., Zaza F.

122 124 PUBLICATIONS IN 2013 Synteza perowskitu komponentu materiałów typu SYNROC z wykorzystaniem kompleksowej metody zol-żel (Complex sol-gel process for the synthesis of perovskite component of SYNROC materials). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, P Sommer S., Montero Gil O., Jaworska A., Kulka U., Oestreicher U., Ugletveit F., Vas P., Romm H. Critical parameters that influence efficient cooperation inside the biological dosimetry network (RENEB) in an emergency situation. Global Conference on Radiation Topics ConRad 2013, Munich, Germany, Abstracts, [2] p Sommer S., Wewiór I., Buraczewska I., Bartłomiejczyk T., Szumiel I., Kruszewski M. PCC methods in biological dosimetry: PCC fragments, PCC rings, unusually long PCC fragments, the rapid interphase chromosome assay (RICA). Global Conference on Radiation Topics ConRad 2013, Munich, Germany, Abstracts, [1] p Steczek Ł., Narbutt J. Reekstrakcja uranu(vi) z roztworów organicznych nowym hydrofilowym ligandem poli-n-dentnym (Reextraction of uranium(vi) from organic solutions with a new hydrophilic poly-n-dentate ligand). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium naukowe w ramach projektu POIG /09, Warszawa, Poland, Streszczenia referatów, p Sterniczuk M., Sadło J., Bugaj A., Strzelczak G., Michalik J. EPR study of paramagnetic center generated radiolytically in zeolites. Porous and Powder Materials Symposium and Exhibition PPM 2013, Cesme Izmir, Turkey, , p Sterniczuk M., Sadło J., Strzelczak G., Bugaj A., Michalik J. Paramagnetic centres generated radiolytically in molecular sieves exposed to carbon monoxide. 6th European Young Investigator Conference, Słubice, Poland, Book of abstracts, p Stępień K., Wylazowska A., Konarska A., Wolszczak M., Węgierek-Ciuk A., Kruszewski M., Wojewódzka M., Lankoff A. Influence of selected protoberberines on the frequency of ionizing radiation-induced micronuclei in HeLa cells. XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p Sulich A., Grodkowski J., Mirkowski J., Kocia R. Radioliza impulsowa roztworu acetofenonu w wybranej cieczy jonowej (The pulse radiolysis of an acetophenone solution in a selected ionic liquid). XVII Mikrosympozjum: Kinetyczne metody badania mechanizmów reakcji w roztworach, Poznań, Poland, , P Sulich A., Grodkowski J., Mirkowski J., Kocia R. Wczesne etapy radiolizy wybranych rozcieńczalników w warunkach procesu SANEX (The early periods of the selected diluents radiolysis in the SANEX process conditions). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, K Sulich A., Grodkowski J., Mirkowski J., Kocia R., Foreman M.R.St.J., Hudson M.J. Kinetyka reakcji pierwotnych produktów radiolizy oktanolu z benzofenonem i ligandami z rodziny BT(B)P (Kinetics of the reaction of original radiolysis products of octanol with benzophenone and ligands from the BT(B)P family). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p Sulich A., Grodkowski J., Mirkowski J., Kocia R., Foreman M.R.St.J., Hudson M.J. Radioliza roztworów wybranych ligandów z rodziny BT(B)P w oktanolu (Radiolysis of the selected ligands from the BT(B)P family in octanol). ChemSession 13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, Streszczenia, p Szczygłów K. Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych (Analysis of the possibilities of obtaining uranium from domestic resources for nuclear engineering).

123 PUBLICATIONS IN Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium naukowe w ramach projektu POIG /09, Warszawa, Poland, Streszczenia referatów, p Trojanowicz M. Recent developments in miniaturization of flow analysis. 18th International Conference on Flow Injection Analysis (18th ICFIA), Porto, Portugal, , p Walo M., Przybytniak G. Biokompatybilizacja powierzchni poliuretanów za pomocą radiacyjnie inicjowanej polimeryzacji RAFT (Biocompatibility of the surface of polyurethanes by means of radiation-induced polymerization). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p Walo M., Przybytniak G. Functionalization of poly(ester-urethane) surface by radiation-induced grafting. 28th Miller Conference on Radiation Chemistry, Dead Sea, Israel, , p Walo M., Przybytniak G. Grafting of N-isopropylacrylamide onto polyurethane surface by gamma initiated RAFT polymerization. 17th International Meeting on Radiation Processing, Shanghai, China, , pp Wasyk I., Buraczewska I., Lankoff A., Sommer S., Wojewódzka M., Kruszewski M. Automatyczny test mikrojądrowy w komórkach ludzkiej osteosarkomy i limfocytach kurzych (Automatic micronuclei test in human osteosarcoma cells and chicken lymphocytes). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p Wawszczak D., Łada W., Miłkowska M., Deptuła A., Olczak T., Brykała M., Smoliński T. Badania nad ługowaniem rud miedzianonośnych i odpadów poflotacyjnych (Studies of leaching of copper ores and flotation wastes). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, K Węgierek-Ciuk A., Arabski M., Lisowska H., Kędzierawski P., Florek A., Góźdź S., Wójcik A., Lankoff A. Relationship between chromosomal radiosensitivity, SNP polymorphisms in XRCC1, XRCC3, OGG1 genes and susceptibility to prostate cancer. 40th Annual Meeting of the European Radiation Research Society, Dublin, Ireland, , M Węgierek-Ciuk A., Lisowska H., Wójcik A., Kędzierawski P., Florek A., Góźdź S., Lankoff A. Analiza promieniowrażliwości in vitro i in vivo limfocytów pacjentek z nowotworem szyjki macicy korelacja z odczynami popromiennymi (Analysis of in vitro and in vivo radiosensitivity of lymphocytes from cervix cancer patients correlation with side effects after radiotherapy). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p Wojewódzka M., Sommer S., Sikorska K., Lankoff A., Kruszewski M. Usefulness of the premature chromosome condensation assay for biological dosimetry comparison with the comet assay, the micronucleus assay and the γ-h2ax assay. 10th International Comet Assay Workshop, Porto, Portugal, Book of abstracts, p Wojtowicz P., Deptuła A., Łada W., Wawszczak D., Olczak T., Smoliński T., Brykała M., Rogowski M., Chmielewski A.G. Synteza i badanie struktury żeli krzemiankowych metodą zol-żel (Synthesis and investigation of the structure of silica gels by sol-gel method). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, Streszczenia, P Wójcik A., Romm H., Oestreicher U., Thierens H., Vral A., Rothkamm K., Ainsbury E., Bendertitter M., Barquinero F., Fattibene P., Lindholm C., Barrios L., Sommer S., Woda K., Scherthan H., Beinke C., Vojnovic B., Trompier F., Bajinskis A., Jaworska A. MULTIBIODOSE: multi-disciplinary biodosimetric tools to manage high scale radiological casualties results and conclusions. Global Conference on Radiation Topics ConRad 2013, Munich, Germany, Abstracts, [1] p.

124 126 PUBLICATIONS IN Wójciuk G., Wójciuk K., Kruszewski M. Pentapeptydowa pochodna DTPA znakowana izotopem lutetu-177 i jej potencjalne zastosowanie w diagnostyce i terapii antynowotworowej (Pentapeptide derivative of DTPA labeled of lutetium-177 and its potential use in diagnosis and therapy applications). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p Wójciuk K., Wójciuk G., Kruszewski M. Właściwości nowych peptydowych nośników izotopu jodu-131 (Properties of new peptide carriers of iodine-131). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, Materiały konferencyjne, p Zakrzewska-Trznadel G., Kiegiel K., Abramowska A., Zielińska B., Biełuszka P., Steczek Ł., Chajduk E., Wołkowicz S. Recovery of uranium from post-leaching solutions by solvent extraction: state of the art and new technological possibilities. Nuclear 2013: The 6th Annual International Conference on Sustainable Development through Nuclear Research and Education, Pitesti, Romania, Book of abstract, p Zakrzewska-Trznadel G., Kiegiel K., Frąckiewicz K., Herdzik I., Zielińska B., Biełuszka P., Gajda D., Miśkiewicz A., Jaworska A., Szczygłów K., Dybczyński R., Danko B., Polkowska-Motrenko H., Samczyński Z., Chajduk E., Chwastowska J., Bartosiewicz I., Wołkowicz S., Miecznik J.B. Analiza możliwości pozyskania uranu dla energetyki jądrowej z zasobów krajowych (Analysis of the possibility of uranium supply from domestic resources). Konferencja naukowo-techniczna: Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, , pp Zakrzewska-Trznadel G., Miśkiewicz A., Harasimowicz M., Niesłuchowska W., Nieścior P., Kulisa K. Rozwój technik i technologii w zakresie postępowania z nisko- i średnioaktywnymi odpadami promieniotwórczymi: procesy hybrydowe (Development of techniques and technologies in proceeding with low and medium level radioactive wastes: hybrid processes). Konferencja naukowo-techniczna: Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, , p Zakrzewska-Trznadel G., Miśkiewicz A., Jaworska A., Kiegiel K., Gajda D., Bilewicz A., Sartowska B., Kruszewski M. Włączanie nowych krajów członkowskich Unii Europejskiej w struktury zaawansowanych badań w ramach Euroatomu (New MS linking for an advanced cohesion in Euratom (NEWLANCER)). Konferencja naukowo-techniczna: Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, , p Zakrzewska-Trznadel G., Miśkiewicz A., Mysłek-Laurikainen B. Wdrażanie polityki współuczestnictwa społeczeństwa w procesach decyzyjnych związanych ze składowaniem odpadów radioaktywnych (Implementing public participation approaches in radioactive waste diposal (IPPA)). Konferencja naukowo-techniczna: Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, , p Zimek Z., Duch P., Roman K. Electron accelerator for R&D study and radiation processing. 11th International Topical Meeting on Nuclear Applications of Accelerators, Bruges, Belgium, , pp Zuba M., Chajduk E., Polkowska-Motrenko H. Wydzielanie 226 Ra z próbek środowiskowych dla pomiarów przy użyciu spektrometrii mas z jonizacją w plazmie indukcyjnie sprzężonej (ICP-MS) i spektrometrii promieniowania gamma (Separation of 226 Ra from environmental samples for measurements with the use of ICP-MS and gamma radiation spectrometry). ChemSession 13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, Streszczenia, p. 240.

125 PUBLICATIONS IN 2013 SUPPLEMENT LIST OF THE PUBLICATIONS IN Chajduk E. Neutronowa analiza aktywacyjna (Neutron activation analysis). In: Platynowce. Zastosowanie i metody oznaczania. Pod red. B. Godlewskiej-Żyłkiewicz i K. Pyrzyńskiej. Wydawnictwo MALAMUT, Warszawa 2012, pp Eppard E., Pruszyński M., Mikołąjczak R., Koumarianou E., Miederer M., Baum R., Roesch F. 44 Sc-labelled octreotides: Synthesis, stability, in vitro, ex vivo, and in vivo behaviour. Journal of Nuclear Medicine, 53, Suppl. 1, 458 (2012). 3. Kasperek A., Bilewicz A. Nieorganiczne nanocząstki w medycynie nuklearnej (Inorganic nanoparticles in nuclear medicine). Wiadomości Chemiczne, 66, 7-8, (2012). 4. Leszek P., Sochanowicz B., Brzóska K., Komuda-Leszek E., Danko B., Kuśmierski K., Piotrowski W., Rywik T., Różański J., Kruszewski M. Myocardial erythropoietin and its receptor in heart failure beyond treatment of anemia. Congress of the European Society of Cardiology, Munchen, Germany, European Heart Journal, 33, Suppl. 1, (2012). 5. Leszek P., Sochanowicz B., Brzóska K., Komuda-Leszek E., Kraj L., Danko B., Kolsut P., Piotrowski W., Różański J., Kruszewski M. Hepcidin a key regulator of iron homeostasis in advanced heart failure. Congress of the European Society of Cardiology, Munchen, Germany, European Heart Journal, 33, Suppl. 1, 1104 (2012). 6. Leszek P., Sochanowicz B., Brzóska K., Komuda-Leszek E., Kuśmierczyk M., Piotrowski W., Rywik T., Różański J., Kruszewski M. Heart failure remodeling could the failing myocytes be the additional source of endogenous erythropoietin? Congress of the European Society of Cardiology, Munchen, Germany, European Heart Journal, 33, Suppl. 1, 1102 (2012). 7. Leszek P., Sochanowicz B., Brzóska K., Piotrowski W., Danko B., Kuśmierczyk M., Różański J., Rywik T., Kruszewski M. Heart failure remodeling local endogeneous erythropoietin and erythropoietin receptor expression. Basic Cardiovascular Sciences Scientific Session, New Orlean, USA, Circulation Research, 111, 4, Suppl. S, 236 (2012). 8. Leszek P., Sochanowicz B., Szperl M., Kolsut P., Brzóska K., Piotrowski W., Rywik T., Danko B., Różański J., Kruszewski M. A proper characterization of myocardial iron and homeostasis based on serum markers in advanced heart failure. 2nd Congress of the European Society of Cardiology Council on Basic Cardiovascular Science Frontiers in Cardiovascular Biology, London, England, Cardiovascular Research, 93, Suppl. 1, S17 (2012). 9. Pruszyński M., Majkowska-Pilip A., Loktionowa N.S., Eppart E., Roesch F. Radiolabelling of DOTATOC with the long-lived positron emitter 44 Sc. Applied Radiation and Isotopes, 70, (2012). 10. Przybytniak G., Kornacka E., Sadło J., Michalik J., Buczkowski M., Sartowska B., Starosta W. Radiation supporting synthesis and curing of nanocomposites suitable for practial application. In: Report of the second RCM on radiation curing of composites for enhancing the features and utility in health care and industry, Cairo, Egypt, November Working material. IAEA, Vienna 2012, pp

126 128 NUKLEONIKA 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. 1/2013 Proceedings of the 9th All-Polish Seminar on Mössbauer Spectroscopy OSSM 2012, June 2012, Lublin - Kazimierz Dolny, Poland 1. Inter- and inframolecular dynamics of iron porphyrins K. Dziedzic-Kocurek, D. Okła, J. Stanek 2. Mosgraf-2009: The Mössbauer data processing suite of applications Ł. Duraj, K. Ruebenbauer 3. The Mössbauer spectrometer MsAa-4 R. Górnicki, K. Ruebenbauer Gd isomer shifts. The case study: GdT 2 Si 2 K. Łątka 5. Mössbauer study of vacuum annealed Fe 100 x Ga x (10 x 35) thin films T. Szumiata, B. Górka, K. Brzózka, M. Gawroński, M. Gzik-Szumiata, A. Javed, N.A. Morley, M.R.J. Gibbs 6. Crystal electric field parameters determination for R 2 Fe 14 B compounds based on Yamada-Kato model B.F. Bogacz, A.T. Pędziwiatr 7. Chemical preparation of core-shell nanoparticles B. Kalska-Szostko, U. Wykowska, A. Basa, K. Szymański 8. Sedimentation of Fe 2 O 3 and metallic iron nanoparticles exhibiting Brownian movement P. Fornal, J. Stanek 9. Structural, magnetic, and Mössbauer effect studies of bornite J. Przewoźnik, J. Żukrowski, Ł. Gondek, K. Gąska, A. Lemański, C. Kapusta, A. Piestrzyński 10. Hyperfine interactions and irreversible magnetic behavior in multiferroic Aurivillius compounds E. Jartych, K. Gąska, J. Przewoźnik, C. Kapusta, A. Lisińska-Czekaj, D. Czekaj, Z. Surowiec 11. Hyperfine interactions in x Bi 0.95 Dy 0.05 FeO 3 -(1 x) Pb(Fe 2/3 W 1/3 )O 3 multiferroics P. Zachariasz, A. Stoch, P. Stoch, J. Maurin 12. X-ray diffraction, Mössbauer spectroscopy, and magnetoelectric effect studies of (BiFeO 3 ) x -(BaTiO 3 ) 1 x solid solutions K. Kowal, E. Jartych, P. Guzdek, P. Stoch, B. Wodecka-Duś, A. Lisińska-Czekaj, D. Czekaj 13. Mössbauer spectroscopy study of 60P 2 O 5-40Fe 2 O 3 glass P. Stoch, M. Ciecińska, P. Zachariasz, J. Suwalski, L. Górski, T. Wójcik 14. Ordering process in Fe-Al28Cr5 alloys studied by Mössbauer spectroscopy A. Hanc-Kuczkowska, J. Kansy, J. Deniszczyk

127 NUKLEONIKA Hyperfine interactions in (Cr 0.99 Fe 0.01 ) 3+x Si 1 x D. Satuła, K. Szymański, W. Olszewski, B. Kalska-Szostko, J. Waliszewski, K. Rećko 16. Hydrogen ordering effects in Laves-phase YFe 2 A. Ostrasz 17. Magnetic interactions in frozen solutions of ironporphyrins K. Dziedzic-Kocurek, D. Okła, J. Stanek 18. Synthesis and characterization of iron-cobalt nanoparticles embedded in mesoporous silica MCM-41 Z. Surowiec, M. Wiertel, M. Budzyński, W. Gac 19. Thermodynamic properties of Au-Fe alloys studied with 57 Fe Mössbauer spectroscopy R. Idczak, R. Konieczny, J. Chojcan 20. Structure of friction products and the surface of tribological system elements K. Brzózka, W. Żurowski, B. Górka 21. Structural and magnetic properties of the as-cast Nd 10 Fe 83 Zr 1 B 6 ribbons, studied by X-ray diffraction and Mössbauer spectroscopy A. Ceglarek, D. Płusa, P. Pawlik, P. Gębara 22. Chemical, magnetic and Mössbauer effect analysis of road dust from expressway T. Szumiata, M. Gawroński, B. Górka, K. Brzózka, R. Świetlik, M. Trojanowska, M. Strzelecka 23. Phase constitution of an LaFe 11.0 Co 0.8 (Si 0.4 Al 0.6 ) 1.2 alloy investigated by Mössbauer spectroscopy P. Gębara, P. Pawlik, J.J. Wysłocki, M. Szwaja 24. Structure of the superficial region and mechanical properties of nitrided cast steels B. Górka, T.W. Budzynowski, K. Brzózka 25. Point defects in the B2-phase region of the Fe-Al system studied by Mössbauer spectroscopy and X-ray diffraction A. Hanc-Kuczkowska 26. Phase composition of metallurgical slag studied by Mössbauer spectroscopy I. Jonczy, J. Stanek 27. Hyperfine interactions in Tb 0.27 x Y x Dy 0.73 Fe 2 compounds at 295 K A. Krawczyk, A. Zwoźniak, P. Guzdek, P. Stoch, P. Zachariasz, J. Suwalski, J. Pszczoła 28. An application of Mössbauer spectroscopy in the studies of iron-molybdenum silica mesoporous materials Z. Surowiec, M. Wiertel, A. Marynowska, W. Gac, W. Zawadzki 29. Structure and hyperfine interactions of multiferroic Bi m+1 Ti 3 Fe m 3 O 3m+3 ceramics prepared by mechanical activation M. Mazurek, E. Jartych, D. Oleszak 30. Study of B8-type solid solutions of Al and Si in manganese antimonide M. Budzyński, V.I. Mitsiuk, V.M. Ryzhkovskii, Z. Surowiec, T.M. Tkachenka 31. Correlations between hyperfine magnetic field and some macroscopic magnetic quantities in mechanosynthesized Co x Fe y Ni z alloys T. Pikula 32. Characterization of phase constitution and magnetic properties of the hard magnetic nanocrystalline Nd 9.5 Fe B Nb 5 alloy ribbons M. Szwaja, K. Pawlik, J.J. Wysłocki, P. Pawlik, P. Gębara 33. Mössbauer investigation of some bcc, Fe-based, multicomponent alloys W. Olszewski, K. Szymański, D. Satuła, D. Oleszak 34. Mössbauer investigations of Mn 2 x Fe x P 0.5 As 0.5 V.I. Mitsiuk, T.M. Tkachenka, M. Budzyński, Z. Surowiec, V.I. Valkov 35. Structural and magnetic properties of Sc(Fe 1 x Cu x ) 2 compounds studied by means of Mössbauer effect and neutron diffraction M. Wiertel, Z. Surowiec, M. Budzyński, J. Sarzyński, A.I. Beskrovnyi 36. Hyperfine interactions in Dy(Co 0.4 x Ni x Fe 0.6 ) 2 compounds at 295 K A. Zwoźniak, A. Krawczyk, P. Stoch, P. Guzdek, P. Zachariasz, J. Suwalski, J. Pszczoła

128 130 NUKLEONIKA Proceedings of the 40th Polish Seminar on Positron Annihilation PSPA'2012, June 2012, Kazimierz Dolny, Poland 37. Positrons in naphthalene. Critical remarks on the relation between o-ps lifetime and void size T. Goworek, B. Zgardzińska, J. Wawryszczuk 38. Photoluminescence and positron annihilation lifetime studies on pellets of ZnO nanocrystals A. Karbowski, K. Fedus, J. Patyk, Ł. Bujak, K. Służewski, G. Karwasz 39. PALS investigation of resorcinol under high pressure M. Tydda, B. Jasińska, A. Pieniążek 40. Influence of neoplastic therapy on the investigated blood using positron annihilation lifetime spectroscopy R. Pietrzak, S. Borbulak, R. Szatanik 41. Uniqueness of studies on electron densities in the extended momentum space G. Kontrym-Sznajd 42. Utilization of symmetry of solids in some experiments G. Kontrym-Sznajd 43. Momentum distributions in positron annihilation with tightly bound electrons in Al E. Boroński 44. Annealing behaviour of plastically deformed stainless steel studied by positron annihilation methods E. Dryzek, M. Sarnek, K. Siemek 45. Change of the defect structure in FeAl alloy as a result of its aging at ambient temperature J. Kansy, A. Hanc-Kuczkowska, D. Giebel 46. Positron annihilation in precious and common opals J. Chojcan, M. Sachanbiński, R. Idczak, R. Konieczny 47. Gas filling of SBA-15 silica micropores probed by positron annihilation lifetime spectroscopy (PALS) M. Gorgol, R. Zaleski, A. Kierys 48. Ortho-positronium migration in mesopores of MCM-41, MSF and SBA-3 R. Zaleski, A. Błażewicz, A. Kierys 49. Porosity structure in photon active glasses B. Jasińska, M. Śniegocka, R. Reisfeld, E. Zigansky 50. Positron annihilation studies of mesoporous iron modified MCM-41 silica M. Wiertel, Z. Surowiec, M. Budzyński, W. Gac CONTENTS OF No. 2/ Deuterium isotope effects in oxidation of dopamine by tyramine oxidase M. Pająk, W. Byszewska, M. Kańska 2. Synthesis and in vivo evaluation of both (2R,3R)-[ 123 I]- and (2S,3S)-[ 12 3I]-trans-2-hydroxy-5-((E)-3-(iodo)allyloxy)-3-(4-phenyl-1-piperazinyl) tetralin as SPECT radiotracer T. Assaad, A.H. Al Rayyes 3. Synthesis and biodistribution of both (±)-5-[ 18 F]-fluoroethoxy and (±)-5-[ 18 F]-fluoropropoxy piperazine analogs of benzovesamicol as vesicular acetylcholine transporter ligands (VAChT) T. Assaad, A.H. Al Rayyes 4. Tumor dose enhancement by gold nanoparticles in a 6 MV photon beam: a Monte Carlo study on the size effect of nanoparticles D. Pakravan, M. Ghorbani, M. Momennezhad 5. A new method of determining the parameters of thermonuclear plasma on the basis of multichannel polarimetric measurements J. Chrzanowski, Yu.A. Kravtsov 6. Correction methods for pulsed neutron source reactivity measurement in accelerator driven systems P. Gajda, J. Janczyszyn, W. Pohorecki

129 NUKLEONIKA Diffusion of helium in the perfect uranium and thorium dioxide single crystals L. Dąbrowski, M. Szuta 8. Adaptive neurofuzzy predictive control of nuclear steam generators Z. Ahmad 9. The PSA analysis of PWR emergency coolant injection availability following SBLOCA M. Borysiewicz, K. Bronowska, P. Kopka, K. Kowal, T. Kwiatkowski, A.M. Prusiński, P.A. Prusiński, G. Siess 10. Efficient dead time correction of G-M counters using feed forward artificial neural network M. Arkani, H. Khalafi, M. Arkani 11. A study of stable isotope composition of chosen foodstuffs from the Polish market K. Malec-Czechowska, R. Wierzchnicki 12. Determination of uranium concentrations in some building materials in Iraq L.A. Najam, N.F. Tawfiq, Q.A. Yassen 13. Algorithms for digital γ-ray spectroscopy Z. Guzik, T. Krakowski CONTENTS OF No. 3/2013 Proceedings of the 2nd Electron Magnetic Resonance Forum EMR-PL, May 2012, Częstochowa-Hucisko, Poland 1. Higher-order field-dependent terms in spin Hamiltonians for transition ions implications for high-magnetic field and high-frequency EMR measurements C. Rudowicz 2. Modelling of EMR data for Fe 2+ (S=2) ions in a [2Fe-2S] cluster in the reduced ferredoxin C. Rudowicz, D. Piwowarska, P. Gnutek 3. Interaction of diatomic molecules with nickel ions inside the channels of high silica zeolites an EPR and DFT study T. Mazur, K. Podolska, P. Pietrzyk, Z. Sojka 4. EPR study of ZnO:Co thin films grown by the PLD method B. Cieniek, I. Stefaniuk, I. Virt 5. A review of phase transitions in RbIn-molybdate M.B. Zapart, W. Zapart 6. Localized states in nanocarbons W. Kempiński, M. Kempiński, D. Markowski, S. Łoś 7. Bloch-Siegert shift in the Rabi oscillations on the dressed electron spin states R. Fedaruk, A. Kolasa, A.P. Saiko 8. EPR spectroscopy of Cu 2+ and Mn 2+ in borate glasses A. Drzewiecki, B. Padlyak, V. Adamiv, Ya. Burak, I. Teslyuk 9. EPR study of guanidine zinc sulphate crystals K. Gruszka, R. Hrabański, J. Ozga, Z. Czapla 10. EPR measurements of ceramic cores used in the aircraft industry I. Stefaniuk, I. Rogalska, P. Potera, D. Wróbel 11. Computer program superposition model-monte Carlo (SPM-MC) and its applications in EMR studies of transition ions at low symmetry sites Fe 3+ doped YAP crystals I. Stefaniuk, C. Rudowicz 12. EPR studies of Cladosporium cladosporioides complexes with amphotericin B M. Zdybel, B. Pilawa, E. Buszman, T. Witoszyńska 13. Effect of microwave power on EPR spectra of DOPA-melanin-netilmicin complexes with different drug concentrations a study at temperatures in the range of K M. Zdybel, B. Pilawa, E. Buszman, D. Wrześniok, R. Krzyminiewski, Z. Kruczyński 14. EPR studies of free radicals in thermally sterilized famotidine P. Ramos, B. Pilawa, E. Stroka

130 132 NUKLEONIKA 15. Spectroscopic study of a bis(imidazole)(octaethylporphyrinato)iron(iii) complex I. Rutkowska, K. Dziliński, T. Kaczmarzyk, J. Stanek 16. Study on organic radicals giving rise to multicomponent EMR spectra in dried fruits expose to ionizing radiation II. D-Glucose G.P. Guzik, W. Stachowicz 17. Electron paramagnetic resonance (EPR) study of the short-living radicals generated thermally in phosphorylated maize starch with different amounts of amylose E. Bidzińska, K. Dyrek, K. Kruczała, J. Szczygieł, E. Wenda, W. Błaszczak, J. Fornal 18. Modification of the hydrogen bonding network at the reversed micelles interface by near infrared radiation T. Walski, K. Gałecka, K. Grzeszczuk-Kuć, M. Komorowska 19. The impact of humic substances on the liposome structures: ESR method D. Man, I. Pisarek, M. Braczkowski 20. The influence of selected amino acids on the dynamic properties of the liposome membranes: ESR study D. Man, M. Broda, A. Buczek, A. Kawecka, D. Siodłak 21. Antioxidant properties of wines produced in the Podkarpacie region A. Szterk, I. Stefaniuk, B. Cieniek, M. Kuźma CONTENTS OF No. 4/ Bonding xenon on the surface of uranium dioxide single crystal L. Dąbrowski, M. Szuta 2. Atomic force microscopy investigation of electron beam (EB) irradiated composites based on biodegradable polymers and coconut fiber Y. Kodama, A. Oishi, N. Nagasawa, K. Nakayama, M. Tamada, L.D.B. Machado 3. Studies of colored varieties of Brazilian quartz produced by gamma radiation C.T. Enokihara, R.A. Schultz-Güttler, P.R. Rela, W.A.P. Calvo 4. Deuterium isotope effects in oxidation of dopamine and norepinephrine catalyzed by horseradish peroxidase W. Byszewska, M. Pająk, M. Kańska 5. Estimation of the acute cesium toxicity by the microbial assay for risk assessment (MARA) test M. Bronowska, R. Stęborowski, G. Bystrzejewska-Piotrowska 6. Analysis of radionuclide release through EBS of conceptual repository for Lithuanian RBMK spent nuclear fuel disposal case of canister with initial defect P. Poskas, A. Narkuniene, D. Grigaliuniene, R. Kilda 7. Radioactivity of the atmospheric aerosols measured in Poland following the accident in the Fukushima Dai-ichi nuclear power plant in 2011 M. Fujak, K. Isajenko, P. Lipiński, B. Piotrowska, I. Kwiatkowska 8. EPR study of γ-irradiated feather keratin and human fingernails concerning retrospective dose assessment G. Strzelczak, M. Sterniczuk, J. Sadło, M. Kowalska, J. Michalik 9. Radioisotopic investigation of crosslinking density in bovine pericardium used as a biomaterial A. Turek, B. Cwalina, M. Kobielarz 10. A Whole-Body Spectrometer (WBS) at the Institute of Nuclear Physics, Kraków design and results for Polish citizens visiting Japan during the Fukushima accident J.W. Mietelski, P. Janowski, R. Kierepko, R. Hajduk, J. Bogacz, J. Jurkowski, E. Ochab 11. Does occupational exposure to low ionizing radiation affect endothelium health? G. Al-Massarani, F. Najjar 12. An improved formula for dead time correction of G-M detectors M. Arkani, H. Khalafi, M. Arkani 13. The cancer risk among workers of the nuclear centre at Świerk, Poland K.W. Fornalski, L. Dobrzyński 14. In memoriam Professor Janusz Z. Beer

131 NUKLEONIKA 133 Information INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY NUKLEONIKA Dorodna 16, Warszawa, Poland phone: ; fax: ; Abstracts and full texts are available on-line at

132 134 POSTĘPY TECHNIKI JĄDROWEJ POSTĘPY TECHNIKI JĄDROWEJ EDITORIAL BOARD Stanisław Latek (Editor-in-Chief), Wojciech Głuszewski, Maria Kowalska, Łukasz Kuźniarski, Andrzej Mikulski, Marek Rabiński, Edward Rurarz, Elżbieta Zalewska CONTENTS OF No. 1/ Nowe możliwości pomiarowe Śląskiego Centrum Radiometrii Środowiskowej Głównego Instytutu Górnictwa (New measuring possibilities in the Silesian Centre for Environmental Radioactivity of the Central Mining Institute) M. Wysocka, B. Michalik, K. Skubacz 2. Radiacyjna metoda higienizacji i utrwalania żywności (Radiation method of the food products hygienization and preservation) W. Migdał, U. Gryczka 3. Raport z eksploatacji reaktora badawczego MARIA w 2012 roku (Report on the operation of the research reactor MARIA in 2012) A. Gołąb 4. Analiza izotopów uranu i plutonu przy użyciu detektora półprzewodnikowego LEGe oraz kodów MGAU, MGA (Analysis of uranium and plutonium isotopes by using semiconductor detector LEGe and numerical codes MGAU, MGU) M. Fujak, P. Lipiński, K. Isajenko, B. Piotrowska 5. Promieniowanie naturalne w Polsce a śmiertelność nowotworowa (Natural radiation in Poland and the cancer mortality) K.W. Fornalski, L. Dobrzyński 6. Energetyka jądrowa, efekt cieplarniany i polityka (Nuclear power, greenhouse effect and politics) D.W. Kulczyński 7. Bułgaria przez referendum do buntu obywatelskiego (Bulgaria from referendum to the civil revolt) N. Uzunow CONTENTS OF No. 2/ Wywiad z prof. Sueo Machi m (Interview with Professor Sueo Machi) S. Latek 2. Probabilistyczna analiza bezpieczeństwa nowych reaktorów jądrowych (Probalilistic safety analysis of new nuclear reactors) E. Staroń 3. Reaktor EWA jako stymulator awansu naukowego pracowników IBJ na przykładzie jednego z zakładów (The EWA research reactor as a stimulator of the INR scientists promotion exemplified by one of the Institute departments) J. Leciejewicz 4. Bezpieczeństwo jądrowe i ochrona radiologiczna w spółkach jądrowych PGE (Nuclear safety and radiological protection in the PGE nuclear companies) K.W. Fornalski 5. Identyfikacja napromieniowania produktów spożywczych w IChTJ (Identification of the irradiated food products in the INCT) W. Stachowicz 6. Napromieniowany czy promieniotwórczy? (Irradiated or radioactive?) W. Głuszewski

133 POSTĘPY TECHNIKI JĄDROWEJ Analiza 23. cyklu aktywności Słońca w oparciu o pomiary Be-7 w przyziemnej warstwie powietrza atmosferycznego (Analysis of the 23rd cycle of the Sun activity based on Be-7 activity measurements in the ground level of atmospheric air) A. Fujak, P. Lipiński, K. Isajenko, B. Piotrowska, I. Kwiatkowska 8. Eksperyment AMS pomiar nadwyżki antymaterii w przestrzeni kosmicznej (CERN s AMS experiment the measurement of the antimatter excess in the cosmic space) M. Nowina-Konopka 9. Centrum Cyklotronowe Bronowice rozpoczyna działalność (Bronowice Cyclotron Centre just started its activity) M. Jeżabek, P. Olko CONTENTS OF No. 3/ Nobel za boską cząstkę (Nobel prize for the divine particle ) S. Latek 2. Synteza najcięższych jąder atomowych i pierwiastków chemicznych. Stan obecny (Syntesis of the heaviest atomic nuclei and chemical elements. Current state) A. Sobiczewski 3. Blaski i nędze życia kilku cyklotronów w Polsce i na świecie (Advantages and disadvantages of life of several cyclotrons in Poland and in the world) E. Rurarz lat bankowania i sterylizacji radiacyjnej tkanek w Polsce (50 years of banking and radiation sterilization of tissues in Poland) A. Kamiński, J. Komender, J. Michalik lecie lampy rentgenowskiej (100 years of the Roentgen lamp) G. Jezierski 6. Wyjazdy do Czarnobyla (Visits to Chernobyl) M. Rabiński 7. Techniki radiacyjne w konserwacji obiektów o znaczeniu historycznym (Radiation techniques in preservation of objects of historical importance) W. Głuszewski 8. Badanie PET i cyklotron (PET examination and a cyclotron) A. d Amico, A. Florczak lat współczesnej edycji Postępów Techniki Jądrowej (20 years of the new edition of the Postępy Techniki Jądrowej journal) S. Latek 10. Energetyka jądrowa w Polsce próba bilansu ostatniego 5-lecia (Nuclear power in Poland an attempt of balance for the last 5 years) A. Mikulski 11. Jubileusz 20-lecia nowej edycji PTJ (Jubilee of the Postępy Techniki Jądrowej new edition) E. Zalewska, M. Rabiński, S. Latek CONTENTS OF No. 4/ Jubileusz Postępów Techniki Jądrowej : celebracja i sprawy poważne (Jubilee of the Postępy Techniki Jądrowej : celebration and serious matters) S. Latek 2. Porozumienie o współpracy między SFEN i PTN (Agreement on the cooperation between SFEN and PTN) W. Głuszewski 3. Po 20 latach nowej edycji czasopisma Postępy Techniki Jądrowej (After 20 years of the journal Postępy Techniki Jądrowej new edition) B. Andrzejak 4. O programie polskiej energetyki jądrowej (On the Polish Nuclear Power Programme) Z. Kubacki

134 136 POSTĘPY TECHNIKI JĄDROWEJ 5. Co dalej po IPPA? (What to do next after finishing IPPA project?) S. Latek 6. Los odpadów promieniotwórczych (A fate of radiological wastes) D.W. Kulczyński 7. Nowe możliwości medycyny nuklearnej w Polsce (New possibilities of the nuclear medicine in Poland) W. Głuszewski 8. Inżynierskie wybory Adama Rozwadowskiego (Engineering choices of Adam Rozwadowski) M. Bielski 9. Kryptonim Absolwenci. Nabór pracowników naukowych do IBJ w roku 1955 (Code name: Absolvents. Recruitment of new scientists to the Institute of Nuclear Research in the year 1955) J. Leciejewicz 10. Modelowanie słabości czynnika kognitywnego w zarządzaniu zgrożeniami w elektrowniach jądrowych: perspektywa ontologiczna meta-teorii TOGA (Human cognitive vulnerabilities in nuclear power plant emergency management: the TOGA meta-theory ontological perspective) A.M. Gadomski, M.W. Wronikowska 11. Parę słów o cyklotronie (Some words on a cyclotron) K. Górczewski Information INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY POSTĘPY TECHNIKI JĄDROWEJ Dorodna 16, Warszawa, Poland phone: ; fax: ; [email protected]

135 INTERVIEWS IN INTERVIEWS IN Łada W. Fober I.: Meganadzieja w mikrosferach (Megahope in microspheres). Przegląd Techniczny, 3-4, 14 (2013). Gajda D. Szwed M.: Mamy uran w Polsce nowe spojrzenie na sprawę (We have got uranium in Poland a new look at the issue). Seria: Potencjał Polskiej Nauki. mamy-uran-w-polsce-nowe-spojrzenie-na-sprawe,12737 ( ). Gajda D. Szwed M.: Mamy uran w Polsce nowe spojrzenie na sprawę (We have got uranium in Poland a new look at the issue). -w-polsce-nowe-spojrzenie-na-sprawe.html ( ). Gajda D. Szwed M.: Mamy uran w Polsce nowe spojrzenie na sprawę (We have got uranium in Poland a new look at the issue). ( ).

136 138 THE INCT PATENTS AND PATENT APPLICATIONS IN 2013 THE INCT PATENTS AND PATENT APPLICATIONS IN 2013 PATENTS Urządzenie do radiacyjnego oczyszczania przemysłowych gazów odlotowych (Device for the radiation purification of industrial flue gases) A.G. Chmielewski, A. Pawelec, A. Dobrowolski, N.N. Dutskinov, K.L. Nikolov, L.K. Stamatov, Y.G. Pelovski Polish Patent (with TPP Svilosa JSCo., Sofia, Bulgaria) Sposób otrzymywania opatrunków hydrożelowych zawierających kompleks radiacyjnie degradowanego polisacharydu i srebra (Method for the preparation of hydrogel wound dressings containing complex of radiation-degraded polysaccharide with silver) D. Chmielewska, W. Migdał, A.G. Chmielewski, U. Gryczka, P. Kik Polish Patent (with KIK Mirosław Przedsiębiorstwo Produkcyjno-Handlowe KIK, Poland) Sposób degradacji usieciowanych odpadowych żywic epoksydowych oraz zastosowanie produktu degradacji usieciowanych odpadowych żywic epoksydowych (Method of degradation of cross-linked epoxy resin wastes and utilization of the degradation products of epoxy resin wastes) I. Legocka, E. Wierzbicka, G. Przybytniak, A. Nowicki Polish Patent (with the Industrial Chemistry Research Institute, Warszawa, Poland) Sposób unieszkodliwiania odpadów promieniotwórczych w szkłach krzemionkowych (Method for the disposal of radioactive wastes in structures of silica glasses) A.G. Chmielewski, A. Deptuła, M. Miłkowska, W. Łada, T. Olczak Polish Patent Sposób rozpuszczania tlenku toru (Method of dissolution of thorium oxide) K. Łyczko, M. Łyczko, I. Herdzik, B. Zielińska Polish Patent Radiofarmaceutyk terapeutyczny znakowany radionuklidami radu oraz sposób jego wytwarzania (Therapeutic radiopharmaceutical labelled with radionuclides of radium and method for its obtaining) A. Kasperek, A. Bilewicz, T. Olczak Polish Patent Process for the preparation of uranium dioxide with spherical and irregular grains A. Deptuła, M. Brykała, W. Łada, D. Wawszczak, T. Olczak, A.G. Chmielewski Belarus Patent Method for the preparation of hydrogel wound dressings D. Chmielewska, W. Migdał, A.G. Chmielewski, U. Gryczka, P. Kik Belarus Patent (with KIKGEL, Poland) PATENT APPLICATIONS Sposób otrzymywania sferycznych ziaren ditlenku uranowo-neodymowego metodą dwustopniowej ekstrakcji (Method for producing of spherical particles of uranium-neodymium dioxide by double extraction process) M. Brykała, A. Deptuła, W. Łada, T. Olczak, M. Rogowski, A.G. Chmielewski Polish Patent Application P Prekursor radiofarmaceutyku, sposób jego wytwarzania, radiofarmaceutyk oraz jego zastosowanie (Precursor of the radiopharmaceutical, the method for its production, radiopharmaceutical and its applications) G. Wójciuk, M. Kruszewski Polish Patent Application P

137 THE INCT PATENTS AND PATENT APPLICATIONS IN Sposób wytwarzania stabilizowanego ditlenku cyrkonu w postaci matrycy inertnej do transmutacji aktynowców mniejszościowych (Method for producing of stabilized zirconium dioxide in the form of inert matrix for the transmutation of minor actinides) M. Brykała, R. Walczak, M. Rogowski, W. Łada, D. Wawszczak Polish Patent Application P Sposób jednorodnego sieciowania wykonanych z poliolefin izolacji i osłon przewodów i kabli elektrycznych przy wykorzystaniu wiązki elektronów (Application of electron beam for uniform cross-linking of electrical cable insulations and jackets made of polyolefins) Z. Zimek, G. Przybytniak, A. Nowicki, K. Roman Polish Patent Application P Prekursor radiofarmaceutyku oraz sposób jego wytwarzania (Precursor of a radiopharmaceutical and the method for its production) A. Bilewicz, M. Łyczko, A. Piotrowska, E. Leszczuk Polish Patent Application P Sposób oddzielania ameryku(iii) i ewentualnie kiuru od lantanowcowych produktów rozszczepienia w układach ekstrakcyjnych ciecz-ciecz (Method for the separation of americium(iii) and possibly curium from lanthanide fission products in solvent extraction systems) J. Narbutt, M. Rejnis, I. Herdzik-Koniecko Polish Patent Application P Prekursor radiofarmaceutyku i radiofarmaceutyk oparty na analogach dezacylogreliny, sposób ich wytwarzania oraz ich zastosowanie (Precursor of the radiopharmaceutical and the radiopharmacutical based on des-acyl ghrelin analogs, the method for producing and their applications) G. Wójciuk, M. Kruszewski Polish Patent Application P m 8. Sposób otrzymywania diagnostycznych ilości radionuklidu Tc (Method for the obtaining of diagnostic amounts of the 99m Tc radionuclide) A. Bilewicz, M. Gumiela Polish Patent Application P Sposób unieszkodliwiania odpadów radioaktywnych w syntetycznej skale (Method of the disposal of radioactive wastes in the synthetic rock ) T. Smoliński, A.G. Chmielewski, A. Deptuła, W. Łada, T. Olczak European Patent Application EP Sposób otrzymywania opatrunków hydrożelowych (Method for the preparation of hydrogel wound dressings) D. Chmielewska, W. Migdał, A.G. Chmielewski, U. Gryczka, P. Kik European Patent Application EP (with KIKGEL, Poland)

138 140 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2013 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN REFERENCE GROUP MEETING No. 5 WITHIN THE FP7 EU PROJECT IPPA (IM- PLEMENTING PUBLIC PARTICIPATION APPROACHES IN RADIOACTIVE WASTE DISPOSAL), 24 JANUARY 2013, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology Organizing Committee: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT, Agnieszka Miśkiewicz, Ph.D. 2. EXPERT GROUP MEETING WITHIN THE FP7 EU PROJECT NEWLANCER (NEW MS LINKING FOR AN ADVANCED COHESION IN EURATOM RESEARCH), 28 FEBRUARY 2013, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology Organizing Committee: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT, Katarzyna Kiegiel, Ph.D. 3. SCIENTIFIC MEETING CONCERNING COOPERATION BETWEEN THE ÉLECTRI- CITÉ DE FRANCE AND THE INSTITUTE OF NUCLEAR CHEMISTRY AND TECH- NOLOGY, 4 APRIL 2013, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology 4. CONSULTANCY MEETING ON NETWORKING OF USERS OF EB FACILITIES AND THE ROLE OF THE IAEA COLLABORATING CENTRES, 8-12 APRIL 2013, WARSZA- WA, POLAND Organized by the Institute of Nuclear Chemistry and Technology, International Atomic Energy Agency Organizing Committee: Zbigniew Zimek, Ph.D., Magdalena Antoniak, M.Sc., Sunil Sabharwal, Ph.D. 5. PlasTEP+ (PLASMA TECHNOLOGIES FOR ENVIRONMENT PROTECTION) WORK- SHOP NEW PLASMA AND ELECTRON BEAM TECHNOLOGIES INCLUDING NEW TRENDS IN WATER CLEANING, 11 APRIL 2013, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology Organizing Committee: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc., Andrzej Pawelec, Ph.D., Sylwia Witman-Zając, M.Sc. 6. VI KRAJOWA KONFERENCJA RADIOCHEMII I CHEMII JĄDROWEJ (VI NATIONAL CONFERENCE ON RADIOCHEMISTRY AND NUCLEAR CHEMISTRY), APRIL 2013, KRAKÓW-PRZEGORZAŁY, POLAND Organized by the Institute of Nuclear Chemistry and Technology, AGH University of Science and Technology Organizing Committee: Leon Fuks, Ph.D., Agata Oszczak, M.Sc., Marcin Brykała, M.Sc., Barbara Kubica, Ph.D., D.Sc., AGH professor, Katarzyna Szarłowicz, Ph.D., Marcin Stobiński, Ph.D. 7. II WORKSHOP WITHIN THE FP7 EU PROJECT IPPA (IMPLEMENTING PUBLIC PARTICIPATION APPROACHES IN RADIOACTIVE WASTE DISPOSAL) ENTITLED: SOCIAL COMMUNICATION IN POTENTIALLY CONFLICTING SITUATIONS AND

139 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN PRESENTATION AND PARTICIPATION IN DEBATES, APRIL 2013, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology Organizing Committee: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT, Agnieszka Miśkiewicz, Ph.D., Dorota Gajda, M.Sc. 8. CZY POTRZEBUJEMY NOWEGO SKŁADOWISKA ODPADÓW PROMIENIOTWÓR- CZYCH? PIERWSZE WYSŁUCHANIE W RAMACH EUROPEJSKIEGO PROJEKTU IPPA (PUBLIC HEARING WITHIN THE FP7 EU PROJECT IPPA ENTITLED DO WE NEED A NEW REPOSITORY FOR THE RADIOACTIVE WASTE? ), 8 MAY 2013, WAR- SZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology Organizing Committee: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT, Agnieszka Miśkiewicz, Ph.D., Dorota Gajda, M.Sc., Wioleta Niesłuchowska, M.Sc., Paulina Niescior-Browińska, M.Sc., Anna Abramowska, M.Sc., Katarzyna Szczygłów, M.Sc. 9. XII SZKOŁA STERYLIZACJI I MIKROBIOLOGICZNEJ DEKONTAMINACJI RADIA- CYJNEJ (XII TRAINING COURSE ON RADIATION STERILIZATION AND HYGIENI- ZATION), OCTOBER 2013, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology Organizing Committee: Zbigniew Zimek, Ph.D., Andrzej Rafalski, Ph.D., Wojciech Głuszewski, Ph.D., Magdalena Antoniak, M.Sc. 10. III WORKSHOP WITHIN THE FP7 EU PROJECT IPPA (IMPLEMENTING PUBLIC PARTICIPATION APPROACHES IN RADIOACTIVE WASTE DISPOSAL), 4-5 NOVEM- BER 2013, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology Organizing Committee: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT, Agnieszka Miśkiewicz, Ph.D., Dorota Gajda, M.Sc., Wioleta Niesłuchowska, M.Sc., Katarzyna Szczygłów, M.Sc., Paulina Niescior-Browińska, M.Sc. 11. SEMINARIUM NAUKOWE ANALIZA MOŻLIWOŚCI POZYSKIWANIA URANU DLA ENERGETYKI JĄDROWEJ Z ZASOBÓW KRAJOWYCH (SCIENTIFIC SEMINAR ON ANALYSIS OF THE POSSIBILITY OF URANIUM SUPPLY FROM DOMESTIC RE- SOURCES ), 19 NOVEMBER 2013, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology Organizing Committee: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT, Katarzyna Kiegiel, Ph.D., Agnieszka Miśkiewicz, Ph.D., Dorota Gajda, M.Sc., Wioleta Niesłuchowska, M.Sc. 12. REFERENCE GROUP MEETING No. 6 WITHIN THE FP7 EU PROJECT IPPA (IM- PLEMENTING PUBLIC PARTICIPATION APPROACHES IN RADIOACTIVE WASTE DISPOSAL), 9 DECEMBER 2013, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology Organizing Committee: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT, Agnieszka Miśkiewicz, Ph.D., Wioleta Niesłuchowska, M.Sc.

140 142 Ph.D. THESES IN 2013 Ph.D. THESES IN Macin Brykała, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Synteza ziaren ditlenku uranu dotowanych wybranymi pierwiastkami przy zastosowaniu kompleksowej metody zol-żel (CSGP) (Synthesis of uranium dioxide particles doped with selected elements by complex sol-gel process (CGSP)) supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, Izabela Cydzik, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Radiolabelling of nanoparticles for biological studies supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, Rafał Kocia, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) p-terfenyl jako sonda pierwotnych procesów radiacyjno-chemicznych w wybranej cieczy jonowej (p-terphenyl as a sensor of the primary radiation-chemical processes in the selected ionic liquid) supervisor: Jan Grodkowski, Ph.D., D.Sc., professor in INCT Institute of Nuclear Chemistry and Technology, Seweryn Krajewski, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Metaloorganiczne i chelatowe kompleksy 105 Rh i 103m Rh jako potencjalne prekursory radiofarmaceutyków terapeutycznych (Organometallic and chelate complexes of 105 Rh and 103m Rh as potential precursors of therapeutic radiopharmaceuticals) supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, Agnieszka Miśkiewicz, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Nowe znaczniki promieniotwórcze fazy ciekłej i stałej do zastosowań w badaniach procesów membranowych (New radiotracers of liquid and solid phases for applications in researches of membrane processes) supervisor: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT Institute of Nuclear Chemistry and Technology, Macin Sterniczuk, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Centra paramagnetyczne generowane radiacyjnie w sitach molekularnych z zaadsorbowanym tlenkiem węgla (Paramagnetic centres generated radiolytically in molecular sieves exposed to carbon monoxide) supervisor: Prof. Jacek Michalik, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, 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 induced modification of poly(ester-urethane)s) supervisor: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT Institute of Nuclear Chemistry and Technology, Grzegorz Wójciuk, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Analog des-acyl greliny jako nowy nośnik radionuklidów i potencjalny radiofarmaceutyk (Des-acyl ghrelin analog as a new carrier of radionuclides and a potential radiopharmaceutical) supervisor: Prof. Marcin Kruszewski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology,

141 EDUCATION 143 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 at the Institute. The candidates can apply for a doctoral scholarship. The INCT offers accommodation in 10 rooms in the guesthouse 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 publication; final examination and public defence of the dissertation thesis. In 2013, the following lecture series were organized: Metals in medicine selected aspects Arkadiusz Bonna, Ph.D. (Institute of Biochemistry and Biophysics, Polish Academy of Sciences, Warszawa, Poland); Safe nuclear energy production vs. alternative prospects Holger Tietze-Jaensch, Ph.D. (Forschungszentrum Jülich GmbH, Germany); Basis of radiobiology Sylwester Sommer, Ph.D. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland); Radiochemical methods for the determination of long-lived radionuclides Nora Vajda, Ph.D. (RadAnal Ltd., Budapest, Hungary). 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: , [email protected]); secretary: Dr. Ewa Gniazdowska (phone: , [email protected]). TRAINING OF STUDENTS Institution Country Number of participants Period International Atomic Energy Agency Egypt 1 3 months International Atomic Energy Agency Ghana 1 2 months Technical University of Łódź, Faculty of Chemistry, Institute of Applied Radiation Chemistry Poland 9 one-day course

142 144 EDUCATION Institution University of Warsaw, Faculty of Chemistry Country Number of participants Period Poland 8 3 weeks Poland 1 2 months Poland 1 6 months University of Waterloo Canada 1 3 months Warsaw University of Technology, Faculty of Chemistry Poland 6 1 month Warsaw University of Technology, Faculty of Physics Warsaw University of Technology, Faculty of Power and Aeronautical Engineering WAT Military University of Technology, Department of Chemistry and New Technologies 1 1 month Poland 25 one-day course Poland 1 2 months Poland month

143 RESEARCH PROJECTS AND CONTRACTS 145 RESEARCH PROJECTS AND CONTRACTS RESEARCH PROJECTS GRANTED BY THE NATIONAL SCIENCE CENTRE IN 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. Radiochemical separation of arsenic from selenium and its potential usage in the generator 72 Se/ 72 As construction. supervisor: Ewelina Chajduk, Ph.D. 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. Participation of radiation chemistry in systems chemistry, especially in prebiotic chemistry. supervisor: Prof. Zbigniew P. Zagórski, Ph.D., D.Sc. Functionalization of polyurethane surface by radiation-induced grafting (Preludium). supervisor: Marta Walo, Ph.D. Nanozeolites as a carrier for radium in targeted therapy. supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc. Paramagnetic centres generated radiolytically in molecular sieves exposed to carbon oxides. supervisor: Marcin Sterniczuk, Ph.D. Des-acyl ghrelin analog as a new carrier of radionuclides and a potential radiopharmaceutical. supervisor: Grzegorz Wójciuk, Ph.D. Physicochemical and biochemical studies of selected biological conveyers of nitrogen oxide. Relation between the molecular structure and distribution of electric charge and the biological activity of nitrosyl complexes of iron. supervisor: Hanna Lewandowska-Siwkiewicz, Ph.D. DEVELOPMENT PROJECTS GRANTED BY THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT IN 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. 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. INNOTECH PROJECTS GRANTED BY THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT IN A mobile membrane installation for the enrichment of gas in methane (project INITECH). supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

144 146 RESEARCH PROJECTS AND CONTRACTS Elaboration and certification of new reference materials needed for obtaining European accred 2. i- tation by Polish laboratories involved in industrial analytics (project INNOTECH, MODAS). supervisor: Halina Polkowska-Motrenko, Ph.D., D.Sc., professor in INCT APPLIED RESEARCH PROGRAMME OF THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT IN Optimization of two stages bioreactor for biogas with high methane contents production - elaboration of biostarters and biomarkers of methane fermentation. Task 2.1. Construction in laboratory scale of two stages bioreactors for biogas production with high methane concentration. supervisor: Jacek Palige, Ph.D. 2. Alternative methods for technetium-99m production. Task 8. Isolation of Tc-99m using zirconium modified TiO 2 nanotubes and by extraction method with HDEHP. supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc. INTERNATIONAL PROJECTS CO-FUNDED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN Radiation supporting synthesis and curing of nanocomposites suitable for practical applications. supervisor: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT Ageing diagnostics and prognostics of low-voltage I&C cables (ADVANCE). supervisor: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT Multi-disciplinary biodosimetric tools to manage high scale radiological casualties (MULTI- BIODOSE). supervisor: Sylwester Sommer, Ph.D. Implementing public participation approaches in radioactive waste disposal (IPPA). supervisor: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT PGAM5 protein as a signalling factor in the crosstalk between the oxidative stress protective pathway NRF2/KEAP1 and apoptosis and autophagy related to the activation of ASK1 kinase. The testing of the hypothesis and implications in Parkinson s disease (Iuventus Plus). supervisor: Tomasz Stępkowski, M.Sc. Advanced fuels for generation IV reactors: reprocessing and dissolution (ASGARD). supervisor: Andrzej Deptuła, Ph.D. Upgrading the capacities and capabilities in nuclear and radiation processing technology and applications by increasing the proficiency level in national nuclear institutions. supervisor: Dagmara Chmielewska-Śmietanko, M.Sc. Formation, investigations and characterization of advanced nanoporous materials. supervisor: Bożena Sartowska, Ph.D. Safety of actinide separation processes (SACSESS). supervisor: Prof. Jerzy Narbutt, Ph.D., D.Sc. Transnational access to large infrastructure for a safe management of actinide (TALISMAN). supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. Characterization of modified surface layer of austenitic stainless steel enriched with rare earth elements (REE) formed using ions and plasma beams with RBS measurements. supervisor: Bożena Sartowska, Ph.D. Based on starch-pva system and cellulose reinforced active packaging materials for food prepared using of radiation modification (PackRad). supervisor: Krystyna Cieśla, Ph.D., D.Sc., professor in INCT Studies on the methods of synthesis of hybrid porous metallo-organic nanomaterials of separation and sorption properties (NANOSYNT). supervisor: Wojciech Starosta, Ph.D.

145 RESEARCH PROJECTS AND CONTRACTS Attracting investments in plasma-based air and water cleaning technologies (PlasTEP+). supervisor: Andrzej Pawelec, Ph.D. STRATEGIC PROJECT TECHNOLOGIES SUPPORTING DEVELOPMENT OF SAFE NUCLEAR POWER ENGINEERING Scientific problem no. 3: Principles to secure fuel needs for the Polish nuclear energy. supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. Scientific problem no. 4: Development of spent nuclear fuel and radioactive waste management techniques and technologies. supervisor: Leon Fuks, Ph.D. 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. 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. Scientific problem no. 7: Analysis of hydrogen generation processes in nuclear reactor during normal exploitation and nuclear accidents in order to increase safety standards. supervisor: Prof. Jacek Michalik, Ph.D., D.Sc. Scientific problem no. 8: Study of processes occurring under regular operation of water circulation systems in nuclear power plants with suggested actions aimed at upgrade of nuclear safety. supervisor: Anna Bojanowska-Czajka, Ph.D. STRATEGIC PROJECT ADVANCED TECHNOLOGIES FOR GAINING ENERGY 1. 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. IAEA RESEARCH CONTRACTS IN Radiation supporting synthesis and curing of nanocomposites suitable for practical applications (NANO-RAD). No principal investigator: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT Laboratory and feasibility study for industrial waste water effluent treatment by radiation. No principal investigator: Zbigniew Zimek, Ph.D. Application of hybrid nuclear techniques in the multiphases flows investigations in wastewater treatment and biogases production plants. No principal investigator: Jacek Palige, Ph.D. Based on starch-pva system and cellulose reinforced active packaging materials for food prepared using of radiation modification (PackRad). No principal investigator: Krystyna Cieśla, Ph.D., D.Sc., professor in INCT.

146 148 RESEARCH PROJECTS AND CONTRACTS 5. The study of the influence of the environmental factors on the isotopic compositions of dairy products. No principal investigator: Ryszard Wierzchnicki, Ph.D. IAEA TECHNICAL AND REGIONAL CONTRACTS IN Developing of an advanced industrial gamma scanning system with wireless data acquisition. POL/0/010 Regional Training on IAEA Validation and Process Control for Electron Beam Radiation Processing. RER/1/011 Supporting radiation synthesis and the characterization of nanomaterials for health care, environmental protection and clean energy applications. RER/8/014 Using nuclear techniques for the characterization and preservation of cultural heritage artefacts in the European Region. RER/8/015 Enhancing quality control methods and procedures for radiation technology. RER/8/017 PROJECTS WITHIN THE FRAME OF EUROPEAN UNION FRAME PROGRAMMES IN FP7 EURATOM, Fission: Multi-disciplinary biodosimetric tools to manage high scale radiological casulaties (MULTIBIODOSE). principal investigator: Sylwester Sommer, Ph.D. FP7 EURATOM, Fission: Ageing diagnostics and prognostics of low-voltage I&C cables (ADVANCE). principal investigator: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT FP7 EURATOM, Fission: Implementing public participation approaches in radioactive waste disposal (IPPA). principal investigator: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT FP7 EURATOM, Fission: New MS linking for an advanced cohesion in Euratom research (NEWLANCER). principal investigator: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT FP7 EURATOM, Fission: Advanced fuels for generation IV reactors: reprocessing and dissolution (ASGARD). principal investigator: Andrzej Deptuła, Ph.D. FP7 EURATOM, Fission: Realizing the European Network in Biodosimetry (RENEB) principal investigator: Sylwester Sommer, Ph.D. FP7 Transnational access to large infrastructure for a safe management of actinide (TALIS- MAN). principal investigator: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. FP7 Safety of actinide separation processes (SACSESS). principal investigator: Prof. Jerzy Narbutt, Ph.D., D.Sc. FP7 Assessment of regional capabilities for new reactors development through an integrated approach (ARCADIA). principal investigator: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT FP7 Enhancing education, training and communication processes for informed behaviors and decision-making related to ionizing radiation risks (EAGLE). principal investigator: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT

147 RESEARCH PROJECTS AND CONTRACTS FP7 Building a platform for enhanced societal research related to nuclear energy in Central and Eastern Europe (PLATENSO). principal investigator: Grażyna Zakrzewska-Kołtuniewicz, 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. Attracting investments in plasma-based air and water cleaning technologies 2. (PlasTEP+). supervisor: Andrzej Pawelec, Ph.D. OTHER INTERNATIONAL RESEARCH PROGRAMMES IN 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 (with Joint Institute for Nuclear Research, Dubna, Russia). supervisor: Prof. Zbigniew Zagórski, Ph.D., D.Sc. 2. Formation, investigations and characterization of advanced nanoporous materials (with Joint Institute for Nuclear Research, Dubna, Russia). supervisor: Bożena Sartowska, Ph.D. 3. Studies on synthesis methods of nanoscale metal organic framework type materials (with Joint Institute for Nuclear Research, Dubna, Russia). supervisor: Wojciech Starosta, Ph.D. 4. Support of public and industrial research using ion beam technology (SPIRIT). supervisor: Bożena Sartowska, Ph.D. 5. Electron beam flue gas treatment pilot test (for ARAMCO Overseas Company B.V.). supervisor: Andrzej Pawelec, Ph.D. STRUCTURAL FUNDS: OPERATIONAL PROGRAMME INNOVATIVE ECONOMY Analysis of the possibilities of uranium supply from domestic resources. supervisor: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT POIG /09 New generation of electrical wires modified by radiation. supervisor: Zbigniew Zimek, Ph.D. POIG /09 Development of a multi-parametric triage approach for an assessment of radiation exposure in a large -scale radiological emergency. supervisor: Prof. Marcin Kruszewski, Ph.D., D.Sc. POIG /09

148 150 LIST OF VISITORS TO THE INCT IN 2013 LIST OF VISITORS TO THE INCT IN Abel Trixie, International Atomic Energy Agency (IAEA), Austria, Armah Jonathan Okai, International Atomic Energy Agency (IAEA), Ghana, Avivar Cerezo Jessica, Department of Chemistry, University of the Balearic Islands, Spain, Bonifacic Marija, Ruđer Bošković Institute, Zagreb, Croatia, Cerdà Victor, Department of Chemistry, University of the Balearic Islands, Spain, Dzeba Eva, Ruđer Bošković Institute, Zagreb, Croatia, Erdogan Huriye, ETH Zurich, Switzerland, Etoom Mohammad Amer, International Atomic Energy Agency (IAEA), Jordan, Fuente Julio De la, Universidad de Chile, Santiago de Chile, Chile, Humbert D., University of Paris, France, Kattan Munzer, International Atomic Energy Agency (IAEA), Syria, , Lazunik Valentin, V.N. Karazin Kharkiv National University, Ukraine, Maalouf Manale, ETH Zurich Switzerland, Mahmoudi Leila, ETH Zurich, Switzerland, Maspoch Daniel, Catalan Institute of Nanotechnology, Bellatera, Spain, Miranda Enrigue Francisco, International Atomic Energy Agency (IAEA), Cuba, Molina Christian, ETH Zurich, Switzerland, Mothersill Carmel, McMaster University, Hamilton, Canada, Orelovitch Oleg L., Joint Institute for Nuclear Research (JINR), Dubna, Russia, Popov Genadii, V.N. Karazin Kharkiv National University, Ukraine, Seymour Colin, McMaster University, Hamilton, Canada, Soliman Yasser Shaaban, International Atomic Energy Agency (IAEA), Egypt, Tietze-Jaensch Holger, Institute of Energy and Climate Research IEK-6, Forschungszentrum Jülich GmbH, Germany, , Terzidis Michael, Institute of Organic Synthesis and Photoreactivity (ISOF), National Research Council, Bolonia, Italy, Vajda Nora, RadAnal. Ltd., Budapest, Hungary, Wordman Peter, University of Oxford, United Kingdom,

149 THE INCT SEMINARS IN THE INCT SEMINARS IN Dr. Jessica Avivar Cerezo (Department of Chemistry, University of the Balearic Islands, Spain) How to automate radiochemical analysis exploiting flow techniques Paweł Biełuszka, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Zastosowanie kontaktorów membranowych w procesach ekstrakcji uranu z rud uranowych (Application of membrane contactors in processes of uranium extraction from uranium ores) Jacek Boguski, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Dobór kryteriów oceny degradacji radiacyjnej i termicznej kabli (Criteria for the evaluation of radiation and thermal degradation of cables) Arkadiusz Bonna, Ph.D. (Institute of Biochemistry and Biophysics, Polish Academy of Sciences, Warszawa, Poland) Zastosowanie peptydów w badaniach procesów biochemicznych (Application of peptides in studies of biochemical processes) Prof. dr. Victor Cerdà (Department of Chemistry, University of the Balearic Islands, Spain) Automation of analytical methods by flow techniques: history and new trends Prof. Rajmund Dybczyński, Ph.D., D.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) 50 lat przygód z neutronową analizą aktywacyjną (Fifty years with neutron activation analysis) Maciej Jarzębski, Ph.D. (NanoBioMedical Centre (NBMC), Adam Mickiewicz University, Poznań, Poland) Modelowanie systemów nanocząstek i układów koloidowych w potencjalnych aplikacjach medycznych, systemach dostarczania leków i diagnostyce (Modelling of systems of nanoparticles and colloidal sets in potential medical applications, in systems of supplying medicines and in diagnosis) Prof. Jerzy Jastrzębski, Ph.D., D.Sc., Jarosław Choiński, Ph.D. (Heavy Ion Laboratory, University of Warsaw, Warszawa, Poland) Ośrodek Produkcji i Badania Radiofarmaceutyków w ŚLCJ (Radiopharmaceuticals Production and Research Centre, HIL) Prof. Leszek Królicki, Ph.D., D.Sc. (Medical University of Warsaw, Warszawa, Poland) Terapia i diagnostyka chorób nowotworowych (Therapy and diagnosis of tumour diseases) Prof. Daniel Maspoch (Catalan Institute of Nanotechnology, Bellaterra (Barcelona), Spain) Nanochemistry is in the air and on surfaces: synthesis and assembly of nanoscale metal-organic frameworks Adam Mieczkowski, Ph.D. (Institute of Biochemistry and Biophysics, Polish Academy of Sciences, Warszawa, Poland) Nukleozydy i benzodiazepiny jako struktury uprzywilejowane ( privileged structures ), wykorzystywane w projektowaniu i poszukiwaniu nowych leków (Nucleosides and benzodiazepines as the privileged structures used in the designing and searching for new medicines) Prof. Carmel Mothersill (McMaster University, Hamilton, Ontario, Canada) Radiation-induced non-targeted effects adaptive responses or damaging low dose effects? Paweł Ochman, Ph.D. (Maria Skłodowska Curie Memorial Cancer Centre and Institute of Oncology, Warszawa, Poland) Substancje biologicznie czynne znakowane radionuklidami w diagnostyce i terapii onkologicznej (Active biological substances labelled with radionuclides in diagnosis and oncological theraphy) Prof. Colin Seymour (McMaster University, Hamilton, Ontario, Canada) Why is radiotherapy not delivering the expectations of radiobiology? Yongxia Sun, Ph.D. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Degradation of air pollutants in non-thermal plasma generated by electron beam. Experimental and theoretical study

150 152 THE INCT SEMINARS IN Prof. Peter Wardman (emeritus professor, formerly with the University of Oxford, United Kingdom) Redox properties of free radicals and their effects on the rates of reactions Prof. Kazimierz Piotr Zaleski, Ph.D. (Paris-Dauphine University, France) Przyszłość energetyki jądrowej na świecie (The future of nuclear power in the world)

151 LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2013 LECTURES Bilewicz A. Emitery promieniowania korpuskularnego w celowanej terapii radionuklidowej (Emitters of corpuscular radiation for target radiotherapy). II Letnia Szkoła Energetyki i Chemii Jądrowej, Warszawa, Poland, Bilewicz A. Własności chemiczne pierwiastków transaktynowych (Chemical properties of transactinides). II Letnia Szkoła Energetyki i Chemii Jądrowej, Warszawa, Poland, Boguski J., Przybytniak G. Changes in thermal properties of radiation aged cables. Symposium on Ageing Management of Nuclear Plant Cables, Moret sur Loing, France, Brykała M., Deptuła A., Rogowski M., Modolo G., Schreinemachers Ch. Synthesis of uranium oxides and carbide doped by surrogates of MA by complex sol-gel process (CSGP). ACTINET-i3 ThUL School in Actinide Chemistry, Karlsruhe, Germany, Brzóska K. Classical and modern methods in biological dosimetry. Regional Worshop on Regulatory Control of Radioactive Discharges to the Environment, Warszawa, Poland, Chmielewski A.G. European energy mix tomorrow. CEE Meeting Sustainable Energy for Europe, Warszawa, Poland, Chmielewski A.G. Rola chemii i technologii radiacyjnej w rozwoju energetyki jądrowej oraz zastosowaniach gospodarczych (Role of chemistry and radiation technology in the development of nuclear energy and economic applications). II Letnia Szkoła Energetyki i Chemii Jądrowej, Warszawa, Poland, Chmielewski A.G. Science and industry partnership in the construction and operation of a NPP. European debates in Poland: A civil society initiative to take ownership of the nuclear power issue, Warszawa, Poland, Chmielewski A.G. Environmental applications of ionizing radiation. International Meeting on Radiation Processing IMRP 17, Shanghai, China, Kunicki-Goldfinger J.J. Uwagi na marginesie badań witraży średniowiecznych (Remarks on the research of medieval stained glass). Posiedzenie plenarne Polskiego Komitetu Narodowego Association Internationale pour l Historie du Verre, Warszawa, Poland, Lewandowska H., Stępkowski T., Sadło J., Kruszewski M. Formation of glutationyl dinitrosyl iron complexes does not alleviate iron genotoxicity. International Conference on Bioinorganic Chemistry ICBIC 16, Grenoble, France, Ostyk-Narbutt J. Rozdzielanie jonów metali metodą ekstrakcji ciecz-ciecz. Podstawy termodynamiczne (Solvent extraction separations of metal ions. Thermodynamics).

152 154 LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN II Letnia Szkoła Energetyki i Chemii Jądrowej, Warszawa, Poland, Ostyk-Narbutt J. Wydzielanie aktynowców mniejszościowych z odpadów jądrowych metodą ekstrakcji ciecz-ciecz (Separation of minor actinides from nuclear waste by solvent extraction). II Letnia Szkoła Energetyki i Chemii Jądrowej, Warszawa, Poland, Sartowska B., Starosta W., Pieniążek A., Orelovitch O., Apel P. Template synthesis of nanoscale porous materials nanoscale metal-organic frameworks (MOFs). Third International Conference on Multifunctional, Hybrid and Nanomaterials HYMA 2013, Sorrento, Italy, Schlegel-Zawadzka M., Gryczka U., Migdał W., Bertrandt J., Siegień F. The freez-drying food and their method of preservation for healthy diet and different purpose. IUNS 20th International Congress of Nutrition, Granada, Spain, Stępkowski T., Wasyk I., Kruszewski M. The differenctition of Lund Human Mesencephalon (LUHMES) cells to a dopaminergic neuron like phenotype leads to the decrease in expression of mitochondrial PGAM5 phosphatase. Cell Symposium Mitochondria: from Signaling to Disease, Lisbon, Portugal, Trojanowicz M. Pharmaceutical residues in the environment importance, analysis and removal. International Conference on Environmental Pollution and Remediation, Toronto, Canada, Zimek Z. Technology solutions: accelerators for sludge treatment. HEPTech Academia meets Industry: Environmental Applications of Accelerators, Warrington, United Kingdom, Zimek Z. Technology solutions: accelerators for treating water. HEPTech Academia meets Industry: Environmental Applications of Accelerators, Warrington, United Kingdom, SEMINARS Gajda D. Dlaczego potrzebujemy nowego składowiska odpadów promieniotwórczych (Why do we need a new repository for radioactive wastes). Maria Skłodowska-Curie Museum, Warszawa, Poland, Lewandowska-Siwkiewicz Hanna Przenoszenie ładunku wzdłuż dupleksu DNA konsekwencje biologiczne (Charge transfer along the DNA-duplex biological consequences). Faculty of Civil and Environmental Engineering, Białystok University of Technology, Białystok, Poland, Polkowska-Motrenko Halina Certyfikowane materiały odniesienia dla nieorganicznej analizy śladowej produkowane przez Instytut Chemii i Techniki Jądrowej (Certified reference materials for inorganic trace analysis produced by the Institute of Nuclear Chemistry and Technology). XV International Trade Fair for Analytical, Measurement and Control Technology EuroLab 2013, Warszawa, Poland, Polkowska-Motrenko Halina Procedury przygotowania certyfikowanego materiału (Procedures of preparation of certified reference material). Faculty of Chemistry, University of Warsaw, Warszawa, Poland, Trojanowicz M. Zastosowanie nanostruktur w wysokosprawnych metodach rozdzielania (Application of nanostructures to high-performance separation methods). Institute of Chemistry, Faculty of Mathematics, Physics and Chemistry, University of Silesia, Katowice, Poland,

153 AWARDS IN AWARDS IN Method for the disposal of radioactive wastes in structures of silica glasses (authors: Andrzej G. Chmielewski, Andrzej Deptuła, Magdalena Miłkowska, Wiesława Łada, Tadeusz Olczak) Gold Medal at the XVI Moscow International Salon of Inventions and Innovation Technologies Archimedes-2013, Moscow, Russia, Institute of Nuclear Chemistry and Technology 2. Method and system of transferring and mixing of a biomass slurry in a hydrolyser and fermenter (authors: Adam Kryłowicz, Janusz Usidus, Andrzej G. Chmielewski, Kazimierz Chrzanowski) Silver Medal at the XVI Moscow International Salon of Inventions and Innovation Technologies Archimedes-2013, Moscow, Russia, Institute of Nuclear Chemistry and Technology 3. Method for the disposal of radioactive wastes in structures of silica glasses (authors: Andrzej G. Chmielewski, Andrzej Deptuła, Magdalena Miłkowska, Wiesława Łada, Tadeusz Olczak) Special Prize of the German Institute ERINET (Forschungsinstitut für Erfinderförderung, Innovationen und Netzwerkmanagement) at the International Trade Fair Ideas Inventions New Products iena-2013, Nuremberg, Germany, Institute of Nuclear Chemistry and Technology 4. Method and system of transferring and mixing of a biomass slurry in a hydrolyser and fermenter Silver Medal at the International Trade Fair Ideas Inventions New Products iena-2013, Nuremberg, Germany, Adam Kryłowicz, Janusz Usidus, Andrzej G. Chmielewski, Kazimierz Chrzanowski 5. Mobile membrane installation MMI (authors: Andrzej G. Chmielewski, Jacek Palige, Otton Roubinek, Agata Urbaniak, Henryk Burliński, Katarzyna Wawryniuk) Grand Prix at the 11th International Conference and Exhibition OIL & GAS 2013, Warszawa, Poland, Institute of Nuclear Chemistry and Technology 6. The IMRP 17 Laureate Award for Science Life Time Award in recognition of the outstanding contribution to the development of the irradiation processing industry Andrzej G. Chmielewski 7. The Hevesy Medal Award 2013 in recognition of the outstanding contributions to the field of radiochemical neutron activation analysis (RNAA), in particular for proposing the idea of definitive methods by RNAA, and to the certification of reference materials Rajmund S. Dybczyński 8. Maria Skłodowska-Curie Medal No. 42 of the Maria Skłodowska-Curie Polish Radiation Research Society in recognition of his outstanding contribution to the development of radiation research Krzysztof Bobrowski 9. Sposób otrzymywania sferycznych ziaren trójtlenku itru (Method for obtaining spherical grains of yttrium trioxide; authors: Wiesława Łada, Danuta Wawszczak, Andrzej Deptuła, Edward Iller, Leszek Królicki, Jerzy Ostyk-Narbutt) Diploma of the Ministry of Science and Higher Education Institute of Nuclear Chemistry and Technology 10. Sposób unieszkodliwiania odpadów radioaktywnych w syntetycznej skale (Method of disposal of nuclear waste in the synthetic rock ; authors: Tomasz Smoliński, Andrzej G. Chmielewski, Andrzej Deptuła, Wiesława Łada, Tadeusz Olczak) Diploma of the Ministry of Science and Higher Education Institute of Nuclear Chemistry and Technology 11. Badania złóż uranonośnych oraz specjacji pierwiastków w piaskowcach (Works on analytical methods for uranium ores and speciation of elements in sandstones) Diploma at the XXII Konwersatorium Analityczne Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków, Poznań, Poland,

154 156 AWARDS IN 2013 Halina Polkowska-Motrenko, Ewelina Chajduk, Iwona Bartosiewicz, Witold Skwara, Jakub Dudek, Jadwiga Chwastowska, Marta Pyszynska 12. Oddzielenie związków uranu od metali towarzyszących z roztworów otrzymanych po ługowaniu piaskowców pochodzących z polskich złóż, metodą chromatografii jonowymiennej (Separation of uranium from associated metals from the solutions obtained after leaching of Polish sandstone ores by ion exchange chromatography) Award for the most interesting work in the field of chemical technology presented at the X Warszawskie Seminarium Doktorantów Chemików ChemSession 13, Warszawa, Poland, Dorota Gajda 13. Wydzielanie Tc-99m z aktywowanej w cyklotronie tarczy molibdenowej (Tc-99m separation from isotopically enriched 100 Mo via proton bombardment) Second award for the most interesting work presented at the X Warszawskie Seminarium Doktorantów Chemików ChemSession 13, Warszawa, Poland, Magdalena Gumiela 14. Analiza możliwości pozyskania uranu dla energetyki jądrowej z zasobów krajowych (Analysis of the possiblity of uranium supply from domestic resources) Diploma of the Polish Nuclear Society in the competition for the best poster presentation at the conference Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, Dorota Gajda 15. Badania nad otrzymywaniem spiekalnego ditlenku uranu za pomocą kompleksowej metody zol-żel (Studies on the preparation of sinterable uranium dioxide by complex sol-gel process (CSGP)) Diploma of the Polish Nuclear Society in the competition for the best poster presentation at the conference Nauka i technika wobec wyzwania budowy elektrowni jądrowej Mądralin 2013, Warszawa, Poland, Marcin Rogowski 16. First degree individual award of the Maria Skłodowska-Curie Polish Radiation Research Society in the field of radiation chemistry and photochemistry for a series of three review works on the significance of radiation chemistry to get to know processes with the participation of the free radicals in chemical and biological systems Krzysztof Bobrowski 17. Second degree group award of the Maria Skłodowska-Curie Polish Radiation Research Society in the field of radiobiology for a series of three papers concerning studies on factors affecting cell radiosensitivity Maria Wojewódzka, Halina Lisowska, Aneta Węgierek-Ciuk, Anna Banasik-Nowak, Janusz Braziewicz, Andrzej Wójcik, Anna Lankoff, Li Dang, Sara Shakeri Manesh, Alice Sollazzo, Marta Deperas-Kamińska, Elina Staaf, Siamak Haghdoost, Karl Brehwens, Ingela Parmryd 18. Nowe znaczniki promieniotwórcze fazy ciekłej i stałej do zastosowań w badaniach procesów membranowych (New radiotracers of liquid and solid phases for applications in researches of membrane processes) First degree award of the Polish Nuclear Society for the best doctoral thesis concerning nuclear sciences Agnieszka Miśkiewicz 19. New type of track membranes with asymmetric pores for a wide spectrum of nanotechnology applications The First Prize of the Joint Institute for Nuclear Research (Dubna, Russia) Bożena Sartowska 20. Knight s Cross of Order of Polonia Restituta for the outstanding contribution to the public and social activity, in the creation, deepen and propagation of religious, intelectual, artistic and political culture, for the educational activity in favour of children and young people Stanisław Latek 21. First degree team award of Director of the Institute of Nuclear Chemistry and Technology in 2013 for the application achievements elaboration of the project of mobile membrane installation for enrichment of biogas in methane Jacek Palige, Katarzyna Wawryniuk, Otton Roubinek, Agata Urbaniak, Henryk Burliński, Andrzej G. Chmielewski 22. Second degree team award of Director of the Institute of Nuclear Chemistry and Technology in 2013 for the application achievements realization of the project Studies of the technology of purification of flue gases with electron beam method on a pilot scale Andrzej Pawelec, Sylwia Witman-Zając, Janusz Licki, Andrzej G. Chmielewski

155 AWARDS IN Second degree team award of Director of the Institute of Nuclear Chemistry and Technology in 2013 for a series of four articles concerning the removal of harmful impurities from waters and sewages with membrane technology Grażyna Zakrzewska-Kołtuniewicz, Agnieszka Miśkiewicz, Marian Harasimowicz 24. Third degree team award of Director of the Institute of Nuclear Chemistry and Technology in 2013 for the application achievements implementation of new measurement methods related to the tightness of installations and industrial pipelines Janusz Kraś, Cezary Nobis, Tadeusz Bilka, Mirosław Gurniak, Mariusz Wieczorek, Grażyna Giers, Natalia Pawlik 25. Third degree individual award of Director of the Institute of Nuclear Chemistry and Technology in 2013 for a series of works concerning the removal of volatile organic compounds from gases emitted to the atmosphere Yongxia Sun 26. Third degree team award of Director of the Institute of Nuclear Chemistry and Technology in 2013 for a series of three articles concerning the application of radionuclides of scandium to the diagnosis and radionuclide theraphy Agnieszka Majkowska-Pilip, Marek Pruszyński, Barbara Bartoś, Aleksander Bilewicz 27. Distinction of the first degree of Director of the Institute of Nuclear Chemistry and Technology in 2013 for the achieved progress in the preparation of thesis and professional activity, including published articles, participation in the actions organized and co-organized by the Institute and participation in the preparation and realization of research projects and contracts outside the Institute Agata Piotrowska 28. Distinction of the second degree of Director of the Institute of Nuclear Chemistry and Technology in 2013 for the achieved progress in the preparation of thesis and professional activity, including published articles, participation in the actions organized and co-organized by the Institute and participation in the preparation and realization of research projects and contracts outside the Institute Kamila Kołacińska 29. Distinction of the second degree of Director of the Institute of Nuclear Chemistry and Technology in 2013 for the achieved progress in the preparation of thesis and professional activity, including published articles, participation in the actions organized and co-organized by the Institute and participation in the preparation and realization of research projects and contracts outside the Institute Konrad Skotnicki 30. Distinction of the INCT Scientific Council for the Ph.D. thesis Metaloorganiczne i chelatowe kompleksy 105 Rh i 103m Rh jako potencjalne prekursory radiofarmaceutyków terapeutycznych (Organometallic and chelate complexes of 105 Rh and 103m Rh as potential precursors of therapeutic radiopharmaceuticals) Seweryn Krajewski

156 158 INDEX OF THE AUTHORS INDEX OF THE AUTHORS A Abramowska Anna 25, 48 Ayers Tim 78 B Barlak Marek 76 Bańkowski Krzysztof 31 Bartłomiejczyk Teresa 58, 59 Bartosiewicz Iwona 48 Biełuszka Paweł 48 Bilewicz Aleksander 34, 37, 39 Bobrowski Krzysztof 17 Bojanowska-Czajka Anna 64 Boguski Jacek 25 Borowiecka Sylwia 64 Brykała Marcin 52 Brzóska Kamil 57 Bugaj Anna 21 Bułka Sylwester 81 Buczkowski Marek 25 Buraczewska Iwona 57, 58, 59, 60 C Cañete Alvaro 17 Celuch Monika 19 Chajduk Ewelina 48 Chmielewski Andrzej G. 81 Choiński Jarosław 37 Chwastowska Jadwiga 48 Cieśla Krystyna 25 D Danko Bożena 48 Deptuła Andrzej 52 Dudek Jakub 48 Dybczyński Rajmund 48 F Filipowicz Barbara 39 Frąckiewicz Kinga 48 Freestone Ian C. 78 Fuente Julio De la 17 Fuks Leon 31, 42 G Gajda Dorota 48 Gilderdale-Scott Heather 78 Gładysz-Płaska Agnieszka 42 Gniazdowska Ewa 31, 34 Grądzka Iwona 57, 60 Gumiela Magdalena 34 Guzik Grzegorz P. 95 H Harasimowicz Marian 48 Herdzik-Koniecko Irena 48 Hobot Jan A. 78 I Iwaneńko Teresa 57, 58 J Jakowiuk Adrian 100 Janik Ireneusz 19 Jastrzębski Jerzy 37 Jaworska Agnieszka 48 K Karlińska Magdalena 90 Kiegiel Katarzyna 48 Kołacińska Kamila 67 Korzeniowska-Sobczuk Anna 90 Kosno Katarzyna 19 Kowalska Ewa 100 Koźmiński Przemysław 31 Krajewski Seweryn 39 Królicki Leszek 31 Kruszewski Marcin 57, 58, 59 Kunicki-Goldfinger Jerzy J. 78 L Lankoff Anna 58, 59 Leciejewicz Janusz 72 Leszczuk Agata 37 Liśkiewicz Grażyna 96 Ł Łada Wiesława 52 Łuniewski Wojciech 31 Łyczko Krzysztof 35 Łyczko Monika 35, 37, 39 M Majdan Marek 42 Malec-Czechowska Kazimiera 86, 87 McDonald Iain 78 Michalik Jacek 21 Miecznik Jerzy B. 48 Miłkowska Magdalena 52 Mirkowski Jacek 19 Mirkowski Krzysztof 23 Miśkiewicz Agnieszka 45, 48

157 INDEX OF THE AUTHORS 159 Modzelewski Łukasz 100 N Nichipor Henrietta 81 Nowicki Andrzej 23, 25 O Olczak Tadeusz 52 Olszewska Wioleta 45, 48 Oszczak Agata 42 P Palige Jacek 100 Pawelec Andrzej 82 Pieńkos Jan 100 Piotrowska Agata 37 Polkowska-Motrenko Halina 48 Pogocki Dariusz 19 Pruszyński Marek 39 Przybytniak Grażyna 23 R Rogowski Marcin 52 S Sadło Jarosław 21 Samczyński Zbigniew 48 Sartowska Bożena 45, 76 Senatorski Jan 76 Sikorska Katarzyna 58, 59, 60 Smoliński Tomasz 52 Skotnicki Konrad 17 Sochanowicz Barbara 57, 60 Sommer Sylwester 58, 59 Stachowicz Marcin 35 Stachowicz Wacław 95, 96 Starosta Wojciech 72, 76 Sterniczuk Aneta 90 Sterniczuk Marcin 21 Stępkowski Tomasz 57 Stolarz Anna 37 Strzelczak Grażyna 21 Sun Yongxia 81 Szczygłów Katarzyna 48 Szkliniarz Katarzyna 37 Szumiel Irena 58, 60 T Tchórzewski Paweł 25 Trojanowicz Marek 64, 67 Trzcińska Agnieszka 37 W Waliś Lech 76 Wasyk Iwona 58, 59 Wawszczak Danuta 52 Wąs Bogdan 37 Wierzchnicki Ryszard 86, 87 Witman-Zając Sylwia 82 Wojewódzka Maria 57, 58, 59 Wojtowicz Patryk 52 Wołkowicz Stanisław 48 Woźniak Krzysztof 35 Wójciuk Grzegorz 57, 60 Wójciuk Karolina 58, 60 Z Zakrzewska-Kołtuniewicz Grażyna 45, 48 Zielińska Barbara 48 Zimek Zbigniew 81 Zipper Wiktor 37 Zwolińska Ewa 81