INCT Annual Report 2013

ISSN 1425-204X AANNUAL NNUAL RREPORTEPORT 22013013

INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY

Dorodna 16, 03-195 Warszawa, Poland phone: +48 22 504 12 05, fax: +48 22 811 15 32 e-mail: [email protected] www.ichtj.waw.pl IINSTITUTENSTITUTE OOFF NNUCLEARUCLEAR CCHEMISTRYHEMISTRY AANDND TTECHNOLOGYECHNOLOGY ANNUAL REPORT 2013

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

GENERAL INFORMATION 7

MANAGEMENT OF THE INSTITUTE 9 MANAGING STAFF OF THE INSTITUTE 9 HEADS OF THE INCT DEPARTMENTS 9 SCIENTIFIC COUNCIL (2011-2015) 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 99mTc. SEPARATION OF 99mTc FROM 100Mo 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 211At 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 137Cs 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 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 NOx 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 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 2013 102 ARTICLES 102 BOOKS 107 CHAPTERS IN BOOKS 107 THE INCT PUBLICATIONS 108 CONFERENCE PROCEEDINGS 109 CONFERENCE ABSTRACTS 110 SUPPLEMENT LIST OF THE PUBLICATIONS IN 2012 127

NUKLEONIKA 128

POSTĘPY TECHNIKI JĄDROWEJ 134

INTERVIEWS IN 2013 137

THE INCT PATENTS AND PATENT APPLICATIONS IN 2013 138 PATENTS 138 PATENT APPLICATIONS 138

CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2013 140

Ph.D. THESES IN 2013 142

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 2013 145 DEVELOPMENT PROJECTS GRANTED BY THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT IN 2013 145 INNOTECH PROJECTS GRANTED BY THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT IN 2013 145 APPLIED RESEARCH PROGRAMME OF THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT IN 2013 146 INTERNATIONAL PROJECTS CO-FUNDED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN 2013 146 STRATEGIC PROJECT “TECHNOLOGIES SUPPORTING DEVELOPMENT OF SAFE NUCLEAR POWER ENGINEERING” 147 STRATEGIC PROJECT “ADVANCED TECHNOLOGIES FOR GAINING ENERGY” 147 IAEA RESEARCH CONTRACTS IN 2013 147 IAEA TECHNICAL AND REGIONAL CONTRACTS IN 2013 148 PROJECTS WITHIN THE FRAME OF EUROPEAN UNION FRAME PROGRAMMES IN 2013 148 EUROPEAN REGIONAL DEVELOPMENT FUND: BALTIC SEA REGION PROGRAMME 149 OTHER INTERNATIONAL RESEARCH PROGRAMMES IN 2013 149 STRUCTURAL FUNDS: OPERATIONAL PROGRAMME INNOVATIVE ECONOMY 149

LIST OF VISITORS TO THE INCT IN 2013 150

THE INCT SEMINARS IN 2013 151

LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2013 153 LECTURES 153 SEMINARS 154

AWARDS IN 2013 155

INDEX OF THE AUTHORS 158 GENERAL INFORMATION 7

GENERAL INFORMATION

Poland decided to start a national nuclear energy programme 55 years ago and the Insti- tute of Nuclear Research (IBJ) was established. Research in nuclear and analytical chemistry, nuclear chemical engineering and technology (including fuel cycle), radiochemistry and radiation chemistry, and radiobiology were carried out mainly in the Chemistry Divi- sion, located at Warsaw Żerań, which became the interdisciplinary Institute of Nuclear Chemistry and Technology (INCT) in 1983. The INCT is Poland’s most advanced institution in the fields of radiochemistry, radiation chemistry, nuclear chemical engineering and technology, application of nuclear methods in material engineering and process engineering, radioanalytical techniques, design and production of instruments based on nuclear techniques, environmental research, cellular radiobiology, etc. The results of work at the INCT have been implemented in various branches of the national economy, particularly in industry, medicine, environmental protection and agriculture. Basic research is focused on: radiochemistry, chemistry of isotopes, physical chemistry of separation processes, cellular radiobiology, and radiation chemistry, particularly that based on 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 SO2 and NOx 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 Collabo- rating Centre in Radiation Technology and Industrial Dosimetry. The INCT is editor of the scientific journal “Nukleonika” (www.nukleonika.pl) 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 Decem- ber 2013. 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. 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 Gur- niak, 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. MANAGEMENT OF THE INSTITUTE 9

MANAGEMENT OF THE INSTITUTE

MANAGING STAFF OF THE INSTITUTE

Director Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. Deputy Director for Research and Development Prof. Jacek Michalik, Ph.D., D.Sc. Deputy Director of Finances Wojciech Maciąg, M.Sc. Deputy Director of Maintenance and Marketing Roman Janusz, M.Sc. Accountant General Maria Małkiewicz, M.Sc.

HEADS OF THE INCT DEPARTMENTS

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

SCIENTIFIC COUNCIL (2011-2015)

1. Prof. Grzegorz Bartosz, Ph.D., D.Sc. 5. Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. University of Łódź Institute of Nuclear Chemistry and Technology 2. Prof. Aleksander Bilewicz, Ph.D., D.Sc. 6. Andrzej Chwas, M.Sc. Institute of Nuclear Chemistry and Technology Ministry of Economy 3. Prof. Krzysztof Bobrowski, Ph.D., D.Sc. 7. Jadwiga Chwastowska, Ph.D., D.Sc., professor (Vice-chairman) in INCT Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology 4. Marcin Brykała, Ph.D. 8. Krystyna Cieśla, Ph.D., D.Sc., professor in INCT Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology 10 MANAGEMENT OF THE INSTITUTE

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

HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (2011-2015)

1. Prof. Sławomir Siekierski, Ph.D. 3. Prof. Irena Szumiel, Ph.D., D.Sc. 2. Prof. Zbigniew Szot, Ph.D., D.Sc. 4. Prof. Zbigniew Paweł Zagórski, Ph.D., D.Sc. MANAGEMENT OF THE INSTITUTE 11 ORGANIZATION SCHEME

Scientific DIRECTOR Council

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

Deputy Director for Research and Development

Laboratory of Nuclear Analytical Methods

Centre for Radiation Research and Technology Stable Isotope Laboratory

Pollution Control Technologies Centre for Radiobiology Laboratory and Biological Dosimetry

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

Laboratory of Material Research

Laboratory of Nuclear Control Systems and Methods 12 SCIENTIFIC STAFF

SCIENTIFIC STAFF

PROFESSORS

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

SENIOR SCIENTISTS (Ph.D.)

1. Bartłomiejczyk Teresa 5. Brzóska Kamil biology biochemistry 2. Bojanowska-Czajka Anna 6. Buczkowski Marek chemistry physics 3. Borowik Krzysztof 7. Chajduk Ewelina chemistry chemistry 4. Brykała Marcin 8. Danilczuk Marek chemistry chemistry SCIENTIFIC STAFF 13 9. Deptuła Andrzej 31. Męczyńska-Wielgosz Sylwia chemistry chemistry 10. Dobrowolski Andrzej 32. Mirkowski Jacek chemistry nuclear and medical electronics 11. Dudek Jakub 33. Miśkiewicz Agnieszka chemistry chemistry 12. Fuks Leon 34. Nowicki Andrzej chemistry organic chemistry and technology, high-temperature technology 13. Głuszewski Wojciech 35. Ostrowski Stanisław chemistry chemistry 14. Gniazdowska Ewa 36. Palige Jacek chemistry metallurgy 15. Grądzka Iwona 37. Pawelec Andrzej biology chemical engineering 16. Harasimowicz Marian 38. Pruszyński Marek technical nuclear physics, theory of elementary particles chemistry 17. Herdzik-Koniecko Irena 39. Ptaszek Sylwia chemistry chemical engineering 18. Kciuk Gabriel 40. Rafalski Andrzej chemistry radiation chemistry 19. Kiegiel Katarzyna 41. Roubinek Otton chemistry chemistry 20. Kierzek Joachim 42. Sadło Jarosław physics chemistry 21. Kocia Rafał 43. Samczyński Zbigniew chemistry analytical chemistry 22. Kornacka Ewa 44. Sartowska Bożena chemistry material engineering 23. Koźmiński Przemysław 45. Skwara Witold chemistry analytical chemistry 24. Krajewski Seweryn 46. Sochanowicz Barbara chemistry biology 25. Kunicki-Goldfinger Jerzy 47. Sommer Sylwester conservator/restorer of art radiobiology, cytogenetics 26. Latek Stanisław 48. Stachowicz Wacław nuclear physics radiation chemistry, EPR spectroscopy 27. Lewandowska-Siwkiewicz Hanna 49. Starosta Wojciech chemistry chemistry 28. Łyczko Krzysztof 50. Sterniczuk Macin chemistry chemistry 29. Łyczko Monika 51. Strzelczak Grażyna chemistry radiation chemistry 30. Majkowska-Pilip Agnieszka 52. Sun Yongxia chemistry chemistry 14 SCIENTIFIC STAFF 53. Szreder Tomasz 59. Wiśniowski Paweł chemistry radiation chemistry, photochemistry, biophysics 54. Waliś Lech 60. Wojewódzka Maria material science, material engineering radiobiology 55. Walo Marta 61. Wójciuk Grzegorz chemistry chemistry 56. Warchoł Stanisław 62. Wójciuk Karolina solid state physics chemistry 57. Wawszczak Danuta 63. Zimek Zbigniew chemistry electronics, accelerator techniques, radiation processing 58. Wierzchnicki Ryszard chemical engineering 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. The unique technical basis makes it possible to organize a wide internal and international cooperation in the field of radiation chemistry and radiation processing including programmes supported by the European Union and the International Atomic Energy Agency (IAEA). It should be noticed that currently there is no other suitable European experimental basis for study radiation chemistry, physics and radiation processing in a full range of electron energy and beam power. Since 2010, at the INCT on the basis of the Centre for Radiation Research and Technology, an IAEA Collaborating Centre for Radiation Processing and Industrial Dosimetry is function- ing. That is the best example of capability and great potential of concentrated equipment, methods and staff working towards application of innovative radiation technology. CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 17 ONE-ELECTRON OXIDATION AND REDUCTION OF 3-METHYLQUINOXALIN-2-ONE Konrad Skotnicki, Krzysztof Bobrowski, Julio De la Fuente1/, Alvaro Cañete2/ 1/ Universidad de Chile, Santiago de Chile, Chile 2/ Pontificia Universidad Católica de Chile, Chile

Quinoxalin-2-ones are the class of compounds either amino acid residues or radicals derived from showing a variety of pharmacological properties, them. Certain amino acid residues – tyrosine (Tyr), such as antimicrobial [1], antiviral [2], anti-inflam- tryptophan (Trp), and cysteine (Cys) are particu- matory [3], antithrombotic [4, 5], anticancer [6-9] larly vulnerable to oxidation. Therefore, the radical activity. cations derived from quinoxalin-2-ones can modify A key factor decisive about their biological activity these amino acids which are reasonably good elec- is a substitution at the carbon-3 in the pyrazine tron donors and can be oxidized to tyrosyl (TyrO●), ring and at the carbons 6 and 7 in the benzene ring tryptophyl (Trp●), and thiyl (Cys●) radicals, respec- in a primary quinoxalin-2-one structure (Chart 1). tively. On the other hand, these radicals are rea- Nearly all biologically active derivatives are sub- sonably good electron acceptors and can act po- stituted in these specific positions. tentially 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 Chart 1. Structural formula of quinoxalin-2-one. of their high concentration in cells [11]. In prin- ciple, oxidation and reduction processes in pro- The structure activity relationship (SAR) studies teins can occur everywhere and involve the protein have revealed that quinoxalin-2-ones derivatives backbone, amino acid residues and also intercalat- bound to proteins receptors are generally located ed molecules (e.g. quinoxalin-2-ones). The primary close to the adenosine triphosphate (ATP) bind- steps leading to these modifications are extremely ing pocket [6, 10], e.g. in cyclin-dependent kinases fast, consist of one electron loss and very often a (Cdk). The fact that these compounds are bound subsequent one electron capture, resulting in cre- in the very specific position in proteins may have ation of very reactive transients (radicals and radi- serious consequences in their interactions with cal 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 N2O-saturated 0.1 mM 3-methylquinoxalin-2-one, at pH 8. Insets: kinetics traces of formation and decay recorded at 370 and 460 nm. 18 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY actions. For these reasons it is important to char- after the pulse are characterized by two distinct acterize spectral properties of transients derived absorption maxima located at λ = 370 and 460 nm from quinoxalin-2-ones (those derived from amino (Fig.1). The first one is stable within 1.5 ms time acids are mostly known) and to measure kinetic domain. Complementry steady-state γ-radiolysis ex- parameters of the primary and secondary reac- periments revealed that this absorption is stable tions involving quinoxalin-2-ones and amino acid and is associated with a stable reaction product. k residues. These reactions lead to production of The second-order rate constants Q+OH• were de- various free radicals, including those derived either termined from the kinetic traces at 370 and 460 nm from amino acids or quinoxalin-2-ones. in pseudo first-order conditions and were found

− Fig.2. Transient absorption spectra obtained by esolv 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. k 9 −1 −1 Radical oxidation and reduction of 3-methyl- to be equal to 370 = 4.6 ± 0.2 × 10 M s and k 9 −1 −1 quinoxalin-2-one and kinetics of its reactions with 460 = 4.4 ± 0.2 × 10 M s . ● − hydroxyl radicals ( OH) and solvated electrons Reaction with eaq has been performed in − (eaq ), respectively, were studied by pulse radiolysis Ar-saturated aqueous solution containing tert-bu- technique coupled with the time-resolved UV/Vis tanol at pH 8. One-electron reduction of 3-methyl- spectrophotometric detection system. Reactions quinoxalin-2-one leads to the formation of at least were studied in aqueous solutions saturated either two products, with the respective absorption maxi- with N2O or argon. ma at λ = 370 and 430 nm (Fig.2). The second- k Pulse radiolysis studies in N2O-saturated aque- -order rate constant Q+e was determined from ous solution at pH 8 has been performed in order the kinetic traces at 720 nm (absorption maximum to check whether 3-methylquinoxalin-2-one is able of solvated electron absorption in water) in pseudo to scavenge ●OH radicals. ●OH-induced oxidation first-order conditions and was found to be equal k 10 −1 −1 generally leads to one-electron oxidation prod- to 720 = 2.8 ± 0.2 × 10 M s . ucts. However, it is well known, that the formation Additional experiments performed in different of OH adducts is another possible reaction path- pH values and with similar compounds allow to as- way. Transient absorption spectra observed 4 μs sume that one-electron reduction results in the for- H H H N O N O + N O esolv H

- C C N N N H Scheme 1. A proposed mechanism for one-electron reduction of 3-methylquinoxalin-2-one. CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 19 mation of a radical anion followed by a rapid pro- [3]. El-Sabbagh O.I. et al.: Med. Chem. Res., 18(9), tonation to a neutral protonated radical. Proposed 782-797 (2009). reaction mechanism is presented in Scheme 1. [4]. Ries U.J. et al.: Bioorg. Med. Chem. Lett., 13(14), 2297-2302 (2003). Obtained results indicated that quinoxalin-2- et al ● [5]. Willardsen J.A. .: J. Med. Chem., 47(16), -ones are able to scavenge OH radicals with high 4089-4099 (2004). k 9 −1 −1 rate constants ( = 4.5 × 10 M s ) which is a very [6]. Hirai H. et al.: Invest. New Drugs, 29(4), 534-543 promising result for their possible medical use. (2011). One-electron reductions leads to the formation of [7]. Kotb E.R. et al.: Phosphorus, Sulfur Silicon Relat. radical anion and protonated radical with a rate Elem., 182(5), 1119-1130 (2007). constant close to a diffusion control (k = 2.8 × 1010 [8]. Lawrence D.S., Copper J.E., Smith C.D.: J. Med. M−1s−1). Further studies concerning interactions of Chem., 44(4), 594-601 (2001). quinoxalin-2-ones with amino acids will be per- [9]. Yuan H.Y. et al.: Med. Chem. Res., 18(8), 671-682 formed. (2009). [10]. Mori Y. et al.: Chem. Pharm. Bull., 56(5), 682-687 References (2008). [11]. Dean R.T. et al.: Free Radical Biol. Med., 11(2), et al. [1]. Ajani O.O. : Bioorg. Med. Chem., 18(1), 214-221 161-168 (1991). (2010). [2]. Xu B.L. et al.: Bioorg. Med. Chem., 17(7), 2767-2774 (2009).

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 acts through a variety of reaction mechanisms, commonly known natural alkaloid present mainly including direct electron transfer, hydrogen ab- in tobacco plants and is characterized by a stimu- straction, and addition to unsaturated bonds. In lant action. It interacts with the nicotinic acetyl- case of nicotine every three pathways are possible. choline receptors and cause the release of many 3' 4' neurotransmitters responsible for mood (e.g. nor- adrenaline, serotonin and dopamine). This is the 4 3 main reason of its strong addictive power. How- 5 5' ever, nicotinic stimulation has also positive effects 2' N as it is used in the therapy of some neurodegen- 1' erative disorders and diseases [1]. 6 2 CH3 N 6' Because of its antioxidative properties, nico- 1 tine has the potential to be widely used as a free radical scavenger. It can be used to protect nerve Fig.1. Structural formula of nicotine. cells in some major neurodegenerative disorders Considering the electron density and favourable and diseases such as Alzheimer’s and Parkinson’s energetic effect, substitution occurs mainly at the diseases, Tourette’s syndrome or schizophrenia. meta position, the most probable product of hy- Neurodegeneration associated with these diseases drogen abstraction is radical located at a chiral is accompanied by an extensive oxidative stress, carbon and the cation radical is formed at pyrroli- caused by the imbalance in the production of re- dine nitrogen. However, nicotine is a weak base K K active oxygen species and the biological system’s with a p a1 of 8.02 (p a2 = 3.12) in aqueous solu- inability to detoxify them. Nervous tissue is con- tion at 25oC [3] and the protonation state has the tinuously exposed to the presence of toxic oxygen influence on its radical reactions. According to radicals beyond a threshold for proper antioxidant DFT calculations, protonation of pyrrolidine ni- neutralization. Nicotine can easily pass through trogen increases the dissociation enthalpy of the the blood-brain barrier and prevent this destruc- C2’-H bond. Some reaction pathways can be even tive radical action thanks to its antioxidative prop- blocked in acidic solutions. erties. There are some evidence that nicotine can The main experimental technique used to study react with the most dangerous ●OH radical pro- the radical oxidation of nicotine was pulse radio- ducing neutral or less aggressive radical products lysis coupled with a time-resolved UV/Vis detec- [2]. However, it has not been confirmed so far and tion system, which enables to study molecular more data about the mechanism of nicotine radi- processes close to or even beyond the diffusion cal processes should be obtained. The knowledge controlled reaction limit. Experiments were per- about the reactions kinetic is also important, be- formed with the LAE 10 [4] (Institute of Nuclear cause the rate of nicotine radical reactions need to Chemistry and Technology) and Titan Beta Model be high enough to exclude competitive reactions. TBS-8/16-1 [5] (Notre Dame Radiation Labora- Nicotine molecule is made of two rings: aro- tory) linear accelerators. Analysis was done in the matic pyridine and aliphatic pyrrolidine with chi- broad range of pH giving data for protonated and ral carbon C2’ atom (Fig.1). The ●OH radical re- unprotonated forms of nicotine. Using pyridine 20 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY

Fig.2. Reaction scheme for the oxidation of nicotine by azide radical. and N-methylpyrrolidine as nicotine model com- with a sharp maximum at 274 nm. Reaction of pounds enabled to divide radical reactions into one-electron oxidation can only occur with the occurring with aromatic and aliphatic part of the aliphatic nitrogen (Fig.2C). Azide radical will not molecule. react with aromatic ring, because according to In order to check if nicotine oxidation can pro- data obtained by Schuler, the rate of its reaction ceed with single-electron transfer, its reaction with pyridine is lower than 3 × 105 M–1s–1 [6]. Al- with azide radical has been studied. Azide radical though there are no reports that azide radicals reis a strong one-electron oxidant and it can be read- acts by hydrogen abstraction, theoretically in fa- ily prepared radiolytically by ●OH oxidation of vourable reaction conditions there is such a possi- azide anions in aqueous solution (Fig.2A,B). It ex- bility (Fig.2D). The bond dissociation energy for a hibits moderate absorption only in the UV range bond between hydrogen atom and asymmetric car-

5x105 k = 5.23 x 107 M-1s -1 (Nic + N3.) 4 1.3x10 4x105 ) -1 3x105 4 (s app

1.0x10 k 2x105 /J] 2 1x105 7.5x103 [m

ε 0 0246810 -3 -3 3 [Nic] (10 mol dm ) G × 5.0x10 1 mM Nic + 10 mM NaN3 2.5x103 pH 10 pH 5.6

300 350 400 450 500 550 λ [nm]

Fig.3. Transient absorption spectra recorded 10 μs after the electron pulse in N2O-saturated, 10 mM aqueous solution of NaN3 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 NaN3, N2O-saturated, aqueous solution at pH 10 as a function of nicotine concentration. CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 21 bon in nicotine molecule is about 25 kJ/mol lower radical should react with N-methylpyrrolidine also than the N-H bond dissociation energy in hydra- by electron transfer (Fig.4B). After the pyrrolidinyl zoic acid. nitrogen protonation this way of reaction is block- K The reaction of nicotine with azide radical was ed. N-methylpyrrolidine has a p a of 10.46, so the studied for two protonation states of the pyrro- experiments were done at pH 11.4, where there is lidinyl nitrogen. Transients obtained in the reac- about 90% of the unprotonated form. tion of unprotonated nicotine at pH 10 gave spec- The kinetic studies of the 520 nm absorbance trum with one distinct absorption band with λmax changes have been done using a competition = 330 nm and a broad absorption band with λmax method. N-methylpyrrolidine will compete with ca. 460 nm, both growing with the same rate (Fig.3). tryptophan and react with azide radicals, what It is very similar to the spectrum obtained for nico- causes a decrease in the absorbance with increas- tine reaction with hydroxyl radicals, what may sug- ing alkaloid concentration. The rate constant for gest that we also observe here mainly radical at the reaction of N-methylpyrrolidine with azide chiral carbon. For the protonated aliphatic nitro- radical was determined to be 5.6 × 107 M–1s–1. Such gen at pH 5.6, the absorption at 330 nm is almost a low reaction rate suggest that the electron trans- 20 times lower and we observed a weak band at fer will have a minor contribution to the mecha- A

Fig.4. Mechanism of the azide radical reaction with tryptophan and N-methylpyrrolidine. 280 nm, which can be assigned to azide radicals. nism of nicotine reaction with azide radical. Ob- This indicates that azide radical does not react tained results indicate that azide radical, although with protonated form of nicotine, because the is a well-known one-electron oxidant, in energeti- electron transfer is blocked. Hydrogen abstraction cally favourable conditions it can also abstract hy- from chiral carbon is also inhibited because of the drogen atoms. higher C*–H bond dissociation energy than in un- References protonated form. The reaction with the unprotonated form is second order with a rate constant of [1]. Pogocki D., Ruman T., Danilczuk M., Danilczuk M., 5 × 107 M–1s–1. Celuch M., Wałajtys-Rode E.: Eur. J. Pharm., 563, To confirm that azide radical can oxidize the 18-39 (2007). [2]. Wang S.-L., Wang M., Sun X.-Y., Li W., Ni Y.: Spec- pyrrolidinyl nitrogen, we studied its reaction with N-methylpyrrolidine in the presence of trypto- trosc. Spect. Anal., 23, 481-483 (2003). [3]. CRC Handbook of Chemistry and Physics on CD-ROM. phan. Tryptophan is a natural amino acid existing CRC Press, 2004. in proteins. Its reaction with azide radical is well [4]. Bobrowski K.: Nukleonika, 50, 3, 67-76 (2005). known (Fig.4A). It proceeds with electron trans- [5]. Hug G.L., Wang Y., Schöneich Ch., Jiang P.-Y., Fessen- fer and generates radicals absorbing at 320 and den R.W.: Radiat. Phys. Chem., 54, 559-566 (1999). 520 nm with high extinction coefficients. The rate [6]. Schuler R.H., Alfassi Z.B.: J. Phys. Chem., 89, 3359-3363 of this reaction at pH 11.4 is 4.5 × 109 M–1s–1. Azide (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 only effective and highly selective but also resis- wastes is a challenging task for the management tant to radiation for very long time [1-3]. of waste disposal. Sorbents containing radionu- In this report we present the studies on para- clides are exposed to high level of radiation dose magnetic species formed in γ-irradiated saponite which generates changes in sorbent structure. It is and crystalline sitinakite (Fig.1) containing ex- expected that new sorption materials will be not changeable Ag+ cations. Saponite is a layered clay 22 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY mineral belonging to smectite group composed of polyhedral sheets with Si4+ in tetrahedral sites and Al3+ and/or Mg2+ in octahedral ones. The structure of sitinakite [molecular formula Na2Ti2O3(SiO4) · 2H2O] is similar to commercially available synthetic titanosilicate IONSIV* IE-911. Both materials are successfully used for sorption of radionuclides from Fukushima radioactive wastewaters. A

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.

Dehydrated Na-sitinakite shows strong anisotropic singlet T with orthorhombic symmetry of g-factor: g = 2.003, g = 2.011 and g = 2.024 Fig.1. Crystal structure of saponite (A) and sitinakite (B). 1 2 3 (Fig.2a). Hydrated Na-sitinakite sample shows the Electron paramagnetic resonance (EPR) spec- same signal. Similar EPR signal was recorded in troscopy is very useful tool for characterization of TiO2 colloids and was assigned to the hole trap- paramagnetic species like radicals and paramag- ped on the colloidal surface – Ti4+O2–Ti4+O*– [4]. netic atoms or cations generated by radiation in In Ag-sitinakite both in hydrated and dehydrated sorbent materials. form, signal T is also recorded but then is accom- Fission product radioisotopes can get into re- panied by strong signals of paramagnetic silver actor primary cooling system as a result of zirco- species. In hydrated Ag-sitinakite the most pro- 110m nium cladding damage. Silver Ag together with nounced signal is anisotropic doublet with g⊥ = 60 137 Co, Cs and others belongs to long-lived radio- 2.039, gII = 2.242, A⊥ = 3.2 mT, AII = 4.0 mT isotopes which for safety reasons should be re- (Fig.2b). Doublet with similar g-factors and hy- moved from cooling water. Sorption on micropo- perfine splitting values was earlier observed after rous materials like zeolites or clays is usually used irradiation of hydrated zeolite A and was assigned for that purpose. For model studies of radiation to Ag2+ divalent cation [5]. In dehydrated Ag-siti- changes of metal valence state by EPR we use nakite perpendicular component of Ag2+ signal silver as an exchangeable cation. Both silver iso- shows additional splittings which indicate the over- topes 107Ag and 109Ag have nuclear spin ½ and lapping of Ag2+ EPR line with unknown signal large magnetic moments which usually makes (Fig.2c). We speculate that three lines labelled x possible to identify paramagnetic silver species with splitting ~10 mT belongs to the same signal like silver atoms, cations and clusters produced but at this moment we are unable to identify its by radiation. origin. Doublet H with hyperfine splitting equal Saponite and sitinakite samples after degas- ~50 mT present in all spectra in Fig.2 represents sing on vacuum line at room temperature or dehy- hydrogen atoms trapped in spectrosil tubings. drating at 120oC were irradiated at 77 K with dose Figure 3 shows the EPR spectra of γ-irradiated of 10 kGy in Co-60 source. EPR spectra were samples of hydrated saponite synthetized in NIMS, measured using EPR Bruker X-band ESP 300 Tsukuba, Japan. The exchangeable cations were in- spectrometer in the temperature range 100-280 K. troduced into gel before synthesis. In all cases samples before irradiation did not In Na-saponite (Fig.3a) three major lines W, Y, show any EPR signals. Z showing asymmetric shape and additional split- The EPR spectra of γ-irradiated sitinakite mea- ting represent unidentified radiation-induced para- sured at 130 K are presented in Fig.2. magnetic defects in clay layers. Moreover, in the CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 23 sample with exchanged Ag+ ions (Fig.3b) appears because then only two lines should be observed at a weak doublet with hyperfine splitting 64 mT. It high magnetic field and two ones at low field. In represents silver atoms Ag0. In saponite sample conrast both field regions show four lines which indicates that Ag0 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 110mAg cations in saponite clays. The research described herein was supported by the National Centre for Research and Develop- ment, 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), 477-481 (2005). Fig.3. EPR spectrum at 160 K of γ-irradiated hydrated sa- [2]. Allard T., Calas G.: Appl. Clay Sci., 43(2), 143-149 ponite with: (a) Na+; (b) Na+ and Ag+; (c) Na+, Ag+ and (2009). Cs+. [3]. Anthony R.G. et al.: Ind. Eng. Chem. Res., 33(11), 2702-2705 (1994). + + + containing Na , Ag and Cs cations (Fig.3c) the [4]. Micic O.I. et al.: J. Phys. Chem., 97(28), 7277-7283 0 Ag lines clearly shows additional splittings la- (1993). belled 1, 2, 3 and 4. They are not only due to the [5]. Sadlo J., Wasowicz T., Michalik J.: Radiat. Phys. different hyperfine splittings of 107 Ag0 and 109Ag0 Chem., 45(6), 909-915 (1995).

RADIATON-INDUCED CURING OF EPOXY RESINS AND ITS NANOCARBON COMPOSITES

Grażyna Przybytniak, Andrzej Nowicki, Krzysztof Mirkowski

Recently published papers have reported that cur- ity make the resins usable under harsh/degradable ing of epoxy resins might be supported by ionizing conditions for many years. In order to obtain good radiation and that such a treatment provides ma- quality material usually a photoinitiator at a con- terials with high glass transition temperatures. Al- centration of 1% or more is required. The final though flexural strength of radiation cured epoxy product shows better features than the resins based resin is comparable to thermally cured ones, other on polyamine hardeners [1-3]. mechanical parameters are more advantageous. In our studies primary objective was to esti- Enhanced toughness and unusual long-term stabil- mate if radiation technique might be applied for (1) 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]. (2) The work was focused on the studies related to radiation curing of epoxy resins based on digly- cidyl ether of bisphenol A (DGEBA) in the presence of cationic photoinitiator Rhodorsil in the form of [4(1-methylethyl)phenyl][4-methylphe- nyl]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 Scheme 1. Formulae of DGEBA (1) and cationic initiator Nuclear Chemistry and Technology (INCT) as a used for radiation-induced curing Rhodorsil 2074 (IPB) (2). suspension in dichloromethane (CH2Cl2). The ini- 24 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY tiator was dissolved in DGEBA at 60-65oC in an tiated polymerization are presented for several ultrasonic bath. In the same way carbon based systems. 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

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 5000. a, c – irradiation at 6.4 kGy/h; d-i – irradiation at 3.2 kGy/h. For all specimens, except this one comprising Fig.1. Thermal effects for the selected materials placed in RGO (“i” peak), the rapid temperature increase a Gamma Chamber 5000 at a dose rate of 6.4 kGy/h. has been confirmed for irradiation lasting less than 60 min, i.e. when temperature in the chamber radiation energy by the walls were observed. In loaded with the materials free from initiator does order to estimated these consequences, the ther- not reach 30oC. This reflects an accumulation of mal measurements were conducted for the cham- the radical centres generated in the presence of ber unloaded and loaded with water or epoxy resin the initiator at the first stage of the process. When free from initiator (Fig.1). The diagrams indicate their population achieves an appropriate level a that even after 6 h temperature in the loaded rapid combination of radicals gives strong exo- chamber is less than 45oC and has not reached thermic effect which initially intensifies curing but equilibrium yet. On the basis of these results it was upon depletion of the initiator goes out with de- assumed that ionizing radiation effects predomi- creasing amount of the active centres. Radiation nantly initiate cross-linking in the presence of the energy has to initiate thermal curing which re- initiator at the first stage. The conclusion confirms quires about 170oC (Fig.2), as just above this tem- thermogram recorded by the DSC method show- perature thermal effect prevails over radiation-in- ing intensive thermal curing of the system only duced phenomena. Worth noting that in spite of above 170oC (Fig.2). various dose rates and initiator concentrations maximum temperature of exothermic curing is above 200oC for all comprising IPB systems irradiated in the GC 5000. 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 de- struction 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 Fig.2. Thermogram of DGEBA in the presence of 1% ini- o kGy), respectively. These discrepancies arise from tiator, heating rate – 5 C/min. various phenomena standing behind electron beam Figure 3 shows the progress of temperature in- and gamma-ray irradiations. In the former case, crease for the radiation-initiated curing of epoxy the temperature does not reach value high enough resin and its nanocomposites in the presence of to begin thermal curing thus polymerization is cationic initiator – Rhodorsil. The profiles of tem- completely radiation-dependent. Such a course of perature variations related to the radiation-ini- the processes results from generation in situ a suf- CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 25 ficient population of intermediates due to the high nature of nanofillers. The induction time of poly- dose rate what causes fast exhaustion of the initia- merization is even twice longer for graphene based tor combined with decay of radicals. Therefore, composites than for non-filled matrix due to limit- the system cannot be thermally cured, contrary to ing access to the initiator absorbed on the surface gamma-initiated processes. of dispersed phase. The presence of graphene derivatives extends The work was financially supported by the In- the induction time of exothermic polymerization, ternational Atomic Energy Agency (IAEA) – CRP particularly in the case of RGO, what can results contract No. 16666 and the Ministry of Science and from adsorption of the part of initiator by the de- Higher Education, Poland – project ID 225404. veloped surface of the filler. On the other hand, References carbon nanotubes that have not oxygen containing functional groups do not reveal such phenom- [1]. Degrand H., Cazaux F., Coqueret X., Defoort B., ena. Therefore, it seems that access to polar sub- Boursereau F., Larnac G.: Radiat. Phys. Chem., 68, 5, stituents in GO and RGO facilitates binding of 885-891 (2003). the initiator to the carbon nanostructures what [2]. Alessia S., Parlato A., Dispenza C., De Maria M., Spa- delays curing of the resin. daro G.: Radiat. Phys. Chem., 76, 8-9, 1347-1350 (2007). [3]. Alessi S., Dispenza C., Fuochi P.G., Corda U., Lavalle On the basis of the studies it was found that the M., Spadaro G.: Radiat. Phys. Chem., 76, 8-9, 1308-1311 temperature profiles recorded during radiation (2007). curing of epoxy resins in the presence of cationic [4]. Sui G., Zhang Z-G., Liang Z-Y., Chen Ch.-Q.: Mater. photoinitiators and selected carbon nanofillers Sci. Eng. A, 342, 28-37 (2003). were determined by the type of radiation and its [5]. Rhodorsil photo initiator 2074 – Material Safety Data dose rate, the concentration of initiator and the 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 the biodegradable films based on starch and PVA plastic waste induces the interest in substitution of and examination of the effect of gamma irradia- traditional packaging by the biodegradable mation on the properties of the obtained materials. terials. Preparation of the films in the mixed sys- Four PVAs (products of Sigma and of Alfa tems composed of variety of natural polymers Aesar) characterized by various molecular masses (polysaccharides or proteins) as well as containing (Mw; PVA1: 145000, PVA2: 90000, PVA3: 60000, polysaccharide – artificial biodegradable polymer and PVA4: 15000-30000) as well as two corn- seems to be one of the abilities to obtain better starches – SC1 (by Sigma) and SC2 (by Cerestar) and more friendly for the environment packaging and two potato starches – S8 (Sigma product) and material. S7 (commercial, local market) were selected for Starch is an abundant and cheap biopolymer the films preparation. Moreover, the starches SC1d with a good film forming ability and therefore it and S8d degraded by the way of irradiation with a appears to be an appropriate source for prepara- dose of 10 kGy (in purpose to reduce their viscos- tion of the cheap biodegradable packaging [1-3]. ity [1, 5]) were prepared and applied. In purpose to improve mechanical and barrier Films were prepared by the solution casting properties of starch films various modification method after addition of glycerol as a plasticizer methods are applied for the starch substrate as at a level of 0, 20 and 30% (in relation to the well as blending starch with the other natural or starch-PVA mass). The films were dried, peeled artificial biodegradable polymer. PVA (polyvinyl from the substrate and conditioned during couple alcohol) can be used for packaging purposes, and of days at a relative humidity of 43% before test- is known to be the appropriate polymer for blending. ing with starch [3]. Irradiations were carried out with Co-60 gam- The potential application for packing of the ma radiation in vacuum or in air at ambient tem- products subjected to radiation decontamination perature in a Gamma Chamber 5000 placed in the and the possibility of radiation modification of its Centre for Radiation Research and Technology, structure and properties makes interesting to ex- INCT. Irradiations of the PVA films were con- amine the effect of ionizing radiation on biode- ducted with a dose of 100 kGy and irradiation of gradable polymer [4]. Our previous results have the the starch and starch-PVA were carried out already shown that using the irradiated starch en- using a dose of 25 kGy. ables to obtain films with better functional prop- Mechanical tests were carried out using an erties as compared to those prepared basing on Inström testing machine [2]. The average values the native starch [1, 2]. of tensile strength and elongation at break were Accordingly, our present studies were focused calculated on the basis of 6-8 measurements per- on the elaboration of method for preparation of formed for each composition. For evaluation of 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. 35oC.

Dose 0 kGy Dose 100 kGy Glycerol content PVA [wt.%] tensile strength elongation at break tensile strength elongation at break [MPa] [%] [MPa] [%] 0 56.6 119.3 58.3 105.9 PVA1 20 37.9 168.2 33.9 141.6 30 30.3 133.8 25.6 125.8 0 59.2 160.9 53.8 112.3 PVA2 20 40.8 223.9 33.0 175.0 30 32.4 268.6 39.6 253.8 0 53.1 35.0 57.5 29.1 PVA3 20 31.9 224.9 36.3 218.3 30 30.0 222.0 27.3 162.8 0 41.6 296.7 47.8 172.4 PVA4 20 26.3 211.5 30.2 216.1 30 20.7 278.0 20.5 188.6 hydrophilic/hydrophobic properties the capability shown that the films prepared using the starch ir- for water uptake and the wetting angle for water radiated with a 10 kGy dose reveal better prop- were measured using an instrument constructed erties as compared to the films prepared basing in the Laboratory of Material Research, INCT on the non-irradiated starch. In result of the opti- and the method described in [2]. In purpose to mization the experimental procedure homogene- evaluate the polymer degradation/crosslinking de- ous starch-PVA films were finally obtained. Basing gree gel content in the starch containing films was on these results the PVA1 and cornstarch SC1d determined after heating in water [1, 6]. (pre-irradiated) were selected for the further more At the beginning, the experimental conditions advanced experiments. enabling preparation of PVA and starch films Flexible PVA films and stiff starch films were were optimized using all the substrates. Then, op- obtained. Elasticity of PVA film was lower when timization of the conditions for preparation of the Mw of the substrate was higher (Table 1). The low- starch-PVA films was conducted. The film compo- est tensile strength values were determined for sitions were based on PVA : starch ratio 1:1. Two the films based on the PVA4 characterized by the sets of syntheses were carried out. lowest Mw. Increase in elasticity and decrease in Solubilization of PVAs and preparation of tensile strength were connected with an increase starch gels appear to be the crucial step in the in the glycerol content in the films. films synthesis. Moreover, phase separation was All the PVA and starch films shown limited hy- observed in the starch-PVA films. Therefore, tem- drophilicity (PVA – contact angle ca. 70o). In the perature and time of the PVA solvation and of the majority of cases the hydrophilicity of PVA films starch gelatinization were adapted, as well as the was higher when Mw was smaller and when plasti- amount of plastificator and conditions applied for ficator content was higher (for example the water its addition. Glycerol was introduced into the film uptake determined after 11 days for PVA1 films forming solution before the starch gelatinization containing 0, 20 and 30% of glycerol was equal or prior to casting. The difficulties arise in obtain- to 28.07, 30.78 and 27.89, respectively, as coming homogeneous starch films based on the native pared to the values of 36.72, 58.71 and 59.05 found starches in regard to the high viscosity of the gels for PVA4). Hydrophilicity (shown by the contact formed at the intermediate step of the syntheses. angle data) decreases during storage of the films. Accordingly, application of the starches degraded A contact angle determined for the films contain- on the way of irradiation were expected to be ad- ing native starches and 30% of glycerol varied in vantageous [1, 5]. Our present experiments have the range 60-81o. 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 20oC.

Dose 0 kGy Dose 25 kGy Composition tensile strength [MPa] elongation at break [%] tensile strength [MPa] elongation at break [%] PVA3 + SC2 17.5 14.3 17.1 11.9 PVA3 + SC1 14.1 16.5 13.2 17.2

PVA1 + SC1d 16.3 56.6 16.9 64.5 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 27 the pre-irradiated specimens reach higher contact tion at break value occurs as compared to the non- angle value (till 90o) as compared to those ob- -irradiated films. None particular differences were tained using the non-irradiated starches. found in the contact angle data determined for Starch-PVA films were characterized by the the non-irradiated and the irradiated films. How- relatively good mechanical properties (Tables 2 ever, the moisture uptake was somewhat higher in and 3). The values of the wetting angle of the 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.

Dose 0 kGy Dose 25 kGy, oxygen absence Dose 25 kGy, air Composition tensile strength elongation tensile strength elongation tensile strength elongation [MPa] at break [%] [MPa] at break [%] [MPa] at break [%]

a) PVA2 + SC1d 19.6 57.3 21.3 29.9 20.2 35.3 a) PVA1 + SC1d 18.6 23.2 8.9 49.9 10.4 27.9 b) c) c) PVA1 + SC1d 24.4 31.7 26.9 14.0 24.4 25.1 a) Glycerol introduced prior to casting. b) Glycerol introduced before starch gelatinization. c) Measurements carried out after one month. starch-PVA films (77-88o, Table 4) were generally The effect of irradiation on the mechanical higher as compared to those of pure PVA films properties of the starch-PVA films depends on (ca. 70o). However, the water uptake by those their composition and the conditions applied dur- films (Table 4) were higher as compared to the ing synthesis and irradiation. Therefore, none par- PVA films. For example, the water uptake of the ticular differences, a decrease in tensile strength blends of PVA1 with various starches (20% of with a simultaneous increase in elasticity as well as glycerol) were in the range of 50.86-61.32% as decrease in elasticity with negligible effect on compared to 30.78% determined for the pure strength were found after irradiation (Tables 2 PVA1 under similar conditions. and 3). Degree of radiation effect differs after ir- Mechanical data (Table 1) obtained for the radiation of the same sample in air and in oxygen PVA films prepared without glycerol addition or free atmosphere, although the directions of the using 20% of glycerol suggest that the application changes are the same. This result suggest that deg- of gamma radiation might result in an increase in radation of the material is the prevailing process tensile strength, in particular in the case of PVAs taking place in air. with a low molecular mass (PVA4 and PVA3). A The increase in the films homogeneity after ir- negligible differences were noticed in the case of radiation might be concluded basing on the SEM the films containing 30% of glycerol. In the cases observation (Fig.1) and the smaller dispersion of of the PVA with the high molecular mass a small the mechanical results. decrease in tensile strength was noticed and the Hydrophilicity of the majority of the starch- higher decrease was observed when the samples -PVA films has increased after irradiation (Tables contained a higher amount of glycerol. In all the 4 and 5). However, in some cases these properties cases of the irradiated films a decrease in elonga- became unchanged or even decreases. Table 4. Wetting angle, moisture uptake at 20oC after two weeks and gel fraction determined for the selected starch-PVA films (non-irradiated and irradiated in the oxygen absence (25 kGy).

PVA Starch Glycerol content Dose Gel fraction % of the gel fraction Moisture uptake Wetting angle type sample [%] [kGy] [%] of the initial film [%] [o] PVA3 SC1 30 0 57.42 100 52.14 77.25 PVA3 SC1 30 25 19.22 33 61.24 80.18 PVA3 SC1 20 0 59.81 100 51.25 80.04 PVA3 SC1 20 25 11.20 19 47.24 79.12 PVA3 SC2 30 0 47.51 100 66.22 88.19 PVA3 SC2 30 25 36.55 76 62.46 91.76 PVA3 SC2 20 0 49.39 100 54.15 82.84 PVA3 SC2 20 25 44.68 90 50.72 81.19

PVA1 SC1d 30 0 52.25 100 57.35 84.91

PVA1 SC1d 30 25 40.43 77 67.39 79.97

PVA1 SC1d 20 0 65.30 100 50.86 77.22

PVA1 SC1d 20 25 10.27 16 50.51 72.26 28 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY

A 1000 x B

Fig.1. The exemplar images of the starch-PVA films (SC1d-PVA1, 30% of glycerol): A – initial, B – irradiated in vacuum with a dose of 25 kGy. Decrease in the gel fraction content was found particpation might be even more important than after irradiation in the majority of the samples that of degradation. None particular effect of ir- (Tables 4 and 5) showing the occurring degrada- radiation on mechanical properties found in some tion processes. However, the degree of this de- cases suggests that the materials based on the ex- crease differs in the cases of particular samples. amined system, properly prepared, might appear Moreover, it seems to be in some cases insignifi- appropriate for packing products predicted for ra- cant, or at least lower than can be expected after diation decontamination. Table 5. Moisture uptake at 4oC 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 + SC1d 0 47.90 100 35.54 a) c) PVA2 + SC1d 25 41.39 86 40.84 a) d) PVA2 + SC1d 25 31.53 66 45.60 a) PVA1 + SC1d 0 41.91 100 55.57 a) c) PVA2 + SC1d 25 32.90 76 43.28 a) d) PVA2 + SC1d 25 33.26 79 35.85 b) PVA1 + SC1d 0 49.58 100 25.52 b) c) PVA2 + SC1d 25 37.34 75 24.79 b) d) PVA2 + SC1d 25 37.60 76 24.64 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 The work was sponsored in the frame of the example, it reach the value ca. 75% in the case of International Atomic Energy Agency (IAEA) re- PVA1-SC1d (pre-irradiated starch, 30% of glycerol) search contract No. 17493 (CRP F2206). of that obtained for the initial sample (Tables 4 and 5), while the value of ca. 30% was found under References the same conditions for the SC1d pure starch. This [1]. Cieśla K.: Przekształcenia struktury nadcząsteczkowej result suggests that crosslinking accompanies deg- w polimerach naturalnych inicjowane promieniowa- radation in these systems. The last conclusion was niem jonizującym (Transformation of supramolecular supported by thermogravimetry. structure initialized in natural polymers by gamma ir- These preliminary results show the increase in radiation). Institute of Nuclear Chemistry and Tech- the compatibility of the components in the PVA- nology, Warszawa 2009, 223 p. (in Polish). -starch-glycerol systems taking place under gamma [2]. Cieśla K., Nowicki A, Buczkowski M.: Nukleonika, 55, radiation. The effect of irradiation depends on the 2, 233-242 (2010). [3]. Tang X., Alavi S.: Carbohydr. Polym., 85, 1-16 (2011). sample composition and on the applied conditions. [4]. Ryzhkova, Jarzak U., Schäffer A., Bämer M., Swiderek Degradation was found to be the prevailing process P.: Carbohydr. Polym., 83, 608 (2011). taking place in the majority of the films. However, [5]. Cieśla K.: J. Therm. Anal. Calorim., 74, 259-274 (2003). it can be supposed that crosslinking occurs simul- [6]. Cieśla K., Eliasson A-C.: Acta Aliment., 36(1), 111-126 taneously with degradation and in some cases its (2007). 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 2013. 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 Syn- thesis 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 99mTc, 68Ga, or nanobodies with 225Ac and 212Pb. Other studies were directed at labelling peptide vectors (e.g. substance P) with alpha emitters (223Ra, 225Ac 211 via and At) nanoparticles of functionalized zeolite, titanium dioxide and core shell Au2S-Au ones. Also microspheres of yttrium-90 oxide (synthesized at the Laboratory of Sol-Gel Tech- nology) were further tested as potential radiopharmaceuticals for anticancer therapy by radio- embolization. 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. CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 31 SYNTHESIS, PHYSICOCHEMICAL AND BIOLOGICAL EVALUATION OF NOVEL TECHNETIUM-99m LABELLED LAPATINIB AS A POTENTIAL TUMOUR IMAGING AGENT Ewa Gniazdowska, Przemysław Koźmiński, Leon Fuks, Krzysztof Bańkowski1/, Wojciech Łuniewski1/, Leszek Królicki2/ 1/ Pharmaceutical Research Institute, Warszawa, Poland 2/ Nuclear Medicine Department, Medical University of Warsaw, Warszawa, Poland

One of the most important radiopharmaceuticals cedure described in [3]. The coupling reaction of which selectively distribute within given tissues or the isocyanide linker CN-BFCA with the lapatinib organs, are formed by coordination compounds molecule (Scheme 1) was performed according to with diagnostic/therapeutic radiometal firmly at- the procedure described in [4]. Crude product was tached to selected biologically active molecule. purified on a semi-preparative HPLC column (sys- Lapatinib ditosylate (Fig.1A) is an anticancer drug tem 1), alkalized and lyophilized, yield ≈ 35%. used for treatment of solid tumours such as breast MS: m/z: calcd. – 675.17; found – 676.17 [M+H+], or lung cancer, because it exhibits high affinity to- 698.19 [M+Na+].

A O B HO N S O S N Lapatinib N 99mTc CN O HN Cl H S N F O O S HO O O S S O O 99m (NS3) Tc(CN-BFCA-Lapatinib) Fig.1. Lapatinib molecule (A) and 99mTc-labelled lapatinib using the ‘4+1’ approach (B). wards Her-2 receptors [1]. It is expected, that lapa- IR: (KBr plates), cm–1: 2153 (C≡N), 1814, 1785, tinib labelled with technetium-99m may also serve 1729 (succinimidyl ester). 99m as a diagnostic receptor radiopharmaceutical for The (NS3) Tc(CN-lapatinib) conjugate was patients suffering from breast cancer of the Her-2 synthesized in n.c.a. scale in two-step procedure type. according to [4] (Scheme 2). The NS3 molecule The aim of this work was to synthesize conju- coordinates the 99mTc(III) cation and leaves the gate containing technetium-99m complex of the fifth coordination site available for one monoden- ‘4+1’ type and lapatinib as the biologically active tate isocyanide ligand CN-lapatinib.

N N

O O O N N N O O N HN Cl HN Cl H O C + O O + H N N C N O F F O O O O O S S O O

Scheme 1. Coupling reaction of CN-BFCA with lapatinib. molecule (Fig.1B) and to determine physicochem- The reaction progress was checked by TLC ical and biological properties of the conjugate im- (thin layer chromatography) and HPLC (high portant from the radiopharmaceutical point of performance liquid chromatography; system 2) view. methods. The radiochemical yield of the synthe- 99m The conjugate (NS3) Tc(CN-lapatinib) con- sized conjugate was higher than 97%. sists of 99mTc(III) cation coordinated by the tetra- Conditions of HPLC systems were the follow- dentate NS3 tripodal chelator (tris(2-mercapto- ing: EDTA-kit NS3, CN-lapatinib, MeOH 99m - 99m 99m TcO4 Tc-EDTA (NS3) Tc(CN-lapatinib) room temp. 70oC, 30 min 20 min 99m Scheme 2. Two-step synthesis of (NS3) Tc(CN-lapatinib) conjugate in n.c.a. scale. ethyl)-amine; 2,2’,2’’-nitrilotriethanethiol) and a System 1: Phenomenex Jupiter Proteo semi-pre- monodentate isocyanide species CN-BFCA (bi- parative column (4 μm, 90 Å, 250 x 10 mm), UV/Vis functional coupling agent, isocyanobutyric acid suc- detector (220 nm); elution conditions: solvent A cinimidyl ester) previously coupled with lapatinib – water with 0.1% TFA (v/v), solvent B – ace- molecule. The tetradentate NS3 ligand was pre- tonitrile with 0.1% TFA (v/v); gradient – 0-20 min pared by reaction of tris(2-chloroethyl)amine hy- 20 to 80% solvent B, 20-35 min 80% solvent B; 2 drochloride with potassium thioacetate followed ml/min. by reduction with LiAlH4 [2]. The aliphatic linker System 2: Phenomenex Jupiter Proteo analytical CN-BFCA was synthesized according to the pro- column (4 μm, 90 Å, 250 x 4.6 mm), gamma radia- 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% 50 solvent B, 20-35 min 80% solvent B; 1 ml/min. TLC analyses were performed using Merck 60 40 F254 aluminum sheets. All radioactive substances were placed on the strip, developed with appro- 30 priate solutions and dried. Distribution of radio- ) % ID 3 Tc(CN-lapatinib)

activity on the strip was determined using a home- 20 4 99m )

-made automatic TLC analyser SC-05 (INCT). 3 Tc-EDTA TcO Tc(NS (NS 99m The synthesized conjugate was characterized 10 99m 99m by determination of the logarithm of its partition coefficient, log P, in the n-octanol/PBS (pH 7.40) 0 system. Stability of the isolated conjugate was in- 1234 vestigated both as a function of time (HPLC) and 99m Fig.3. Cell binding of (NS3) Tc(CN-lapatinib) conjugate in challenge experiments (in the presence of excess in comparison with other 99mTc species. Cell binding levels of histidine or cysteine), as well as in rat serum. The are expressed as the percentage of added doses (% ID). biological properties of the conjugate were characterized in vitro by investigations of the conjugate each well. Cell count was determined using hemo- affinity to Her-2 receptor using cell line SKOV-3 cytometer and microscope. Preliminary affinity and in vivo by the biodistribution studies. studies were performed by incubating SKOV-3 99m The conjugate (NS3) Tc(CN-lapatinib) is form- cells together with the studied conjugate, as well 99m 99m – ed with high yield and purity (Fig.2). The small as with other Tc-species, namely with Tc O 4 , 99m 99m peaks recorded at RT = 3.4 and 7.9 min correspond Tc-EDTA/mannitol and Tc(NS3). After 45 min of incubation the binding was stopped, the so- 99m (NS 3) Tc(CN-lapatinib) lution from above the cells was quantitatively sep- 60000 arated and the cells were washed three times with cold PBS, pH 7.4 (in order to eliminate unbound RT = 18.5 min radioactivity). Then, the cells were solubilized with 40000 1 M NaOH and activity of solution from above the cells and that of solubilized cells was measured in

cpm the gamma counter. Affinity of the conjugate was 20000 A 3

0 2,5 0 5 10 15 20 25 30 35 2 min 1,5 Bmax = 2.4 nM Fig.2. HPLC chromatogram of the reaction mixture (performed in system 2) after completion of the synthesis of the 1 99m (NS3) Tc(CN-lapatinib) conjugate. % Specific Bound [nM] 0,5 to the intermediate complexes 99mTc-EDTA/man- 99m 0 nitol and Tc(NS3), respectively. The determined lipophilicity value of the con- 0 102030405060 99m jugate was found to be 1.24 ± 0.04 (n = 3). The concentration of (NS3) Tc(CN-lapatinib) [nM] studied conjugate exhibited high stability. After B 24 h of incubation in 10 mM histidine or cysteine 1,2 solution and in rat serum the obtained HPLC chromatograms have shown mainly the existence 1,0 Kd = 3,5 nM of one radioactive species in the solution, with the retention time characteristic for the studied con- 0,8 jugate. 0,6 Biological studies were performed using the B/F SKOV-3 cell line. The cells were maintained in 0,4 McCOY’S 5A Medium (Modified), containing 2 mM of L-glutamine, 10% of fetal bovine serum 0,2 and supplemented with 0.1 IU/ml penicillin and 0.1 mg/ml streptomycin. Cells were cultured at 0,0 37oC in a humidified incubator under an atmos- 0,00 0,50 1,00 1,50 2,00 2,50 3,00 B [nM] phere containing 5% of CO2. The cells were sub- cultured once a week. 99m Fig.4. (A) The saturation curve for (NS3) Tc(CN-lapati- Affinity studies were performed on 6-well plates nib). The specifically bound radioligand is plotted as a 99m (SARSTEDT) in McCOY’S 5A Medium which function of increasing concentrations of (NS3) Tc(CN-la- contained approximately 4 x 105 adherent cells in patinib). (B) Scatchard plot. CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 33 calculated as the ratio of activity bound by cells to between 23 and 28 g, n = 12), according to the rel- the sum of activity bound by cells and that which evant national regulations. The mice were injected remained in the solution above the cells (Fig.3). via tail vein with 3.02-3.66 MBq in 200-210 μL of 99m 99m Binding of the (NS3) Tc(CN-lapatinib) con- aqueous solution of (NS3) Tc(CN-lapatinib) and jugate to Her-2 receptor of SKOV-3 cells was sacrificed at 30 and 60 min after injection of con- found to be saturable and specific in the predomi- 6 nant degree (Fig.4A). The non-specific binding determined in the presence of 0.1 μM solution of 5 lapatinib accounts in general for about 0.3% of 30 min after injection 4 specific binding. The Bmax value was found to be 60 min after injection 2.4 ± 0.3 nM (n = 3), which corresponds to the 3 approximate number of 2 500 000 binding sites per %ID/g 2 cell. The dissociation constant, Kd, usually used to describe the affinity of the conjugate to its receptor 1 (Fig.4B), was found to be 3.5 ± 0.4 nM (n = 3). 0 The low value of Kd indicates high affinity of the 123 4567

studied conjugate. Heart Liv er Blood Lungs Spleen Thyroid

In a competitive binding experiment the unla- Kidneys 99m belled lapatinib molecules inhibited binding of Fig.6. Biodistribution studies of (NS3) Tc(CN-lapatinib) 99m (NS3) Tc(CN-lapatinib) and the inhibitory con- in BALB/c mice after 30 and 60 min p.i. centration of 50% (IC50) obtained for lapatinib was jugate. Then, tissues were dissected, washed free of 100 blood and weighed. Associated radioactivity was counted using gamma counter. The accumulated 80 radioactivity in the tissue of organs was calculated

60 as the percentage of injected dose per gram (% ID/g) of tissue, as well as the percentage of inject- 40 ed dose per gram of blood. The standard source of 99mTc was also measured simultaneously with the % Specific Bound 20 samples in order to perform the decay correction. The presented data show similar uptake of 99m 0 (NS3) Tc(CN-lapatinib) conjugate in liver (4-5% 1,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 ID/g) and in kidney (3-5% ID/g). It points out to log [M] the clearance of the conjugate through the renal 99m and through the hepatic route in the comparable Fig.5. Displacement of (NS3) Tc(CN-lapatinib) by increasing concentration of unlabelled lapatinib. degree. The uptake in other organs remained on the level < 1% ID/g. 99m found to be 41.2 ± 0.4 nM (Fig.5). This value also (NS3) Tc(CN-lapatinib) conjugate is formed 99m confirms satisfactorily high affinity of (NS3) Tc with high yield and presents high stability in solu- (CN-lapatinib) conjugate to Her-2 receptors in the tions containing competitive cysteine/histidine li- SKOV-3 cells. gands. The biological in vitro and in vivo studies of

99m the conjugate showed its high affinity to Her-2 re- Table. Biodistribution studies of (NS3) Tc(CN-lapatinib) conjugate in BALB/c mice at 30 and 60 min p.i. (n = 6, % ceptor and the clearance through the renal and ID/g ± SD). hepatic route in comparable degree. 99m To conclude, (NS3) Tc(CN-lapatinib) conju- Uptake in organ, percentage gate may be considered a promising diagnostic Organ of injected dose per g tissue radiopharmaceutical for patients suffering from [% ID/g ± SD] breast cancer of Her-2 type. Heart 0.10 ± 0.02 0.92 ± 0.04 The work was carried out within the grant No. N R13 0150 10 (National Centre for Research and Kidneys 3.28 ± 0.4 4.98 ± 0.6 Development, Poland). Liver 4.89 ± 0.9 4.55 ± 0.8 References Lungs 0.77 ± 0.08 0.56 ± 0.09 [1]. Burris H.A. et al.: Oncologist, 9, 10-15 (2004). [2]. Spies H., Glaser M., Pietzsch H.-J., Hahn F.E., Lueg- Spleen 0.44 ± 0.3 0.38 ± 0.02 ger T.: Inorg. Chim. Acta, 240, 465-478 (1995). Blood 0.99 ± 0.01 0.48 ± 0.02 [3]. Kuenstler J.-U., Veerenda B., Figueroa S.D., Sieck- man G.L., Rold T.L., Hoffman T.J., Smith C.J., Pietzsch Thyroid 0.94 ± 0.04 0.38 ± 0.02 H.-J.: Bioconjugate Chem., 18, 1651-1661 (2007). [4]. Seifert S., Kuenstler J.-U., Schiller E., Pietzsch H.-J., 99m Biodistribution studies of (NS3) Tc(CN-lapa- Pawelke B., Bergmann R., Spies H.: Bioconjugate tinib) conjugate (Table, Fig.6) were performed on Chem., 15, 856-863 (2004). normal 3 months old male BALB/c mice (of weight 34 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY CYCLOTRON PRODUCTION OF 99mTc. SEPARATION OF 99mTc FROM 100Mo TARGET Magdalena Gumiela, Ewa Gniazdowska, Aleksander Bilewicz

Every day about 70 000 diagnosis procedures us- suitable for use in novel modes of 99mTc producing 99mTc-radiopharmaceuticals are performed ren- tion. Separation of technetium from irradiated dering this the most widely used radioisotope in molybdenum may be carried out using either nuclear imaging. 99mTc is commonly easy available “wet” or “dry” chemical processes. “Wet” separa- from 99Mo/99mTc generators. 99Mo (the mother nu- tion techniques require dissolving of the metallic via clide, t1/2 = 66 h) is produced either thermal target under oxidative conditions and then sep- neutron irradiation of natural Mo in the reaction aration of pertechnetate can be achieved using 98Mo(n,γ)99Mo or thermal fission of highly en- one of many strategies, e.g. liquid-liquid extraction riched 235U (HEU) in the reaction 235U(n,f)99Mo. [3], ion-exchange chromatography [4], aqueous bi- Usually, the operation period of research reactors phasic extraction chromatography using ABEC used for the production of 99Mo is about 40-50 resin [5] and electrochemistry [6]. years. Most reactors used for the preparation of The aim of our studies was to elaborate a simple 99Mo have already reached this age, or they will and fast method for separation of microquantities reach it in the near future. Therefore, there is still of pertechnetate from macroquantities of molyb- growing interest in exploring alternative cyclotron date anions in the process of cyclotron produc- production of 99mTc using 100Mo(p,2n)99mTc reaction of 99mTc. The schematic diagram of proposed tion, the method proposed first by Beaver and methods is presented in Fig.1.

Fig.1. Scheme of the separation process of 99mTc from 100Mo.

Hupf nearly 40 years ago [1]. In other way, some Our studies were carried out using natural mo- amounts of 99Mo suitable for the production of lybdenum powder. We utilized formation of insol- 99Mo/99mTc generators can be obtained in the nu- uble yellow ammonium molybdenum phosphate clear reaction 100Mo(p,pn)99Mo [2]. The significant (AMP) in the reaction of ammonium phosphate advantage of the direct production of 99mTc using with molybdate anions, which takes place accord- cyclotrons is the less nuclear waste production ing to the formula: 99 2– + compared to the fission product method of Mo (NH4)3PO4 · 3H2O + 12MoO4 + 24H → production. On the other hand, due to the rela- (NH4)3P(Mo3O10)4↓ + 5H2O tively short half-life of 99mTc, the method of direct In the first step, metallic molybdenum target was 99m Tc production can be applied only in hospitals dissolved in 3.5 M HNO3. Next, triammonium phos- near cyclotron centres. phate and ammonium nitrate were added, and AMP Natural molybdenum consists of several iso- was precipitated in the form of yellow solid. We have topes including 92Mo, 94Mo, 95Mo, 96Mo, 97Mo, optimized four parameters of the process: the con- 98 100 Mo and Mo. During proton bombardment of centration of NH4NO3 and of (NH4)3PO4 · 3H2O, natural Mo, depending on proton energy, several temperature and the time of precipitation. reaction channels may be present and, apart from The increase in the concentration of ammo- 99mTc, various isotopes of technetium, such as 96Tc, nium nitrate results in lower solubility of AMP 95Tc and 94Tc, can be produced. Therefore, the ap- precipitate. In 0.125 M ammonium nitrate solu- plication of molybdenum target enriched with 100Mo tion the solubility of AMP is nearly twice less than (97.46%) is needed. However, the natural abun- in the case when the precipitation was carried out dance of 100Mo is only 9.63%. High cost associated in the absence of ammonium nitrate. We have also 100 with the isotopic enrichment of Mo from natural found that the concentration of (NH4)3PO4 · 3H2O molybdenum makes necessary to investigate the does not influence the AMP solubility, and no recycling of the 100Mo target material. So, there is excess of triammonium phosphate is needed. In a real necessity to develop separation technologies the next steps, we analysed the influence of tem- CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 35

(NH4)3PO4 and 100 μl 3 M of NH4NO3 is added. The process should be carried out at 80oC for 30 min. The precipitate can be separated by filtration or centrifugation. Finally, we also studied the possibility of 99mTc coprecipitation with AMP. After separation process, under conditions presented above, we found in the filtrate solution 99.6% of the total 99mTc activity. Basically, it means that 99mTc does not co- precipitate with AMP. This proposed process is promising and allows for fast separation of Mo macroamounts from the 99m Fig.2. Concentration of Mo in solution as a function of solution without coprecipitation of Tc. After op- time and temperature of precipitation process. timization of the precipitation conditions, the low- 2– est concentration of MoO4 was only 0.37 mg/ml. perature and time on the precipitation process The final solution will be conducted through a col- (Fig.2). Precipitation process was tested at various umn containing one of the Zr-based sorbents. temperature (40, 60 and 80oC) and time periods References (15 min-1 h). The lowest concentration of Mo in the solution, equal to about 370 μg/ml, was reach- [1]. Beaver J., Hupf H.: J. Nucl. Med., 12, 739-41 (1971). ed in the reaction mixture heated at 80oC. As one [2]. Almeida G.L., Helus F.: Radiochem. Radioanal. Lett., can see in Fig.2, the concentration of Mo in the 28, 205 (1977). reaction mixture only slightly depends on the time [3]. Dallali N., Ghanbari M., Yamini Y., Fateh B., Agrawal Y.K.: Indian J. Chem. A, 46A, 1615-1617 (2007). of sample heating. [4]. Chattopadhyay S., Das S.S., Das M.K., Goomer N.C.: Based on the performed experiments, the fol- Appl. Radiat. Isot., 66, 12, 1814-1817 (2008). lowing optimal conditions for the separation of [5]. Rogers R.D., Bond A.H., Griffin S.T., Horwitz E.P.: 99m microamounts of Tc from Mo target have been Solvent Extr. Ion Exch., 14, 919-946 (1996). selected: 25 mg of metallic Mo target is dissolved [6]. Chakravarty R., Dash A., Venkatesh M.: Nucl. Med. in 0.5 ml of 3.5 M HNO3, next 400 μl 0.44 M of Biol., 37, 21-28 (2010).

THE STRUCTURES OF BISMUTH(III) COMPLEXES WITH TROPOLONE Krzysztof Łyczko, Monika Łyczko, Krzysztof Woźniak1/, Marcin Stachowicz1/ 1/ Department of Chemistry, University of Warsaw, Warszawa, Poland

Tropolone (2-hydroxy-2,4,6-cycloheptatriene-1- and possible usage in cancer therapy [3, 5-8]. Based -one), abbreviated as Htrop, is an aromatic com- on our work concerning of lead(II)-tropolonato pound with a seven-membered carbon ring. It complexes [4], we decided to investigate the effect contains two neighbouring functional groups (car- of counterion and pH of the solution on the for- bonyl and hydroxyl) which make possible its coor- mation of bismuth(III)-tropolonato compounds. dination to various metal ions. The tropolonate The reaction of tropolone with Bi(CF3SO3)3, – anion (trop ) is a bidentate oxygen donor ligand Bi(ClO4)3 and Bi(NO3)3 in methanol solution in forming a five-membered chelate ring upon com- the molar ratios 1:2 and 1:3 led to the formation plexation. of three different bismuth(III) complexes: one In the 1960s the bismuth(III)-tropolonato dimeric and two polymeric. The structures of the 1 2 complexes, such as [Bi(trop)2Cl] [1], Bi(trop)3 and [Bi(trop)2(CF3SO3)]2 ( ), [Bi2(trop)4(ClO4)2]n ( ) 3 Na[Bi(trop)4] [2], were synthesized for the first and [Bi2(trop)4(NO3)2]n ( ) compounds were de- time. In 1995, the preparation and characteriza- termined by single crystal X-ray diffraction tion of new bismuth(III) compounds with tro- (Figs.1-3). A simple tris(tropolonato)bismuth(III) 4 polone and its derivatives were presented. Among complex, Bi(trop)3 ( ), was obtained from bis- them, the structures of only nitratobis(tropolona- muth(III) acetate salt. In the crystal structure of 1 to)bismuth(III) and aquabis(4,5-benzotropolona- two Bi(trop)2(CF3SO3) entities are held together to)bismuth(III) nitrate were published [3]. How- in dimeric units (Fig.1). Compounds 2 and 3 have ever, they are not available in the Cambridge Struc- polymeric structures with the Bi2(trop)4(ClO4)2 tural Database. and Bi2(trop)4(NO3)2 fragments, respectively, re- We have previously reported the formation of peated in the polymeric chains (Figs.2-3). Each three polymeric lead(II)-tropolonato complexes bismuth(III) ion in the compounds 1-3 is chelated – [Pb(trop)(CF3SO3)(H2O)]n, [Pb3(trop)4(ClO4)2]n, by two tropolonato ligands. It is obvious that the [Pb2(trop)2(NO3)2(CH3OH)]n and one dimeric counterions (triflate, perchlorate and nitrate) play compound – [Pb(trop)2]2, which depends on the an important role in the formation of the studied pH of solution and the counterion [4]. compounds, through entering their structures. Bismuth compounds have been extensively Contrary to the complex 1 which has the bismuth studied in respect of their antibacterial properties centres of the same kind, the complexes 2 and 3 36 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY comprise two coordinatively different types of Bi atoms. In all the complexes studied, the tropolonate ions chelate the bismuth(III) ions in an ani-

Fig.3. The structure of [Bi (trop) (NO ) ] (3). Selected Fig.1. The structure of [Bi(trop) (CF SO )] (1). Selected 2 4 3 2 n 2 3 3 2 o − bond lengths, distances [Å] and angles [o]: Bi(1)−O(2) bond lengths [Å] and angles [ ]: Bi(1) O(1) 2.360(2), − − − 2.279(3), Bi(1)−O(1) 2.231(3), Bi(1)−O(12) 2.266(3), Bi(1) O(2) 2.309(2), Bi(1) O(11) 2.269(2), Bi(1) O(12) − − Bi(1)−O(11) 2.164(3), Bi(1)−O(3) 2.870(3), Bi(1)−O(4) 2.189(2), Bi(1) O(3) 2.652(2), Bi(1) O(4) 2.746(2), − − − 2.862(3), Bi(1)−O(1’) 2.657(3), O(1)−Bi(1)−O(2) 70.31(9), Bi(1) O(6’) 2.776(2), Bi(1) O(21) 2.901(2), Bi(1) O(32) − − O(11)−Bi(1)−O(12) 72.19(10). The non-hydrogen atoms 2.630(2), Bi(2) O(21) 2.205(2), Bi(2) O(22) 2.250(2), − − − are shown as the 50% probability ellipsoids. 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), sobidentate manner, with one shorter and one 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), longer Bi O bond. The lengths of the chelating O(21)−Bi(2)−O(22) 71.26(6), O(31)−Bi(2)−O(32) 67.52(6). Bi−O bonds are within the range 2.176-2.376 Å. In The atoms are shown as the 50% probability ellipsoids. Hy- addition, some tropolonato ligands are also bridg- drogen atoms are omitted. ing to one (in 1-3) or two (in 2 and 3) neighbouring bismuth(III) ions. In the studied structures, the metal ions and oxygen atoms of counterions – – – the bridging Bi−O(trop) distances are longer than (CF3SO3 , ClO4 and NO3 ), changing in the range the chelating Bi−O(trop) bonds, and vary in the 2.652-2.909 Å, are similar to the bridging Bi−O(trop) range 2.630-2.960 Å. The bond distances between contacts in respect to distance. The shortest distances of those type (2.652 and 2.658 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(CF3SO3)]2, 8 in [Bi2(trop)4(ClO4)2]n, to 9 in [Bi2(trop)4(NO3)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) 2 Fig.2. The structure of [Bi2(trop)4(ClO4)2]n ( ). Select- and three longer (2.400 Å) Bi−O bond lengths ed bond lengths [Å] and angles [o]: Bi(1)−O(1) 2.304(3), (Fig.4). The arrangement of these six oxygen atoms Bi(1)−O(2) 2.226(3), Bi(1)−O(11) 2.306(3), Bi(1)−O(12) around the metal centre forms strongly distorted 2.176(3), Bi(1)−O(4) 2.823(4), Bi(1)−O(8’) 2.776(3), octahedron (or distorted triangle antiprism) with Bi(1)−O(21) 2.740(3), Bi(1)−O(32) 2.896(3), Bi(2)−O(21) the bismuth(III) ion placed almost on the surface 2.299(3), Bi(2)−O(22) 2.179(3), Bi(2)−O(31) 2.242(3), built up of three O atoms [O(2), O(4) and O(6)] Bi(2)−O(32) 2.193(3), Bi(2)−O(1) 2.753(3), Bi(2)−O(2’) (Fig.4B). 2.870(3), Bi(2)−O(11’) 2.894(4), Bi(2)−O(7’) 2.880(4), s2 O(1)−Bi(1)−O(2) 69.32(12), O(11)−Bi(1)−O(12) 71.59(12), The 6 lone electron pairs on the bismuth(III) O(21)−Bi(2)−O(22) 70.63(12), O(31)−Bi(2)−O(32) 71.29(11). ions seem to be stereochemically active in all com- The atoms are shown as the 50% probability ellipsoids. Hy- plexes studied. The presence of distinct empty drogen atoms are omitted. volumes around the metal ions is the evidence for CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 37 [4], depends on pH of the solution. The pH of me- A thanolic solutions of salts originating from strong acids (Bi(CF3SO3)3, Bi(ClO4)3 and Bi(NO3)3) was much lower (~0 or less) than that (pH > 5) of Bi(CH3CO2)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, 5132-5137 (1964). [2]. Muetterties E.L., Roesky H., Wright C.M.: J. Am. Chem. Soc., 88, 4856-4861 (1966). [3]. Diemer R., Keppler B.K., Dittes U., Nuber B., Sei- B fried V., Opferkuch W.: Chem. Ber., 128, 335-342 (1995). [4]. Lyczko K., Starosta W., Persson I.: Inorg. Chem., 46, 4402-4410 (2007). [5]. Dittes U., Vogel E., Keppler B.K.: Coord. Chem. Rev., 163, 345-364 (1997). [6]. Briand G.G., Burford N.: Chem. Rev., 99, 2601-2657 (1999). [7]. Imam S.K.: Int. J. Radiat. Oncol. Biol. Phys., 51, 271-278 (2001). Fig.4. The calculated molecular structure of tris(tropolo- [8]. Su F-M., Beaumier P., Axworthy D., Atcher R., Fritz- nato)bismuth(III), Bi(trop) (4), in two projections: (A) 3 berg A.: Nucl. Med. Biol., 32, 741-747 (2005). top view and (B) side view. [9]. Mantina M., Chamberlin A.C., Valero R., Cramer C.J., Truhlar D.G.: J. Phys. Chem. A, 113, 5806-5812 the stereochemically active 6s2 lone pair in the com- 1 4 (2009). pounds and [11]. In turn, the observed pattern [10]. Frisch M.J. et al.: Gaussian 09, revision C.01. Gaus- in 2 and 3, with a few adjacent shorter and a few sian, Inc., Wallingford CT, USA 2010. adjacent longer Bi−O distances, can also indicate [11]. Shimoni-Livny L., Glusker J.P., Bock Ch.W.: Inorg. the active character of this lone electron pair [11]. Chem., 37, 1853-1867 (1998). The formation of studied complexes, similarly as in the case of lead(II)-tropolonato compounds

SILVER IMPREGNATED NANOPARTICLES OF TITANIUM DIOXIDE AS 211At CARRIERS Edyta Leszczuk, Monika Łyczko, Agata Piotrowska, Aleksander Bilewicz, Jarosław Choiński1/, Jerzy Jastrzębski1/, Anna Stolarz1/, Agnieszka Trzcińska1/, Katarzyna Szkliniarz2/, Wiktor Zipper2/, Bogdan Wąs3/ 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

211At is one of the most prospective alpha emitters iodine [1]. Thus, the labelling of peptides or anti- studied so far for cancer therapy. It is produced in bodies with 211At is a big challenge. Moreover, bio- the 209Bi(α,2n)211At reaction in cyclotrons. Its half- conjugates labelled with 211At are usually unstable -life of 7.2 h is sufficient for separation, labelling, under physiological conditions, which limits the quality control, shipment and medical application. use of astatinated radiophamaceuticals. It decays by double branch pathway with the mean We propose a new type of 211At carriers, based alpha energy of 6.7 MeV. on TiO2 nanoparticles modified with metallic silver. From chemical point of view, astatine as a heavy The nanoparticles are nanoscale materials (at least halogen has similar properties to other members one dimensions below 100 nm). They exhibit some of the group, but it also exhibits some metallic useful properties, e.g. ultra-small size, high specific character. Therefore, its bonds with aromatic and surface area, high ion exchange properties, possi- aliphatic moieties are much weaker than those of bility of attaching organic compounds to the sur- 38 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY face. Moreover, the surface of TiO2 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]. TiO2 nanoparticles modified with sliver (TiO2/ Ag) were synthesized according to the procedure described by Kang et al. [3]. The bare nanoparticles were added to 0.01 M AgNO3 solution, then stirred for 30 min at room temperature. The product was 211 Fig.1. The leakage of At from TiO2/Ag nanoparticles of carefully washed with distilled water. The loaded different diameter in various solutions after 1 h. nanoparticles were shaken with solutions of ammonia (25%) and glucose (0.1 M). The adsorbed thoxyl silane functionalized PEG was used, be- silver cations were reduced in commonly known cause it can be easily attached to the surface of reaction – “silver mirror” (Tollens’ reaction). The metal oxide nanoparticles via the reaction of hy- colour of the particles changed from white to dark droxyl groups with trimethoxyl silane. The aim of brownish grey. The modified nanoparticles were the surface modification was not only to hamper washed with distilled water and ethanol, then dried the agglomeration process, but also to make the at 100oC. The obtained nanoparticles differing in nanoparticles more resistant to protein adsorp- size (6-100 nm) and in the amount of adsorbed tion and to enhance their biocompatibility [4]. silver, were then labelled with 211At. Thermal gravimetric analysis (TGA) confirmed The labelling of TiO2/Ag nanoparticles with that the TiO2/Ag nanoparticles had been success- 211At was performed in phosphate buffer (pH 7.4). fully covered with PEG molecules. The images 211 2 ml PBS with At (~0.1 MBq/ml) was added to of TiO2/Ag nanoparticles observed under trans- 5 mg TiO2/Ag nanoparticles, and the mixture was mission electron microscope (TEM) are shown in shaken for 1 h. The radiolabelled nanoparticles Fig.2. A B

Fig.2. TEM images of bare TiO2/Ag nanoparticles (A) and TiO2/Ag nanoparticles covered with PEG (B). were separated from the solution by ultracentrifu- Afterwards, the samples of TiO2/Ag nanopar- gation (13 000 000 rpm). In all experiments the ticles covered with PEG molecules were examined distribution coefficient of 211At exceeded 104 cm3/g. for labelling with 211At. The results were similar to 211 The stability of At-labelled nanoparticles was those obtained for uncoated TiO2/Ag nanoparticles. assessed by adding the material (~3 mg) to physio- Also in this case the distribution coefficients were logical salt solution (0.9% NaCl), 0.02 M PBS high (>104 cm3/g). The stability of radiolabelled buffer, 0.001 M cysteine, 0.001 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 ad- ditionally heated to 37oC. After 1 h, the leakage of 211At was less than 6% in all samples (Fig.1). Pro- longed incubation of radiolabelled nanoparticles, caused slight increase in 211At leakage, e.g. 7.8% of 211At activity was detected in human serum after 14 h. We observed that TiO2/Ag nanoparticles tend 211 to agglomerate in aqueous media. In order to sta- Fig.3. The leakage of At from labelled TiO2/Ag nano- bilize them in the dispersed form, the particles particles covered with PEG of different diameter in vari- were coated with polyethylene glycol (PEG). Me- ous solutions after 1 h. CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 39 nanoparticles covered with PEG was tested in the fication of TiO2/Ag nanoparticles by attaching a same solutions as above. No significant leakage of tumour seeking agent. The stability, cell affinity 211At was detected in any of the samples after 1 h and radiotoxicity studies with these new nanopar- (Fig.3). The highest release of 211At (ca. 6%) was ticles will be carried out. detected in human serum. At the longest incuba- References tion time (14 h) the slightly higher leakage of 211At (< 8%) was detected. [1]. Vaidyanathan G., Zalutsky M.R.: Curr. Radiopharm., In conclusion, the new type of nanoparticles 3, 177-200 (2008). was successfully synthesized and tested. Both types [2]. Johnson G.L., Leininger R.F., Segrè E.: J. Chem. Phys., 17, 1-10 (1949). of nanoparticles, TiO2/Ag and TiO2/Ag covered with PEG, exhibited high affinity for 211At and high [3]. Kang J., Sohn Y.: J. Mater. Sci., 47, 824-83 (2012). [4]. Eck W., Craig G., Sigdel A., Ritter G., Old L.J., Tang stability in human serum. Therefore, they are good L., Brennan M.F., Allen P.J., Mason M.D.: ACS Nano, astatine carriers that can be used in nuclear medi- 2, 2263-2272 (2008). cine. Further experiments will focus on the modi-

NANOTITANATE AS A NEW SORBENT FOR 137Cs SEPARATION FROM RADIOACTIVE WASTE Barbara Filipowicz, Seweryn Krajewski, Monika Łyczko, Marek Pruszyński, Aleksander Bilewicz

Radionuclides of 134Cs and 137Cs with the half-lives health of present and future generations. There- of 2 and 30 years, respectively, belong to the main fore, serious attention has been paid to the re- long-lived fission products of 235U. These radionu- moval and separation of radiocaesium, especially clides undergo radioactive decay with the emission 137Cs, from nuclear waste. of beta particles and relatively strong gamma ra- Various approaches and technologies such as diation. Caesium salts, the most common form of coprecipitation and ion exchange have been de- the element easily dissolved in water, which causes veloped for the separation and immobilization of a serious hazard if an accident appears with a nu- radioactive aqueous wastes generated at different clear reactor. Caesium radionuclides leaked into stages of nuclear fuel cycle. Common ion exchange the environment make a serious threat to the resins are not sufficiently efficient for radiocaesium

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0 0 0 200 400 600 800 1000 1200 1400 0 200 400 600 800 1000 1200 1400 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 particles diameter that oscillated between 10-100 inorganic and composite sorbents, such as insoluble nm. Hydrothermal reaction of TiO2 (in the form ferrocyanides [1], zeolites [2], ammonium hetero- of anatase) with a concentrated NaOH solution at polyacid salts [3], titanium dioxide [4] and sodium 140oC resulted formation of nanotubes (Fig.1A). titanates [5], have been systematically studied for Contrary, amorphous TiO2 under the same condi- 137 separation of Cs from nuclear wastewater and tions formed nanofibers (Fig.1B). Amorphous TiO2 safe disposal of the exchanged cations. The advan- was also used as a substrate to produce nanoribbons tage of these materials is their ability to withstand (Fig.1C), when the synthesis was performed with intense radiation and elevated temperature in ad- NaOH solution at 200oC, whereas nanowires dition to their high selectivity for Cs+ ions. (Fig.1D) were obtained in KOH solution. The mor- Nanostructures of titanates play an important phology and elemental composition of the corre- role in the process of binding inorganic cations, in- sponding nanostructures were characterized by cluding radionuclides, because of their good sorp- SEM (scanning electron microscopy) and TEM tion properties. The advantage of some layered (transmission electron microscopy) with EELS nanotitanates is the collapse of their structure, (electron energy-loss spectroscopy). The structure which occurs during the ion exchange, and results and the degree of conversion of the substrate were in tight immobilization of targeted cations in the determined by XRD (X-ray diffraction) spectra. interlayer, thus in irreversible ion exchange [6, 7]. The specific surface area and porosity were mea- Therefore, the aim of our work was to examine sured by the BET method. various nanostructured titanates as sorbents for 137 Table. The Kd values of Cs on nanotitanate and amor- caesium radionuclides. phous TiO in 0.1 M solution of NaNO . To prepare nanotitanates we used the method 2 3 of hydrothermal synthesis (in autoclave). We have 137 Nanostructure Kd Cs (0.1 M NaNO3) obtained four different forms of nanotitanates. The 2 formation mechanism is complex and not clear. Nanotubes 4 x 10 Both, the method used and conditions of the syn- Nanowires 2 x 102 thesis play the key role in obtaining the forms of 2 interest. The morphology of various titanate forms Nanofibers 3 x 10 is shown in Fig.1. The structures displayed an ag- Nanoribbons 1 x 102 gregated shape with heterogeneous morphologi- TiO amorphous 1 x 102 cal distribution of diverse polyhedral forms and 2 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 41 The sorption studies of 137Cs radionuclide were conducted on the all synthesized nanotitanates. 3,0 The distribution coefficients (Kd) were determined in 0.1 M NaNO3. The results are shown in Table. Presumably, similarly as in the case of ferrocyanides and zeolites, Cs+ sorption can occur inside 2,5 the nanotubes, where cations are dehydrated and the selectivity of adsorption depends on the energy log(Kd) of hydration. The inner sorption of Cs+ is relative- 2,0 + nanotubes ly easy, since the energy of hydration for the Cs is nanofibers nanoribbons rather small. This conclusion was also supported nanowires + by the slow kinetics Cs the sorption on the nano- 1234567891011121314 + tubes, which suggest Cs diffusion into the interior. pH Kinetics of ion exchange is one of the most im- Fig.4. Effect of pH on the caesium sorption on titanate na- portant characteristics in defining the efficiency of nostructures. the sorbent. Na-titanate nanostructures revealed high and fast initial sorption of 137Cs+, followed by 137Cs+ ions, probably due to their higher surface apparent saturation, that was especially visible in area compared to other nanostructures. 137 + the case of nanowires and nanotubes (Fig.2). This The Kd values for Cs ions slowly decreased can be explained by the fast initial sorption on the with increasing the NaNO3 or KNO3 concentra- surface of the nanostructure, and a slower ion ex- tions due to the competition and blocking of ac- change inside the nanopores. tive sites on the nanostructures surface. As pre- 137 + + Sorption of Cs ions on four forms of titanate dicted, the Kd values for K are smaller in relation nanostructures with different size and morphology to the values for Na+, what is related to the larger (nanotubes, nanowires, nanoribbons and nano- size of the K+ cation, and thus the greater compe- fibers) was examined also at different concentra- tition with a 137Cs+. –3 –1 137 tions of NaNO3 or KNO3 (10 -10 M). As shown The effect of pH on Cs sorption was studied in + in Fig.3, a linear dependence of log Kd on log Na the pH range of 2-13. The results are shown in and log K+ confirms ion exchange mechanism of Fig.4. sorption. Again, nanotubes and nanowires struc- The observed dependence of log Kd on pH tures had the highest values of sorption towards above pH 9 seems rather unusual for sorption of inorganic cations on oxide sorbents, where the in- A 4,5 crease in pH is usually followed by a simultaneous nanotubes nanowires increase in the Kd values. In the case of nanostruc- 4,0 nanoribbons 137 nanofibers tures the highest sorption of Cs was reached at pH 7-9, and at higher pH the Kd decreased. 3,5 Leaching experiments in NaNO3 solutions showed that the release of 137Cs from titanate nano- 3,0 tubes was negligible. This proves irreversible sorp- + +

log(Kd) tion and suggests that the exchange of Na for Cs 2,5 may result in the change of sorbent structure. The presented results show that nanotitanates, 2,0 in particular nanotubes, efficiently absorb radiocaesium from aqueous solutions, which makes them a 1,5 prospective material for disposal of nuclear waste. -3,5 -3,0 -2,5 -2,0 -1,5 -1,0 -0,5 The work has been carried out within the stra- log[Na+] tegic research project “Technologies for the development of safe nuclear power engineering” (No. B 4,5 nanotubes SP/J/4/143 321/11). nanowires 4,0 nanoribbons nanofibers References

3,5 [1]. Avramenko V., Bratskaya S., Zheleznov V.: J. Nucl. Sci. Technol., 48, 1281-1284 (2011). [2]. Lonin A.Yu., Krasnopyorova A.P.: Probl. Atom. Sci. 3,0 Tech., 3, 67-70 (2009).

log(Kd) [3]. Murthy G.S., Sivaiah M.V., Kumar S.S.: J. Radioanal. 2,5 Nucl. Chem., 260, 109-114 (2004). [4]. Bilewicz A., Dybczyński R., Narbutt J.: J. Radioanal. 2,0 Nucl. Chem., Articles, 148, 359-371 (1991). [5]. Mishra S.P., Dubey S.S., Tiwari D.: J. Radioanal. Nucl. Chem., 261, 457 (2004). 1,5 -3,5 -3,0 -2,5 -2,0 -1,5 -1,0 -0,5 [6]. Li N., Zhang L., Chen Y., Fang M., Zhang J., Wang H.: log[K +] Adv. Funct. Mater., 22, 835-841 (2012). [7]. Yang D.J., Sarina S., Zhu H.Y., Liu H.W., Zheng Z.F., Fig.3. Effect of concentration of: (A) sodium and (B) po- Xie M.X., Smith S.V., Komarneni S.: Angew. Chem. tassium ions on the sorption of 137Cs+. Int. Edit., 50, 10594-10598 (2011). 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-Płaska1/, Marek Majdan1/ 1/ Faculty of Chemistry, Maria Curie-Skłodowska University, Lublin, Poland

Storage of radioactive wastes requires various ricium-241 is also used as a portable source of protective barriers against leaching of the stored both gamma rays and alpha particles applied in radionuclides: metal canisters (tanks), buffers some medical and industrial uses. The 60-keV made of adsorbent of metal ions, and often the gamma-ray emissions from 241Am in these sources surrounding rocks. On the other hand, humidity can be used for indirect analysis of materials in from the outside may penetrate the storage tanks. radiography and X-ray fluorescence spectroscopy, Various biopolymers and naturally occurring inor- as well as for quality control and nuclear denso- ganic adsorbents were examined as inexpensive meters. Because of that, americium-241 is a sig- and abundant materials able to slow down to a significant component of radioactive wastes and it is nificant degree the velocity of migration of the important test efficient barriers for the 241Am con- radionuclides, e.g. [1, 2]. taining repositories. Volclay MX80 bentonite, aluminum silicate clay To check the possibility of application of the ben- formed from volcanic ash, was intensively studied tonite sorbent as the engineering barrier, samples for the last 20 years as a compact barrier for nu- of the granular Volclay bentonite were gamma-ir- clear waste repositories [3], and it has been found radiated in the cobalt bomb at the INCT with the suitable for this purpose. Studies performed in the dose of 100 kGy. Some main properties of the ir- frame of the strategic project “Technologies sup- radiated bentonite, among them sorption, were porting development of safe nuclear power engin- compared with these of the non-irradiated mate- eering” – task 4 “Development of spent nuclear rial. fuel and radioactive waste management techniques Prior to the studies, the commercial Volclay and technologies” concerned bentonite easily avail- bentonite (P.W. Structum Ltd, Lublin, Poland) in able in Poland, which has been tested as potential the granular form was converted to its sodium buffer in the National Radioactive Waste Repo- form (assigned as Na-Vc) by equilibrating 5 g of sitory in Różan (Poland), and also as a sorbent for raw bentonite with 100 mL of 1 mol/dm3 aqueous removing of radionuclides potentially contaminat- solution of NaCl. Chemical composition of the ing water, in particular drawn in the water supply Na-Vc is presented in Table 1. Similarity in the of the Institute of Nuclear Chemistry and Tech- composition of the irradiated material with that of nology (INCT). the non-irradiated one suggests that no decompo- The present work was devoted to the study of sition occurs upon gamma radiation. this bentonite as adsorbent of trivalent ions of Porosity of sorbents and their surface size are americium-241. This radionuclide is the only acti- the fundamental factors for sorption processes of nide element which has been used in the house- the toxic and/or radioactive metals [6]. Therefore, hold – in smoke detectors. These sensors use 241Am in separate studies we determined these properties in the form of dioxide as the source of radiation of Na-Vc. They are summarized in Table 2. that ionizes air [4], because this alpha emitter in Powder X-ray diffraction studies reveal that combination with beryllium forms an efficient neu- Na-Vc is the material of layered structure, both in tron source owing to the large cross-section of be- natural and in the irradiated materials (Fig.1). ryllium-9 for the (α,n) nuclear reaction [5]. Ame- 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 Element non-irradiated irradiated non-irradiated irradiated Al 11.1 ± 1.7 10.9 ± 1.5 Mn 1353.5 ± 203.0 1545.5 ± 231.8 Mg 1.4 ± 0.2 1.5 ± 0.2 Sr 437.0 ± 65.6 588.5 ± 88.3 Na 1.2 ± 0.2 2.5 ± 0.4 Ba 524.0 ± 42.4 674.0 ± 101.1 Si 29.8 ± 4.5 26.3 ± 3.5 V 96.5 ± 14.5 113.5 ± 17.0 Fe 4.4 ± 0.7 4.4 ± 0.7 Zn 99. ± 14.9 127.0 ± 19.1 K 1.3 ± 0.3 0.9 ± 0.1 Pb 32.7 ± 4.9 33.8 ± 5.1 Ca 0.38 ± 0.1 0.35 ± 0.13 Cu 50.0 ± 7.5 30.7 ± 4.6 Rb 55.0 ± 8.3 64.5 ± 9.7 Ce 84.5 ± 12.7 89.0 ± 13.4 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 43 Table 2. Main physicochemical properties of the Volclay The only significant difference in the concentra- bentonite applied in the presented work [7]. tions of sodium cations may be explained by the supposed presence of the excess of these cations Property Value used for the conversion of the bentonite to its sod- Apparent powder density [g/cm3] 1.31 ium form. Post-decontamination liquids were simulated Particle diameter [mm] 0.1 by dissolving 21 g of citric acid in 100 mL of water BET surface [m2/g] 54.08 to obtain 1 M solution prior to americium-241 addition. Micropore surface [m2/g] 17.64 Sorption of americium(III) was studied as a Total volume of the pores [cm3/g] 7.36 · 10–2 function of contact time, initial pH and mass of Volume of the micropores [cm3/g] 0.82 · 10–2 the sorbent, respectively. Except the experiments on the time necessary for reaching the equilibrium, Mean diameter of the pores [Å] 101.74 all examinations were made in parallel: with normal Na-Vc and with the irradiated material. The latter peak from 7.037 to 7.350 deg suggests a decrease seems to be of interest because of its possible ap- in the distance between the layers, from 12.551 to plication as the engineered barrier in radioactive 12.069 Å, which occures upon the irradiation. waste repositories. The potable water was collected in the INCT. As it can be seen from Fig.2, adsorption of Am3+ Content of different ions in the water is presented comprises two stages: a primary rapidly increasing in Table 3 together with the WHO quality stand- phase and a secondary phase, of slower increment. ards. Content of all main cations and anions pre- At the first 1 h, Am3+ removal from the aqueous

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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. sent in the drinkable water and in the water shak- solutions was observed in the rapid stage, while en with the bentonite sample indicates that the from 1 to 6 h, the adsorption increase was slow. It sorbent is both chemically and mechanically stable. reached an equilibrium at about 4 h of shaking Table 3. Content of ions [mg/dm3] in the potable water samples.

Content of ion [mg/dm3]

+ + 2+ 2+ 3+ 2+ 2+ – – – 2– Fresh Na K Mg Ca Fe Zn Cu F Cl NO3 SO4 water 18.50 4.36 8.78 97.2 0.005 1.45 0.21 0.046 20.9 1.58 144.7 ± 1.48 ± 0.35 ± 0.70 ± 7.8 ± 0.001 ± 0.12 ± 0.02 ± 0.004 ± 1.7 ± 0.13 ± 11.6 Agitated 30.98 5.24 8.51 82.39 0.005 0.062 0.005 0.007 22.68 1.66 137.04 water* WHO [8] > 200 - > 500 - > 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. 44 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY with the efficiency of about 99.7%. We may as- binding sites, thus only small increase in the sorp- sume that initially, the uptake can be attributed to tion percentage is observed. the concentration gradient of Am3+ and to the 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, indicat-

Fig.2. Effect of time on Am(III) sorption on Na-bentonite. greater number of available binding sites. In the second stage of the Am3+ intake, the active bonding sites of the sorbent are to a great extent oc- cupied by Am3+, which reduces the number of the remaining active sites [9]. Bentonite clay has a very strong negative ionic Fig.4. Effect of the sorbent mass on sorption of Am(III) by Na-bentonite. charge. This negative charge attracts species of the opposite, positive charge, not only heavy/radioac- ing the greater availability of the adsorption sites. tive metals, but also toxins, harmful bacteria, dyes Around 99% of Am(III) was removed when 1 g of and various pathogens [10]. Thus the acidity of the the sorbent was put in the solution. After reaching solution is an important factor that must be con- this dose, the plateau in the sorption percent values sidered during sorption studies due to the proto- is observed even with further addition of the ad- nation and deprotonation properties of the sor- sorbent. bent surface. The effect of pH on Am(III) removal An attempt to revitalize of the Am(III)-loaded was studied in the pH range from 2.0 to 10.0 for Na-Vc was done by shaking the material at room an adsorbent dose of about 3.5 g L–1. temperature with different types of desorbing i.e. The results presented in Fig.3 clarify that at agents, 0.01 M NaCl, 0.01 M NaNO3, 0.01 M pH < ∼5, the removal of Am(III) is lower due to Na3PO4, 0.01 Na2CO3, 0.01 M Na2SO4, or 1 M + the competition between hydroxonium ions (H3O ) CaCl2 in potable water collected at the INCT. with the metal cations for the adsorption sites of Samples of drinking water of different acidities bentonite. In weakly acidic (pH = 5-7) and basic were also tested. (pH = 7-10) solutions, various hydrolysed poly- The results presented in Fig.5 show that the meric species of Am(III) may appear in the rela- percentage of Am(III) desorption with all agents tive proportions depending on the pH and the studied does not exceed 0.1%. Experiments with total americum concentration. It may be conclud- potable water of the pH in the range of 2.5 to 10.5 + – ed from the plot in Fig.3 that H3O and OH ions also show for strong binding of Am(III) by Na-Vc. in relatively small concentrations do not signifi- No more than 0.4% of the adsorbed radioactivity cantly compete with americium for the bentonite 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 irradiat- ing 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 Fig.3. Effect of pH on sorption of Am(III) by bentonite. technologies” (No. SP/J/4/143 321/11). CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 45 A References [1]. Combined methods for liquid radioactive waste treatment. Final report of a coordinated research project 1997-2001. IAEA, 2003, 250 p. Report IAEA-TEC- -DOC-1336. [2]. Wold S.: Sorption of prioritized elements on mont- morillonite colloids and their potential to transport radionuclides. Svensk Kärnbränslehantering AB, 2010, 40 p. Report SKB-TR-10-20. [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. www.cns-snc.ca/ecc/cnsecc.html. [5]. Americium-241/Beryllium. www.hightechsource.co. uk/Legacy/Resources/Americium-Beryllium.pdf. [6]. Pusch R.: Clay Miner., 27, 353-361 (1992) B [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, 4-6.06.2013, Maria Curie-Skłodowska University, Lublin, Poland, pp. 464-467 (in Polish). [8]. Guidelines for drinking-water quality. Third edition, incorporating first and second addenda. Volume 1. World Health Organization (WHO), Geneva 2008. http://www.who.int/water_sanitation_health/dwq/ gdwq3rev/en/. [9]. Sag Y., Aktay Y.: Process Biochem., 36, 157-173 (2000). [10]. Bentonite clay to remove toxic heavy metals, clear diaper rashes, stop stinky feet and more. http://www. Fig.5. Desorption of Am(III) from Na-Vc: (A) by different naturalnews.com/036972_bentonite_clay_heavy_ aqueous solution, (B) effect of pH on the desorption by metals_detox.html#. potable water collected at the INCT.

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 be used either in their natural form or modified aqueous streams represents a significant environ- with some chemical agents, depending on the tar- mental challenge. Cobalt is classified as heavy metal get pollutants [6]. that can cause serious environmental contamina- Red clay is one such material that is abundant- tion if present at high enough concentration. The ly available and not expensive, so it can also be agriculture, mining, electronics, metallurgical, and considered as an adsorbent like other clay mate- pigment/paint industries are the principal sources rials. Sorption properties of red clay and different of excessive release of cobalt in waste streams. types of clay materials have been extensively in- Zeolites are proven ion exchange materials vestigated for the purpose of Brilliant Green dye where the indigenous (typically sodium) charge bal- removal from aqueous solutions [8]. Red clay was ancing cations are not fixed rigidly to the hydrated also used for sorption of transition metals [9] as aluminosilicate framework and are readily exchang- well as such radioactive elements as Cs-134, Sr-85 ed with cations in solutions [1]. Zeolites were pre- and Zn-65 [10]. viously applied for water and wastewater treatment In the present work red clay and zeolite 5A [2] as well as for radioactive waste processing [3, 4]. were used for cobalt ions removal from aqueous Clay based adsorbents have also emerged as solutions with further perspective of using them for promising adsorbents for wastewater treatment the treatment of radioactive solutions. The idea is [5]. Clays possess certain properties which make to use these materials just as a adsorbents of radio- them an ultimate choice for adsorption process active species or as binding material in ultrafiltra- such as low cost, high availability, and environ- tion/sorption hybrid process for radioactive wastes mentally friendly material. Consequently, clays can processing. Characteristics of red clay (Pałęga min- substitute expensive activated carbon as well as ing) with particle size lower than 0.1 mm is col- low-performing biosorbents [6, 7]. The clays can lected in Table 1. Zeolite 5A (POCH, ACROS OR- 46 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY A B

2+ 2+ Fig.1. Kinetics of sorption of cobalt ions on: (A) red clay – pH = 6, [Co ] 0 = 5 mg/l, [Co ]/[sorbent] = 1/2000; (B) zeo- 2+ 2+ lite 5A – pH = 7, [Co ]0 = 100 mg/l, [Co ]/[sorbent] = 1/20; ♦ – sorption efficiency, ο – sorption capacity (q).

GANIC) used in current studies was in the form 1/1000, and at pH = 6 showed that sorption effi- of powder with particle size lower than 50 μm. ciency of cobalt ions exceeded 80% just after few In the first stage, sorption kinetic studies were minutes of the phases contact (Fig.1A). Even high- performed. Furthermore, the effect of pH, ionic er sorption efficiency, nearly 90%, was observed Table 1. Characteristics of red clay. in the case of using zeolite 5A as a sorbent of cobalt ions. In this experiment lower excess of sor- Mineralogical composition bent was applied, namely 1/20, pH was held at the level of 7. However, in the case of zeolite, the mineral content [%] equilibrium of sorption of cobalt ions was obtain- Illite 23-37 ed only after 10 days of process, what is shown in ca. Kaolinite 6-12 Fig.1B. Generally, zeolite 5A showed 100-times higher sorption capacity than red clay. Chlorite 3-5 Table 2. Sorption efficiency and sorption capacity of two Quartz 30-45 sorbents for different reagent ratio ([Co2+]/[sorbent]). Ex- 2+ Hematite 3-6 periments conditions: red clay – pH = 7, [Co ]0 = 5 mg/l, 2+ teq = 0.5 h; zeolite 5Å – pH = 7, [Co ]0 =100 mg/l, teq = Chemical composition 264 h.

SiO2 64.79 Reagent Sorption efficiency [%] q [mg/g] Al2O3 16.26 ratio red clay zeolite 5A red clay zeolite 5A Fe2O3 7.22 1/10 7.3 43.9 8.5 43 MgO 2.38 1/20 - 99.0 - 51 K2O 2.68 1/100 32.1 98.5 3.75 10 CaO 0.4 1/2000 95.6 - 0.27 - TiO2 0.91 MnO 0.09 Sorption ability of red clay as well as zeolite 5A was dependent on pH. As showed in the ex- strength as well as the ratio of the reagents on the periments, the best conditions of binding Co2+ by efficiency of cobalt ions removal was examined in both sorbents was at pH = 7 (Fig.2). order to select the optimal process parameters. The studies performed also showed that the Kinetic experiments with red clay, carried out most effective reagent ratio was 1/2000 and 1/20 with reagent ratio ([Co2+]/[sorbent]) equal to for red clay and zeolite 5A, respectively. Experi- A B

2+ 2+ Fig.2. Effect of pH on the sorption efficiency of cobalt ions on: (A) red clay – [Co ]0 = 5 mg/l, [Co ]/[sorbent] = 1/2000, 2+ 2+ teq = 0.5 h; (B) zeolite 5A – [Co ]0 = 100 mg/l, [Co ]/[sorbent] = 1/20, teq = 264 h. CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 47 A B

2+ 2+ Fig.3. Effect of salinity on the sorption efficiency of cobalt ions on: (A) red clay – [Co ]0 = 5 mg/l, [Co ]/[sorbent] = 2+ 2+ 1/2000, pH = 7, teq = 0.5 h; (B) zeolite 5A – [Co ]0 = 100 mg/l, [Co ]/[sorbent] = 1/10, pH = 7, teq = 23 h. mental data showing the relation between sorp- After filtration, the whole amount of the prepared tion efficiency and the amount of sorbents are col- solution (1 dm3), which took about 1 h, the mem- lected in Table 2. brane was removed from the filtration cell, dried Finally, the effect of the salinity on the sorp- and observed through the scanning electron micro- tion 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 Fig.4. Retention of cobalt ions during filtration of the sus- aqueous solutions, the ultrafiltration/sorption pro- pension of the red clay and cobalt chloride, using Amicon cess in dead-end mode was performed. This ex- cell with polyethersulphone membrane; cut-off = 10 kDa, 2+ 2+ periment has been conducted using filtration p = 0.3 MPar, [Co ]0 = 1 mg/l, [Co ]/[sorbent] = 1/4000, cell (Amicon) with polyethersulphone membrane pH = 7, teq = 0.5 h. (Millipore Corporation, NMWL 10 000). Model solution of cobalt ions of 1 mg/l concentration scope (DSM 942, Zeiss). The sample images of the with an appropriate amount of the sorbent was membrane surface and deposit collected on the filtered through the membrane. The UF installa- membrane are presented in Fig.5. As can be ob- tion worked under 0.3 MPa pressure. The samples served, clay deposit covers the membrane surface of filtrate were collected for analysis every 15 non-uniformly, and the surface of the deposit par- min. The experiment showed high retention of co- ticle has a rough structure. balt ions using the hybrid ultrafiltration/sorption The results show that the sorption ability of the process (Fig.4). red clay and zeolite 5A are satisfactory. Proper se- A 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. 48 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY lection of process conditions allows adsorption of [3]. Sharygin L.M., Muromskii A.Y.: Radiochemistry, cobalt ions with an efficiency greater than 95%. 46, 2, 185-189 (2004). Moreover, by the use of sorption/ultrafiltration hy- [4]. Çiçek E., Cojocaru C., Zakrzewska-Trznadel G., Ha- brid process it is possible to remove cobalt ions rasimowicz M., Miskiewicz A.: Environ. Technol., 33, 1, 51-59 (2012). from water solution with high efficiency. [5]. Auta M., Hameed B.H.: Chem. Eng. J., 198-199, The research was done in the scope of the stra- 219-227 (2012). tegic research project “Technologies supporting [6]. Nassar M.M., El-Geundi M.S., Al-Wahbi A.A.: De- development of safe nuclear power engineering” salin. Water Treat., 44, 340-349 (2012). – stage 6 of research task 4 “Development of spent [7]. Nandi B.K., Goswami A., Purkait M.K.: J. Hazard. nuclear fuel and radioactive waste management Mater., 161, 387-395 (2009). techniques and technologies”. [8]. Rehman M.S.U., Munir M., Ashfaq M., Rashid N., Nazar M.F., Danish M., Han J.: Chem. Eng. J., 228, References 54-62 (2013). [9]. Takematsu N.: JOSJ (Journal of the Oceanographi- [1]. Breck D.W.: Zeolites molecular sieves: structure, cal Society of Japan), 35, 1, 36-42 (1979). chemistry and use. New Wiley and Sons, New York [10]. Twining J.R., Payne T.E., Itakura T.: J. Environ. Ra- 1974, pp. 634-637. dioact., 71, 71-87 (2004). [2]. Wang S., Peng Y.: Chem. Eng. J., 156, 11-24 (2010).

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 Wołkowicz1/, Jerzy B. Miecznik1/ 1/ Polish Geological Institute – National Research Institute, Warszawa, Poland

One of the objectives of the Polish Nuclear Power finally precipitation of final product yellow cake Programme [1] is the assessment of domestic uran- – U3O8 [3]. ium deposits as a potential source of uranium for The solid-liquid extraction is a very important Polish nuclear reactors. Presently, mining of Polish stage in the technology of uranium production low-grade uranium ores appears uneconomic [2]. from the uranium ores. In the present work at the However, studies on the prospects of recovery of beginning of the extraction process, uranium was uranium from domestic resources are in progress, leached from the ground ore by using sulphuric 2– keeping in mind the inevitable growing uranium acid or carbonate (CO3 ) solutions [4, 5]. In com- demand and perspectives of the global uranium parison with acid processing, alkaline leaching had market. the advantage of being selective for uranium. The The most perspective deposits are in the Lower metals associated with uranium in the ores were Ordovician Dictyonema shale of Podlasie Depress- also present in acidic post-leaching solutions. In ion (North-Eastern Poland) with uranium concen- the case of alkaline leaching process only three or tration of 75-250 ppm and the Lower and Middle two metallic components of the ores were detect- Triassic rocks of the central part of Peribaltic Syne- ed: U, Mo and V (dictyonemic shales) or U and clise, where concentrations reach even 1.5% U small amounts of V (sandstones) (Fig.1). The post- (recent analysis of archive samples). -leaching solutions were separated from the leach- The main objectives of this research were: to ed ore by filtering and washing and then concen- assess the possibility of exploitation of uranium trated and purified using solvent extraction or ion resources in Poland, and to work out methods of exchange chromatography [6]. uranium extraction from the ores for production The helical membrane contactor equipped with of yellow cake – U3O8. rotating part, applied for uranium recovery from The characteristics of the material originating uranium ores, was proposed. In this method leach- from uranium ores vary significantly from deposit ing uranium ores combined with solid-liquid sep- to deposit. The effect of ore mineralogy and min- aration by filtration in one membrane apparatus eral liberation on the leaching behaviour of uran- can be carried out [7]. Series of experiments were ium is not well defined. The procedure of uranium performed using helical contactor for the purpose extraction must be designed to fit specific charac- of testing the leaching uranium and other valuable teristics of the ore; however the general scheme metals from uranium ores. The process parameters of the process is similar for most of the ore mate- varied according to the experimental plan were as rials. The basic steps of processing of uranium ores follows: the velocity of the feed flow (in the range are: crushing and grinding, leaching, solid-liquid from 0.67 to 1.33 L/min) and rotation frequency of separation, ion exchange or solvent extraction, and the inner cylinder (in the range from 0 to 2500 rpm). 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 o o (various deposits) under different process conditions: (A) 10% H2SO4, MnO2, 60 C, 1 h; (B) 10% HCl, 30% H2O2, 60 C, o o 1 h; (C) 8% NaOH/18% Na2CO3, 30% H2O2, 60 C, 1 h; (D) 5% Na2CO3/NaHCO3, KMnO4, 60 C, 1 h.

Results of experiments are presented in Fig.2. It Efficiency of uranium leaching obtained with can be noticed that by increasing flow velocity the acentric membrane contactor was comparable with efficiency of uranium leaching can be enlarged but 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 Fig.2. Comparison of the uranium leaching efficiency de- by stripping to aqueous phase. The extracting pending on feed flow velocity and velocity of the rotor in agents, like for example tributylphosphate (TBP), the helical membrane contactor. di(2-ethylhexyl)phosphoric acid (DEHPA), trioc- tylphosphine oxide (TOPO), triethylamine (TEA), the influence of the speed of the rotor is rather in- tri-n-octylamine (TnOA), and other reagents, were significant. 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. 50 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY mixture of DEHPA and TBP was found as a good Feed solution extractant for uranium and the studies of extraction of uranium from ore-leaching liquors (sulphuric and carbonate) were carried out. The use a eluents different reagents as strip solutions for uranium in organic phase was also investigated. The results are presented in Fig.3. A 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 U extraction/re-extraction with real post-leaching eluents R R B

OH R R OH R HO R OH Ln HO HO Fig.4. The structure of calix[6]arene. Other accompanying metals solutions were proceeded and the high value of Fig.5. Set of two columns with: (A) strongly basic anion recovery of uranium (96%), thorium (81%) and exchanger (DOWEX1 X8), (B) strongly acidic cation exchanger (DOWEX50 WX8). ytterbium (67%) was obtained. The possibility of application of calixarenes good uranophiles in separation processes [10]. They 2+ (Fig.4) as selective extracting agents for uranium may be useful for extracting UO2 from solutions were also considered. The calix[6]arenes act as very after leaching of uranium ores, sea water, radioac-

Fig.6. Elution of metals from columns with: (A) anion exchanger, (B) and (C) cation exchanger; 1 – feed solution, 2 – eluent

0.15 M H2SO4, 3 – eluent 1 M H2SO4, 4 – eluent 1 M H2SO4, 5 – eluent H2O, 6 – eluent 2 M HCl, 7 – eluent 4 M HNO3. CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 51

Table. The precipitation of uranium salts – precursors of U3O8.

Precipitated Concentration of uranyl ions C Temperature [oC]/time [h] Yield [%] uranium compound [mg/mL] H2SO4 0.3 2 M 40oC/4 h 88 0.5 2 M 40oC/4 h 98 0.9 2 M 40oC/4 h 95 (NH4)2U2O7 2.4 2 M 40oC/7 h 99 2.4 0.5 M 60oC/4 h 93 2.4 0.1 M 40oC/4 h 87 12 M60oC/4 h 17 22 M60oC/4 h 28 UO4 ⋅ H2O 2 0.5 M 60oC/4 h 85 12 M90oC/4 h 99 tive waste or contaminated soil. Application of [2]. Miecznik J.B., Strzelecki R., Wolkowicz S.: Prz. such extracting agents enables the use of 10 to 100 Geol., 59, 10, 688-697 (2011), in Polish. times lower ligand concentrations necessary to [3]. Edwards C.R, Oliver A.J.: JOM, 12-20 (2000). reach an assumed extraction yield than with the [4]. Zakrzewska-Trznadel G., Kiegiel K., Frąckiewicz K., Gajda D., Chajduk E., Bartosiewicz I., Chwastowska other existing extractants. J., Wołkowicz S., Miecznik J.B., Strzelecki R.: Studies The purification of uranium from accompanying on the leaching of uranium from lower Triassic Peri- metals could be also achieved by the ion exchange baltic sandstones. In: INCT Annual Report 2011. In- chromatography [6]. Two following columns, one by stitute of Nuclear Chemistry and Technology, Warsza- one, were adapted for purification of acidic post- wa 2012, pp. 47-48. -leaching solution. First column was filled with [5]. Frackiewicz K., Kiegiel K., Herdzik-Konecko I., Chaj- strongly basic anion exchanger (DOWEX1 X8), and duk E., Zakrzewska-Trznadel G., Wolkowicz S., Chwas- the second – with strongly acidic cation exchanger towska J., Bartosiewicz I.: Nukleonika, 58, 4, 451-459 (DOWEX50 WX8) (Fig.5). Feed solution was in- (2012). troduced into the first column (Fig.6A). This col- [6]. Zakrzewska G., Gajda D., Dybczyński R., Samczyński Z., Herdzik I., Chajduk E., Danko B.: The study on umn did not adsorb cations, which are eluted to the the separation of uranium from associated metals in second column (Fig.6B,C). The combination of dif- the post-leaching solution by ion-exchange process. ferent eluents allowed to obtain pure fractions of In: INCT Annual Report 2012. Institute of Nuclear valuable metals. Uranium complexes were adsorb- Chemistry and Technology, Warszawa 2013, pp. 48-50. ed on the anion exchanger and next they were elut- [7]. Zakrzewska-Trznadel G., Jaworska-Sobczuk A., Miś- ed with 1 M (one molar) sulphuric acid. Behaviour kiewicz A., Łada W., Dłuska E., Wroński S.: Method of U and some other metals, when feed solution of obtaining and separation of valuable metallic ele- was poured into the columns is shown in Fig.6. ments, specifically from low grade uranium ores and The precipitation of ammonium diuranate or radioactive liquid wastes. European Patent Applica- tion No. 12196071.0-2122. uranium peroxide forms is the most crucial step in [8]. Kiegiel K., Zielińska B., Biełuszka P., Zakrzewska- the production of uranium oxide. This is followed -Trznadel G., Chajduk E., Wołkowicz S., Miecznik J.B.: by calcination step forming triuranium octoxide Solvent extraction of uranium from post-leaching so- (U3O8). The study of the precipitation was carried lutions. In: INCT Annual Report 2012. Institute of out for the model uranium solution. The influence Nuclear Chemistry and Technology, Warszawa 2013, of concentration of sulphuric acid, temperature pp. 46-48. and concentration of uranyl ion in the solution [9]. Biełuszka P., Zakrzewska G., Chajduk E., Dudek J.: were examined. The representative results are pre- J. Radioanal. Nucl. Chem., 299, 1, 611-619 (2014). sented in Table. [10]. Kiegiel K., Steczek L., Zakrzewska-Trznadel G.: J. Chem., Article ID 762819, 16 p. (2013), http://dx.doi. The present project allowed preparing the set org/10.1155/2013/762819. of methods and technologies that will be ready for [11]. Pochopień H., Szyndler K.: Projekt procesowy instala- subsequent implementation in the nuclear fuel cji pozyskiwania uranu z rud uranowych (The process production to extract uranium from the ores and design of pilot-scale installation for uranium recovery other sources. On the basis of these results, the from uranium ores). Centrum Projektowe Polimex- process design of pilot-scale installation was pre- -Mostostal, Gliwice 2013 (in Polish). pared [11]. The project was completed with tech- [12]. Sprawozdanie – Tom II. Zadania 5-7. Analiza możliwo- nical and economic analysis [12]. ści pozyskiwania uranu dla energetyki jądrowej z za- sobów krajowych POIG.01.01.02-14-094/09 (Report: References Analysis of the possibility of uranium supply from domestic resources POIG.01.01.02-14-094/09. Vol. II. [1]. Program Polskiej Energetyki Jądrowej (Polish Nu- Tasks 5-7). Konsorcjum: Instytut Chemii i Techniki Ją- clear Power Programme). Ministerstwo Gospodarki, drowej i Państwowy Instytut Geologiczny – Państwo- Pełnomocnik Rządu ds. Polskiej Energetyki Jądro- wy Instytut Badawczy, Warszawa 2013 (in Polish). wej, Warszawa, grudzień 2010 (in Polish). 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

In the era of expanding nuclear energy new solu- the Institute of Nuclear Chemistry and Technology tions are increasingly sought for uranium extrac- (INCT). tion from unconventional sources, including phos- Significant deposits of copper ores exist in phate rocks, flotation tailings from copper produc- Poland. Large amounts of flotation wastes are pro- Table 1. The content of important elements in copper ores and copper flotation wastes [ppm] (ICP-MS analysis).

Waste Waste Elements Waste 1 Copper concentrate Waste 3 KGHM 1 PBK Gilów Gilów 2 Ba 350 - 430 905 - - - Co 558 1 178 589 25.0 427 79 1 080 Cu 27 500 170 000 25 000 1 300 44 975 12 225 35 025 Eu 1.0 0.65 1.0 1.1 - - - Fe - - - - 24 500 4 750 27 150 La 21.2 15.5 21.3 15.2 26 8.2 28 Mn 1 713 1 080 1 686 1 552 1 256 769 1 221 Mo - - - - 358 22 277 Ni 330 436 269 25 377 31 556 Th 5.0 4.5 5.1 3.5 8 1.6 10 U 14.7 12.9 15.5 7.3 27 4.5 18 V 788 581 833 144 1 370 55 1 250 Zn 1 217 7 293 987 58.0 362 237 35 tion, wastes from phosphoric acid production, and duced in the process of extraction from the ores. even sea water [1-3]. Studies on uranium leaching Many other valuable metals accompany copper in from copper ores and tailings were carried out at the ores and flotation wastes. Flotation tailings

Table 2. The leaching results for samples roasted, unroasted, and treated with the oxidant (AC method).

Uranium content Material Concd. samples treated samples roasted samples unroasted (initial uranium content) H2SO4 with the oxidant – MnO2 [ppm] [%] [ppm] [%] [ppm] [%] 96% 4.3 29.4 5.1 35.0 7.9 53.6

Waste 1 72% 4.0 27.2 1.7 11.3 6.5 44.6 (14.7 ppm) 48% 5.4 36.7 7.3 49.7 10.8 73.5 24% 0.0 0.2 6.0 41.3 96% 5.4 41.9 14.0 ~100

Copper concentrate 72% 6.6 51.4 8.1 62.9 13.0 ~100 (12.9 ppm) 48% 2.8 21.8 12.1 93.5 2.2 17.1 24% 2.6 19.9 8.4 64.9 96% 6.4 41.2 3.2 20.6 11.0 71.0

Waste 3 72% 9.1 58.8 11.5 74.0 (15.5 ppm) 48% 5.7 3.5 5.9 37.8 5.8 37.3 24% - - 5.3 34.3 96% 4.0 54.2 5.4 73.4

Waste Gilów 72% 6.9 93.9 3.6 49.8 4.1 56.4 (7.3 ppm) 48% 3.2 44.6 2.0 27.1 1.1 15.1 24% - - 1.2 15.9 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 53 from the enrichment process of copper ore are es- four types of flotation wastes (Gilów, Waste 3, timated as about 90% of the amount of the ore Gilów 2, Waste 1). Using ICP-MS (inductively processed. The uranium content in the ore from coupled plasma mass spectrometry) analysis, the the copper mine Sieroszowice Lubin is about 60 content of individual elements in the examined ppm (the copper content – 2%) [4]. Production of samples was determined. It has been found that copper in the basin Lubin-Sieroszowice in 2009 uranium content in the materials studied varies was about 569 kilotons. It is estimated that the from 4.5 to 27 ppm. The other elements that have 14 100 90 12 80 10 70 8 60 50 6

U [ppm] 40

4 U % recovery 30 20 2 10 0 0 unroasted roasted roasted unroasted roasted roasted +MnO2 +MnO2 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. amount of uranium discharged in Poland to land- been determined in these materials are: Cu (4-5% fill waste is about 1700 tons per year. in ores and 0.3-1.7% in the waste), Ag, Re, Mo, The main goal of the present work was the lanthanides, Ni, V, etc. (Table 1). analysis of uranium content in a series of indige- The process of digestion and leaching of uran- nous copper ores and wastes, and the elaboration ium ores and flotation wastes was carried out by of procedures for uranium recovery from the raw two methods. The “acid-cure” (AC) method con- materials. The study involved two types of ore sisted in direct action of concentrated sulphuric (KGHM 1 and PBK), copper concentrate, and acid (H2SO4) on the sample. After 5 h, the sample Table 3. Uranium leaching from the indicated samples (WR method).

Uranium content Material Concd. H SO samples roasted samples unroasted (initial uranium content) 2 4 [ppm] [%] [ppm] [%] 40% 2.6 18.0 1.6 10.6

Waste 1 20% 4.3 29.2 1.2 8.4 (14.7 ppm) 10% - - 0.0 0.1 5%---- 40% 0.7 5.6 1.3 10.3

Copper concentrate 20% 3.4 26.5 2.2 16.9 (12.9 ppm) 10% - - 5.7 43.8 5% - - 4.1 32.1 40% 12.9 83.4 16.1 ~100

Waste 3 20% 1.5 9.4 11.0 71.0 (15.5 ppm) 10% - - 4.2 26.8 5% - - 0.1 0.5 40% 3.77 51.6 3.0 41.3

Waste Gilów 20% 1.6 22.2 2.1 28.8 (7.3 ppm) 10% - - 5.5 75.8 5% - 18.0 0.0 10.6 54 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY was leached with H2O, either at room tempera- fractions the efficiency close to 100% was reached. ture (RT) or at 70oC for 5 h, and then filtered. This For the Waste Gilów such high yields were ob- method was also applied to samples pre-calcined served only for the fraction 0.2-0.5 mm. at 900oC for 2 h and to the samples with addition For evaluation of the two leaching methods of 2% MnO2 as oxidant [5, 6]. The second method, tested, AC and WR, the following parameters were WR, consisted in digestion of the sample for 5 h studied: type of material (ore or waste), concen- with sulphuric acid of various concentrations (40, tration of sulphuric acid, sulphuric acid with a 2% 20, 10 and 5%) at boiling temperatures [7]. oxidizing agent, additional pre-calcination step, The influence of grinding the samples on leach- leaching time, grinding of initial material. ing efficiency, and on the kinetics of leaching was In conclusion, the AC method is definitely also studied. The optimum leaching conditions better than the WR one for the recovery of uran- have been found. The concentrations of uranium ium. The highest yields, nearly 100% leaching, in the final solutions were generally less than 15 have been found for samples initially calcined, ppm. The leaching solutions contained also the and samples treated with oxidizing agent, MnO2. other metals. Simultaneous liquid-liquid extraction of uranium Table 2 presents the leaching results (AC and other metals from the leaching solutions is method) for samples roasted, unroasted, and also under study. In our opinion, only such a combined treated with the oxidant (MnO2), and selected re- procedure could be cost-effective for the recovery sults have been presented more clearly in Fig.1. of uranium together with the accompanying ele- The data show that the highest leaching yields of ments. uranium (> 70%) were obtained for samples roast- The studies were supported from the Opera- ed and treated with MnO2, but only for copper tional Programme Innovative Economy (PO IG) concentrate they approached to 100%. – project “Analysis of the possibility of uranium The results of uranium leaching using the WR supply from domestic resources”, No. POIG process are shown in Table 3. 01.01.02-14-094/09. A 100 References 90 [1]. Afolabi A.S., Muzenda E., Sigwadi R.: Effect of re- 80 agent parameters on recovery of South Africa uranium 70 ore. Proceedings of the 3rd International Conference

60 on Uranium – 40th Annual Hydrometallurgy Meeting, 15-18 August 2010, Saskatoon, Saskatchewan, Canada, 50 Vol.1, p. 481. 40 [2]. Habashi F.: Uranium from phosphate rock. An up-

U % recovery 30 date. Proceedings of the 3rd International Conference

20 on Uranium – 40th Annual Hydrometallurgy Meeting, 15-18 August 2010, Saskatoon, Saskatchewan, Canada, 10 Vol.1, p. 631. 0 [3]. Prasser H.M.: Are the sources of uranium big enough 24 48 72 96 for the nuclear energy industry? Nuclear energy in Concentration of sulfuric acid % Poland: Opportunity or necessity? 20-21 October 2008, Warszawa, Poland. B 100 [4]. Ostrowski M., Skłodowska A.: Małe bakterie wielka 90 miedź (The small bacteria great copper). SCI-ART, 80 Warszawa 1996 (in Polish). 70 [5]. Brejnak E., Pinkas K.: Badania technologiczne nad prze- 60 robem łupków dictyonemowych w skali laboratoryjnej (Technology research on the processing of dictyonema 50 shale on a laboratory scale). Instytut Badań Jądro- 40 wych, Opracowanie wewnętrzne nr 170/Ch-IV/75 (in 30

U % recovery Polish). 20 [6]. Brejnak E., Pinkas K., Deptułowa D.: Badania techno- 10 logiczne nad przerobem łupków dictyonemowych w ska- 0 li laboratoryjnej. Prace uzupełniające (Technology re- 24 48 72 96 search on the processing of dictyonema shale on a laboratory scale. Supplementary work). Instytut Badań Concentration of sulfuric acid % Jądrowych, Opracowanie wewnętrzne nr 171/Ch-IV/75 >1 mm 0,5

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/6/143 339/11), 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 01.03.01-14-054/09). The latter is suport- ed 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 allot- ment 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 2009. 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 (241536 FP7-SECURITY SEC-2009-4.3-02) which continued until April 2013. It was a Capability project funded within the 7th EU Frame- work 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 prepara- tions 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 01.03.01-14-054/09 and SP/J/6/143 339/11) 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 impli- cated 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 nanomaterials. 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. IP2011052071). 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. CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY 57 REAL-TIME PCR ANALYSIS OF EXPRESSION OF DNA DAMAGE RESPONSIVE GENES AS A BIOMARKER FOR BIOLOGICAL DOSIMETRY

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 identifi- added to each tube at a 2:1 ratio with the whole cation of radiation-exposed individuals is crucial blood. The samples were incubated at 37oC in a for triage and optimal medical management. Cur- humidified incubator with 5% CO2 for either 6, rent biological dosimetry methods are inadequate 12, 24, 48 h. The experimental schedule is shown for the task, mainly because of their low through- in Fig.1. put resulting from the time-consuming procedures Total RNA was extracted from samples using and requirement for highly trained and experi- the RiboPure-Blood Kit (Ambion); 500 ng of total enced personnel. Our objective is to develop simple RNA was converted to cDNA in a 20 μl reaction and fast bioassays for biological dosimetry based volume using the High Capacity cDNA Reverse on molecular biomarkers such as gene expression Transcription Kit (Life Technologies). Further, signatures. To this end, we analysed the literature cDNA was diluted to 100 μl with de-ionized, nu- data concerning gene expression changes in the clease-free H2O. Real-time PCR was performed blood cells following irradiation. Based on the in a 20 μl reaction mixture containing 5 μl of di- e.g available literature ( . [1-3]), the following genes luted cDNA, 4 μl of de-ionized, nuclease-free H2O, were chosen as the most promising biomarkers of 10 μl of TaqMan Gene Expression Master Mix radiation exposure: GADD45A, CDKN1A, BBC3, (Life Technologies) and 1 μl of TaqMan Gene Ex- BAX, GDF15, DDB2, MDM2, ATF3, PLK3, SESN2, pression Assay (Life Technologies). All reactions BCL2. were run in duplicate. PCR amplification was To further analyse the expression patterns of carried out using a 7500 Real-Time PCR System the selected genes in irradiated blood we per- (Life Technologies) with an initial 10-min step at formed the experiments outlined as described be- 95oC followed by 40 cycles of 95oC for 15 s and low. Blood samples were collected from three 60oC for 1 min. Relative gene expression was cal- healthy donors with informed consent from all culated using the ΔΔCt method with ITFG1 and subjects. A total of 15 ml of blood was collected DPM1 as reference controls. from each donor into heparin vacutainer tubes. Changes in the mRNA levels in the whole blood Each sample was aliquoted into three tubes (one after X-irradiation for each of the genes studied tube per dose group) and irradiated with a single have shown that mRNA levels of genes such as dose of X-rays. X-irradiation was carried out at GADD45A (cf. Fig.2), CDKN1A, BBC3, BAX, 37oC, with the use of a Smart200 (Yxlon) defecto- GDF15, DDB2 are significantly elevated even 48 scope operating at 200 kV and 4.5 mA, with 3 mm h after irradiation, which allows for correct identi- Al filtration, at a dose rate of 1.14 Gy/min. Fol- lowing 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. fication 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 Fig.1. Schematic representation of the experimental sched- in most cases) after irradiation which, together ule. with substantial variability among donors, preclude 58 CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY their usefulness as a molecular biomarkers in bio- References logical dosimetry. [1]. Paul S., Barker C.A., Turner H.C., McLane A., Wolden These preliminary data indicate that analysis S.L., Amundson S.A.: Radiat. Res., 175, 257-265 (2011). of expression of selected genes in the whole blood [2]. Joiner M.C., Thomas R.A., Grever W.E., Smolinski samples may be useful for fast identification of the J.M., Divine G.W., Konski A.A., Auner G.W., Tucker irradiated individuals and therefore, may consti- J.D.: Radiother. Oncol., 101, 233-236 (2011). tute a promising molecular biomarker for radia- [3]. Budworth H., Snijders A.M., Marchetti F., Mannion tion biodosimetry. Nevertheless, further research B., Bhatnagar S., Kwoh E., Tan Y., Wang S.X., Blakely W.F., Coleman M., Peterson L., Wyrobek A.J.: PLoS is needed to establish a reliable, gene expression- ONE, 7, e48619 (2012). -based test for biological dosimetry.

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 Jose, USA). Isolation of lymphocytes and micro- γ-H2AX foci allow the assessment of DNA double scopic slide preparation was according to stand- strand breaks and DNA repair in cells exposed to ard protocols. chemical, biological and physical factors. γ-H2AX Images of individual cells with γ-H2AX foci assay has been used as a biodosimeter for radia- were recorded as a training data files with an au- tion exposure, drug development, as well as a bio- tomated image acquisition and analysis system marker of radiosensitivity, aging, cancer and chronic Metafer. These files were used to test 10 differ- inflammation (e.g. [1]). Despite the documented ad- ent classifiers varying in parameters dealing with vantages of the γ-H2AX assay, there is a consider- automated cell selection (minimum object area, able variation between laboratories regarding foci maximum object area, maximum concavity depth, formation in the same cell lines and exposure con- maximum aspect ratio and CS object threshold ditions. Automatic or semiautomatic systems sub- %) and object features/spot counting (minimum stantially increase the productivity of the foci count- and maximum intensity of a spot, mean relative ing analysis and are free of the unavoidable op- object area, minimum spot distance, maximum erator subjectivity. However, it was shown that the spot distance). number of foci may be markedly affected by the Statistical analysis of the obtained data was automated quantification method and parameters performed using Statistica 7.1 software (StatSoft. [2]. Since no criteria and recommendations have Inc., Tulsa, USA). The data were expressed as mean been developed to justify the choice of particular ± standard deviation (SD). To compare the fre- parameter values, we investigated the effect of vari- quencies of γ-H2AX foci in individual experiments ous cell selection and object features/spot count- as well as in pooled results, two-way analysis of ing parameters on the number of scored cells and variance followed by post-hoc Tukey’s test was the slope of the γ-H2AX foci dose-response curve, performed. Significant differences were defined using the training data files generated by the Me- at p < 0.05. The dose-response curves were fitted tafer system (Metasystems, Germany). to a linear model: Since no criteria and recommendations have y = αD + C been developed to justify the choice of an appro- where: y – the yield of γ-H2AX foci, D – the dose. priate protocol for the γ-H2AX assay, we evaluat- The coefficients C and α were calculated with the ed the influence of different settings of automated method of iteratively reweighted least squares for image acquisition and analysis system (classifiers) curve fitting. The mean numbers of γ-H2AX foci on the number of scored cells and the slope of the per cell and deviation of the variance for each γ-H2AX foci dose-response curve. point of the dose-response curves were calculated Peripheral blood samples were collected from to test the distribution of γ-H2AX foci among the 34 healthy donors (20 females and 14 males, aver- analysed lymphocytes according to the Poisson’s age age 44 ± 12 yrs) into heparinized (10-20 U/ml) law. Greiner bio-one tubes. None of the donors was The number of γ-H2AX foci obtained by ap- previously exposed to radiation. Venous whole plying various classifiers was used to construct the blood was processed according to four protocols dose-response curves. Two such curves (out of 10) and irradiated at room temperature with 250 kV are presented in Fig. They illustrate the influence X-rays at a dose rate of 1.14 Gy/min with the doses of different settings of automated image acquisi- 0, 0.2, 0.4, 0.6, 0.8, 1, 1.5, 2, 3, 4 Gy (Xylon tion and analysis system on the number of scored International Smart 200-E irradiator, Xylon, San cells and the slope of the γ-H2AX foci dose-re- CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY 59 -H2AX foci per cell -H2AX foci per cell γ γ 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 37oC. sponse curve. The lowest and highest slope values References are shown, for classifiers 3 and 10, respectively. [1]. Rothkamm K., Horn S.: Ann. Ist. Super. Sanita, 45, These results indicate that the combination of cell 265-271 (2009). selection and spot counting parameters have a sig- [2]. Qvarnström O.F., Simonsson M., Johansson K.A., Ny- nificant impact on the number of scored cells and man J., Turesson I.: Radiother. Oncol., 72, 311-317 the slope of dose-response curve for γ-H2AX foci. (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, somes). It has been accepted as an alternative ra- biodosimetry tools will be essential that can pro- pid-scoring approach [1-3] that could be of value vide timely assessment of radiation exposure to in the triage and management of people at risk for the general population and enable the identifica- the acute radiation syndrome [3]. tion of those individuals exposed who should re- ceive 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 spe- cificity 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 ca- pable of conducting the DCA, • evaluating alternative biodosimetry approaches. The latter case is a new scoring technique (termed Fig. Frequencies of dicentric chromosomes determined in QuickScan, i.e. quick scan of dicentric chromo- varying cell numbers. Standard deviation indicated. 60 CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY To investigate how the number of metaphase References spreads influences dose prediction accuracy in our [1]. Flegal F.N., Devantier Y., McNamee J.P., Wilkins R.C.: hands, numbers of dicentrics were analysed in 20, Health Phys., 98, 276-281 (2010). 30, 50 and 100 cells (depending on the dose) in [2]. Flegal F.N., Devantier Y., Marro L., Wilkins R.C.: order to find the lowest number of cells enabling Health Phys., 102, 143-153 (2012). to reconstruct the dose properly. In the range of [3]. Romm H., Wilkins R.C., Coleman C.N., Lillis-Hearne high doses, 2-4 Gy of acute irradiation, even 20 cells P.K., Pellmar T.C., Livingston G.K., Awa A.A., Jenkins were enough to reconstruct the doses properly with M.S., Yoshida M.A., Oestreicher U., Prasanna P.G.: Radiat. Res., 175, 397-404 (2011). 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 per- son was irradiated with a very low dose.

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 com- growth inhibition was strengthened by c9,t11-CLA ponents of human diet. The most abundant isomer, but, interestingly, higher chromosome aberration cis-9,trans-11 CLA (c9,t11-CLA) exhibits strong frequencies were not observed. antitumour activity, and therefore its usefulness as The delay in DSB rejoining was associated with an adjuvant in radiotherapy of cancer is worth con- a diminished activation of DNA-dependent pro- sidering. Previously, we have shown that c9,t11-CLA tein kinase (DNA-PK) – a key enzyme of the non- sensitized human colon cancer HT-29 cells to -homologous DNA end joining (NHEJ). At the X-radiation [1]. The 24-hour supplementation with same time, the nuclear accumulation of epidermal the CLA isomer (70 μM) did not affect the cell growth factor receptor (EGFR), known to activate cycle progression or expression of DNA-repair-re- DNA-PK under ionizing radiation-induced stress, lated genes. Nevertheless, it caused disturbances was restrained. in the rejoining of X-ray inflicted double strand DNA-PK is also involved in Akt1 (protein ki- breaks (DSBs), as shown by pulse-field gel electro- nase B) activation in response to ionizing radia- phoresis. The transient increase in DSB levels dur- tion-inflicted DNA damage (reviewed in [2]). Ac- ing repair in CLA-supplemented cells was reflect- tivation proceeds through phosphorylation of ed in DNA repair foci number (histone γ-H2AX), serine (Ser473). Akt1 forms nuclear foci and colo- immunocytochemically monitored, and in chro- calizes with DNA-PK at DSBs. Akt1 knockout matid fragmentation frequencies, measured by mice resemble the DNA-PK deficiency radiosen- premature chromosome condensation. The cell sitivity phenotype, with increased apoptosis in re-

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). CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY 61 sponse to DNA damage, supporting the notion the absence of CLA supplementation, whereas that DNA-PK/Akt1 pathway has a marked impact CLA considerably decreased the Akt1 pSer473 on cell survival after DNA damage. The above re- content. This effect corresponded with the previ- sults suggest that apart from the role in DSB re- ously observed lowered DNA-PK activity after pair, DNA-PK is the source of anti-apoptotic sig- X-irradiation of CLA-supplemented cells as com- nalling pathway and CLA treatment prevents this pared to the non-supplemented ones [1]. function. Therefore, the effect of c9,t11-CLA on This observation explains the decreased sur- Akt1 activation was examined. HT-29 cells were vival of X-irradiated CLA-supplemented cells as incubated with CLA-supplemented or non-sup- compared to the non-supplemented ones in spite plemented medium as described in [1] and the ex- of the absence of increase in the chromosomal tent of Akt1 phosphorylation and Akt1 level were damage that is usually observed in the case of im- determined with specific antibodies by Western paired DNA-PK activity. It also shows that the blotting in the nuclear and cytoplasmic fractions signalling function of DNA-PK may be affected by of HT-29 cells after X-irradiation with 2 Gy X-rays. composition of the plasma membrane lipids, obvi- X-irradiation induced a pronounced increase ously resulting in a disturbed function of EGFR. in phosphorylation of the nuclear Akt1 with a Direct measurement of apoptosis should provide maximum at 20 min after irradiation, whereas a firm basis for this conclusion. phosphorylation of the cytoplasmic Akt1 was much References smaller but more stable. Further, the ratio of Akt1 pSer473 to unphosphorylated Akt1 was determin- [1]. Grądzka I., Sochanowicz B., Brzóska K., Wójciuk G., ed in the nuclear fraction. Figure presents the Sommer S., Wojewódzka M., Gasińska A., Degen C., Western blots from a representative experiment. Jahreis G., Szumiel I.: Biochim. Biophys. Acta, 1830, It can be seen that X-irradiation induced a pro- 2233-2242 (2013). [2]. Toker A.: Trends Biochem. Sci., 33, 356-359 (2008). nounced phosphorylation of the nuclear Akt1 in 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 Develop- ment (NCBR), Poland “Technologies supporting development of safe nuclear power enegi- neering”. 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 ques- tion 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 LABORATORY OF NUCLEAR ANALYTICAL METHODS RADIOLYTIC REMOVAL OF SELECTED PHARMACEUTICALS AND BISPHENOL A FROM WATERS AND WASTES Anna Bojanowska-Czajka, Sylwia Borowiecka1/, Marek Trojanowicz 1/ Faculty of Chemistry, University of Warsaw, Warszawa, Poland

Increasing presence of human and veterinary phar- tion of pharmaceuticals residues in environment maceuticals in the natural environment is since involve especially different advanced oxidation many years a common environmental problem. processes, based on radical reactions in aqueous This concerns not only wastes of various origin media [9]. Surprisingly, even in this relatively re- and surface waters [1, 2], but also drinking water cent review there is no mention on the application which is produced in conventional water treat- of ionizing radiation as especially effective method ment plants for communal use [3, 4]. A limited ef- of decomposition of pharmaceutical residues. ficiency of waters and wastes conventional treat- There are hundreds of papers published in the ment is well illustrated by data published about last three decades on the application of ionizing the removal of a large group of popular pharma- radiation for decomposition of organic pollutants ceuticals and hormones in Spain [2]. As it is shown in aqueous phase dealing with different groups by histogram in Fig.1, among 20 different examin- of compounds. In the last decade an increasing ed species occurring in wastes at levels from ng/L amount of such applications concerns decomposi- to μg/L, only five of them were completely decom- tion of pharmaceutical residues in waters and posed, and not found in the effluent for treatment wastes. Very recent papers published in the last plant. two years deal, e.g. with a commonly used analge- The research studies dealing with that problem stic and antipyretic drug paracetamol [10], sali- are carried out currently in several areas. Their cylic and methyl substituted salicylic acids [11], three main fields include development of new popular non-steroidal anti-inflammatory drugs analytical methods for efficient monitoring of the such as ketoprofen [12, 13], diclofenac [13-16], presence of pharmaceutical residues in environ- and ibuprofen [13, 17, 18]. Also radiolytic degra- mental samples, toxicological studies on the inter- dation using gamma irradiation was reported reaction of residual pharmaceuticals with human cently for X-ray contrast medium diatriazoate [19], and animal organisms, and studies on the develop- and several other commonly used drugs in waste- ment of new and more efficient methods of their water [13]. removal from waters and wastes. Concerning ana- In the majority of publications, the conducted lytical methods, the most powerful for simultane- studies were focused on the elucidation of mecha- ous determinations at trace and ultra-trace levels nism of radical reactions of the examined species are high-performance separation methods hyphen- with products of water radiolysis, and the deter- ated with mass spectrometry [5], but also flow ana- mination of optimum conditions for decomposi- lysis methods [6], and sensors [7] are being develop- tion of target compounds at mg/L concentration ed mostly for screening purposes and simple use levels. For compounds examined in this study, e.g. by the end users. Toxicological studies in this area for diclofenac it was level from 30 [14] to 296 [16] are mostly focused on the combined interactions mg/L, for ibuprofen – from 28 to 59 mg/L [17], with living organisms of a large number of pharma- while for carbendazim – 1.2 mg/L [17]. On the ceuticals, which are present in the environment at other hand, the highest levels of ibuprofen found trace level [8]. The most advanced studies on the de- in surface water reach 1 μg/L [3], and in wastes – velopment of new methods of efficient decomposi- 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]. LABORATORY OF NUCLEAR ANALYTICAL METHODS 65 ed from 16 countries in effluents from wastewater treatment plants the determined values were up A 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 pol- lutant – bisphenol A. In the coarse of this study the examined standard solutions and environmental samples were gam- B ma-irradiated using a 60Co source Gamma Chamber with a dose-rate of 8.0 kGy/h. The reversed-phase Carbamazepine HPLC analyses of irradiated samples were carried out using a Shimadzu chromatograph with a Bisphenol A diode array UV/Vis detector, a Luna ODS2, 5 μm 250 × 4.6 mm analytical column and a guard col- Diclofenac Ibuprofen 1 umn from Phenomenex (Torrance, CA, USA). 2 3 For simultaneous monitoring of concentrations of target species and products of decomposition, two HPLC procedures with UV detection have Fig.3. Comparison of the application of two developed been developed, for which example of recorded HPLC methods in the determination of investigated ana- chromatograms are shown in Fig.2. In both me- lytes in river water samples. A – chromatograms (3 repeti- thods the base-line separation can be achieved for tions) obtained with method A for river water sample from all analytes, however, in method B the total ana- the Vistula river, collected before treatment plant with lysis time to get the elution of all the determined marked retention times for determined analytes. B – chro- species was about 60 min, while in method A – 12 matograms of river water with added 10 μg/L concentra- min. The HPLC determinations with UV detection of each analyte, obtained with method B for sample prior to the irradiation (1), after gamma irradiation with a tion at μg/L concentration level require an initial dose of 100 (2) and 250 Gy (3). A 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 ad- justed 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 B 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.2. Comparison of HPLC chromatograms for standard (Fig.3B), although in this case LODs values are mixtures of determined analytes obtained with two devel- about one order of magnitude poorer. oped methods of isocratic elution. A – Eluent composition: 40% 0.2 M formic acid, 60% acetonitrile, pH 4.0; injection The investigations of efficiency of radiolytic – 4 mg/L each analyte (method A). B – Eluent composition: decomposition reported already in the literature for ibuprofen [13, 17, 18], and carbamazepine 50% 0.6 mM KH2PO4, 30% acetonitrile, 20% methanol, pH 4.0; injection – 2 mg/L each analyte (method B). In both [13], were broadened in this work by examination cases: flow-rate – 1 mL/min, detection UV at 220 nm. of the effect of pH of the irradiated solutions. At 66 LABORATORY OF NUCLEAR ANALYTICAL METHODS an initial concentration of both compounds 10 samples and hospital effluent (Fig.6). In both cases mg/L, the pH effect for ibuprofen is observed only the monitored samples were irradiated after spik- at doses 0.2-0.6 kGy, where irradiated compound ing them with 10 μg/L each analyte. The obtained is only partly decomposed (Fig.4A). In the case of results confirm that especially the decomposition more resistant towards radiation carbamazepine of carbamazepine and bisphenol A requires much (Fig.3B), the decomposition process in the whole larger irradiation doses in the case of hospital ef- range of employed doses is about 20% less effi- fluent than river water samples. In the case of bi- cient than in neutral or acidic media (Fig.4B). sphenol A the application of 100 Gy absorbed dose allows the decomposition of 95% in river A water, while 70% only in hospital effluent. For carbamazepine those yields were 90 and 37%, respectively. A

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 Fig.6. Comparison of the yield of gamma irradiation of the the irradiation of the hospital effluent with added investigated compounds at different irradiation doses in 10 μg/L each analyte, up to 0.5 kGy irradiation various water matrices for samples spiked with 10 μg/L concentration each: A – river water sample from the Vis- dose was used. One can see, that only in the case tula river, B – effluent from a hospital. of diclofenac and ibuprofen it was sufficient – the complete decomposition was observed at 0.25 Results of this study firmly show a very essen- kGy. A comparison of the effect of matrix of the tial impact of matrix composition of irradiated irradiated solution on the yield of decomposition natural samples on the yield of decomposition of of the examined compounds is illustrated by signal pharmaceutical residues at their examined level, changes in recorded chromatograms for river water 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

Carbamazepine method for the decomposition of pharmaceutical residues from waters and wastes compared to

Bisphenol A methods routinely used nowadays.

1 References Diclofenac Ibuprofen 2 [1]. Nikolaou A., Meric S., Fatta D.: Anal. Bioanal. Chem., 3 387, 1225-1234 (2007).

4 [2]. Pedrouzo M., Borrull F., Pocurull E., Marce R.M.: Water Air Soil Poll., 217, 267-281 (2011). [3]. Mompelat S., Le Bot B., Thomas O.: Environ. Int., Fig.5. HPLC chromatograms recorded for the sample of 35, 803-814 (2009). wastewater from a hospital spiked with 10 μg/L each ana- [4]. Kleywegt S., Pileggi V., Yang P., Hao C., Zhao X., lyte prior to gamma irradiation (1), after irradiation with Rocks C., Thach S., Cheung P., Whitehead B.: Sci. doze 100 (2), 250 (3) and 500 Gy (4). Total Environ., 409, 1481-1488 (2011). LABORATORY OF NUCLEAR ANALYTICAL METHODS 67

[5]. Pitarch E., Portoles T., Marin J.M., Ibanez M., Albar- [14]. Homolok R., Takacs E., Wojnarovits L.: Chemo- ran F., Hernandez F.: Anal. Bioanal. Chem., 397, sphere, 85, 603-608 (2011). 2763-2776 (2010). [15]. Trojanowicz M., Bojanowska-Czajka A., Kciuk G., [6]. Trojanowicz M.: Talanta, 96, 3-10 (2012). Bobrowski K., Gumela M., Koc A., Nałęcz-Jawecki G., [7]. Rodriguez-Mozaz S., Lopez de Alda M., Barcelo D.: Torun M., Ozbay D.S.: Eur. Water, 39, 15-26 (2012). Anal. Bioanal. Chem., 386, 1025-1041 (2006). [16]. Yu H., Nie E., Xu J., Yan S., Cooper W.J., Song W.: [8]. Fent K., Weston A.A., Caminda D.: Aquat. Toxicol., Water Res., 47, 1909-1918 (2013). 76, 122-159 (2006). [17]. Zheng B.G., Zheng Z., Zhang J.B., Luo X.Z., Wang [9]. Klavariotti M., Mantzavinos D., Kassinos D.: Environ. J.Q., Liu Q., Wang L.H., Desalination, 276, 379-385 Int., 35, 402-417 (2009). (2011). [10]. Szabo L., Toth T., Homlok R., Takacs E., Wojnarovits [18]. Illes E., Takacs E., Dombi A., Gajda-Schranz K., Racz L.: Radiat. Phys. Chem., 81, 1503-1507 (2012). G., Gonter K., Wojnarivits L.: Sci. Total Environ., 447, [11]. Ayatollahi S., Kalnina D., Song W., Turks M., Cooper 286-292 (2013). W.J.: Radiat. Phys. Chem., 92, 93-98 (2013). [19]. Velo-Gala I., Lopez-Penalver J.J., Sanchz-Polo M., [12]. Illes E., Takacs E., Dombi A., Gajda-Schranz, Gonter Rivera-Utrilla J.: Chem. Eng. J., 195-196, 369-376 K., Wojnarovits L.: Radiat. Phys. Chem., 81, 1479-1483 (2012). (2012). [20]. Zhang Y., Geissen S., Gal C.: Chemosphere, 73, [13]. Kimura A., Osawa M., Taguchi M.: Radiat. Phys. 1151-1161 (2008). Chem., 81, 1508-1512 (2012).

DETERMINATION OF URANIUM IN FLOW-INJECTION SYSTEM WITH SPECTROPHOTOMETRIC DETECTION Kamila Kołacińska, Marek Trojanowicz

Flow analysis is considered as a very efficient way flow methods in chemical analysis have been de- of carrying out numerous analytical determina- veloped for over 50 years and also numerous tions with different detections and on-line sample others highly specialized systems were invented. treatment processes. The essential feature of the This includes MCFIA – multi-commuted flow in- flow analysis is the possibility of mechanization of jection analysis [4], MSFIA – multi-syringe flow in- numerous on-line processes and automation of all jection analysis [5], MPFS’s – multi-pumping flow analytical procedures, which means a full control system [6] and the most recent option LOV – over the fluid flow, its volumes, flow rates, timing Lab-on-Valve systems [7]. Currently, flow analysis and detection conditions. This improves the effi- has a solid place among other methods of modern ciency of measurements, provides a good repro- analytical chemistry [8, 9], and is widely applied to ducibility of results and also minimizes the human the chemical analysis of environmental samples as error influence by mechanization of all the per- well as geological, industrial or clinical ones. formed processes. The implementation of this technique for the The development of the flow analysis labora- determination of radionuclides is a relatively new tory methods began with the research conducted field of applications; although the first approach by Skeggs in the 1950s, who introduced the air of using FIA in radioanalysis was reported for segmentation of liquid in analytical systems de- measuring vanadate by passage sample through col- signed to study body fluids (SFA – segmented flow umn with radioisotope of silver [10]. The applica- analysis) [1]. A significant technological progress tions of flow analysis to the determination of radio- of the method came through inventing the flow nuclides for different purposes have been devel- injection analysis (FIA) [2]. The operational prin- oped for more than 20 years, which were already a ciple of FIA technique is based on recording the subject of several reviews [11-14]. A choice of a de- transient signal in detector, which corresponds to tection type depends primarily on the nature of the the analyte concentration in the injected sample. sample analysed and analytes to be determined. A FIA measuring system consists of a pumping Generally, for radiochemical analysis few kinds of device, which provides flow of a liquid, a tubing detectors are used, only, such as radiometric, mass manifold, an injection valve with an injection loop spectrometric and also spectrophotometric. to load a sample into system and also a detector. In recent decade several papers were published After the sample is injected into a flowing carrier on the application of flow-injection methods for stream, it moves downstream and mixes with an the determination of uranium [15-29]. Methods introduced reagent in a reactor coil to produce a which were based on the use of spectrophoto- detectable form by a chemical reaction. In a more metric detection [15-22], or amperometric one complex FIA setups there are also different mod- [23] allow the determination of total content of ules for on-line sample processing incorporated uranium in analysed samples. The application of into the flow system. A sequential injection analysis inductively coupled plasma mass spectrometry (SIA) is considered to be a new generation of FIA (ICP-MS) can be used in the determination of method, which compared to FIA, can be regarded particular isotopes such as 234U [24], 236U [25] and as a more flexible because it introduces flow re- 238U [26-29], or isotope ratio 235U/238U [27]. Regard- versal; the change of the flow direction is program- ing the construction of flow systems, a typical FIA med and usually controlled by a computer [3]. The systems are most often used [15, 20-24, 26-28]. 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 report- In this study, initiated recently in the Institute ed for simultaneous determination of 236U, 237Np, of Nuclear Chemistry and Technology (INCT), a and Pu isotopes in sea water [25]. Several at- commercial MSFIA-LOV system from Sciware tempts can be found in the literature on design of Systems (Bunyola, Spain) was employed, which MSFIA systems [16, 17], recently also employing a was already used in the determination of uranium more complex construction of rotary injection in environmental samples with spectrophotomet- valves – LOV with built-in a mini-column for ex- ric detection [18]. The configuration of flow sys- traction, preconcentration and separation of ana- tem is shown schematically in Fig.1. The spectro- lytes [18, 19, 29]. photometric detection was based on the formation 2+ Most commonly in flow injection systems for the of UO2 complex with Arsenazo III (2,2’-(1,8-di- determination of uranium is spectrophotometric hydroxy-3,6-disulfonapthylene-2,7-bisazo)bisben- detection based on the formation of coloured com- zenearsonic acid), whose structure is shown in 2+ plexes of UO2 cation with Arsenazo III [15-20], Fig.2. and also such ligands as Chromazurol S [21] and The maximum of absorption of U(VI) com- Chlorphosphonazo III [22]. With the use of Arse- plex with Arsenazo is at 651 nm, and molar ab- nazo III, limits of detection for different configu- sorption coefficient 4 450 M–1cm–1 [30]. Taking into rations of flow system are in a wide range form 40 account this absorption maximum, as a source of mg/L [16] down to even 5.9 ng/L [19], at a well op- light in MSFIA-LOV system, seven different light timized preconcentration procedure. For on-line emitting diodes (LED) were examined with the trace U(VI) preconcentration, various types of sor- emission maxima from 650 to 660 nm. As the op- bents are employed, including commercially avail- timum one, the LED type L-53SRC/F from King- able extraction chromatography resins TRU-Spec bright (Issum, Germany) was employed, with an [17, 20, 27], UTEVA [18, 19, 24, 25, 29], TEVA emission maximum at 655 nm (Fig.3). Spectro- [28], strong anion exchanger Amberlite IRA-402 photometric measurements were carried out with [20], and also, e.g. a laboratory-made styrene-divi- nylbenzene copolymer modified with dodecylami- doxime [22].

Fig.3. Emission spectrum of light emitting diode L-53SRC/F from Kingbright company used as a source of radiation in 2+ Fig.2. Structure of UO2 complex with Arsenazo III. the MSFIA-LOV system for determination of uranium. 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 HNO3 1 0.8

2 Sample loading U(VI) in 3 M HNO3 1 0.8 3 9 M HCl 0.1 2 Elution of interferences 4 5 M HCl 1 2 5 Elution of uranium 0.01 M HCl 1 0.8 6 Complex forming 0.001% Arsenazo III 1 2

7 Washing the flow system H2O 3.5 2 a 100 cm long waveguide capillary cell (LWCC) tained detectability at this initial stage of the work, from World Precision Instruments (Saracota, USA), is far from satisfactory, the whole measuring pro- and with a CCD detector type USB 2000 from cedure requires further optimization in order to Ocean Optics (Dunedin, USA). improve detection level, examination of complete- Arsenazo III forms also stable complexes with ness of retention and elution of the analyte from Th, Zr, Cd, Zn, Ca and can be used for spectro- the sorbent bed. In further steps also selectivity of photometric determination of those elements. The retention/elution process will be examined in flow selectivity of spectrophotometric determination of injection conditions employed, and eventually ad- U(VI) can be achieved by the application of suit- justed by the modification of the whole procedure. able masking reagents, as it was shown in the si- The developed method will be also examined in multaneous determination of U and Th in FIA the determination of total uranium content in en- system [21], or by the use of the above-mentioned vironmental samples. selective sorbents. In this work, for this purpose The work was financed by the National Centre the extraction resin UTEVA from Triskem (Bruz, for Research and Development, Poland in the frame France) was used. By the use of diamyl amylphos- of the strategic research project “Technologies sup- phonate as extrahent, this resin allows selective porting development of safe nuclear power engi- retention of U(VI) and tetravalent actinides as neering” – task 8 “Study of processes occurring neutral nitrato complexs [31]. The resin (30 mg) under regular operation of water circulation sys- was packed into mini-column of LOV injection tems in nuclear power plants with suggested ac- valve, and all stages of analytical procedure were tions aimed at upgrade of nuclear safety”. 1,4 1000 ppb

1,2

1 100 ppb

0,8

0,6 Abs [a.u.] 0 ppb 1 ppb 10 ppb 0,4

0,2

0 2 502 1002 1502 2002 2502 Time [s] Fig.4. Example of flow-injection signals obtained in the MSFIA-LOV system for injection of uranium solutions at different concentrations. carried out according to the programme shown in References Table. For spectrophotometric detection, 0.001% [1]. Skeggs L.J.: Am. J. Clin. Pathol., 28, 311-322 (1975). Arsenazo III solution in 0.7 M chloroacetic acid [2]. Ruzicka J., Hansen E.H.: Anal. Chim. Acta, 78, – 0.1 M sodium chloroacetate buffer of pH 2.0 was 145-157 (1975). used. In the initial experiments 1 μg/L to 1 mg/L [3]. Ruzicka J., Marshall G.D.: Anal. Chim. Acta, 237, 329-343 (1990). of U(VI) solutions in 3 M HNO3 were injected. Example of the signals recorded in FIA system [4]. Reis B.F., Gine M.F., Zagatto E.A.G., Lima J.L.F.C., are shown in Fig.4. This recording shows that for Lapa R.A.: Anal. Chim. Acta, 293, 129-138 (1994). [5]. Cerdá V., Estela J.M., Forteza R., Cladera A., Becerra 1 mL of the injected sample volume, the whole E., Altimira P., Sitjar P.: Talanta, 50, 695-705 (1999). measurement of 1 sample takes about 3 min, [6]. Lapa R.A.S., Lima J.L.F.C., Reis B.F., Santos J.L.M., which indicates a very efficient way of conducting Zagatto E.A.G.: Anal. Chim. Acta, 466, 125-132 analytical determination in such a system. The ob- (2002). 70 LABORATORY OF NUCLEAR ANALYTICAL METHODS

[7]. Ruzicka J.: Analyst, 125, 1053-1060 (2000). [20]. Nisa Q., Ali A., Haleem Khan M.: J. Radioanal. Nucl. [8]. Advances in flow analysis. Ed. M. Trojanowicz. Wi- Chem., 295, 2203-2214 (2013). ley-VCH, Weinheim 2008. [21]. Hirano Y., Ogawa Y., Oguma K.: Anal. Sci., 19, 303-307 [9]. Westmeier W., Siemon K.: J. Environ. Radioact., 117, (2003). 25-30 (2013). [22]. Oguma K., Suzuki T., Saito K.: Talanta, 84, 1209-1214 [10]. Grudpan K., Nacapricha D.: Anal. Chim. Acta, 246, (2011). 329-331 (1991). [23]. Aguiar M.A.S., Marquez K.S.G., Gutz I.G.R.: Electro- [11]. Grate J.W., Egorov O.B.: Automated radiochemical analysis, 12, 742-746 (2000). separation, analysis and sensing. In: Handbook of [24]. Godoy M.L.D.P., Godoy J.M., Kowsmann R., dos radioactivity analysis. 2nd ed. Ed. M. L’Annunziata. Santos G.M., Petinatti da Cruz R.: J. Environ. Radio- Elsevier Science, USA 2003, pp. 1129-1164. act., 88, 109-117 (2006). [12]. U M., Tölgyessy J.: J. Radioanal. Nucl. Chem., 191, [25]. Qiao J., Hou X., Steier P., Golser R.: Anal. Chem., 85, 413-426 (1995). 11026-11033 (2013). [13]. Grate J.W., Egorov O.B., O’Hara J.M., DeVol T.A.: [26]. Truscott J.B., Bromley L., Jones P., Evans E.H., Tur- Chem. Rev., 108, 543-562 (2008). ner J., Fairman B.: J. Anal. At. Spectrom., 14, 627-631 [14]. Fajardo Y., Avivar J., Ferrer L., Gómez E., Casas M., (1999). Cerdà V.: Trends Anal. Chem., 29, 1399-1408 (2010). [27]. Benkhedda K., Epov V.N., Evans R.D.: Anal. Bio- [15]. De Sousa A.S.F., Ferreira E.M.M., Cassella R.J.: anal. Chem., 381, 1596-1603 (2005). Anal. Chim. Acta, 620, 89-96 (2008). [28]. Schaumlöffel D., Giusti P., Zoriy M.V., Pickhardt C., [16]. Guzmán Mar J.L., López Mertínez L., López de Szpunar J., Łobiński R., Becker J.S.: J. Anal. At. Alba P.L., Ornelas Soto N., Cerdá V.: J. Radioanal. Spectrom., 20, 17-21 (2005). Nucl. Chem., 281, 433-439 (2009). [29]. Avivar J., Ferrer L., Casas M., Cerda V.: J. Anal. At. [17]. Avivar J., Ferrer L., Casas M., Cerdá V.: Anal. Bio- Spectrom., 27, 327-334 (2012). anal. Chem., 397, 871-878 (2010). [30]. Golmohammadi H., Rashidi A., Safadri S.J.: Chem. [18]. Avivar J., Ferrer L., Casas M., Cerdà V.: Talanta, 84, Chem. Technol., 6, 245-249 (2012). 1221-1227 (2011). [31]. Horwitz E.P., Dietz M.L., Chiarizia R., Gatrone R.C., [19]. Avivar J., Ferrer L., Casas M., Cerdá V.: Anal. Bio- Esslin A.M., Bane R.W., Graczyk D.: Anal. Chim. anal. Chem., 400, 3585-3594 (2011). Acta, 266, 25-37 (1992). 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 assem- bling 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 verifica- tion, information on the technology and techniques that were used by a given master and indi- cation 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 Ortho- dox 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 LABORATORY OF MATERIAL RESEARCH STRUCTURAL STUDIES IN Li(I) ION COORDINATION CHEMISTRY Wojciech Starosta, Janusz Leciejewicz

Like diazine carboxylate, diazole and triazole car- bond between carbonyl and carboxylato O atoms boxylate ligands have a number of multifunctional is operating; in all Li ions show trigonal bipy- potential coordination sites involving hetero-ring ramidal coordination environment. N and carboxylate O atoms. They are accessible to PART 19. Triaqua(pyrazole-4-carboxylato-κN1)- metal ions and as such can be coordinated as -lithium mono-, bi- and tetradentate and act as linkers pro- The orthorhombic structure of the title com- viding multibridging modes generating different pound is composed of discrete mononuclear mol- types of coordination polymers. Recent results of ecules in which Li1+ is coordinated by the non-pro- our studies are briefly summarized below: tonated hetero-ring N atom of the ligand molecule • Among 22 new structures determined in course and three aqua O atoms at the apices of distorted of this project only three have been observed to tetrahedron. The observed Li–O and Li–N bond be built of discrete molecules. The latest example distances and bond angles reveal usual values. The is represented by the structure of a complex with carboxylic group is deprotonated. It makes a dihe- pyrazole-4-carboxylate and water ligands [1]. dral angle of 10.7(2)o with the almost planar [r.m.s. • Dinuclear moiety in which two Li ions and two 0.0014(1) Å] pyrazole ring. Bond distances and ligand molecules related by an inversion centre bond angles within the latter are close to those ob- has been observed as a structural unit in 12 com- served in the structure of the parent acid. Complex plexes 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 Fig.1. The molecule of the title compound with atom label- of a Li complex with 5,6-dimethylpyrazine-2,3- ling scheme and 50% probability displacement elipsoids. -dicarboxylate and water ligands composed of molecular ribbons in which Li ions are bridged molecules form layers parallel to the unit cell ac by both N,O bonding sites [4] has been earlier plane (Fig.1) and are stacked along the b axis found in the structures of four Li complexes with (Fig.2). Coordinated water molecules are active pyrazine-2,3-dicarboxylate and water ligands as donors and acceptors in an extended hydrogen [5, 6]. In the structure of one of them nitrato bond system in which carboxylate O atoms are as groups bridge the ribbons giving rise to a three- acceptors. The protonated hetero-ring N atom as -dimensional framework [6]. In all the above a donor and a carboxylate O atom as an acceptor structures an intra-molecular short hydrogen are also observed.

Fig.2. A single molecular layer viewed along the [010] direction. LABORATORY OF MATERIAL RESEARCH 73

PART 20. Di-μ-aqua-bis([aqua(5-carboxylato- PART 21. catena-Poly[[diaquabis(μ3-5-carboxy- -1H-1,2,3-triazole-4-carboxylic acid-κ2N3,O4) lato-1H-pyrazole-3-carboxylic acid-κ 3O3:O3;O5) lithium dilithium(I)] monohydrate] The triclinic unit cell of the title compound The structural unit of the title complex is a comprises two Li(C4H2N3O4)(H2O)2 molecules re- centrosymmetric dinuclear moiety composed of lated by an inversion centre to form a dimeric two Li ions bridged by two bidentate carboxylato moiety in which two Li ions are bridged by an aqua O atoms, each donated by a symmetry related li-

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 gand (Fig.5). The ligand acts in μ3 bridging mode coordination of the Li ion is distorted square py- since apart from the bidentate O1 atom, the O4 ramidal: carboxylate O1, hetero-ring N1, aqua O6 atom of its second carboxylate group is chelated and O5i atoms constitute its base [r.m.s. 0.0798(2) to a Livi ion in the adjacent dimer. In this way a Å], the Li1 ion is 0.1995(2) Å out of it, the aqua Li ion is coordinated by the bridging O1 and O1ii O5i is at the apex. Li-O and Li-N bond distances atoms, the O4i from the adjacent dimer and an are usual. The ligand triazole ring is almost planar aqua O5 atom resulting in a distorted tetrahedral [r.m.s. 0.0006(1) Å]. The carboxylate C6/O1/O2 geometry. The Li–O bond distances which fall in and C7/O3/O4 groups make with it dihedral angles the range between 1.930(2) Å and 1.980(3) Å are of 2.0(1)o and 5.5(1)o, respectively. The Fourier typical of Li complexes with carboxylate and water map indicates clearly that the O2 atom is proto- ligands. The pyrazole ring is planar with r.m.s. of nated and acts as a donor in a fairly short intra- 0.0009(1) Å; the carboxylate group C6/O1/O2 and -molecular hydrogen bond of 2.538(2) Å to the O3 C7/O3/O4 make with it dihedral angles of 2.4(1)o atom as an acceptor. The C7/O3/O4 carboxylic and 5.5(1)o, respectively. The carboxylate O2 atom group remains deprotonated and coordination in- is chelating inactive, the O3 remains protonated active. The bond distances and bond angles within and participates as a donor in the short hydrogen the triazole ring do not differ from those reported bond of 2.516(2) Å to O2vi in an adjacent dimer. in the structures of other complexes. The dimers Bond distances and bond angles within the pyra- form molecular sheets (Fig.4) in which they inter- zole ring do not differ from those reported in the act via an extensive hydrogen bond network; coor- structure of the parent acid. The plane of the dinated water molecules are as donors a hetero- Li,O1,Liii,O1ii dimer core makes a dihedral angle -ring N atom and carboxylate O atoms as accep- of 36.1o with the ligand plane. The dimeric units tors. linked by carboxylate O4 atoms form polymeric

Fig.4. The packing of the dinuclear molecules with hydrogen bonds shown as dashed lines. 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 ing sites form type 1 molecular ribbon. The type 2 water molecule O6 with 50% site occupancy is molecular ribbon is built of units composed of a present in the asymmetric cell resulting in one water coordinated Li(I) cation and a ligand which molecule per a dimer. Moreover, this water mol- also uses its both N,O bonding sites (Fig.7). Both ecule shows 0.5/0.5 positional disorder. The rib- ligands act in μ2 bridging mode. All three Li(I) cat- bons are held together by a system of hydrogen ions show slightly distorted trigonal bipyramidal bonds involving coordinated and crystal water coordination geometry. The Li11 cation is situat- molecules, the carboxylate groups and pyrazole N ed in the equatorial plane composed of O11, O11ii ring atoms resulting in a three-dimensional archi- and O13 atoms; N11 and N11ii atoms are in the tecture (Fig.6). apical positions. The Li12 coordination is form-

Fig.6. The packing of molecular ribbons viewed along their propagation direction. PART 22. catena-Poly[[aqualithium(I)]-μ-3-car- ed by O13, O13iii and O16 atoms, N14 and N14iii boxy-5,6-dimethylpyrazine-2-carboxylato- atoms are at the apices; the Li12 is also coplanar κ 4O2,N1:O3,N4] with the equatorial plane. On the other hand, the The asymmetric unit of the title compound Li21 cation is 0.0142(2) Å out of the equatorial contains two Li(I) ions and two coordinated to plane formed by O21, O21i and O25 atoms; N22i them water molecules, all located on the rotation and N21i are at the apices. The Li-O and Li-N twofold axis, a Li(I) ion, two ligand molecules and bond distances fall in the range observed in the a coordinated to water molecule. Two water coor- structures of other Li complexes with diazine car- dinated Li(I) ions located on the rotation twofold boxylate ligands. Methyl carbon and pyrazine ring axis are bridged by a ligand via its both N,O bond- atoms in both ligands are coplanar with r.m.s. of LABORATORY OF MATERIAL RESEARCH 75

Fig.7. Structural units of the title complex with atom labelling scheme and 50% probability displacement ellipsoids. Sym- metry code: (i) -x, y, -z+3/2; (ii) -x, y, -z+1/2; (iii) x, -y, z+1/2. 0.0062(1) Å in the ligand 1 and 0.0193(2) Å in the propagate in [001] direction (Fig.8). The planes of ligand 2. The carboxylic groups C17/O11/O12 and ribbon 1 and ribbon 2 pairs are inclined 91.1(1)o C18/O13/O14 form with the ligand 1 ring dihedral each to the other. They are held together by a sys- angles of 6.1(1)o and 10.9(1)o, respectively. The di- tem of hydrogen bonds in which water molecules

Fig.8. The packing of molecular ribbons viewed along the [001] direction. hedral angles between ligand 2 and carboxyl groups act as donors and carboxyl O atoms are as accep- C27/O21/O22 and C28/O23/O24 are 1.2(10)o and tors giving rise to a three-dimensional molecular 9.0(1)o, respectively. In both ligands the second car- framework. boxyl O atoms remain protonated and act as do- References nors in the short intramolecular hydrogen bonds with bond distances of 2.378(2) Å and 2.369(2) Å. [1]. Starosta W., Leciejewicz J.: Acta Crystallogr., E69, Two ribbons of the same type form pairs which m438 (2013). 76 LABORATORY OF MATERIAL RESEARCH

[2]. Starosta W., Leciejewicz J.: Acta Crystallogr., E69, [5]. Starosta W., Leciejewicz J.: Acta Crystallogr., E67, m515-m516 (2013). m1133-m1134 (2011). [3]. Starosta W., Leciejewicz J.: Acta Crystallogr., E69, [6]. Starosta W., Leciejewicz J.: Acta Crystallogr., E69, m593-m594 (2013). m62 (2013). [4]. Starosta W., Leciejewicz J.: Acta Crystallogr., E69, m655-m656 (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 Barlak1/, Lech Waliś, Jan Senatorski2/, 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 W/cm2). The plasma pulses were generated in a is applied to change their surface properties. Auste- rod plasma injector (RPI) with its own name IBIS nitic stainless steels are used in numerous indus- described with details in [11]. The pulse energy trial applications, mainly due to their corrosion was high enough for melting the surface layer of resistance in different environments, for example: the material. Heating and cooling processes were nuclear and petrochemical industries and chemi- of non-equilibrium type. cal processing. But poor tribological and mechan- Samples were irradiated with 3 pulses with an ical properties of austenitic stainless steels limited energy density of 3.0 J/cm2, in PID (pulsed implan- their applications. Improvement of the wear resist- tation doping), DPE (deposition by pulse erosion) ance of austenitic stainless steels without loss of and mixed modes with titanium rods coated with corrosion resistance can be achieved using differ- Ce, La or mischmetal tips as electrodes and nitro- ent surface treatment, for example: enrichment of gen as the working gas. Samples of initial and the surface layer with reactive elements or re-so- modified materials were characterized by: scan- lidification techniques using laser, electron or ion ning electron microscopy (SEM) – DSM 942 (Zeiss, beams. Rapid solidification process is useful to Germany), energy dispersive X-ray spectrometry obtain very fine structure with uniform properties (EDS) – Quantax 400 (Bruker, Germany), grazing [1-4]. It is also well known that high oxygen affin- angle X-ray diffraction (GXRD) – diffractometer ity elements such as Y, Ce, La, Er and other rare D8 Advanced (Bruker, Germany). Wear resistance earth elements (REE) added to steels in small measurements were carried out using the Amsler amounts can improve their resistance for wear and method. mechanical properties [5, 6]. REE can be alloyed After the modification process, the initial grain during the steel making process or can be added boundaries (Fig.1A) almost disappeared. Features to the surface region of materials using different typical of the melted and rapidly solidified mate- surface modification techniques such as: ion im- rial of the mixed deposit-substrate forms can be plantation [7-9], sol-gel coating [9] or using plasma seen (Fig.1B-D). beams [10]. Atomic concentrations of REE incorporated Austenitic stainless steel AISI 316L (Cr – 16.3 into specimens were in the range of 0.5-1.8 at.%. wt.%, Ni – 11.5 wt.%, Mo – 2.0 wt.%, Mn – 1.3 GXRD spectra for initial and modified mate- wt.% and Fe – balance) was used as the substrate rial analysis confirm the presence of FCC phase – for investigations. As the REE sources, cerium or austenitic structure with Fm-3m symmetry. Auste- lanthanum or mischmetal (MM) with a composi- nitic peaks (111) present in the spectra of modified tion: Ce – 65.3 wt.%, La – 34.0 wt.% and balance materials are shifted towards bigger angles, what of Fe, Mg, and Pr were used. REE were incorpo- means that lattice parameters were decreased rated into one surface of steel samples using high (Fig.2). Austenite lattice parameters calculated intensity pulsed plasma beams – HIPPB (106-108 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. LABORATORY OF MATERIAL RESEARCH 77

4000 316L 316L+Ce 3500 316L+La

3000

2500

2000

1500 Intensity (counts)

1000

500

0 42,5 43 43,5 44 44,5 45 45,5 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 Conclusions are the following: significantly as a result of remelting and rapid so- • Austenitic phases (FCC) were identified in the lidification of the surface layer. modified surface layer with decreased lattice pa- Table. Lattice parameter of austenitic structure identified rameters as compared with the initial material. in the initial and modified surface layer. • Modified surface layers showed improvement of the tribological properties as compared with Lattice parameter Lattice parameter Material the initial material. [A] change [%] • The present authors suppose that improvement 316L 3.6016 - of the tribological properties of the modified surfaces is connected with the fine grains forma- 316L+Ce 3.5591 -15.3 tion and enrichment of grain boundaries with 316L+La 3.5457 -15.5 REE. 316L+REE 3.5373 -17.9 References [1]. Piekoszewski J., Werner Z., Szymczyk W.: Vacuum, HIPPB modified AISI 316L steel reveals small- 63, 475-581 (2001). er value of linear wear and this means higher wear [2]. Pereira A. et al.: Thin Solid Films, 453-454, 16-21 (2004). resistance – as compared with the initial material et al. (Fig.3). Final value of the linear wear were of [3]. Sartowska B. : Plasma Process. Polym., 4, S314-S318 (2007). about 80% lower for the samples modified with [4]. Wang, X., Lei M.K., Zhang J.S.: Surf. Coat. Technol., HIPPB with a single REE incorporation and 201, 5884-5890 (2007). about 60% for the samples modified with HIPPB [5]. Cheng X.H., Xie C.Z.: Wear, 254, 415-420 (2003). with Ce + La incorporation as compared with the [6]. Liu H., Yan M.F., Wu D.L.: J. Mater. Process. Tech- initial material. nol., 210, 784-790 (2010). Results obtained from GXRD investigations [7]. Abreu C.M., Cristobal M.J., Novoa X.R.: Surf. Coat. and wear tests showed an interesting fact. Prac- Technol., 158, 1, 582-587 (2002). et al. tically no differences were observed in the results [8]. Cleugh D. : Surf. Coat. Technol., 142-144, between alloying AISI 316L steel with Ce or La. 392-396 (2001). [9]. Riffard F. et al.: Appl. Surf. Sci., 199, 107-122 (2002). Differences between alloying using MM or a single [10]. Piekoszewski J. et al.: Surf. Coat. Technol., 206, REE were observed. MM consists not only of 65% 854-858 (2011). Ce + 34% La, it is a mixture of other elements. [11]. Werner Z., Piekoszewski J., Szymczyk W.: Vacuum, These elements can be accepted as impurities with 63, 701-708 (2001). an unknown role in modification processes.

6 316L 316L+Ce 5 316L+La 316L+REE

Linear wear (um) 2

0 0 500 1000 1500 2000 2500 Sliding distance (m) Fig.3. Linear wear of initial material and modified up to 0.8-1.1 at.% REE concentration. 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. Freestone1/, Iain McDonald2/, Jan A. Hobot3/, Heather Gilderdale-Scott4/, Tim Ayers4/ 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 In contrast, the multi-layered glasses were formed energy dispersive X-ray analysis) of 132 examples by the incomplete mixing of an oxidized high-Cu of medieval red window glass reveals the presence and a reduced low-Cu glass. The red colour forms of around 1% copper oxide in all cases. SEM and due to the diffusion of oxidized copper into the TEM (transmission electron microscopy) of se- reduced glass and the nucleation and growth of lected samples confirm the presence of Cu nano- metallic copper during heat-treatment. This repre- particles. Two structural categories of red glass sents a previously unrecognized medieval glass sheet are identified. Sheets comprising a single technology, where red was created by mixing two layer of red glass from a few tens to around 300 weakly coloured glasses, a complex, arcane and μm thick overlying a supporting substrate of white mysterious procedure which must have reinforced glass, with or without a protective cover of white the exclusivity of the craft. The occurrence of the glass, are typically found from the 14th century on- technique has implications for dating windows and wards. However, in the 12th-14th century England, the identification of glass which has been inserted France and Spain, and perhaps elsewhere, typical in early restorations and repairs, for the trade in red glass sheets have a complex microstructure coloured glass and for the transfer of glassmaking comprising multiple coloured striae about 1 μm technologies in medieval times. This provides a thick in a white background. SEM-EDXA, TEM link between stained glass window technology of and LA-ICP-MS (laser ablation inductively coupled the high medieval period and the glass-colouring plasma mass spectrometry) have been used to practices of the late first millennium CE [1]. characterize and investigate the technologies of the two types in detail. The single-layered glasses References were produced using an approach analogous to [1]. Kunicki-Goldfinger J.J., Freestone I.C., MacDonald I., that of copper red glass in the modern period, Hobot J.A., Gilderdale-Scott H., Ayers T.: J. Archaeol. where a red glass is flashed onto a colourless base. Sci., 41(1), 89-105 (2014). 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/NOx 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, etc SO2, CO, O2, .). 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 (Den- mark); • Uppsala University, The Ångström Laboratory (Sweden); • Kaunas University of Technology (Lithuania); • Vilnius Gediminas Technical University (Lithuania); • Robert Szewalski Institute of Fluid-Flow Machinery, Polish Academy of Sciences (Poland); • West Pomeranian University of Technology (Poland); • Ukrainian Engineering Pedagogic Academy (Ukraine). POLLUTION CONTROL TECHNOLOGIES LABORATORY 81

PRELIMINARY MODELLING STUDY OF NOx REMOVAL FROM OIL-FIRED OFF-GAS UNDER ELECTRON BEAM IRRADIATION Yongxia Sun, Andrzej G. Chmielewski, Henrietta Nichipor1/, Sylwester Bułka, Zbigniew Zimek, Ewa Zwolińska 1/ Joint Institute for Power and Nuclear Research – Sosny, National Academy of Sciences of Belarus, Minsk, Belarus

NOx is still one of the most important air pollut- medium and with one another is described by dif- ants to be controlled. It is expected that by 2020 ferential equations: the emissions from international shipping around n dni (n) Europe are forcasted to exceed the emissions of = nkii∑∏ n k (5) these pollutants from all other sources in the Euro- dt nk1= pean Union (EU). Although NOx removal from For given initial concentrations: off-gases was widely studied, most of them were ni(0) = ni0 (6) focused on NOx emission control from off-gases where: ni – concentration of the i-th component 3 (n) generated from power plants, chemical industry [mole/m ], ki – rate constant for n-order chemical and car engine. Fewer investigations were conduct- reaction between the i-th and the k-th components ed on NOx emission from diesel engine of cargo of gas, nk – concentration of the k-th component, ship. Heavy fuel oil (HFO) is the main fuel used in ni0 – initial concentration of the i-th component. the diesel engine of the ship with a high sulphur 10% content up to 4.0 wt.% [1]. In this work we theoretically studied NOx removal from oil-fired off-gas 8% under electron beam (EB) irradiation with the aid of computer simulation. 6% The computer simulation of NOx removal in oil-fired off-gas under EB irradiation was carried 4% out by using the computer code “KINETIC” and 2%

GEAR method. 200 reactions involving 55 species Removal efficiency of NOx were considered for 700 ppm SO2 + (74.3% N2 + 16.2% O2 + 9.5% H2O) + NOx (200 ppm, 1500 0% 70°C 90°C ppm). Five main groups of reactions were includ- Inlet gas temperature ed, the rate constants of reactions were mostly taken from the literatures [2-4]. The units of rate 200ppm 1500ppm Fig.1. Calculation results of NO removal from oil-fired constant are 1/s, m3/mole·s and m6/mole2·s for x off-gases under EB irradiation. first-, second and third-order reactions, respectively. When fast electrons from electron beams are ab- Calculations were made at 8.8 kGy absorbed dose sorbed in the carrier gas, they cause ionization with two different temperatures, 70 and 90oC, re- and excitation process of the nitrogen, oxygen and spectively: 700 ppm SO2 + (74.3% N2 + 16.2% O2 H2O molecules in the carrier gas. Primary species + 9.5% H2O) + NOx (200 and 1500 ppm, respec- and secondary electrons are formed. The second- tively). ary electrons are fast thermalized within 1 ns in air Calculation results of NOx removal from oil-fired at a 1 bar pressure. The G-values (molecules/100 off-gas under EB irradiation at the absorbed dose eV) of main primary species are simplified as fol- of 8.8 kGy are presented in Fig.1, and the corre- lows [4]: sponding experimental results are presented in 2 2 4.43N2 → 0.29N2* + 0.885N( D) + 0.295N( P) + Fig.2 [5]. It is seen that NOx removal efficiency is + + 1.87N + 2.27N2 + 0.69N + 2.96e (1) slightly improved with increasing temperature. The 1 5.377O2 → 0.077O2* + 2.25O( D) + 2.8O + key reactions are listed below: + + 0.18(O*) + 2.07O2 + 1.23O + 3.3e (2) 25% 3 7.33H2O → 0.51H2 + 0.46O( P) + 4.25OH + + + 4.15H + 1.99(H2O ) + 0.01(H2 ) + 20% 0.57(OH+) + 0.67(H+) + 0.06(O+) + 3.3e (3) The generation of active species under the elec- 15% tron beam is described in [4]: 10% dni =ρGDxni (4) dt i 5% Removal efficiency of NOx where: ni – concentration of the i-th component [mole/m3], G – radiation yield of the i-th compo- ni 0% nent of the gas [mole/J],. xi – mole fraction of the 70°C 90°C i-th component, D – dose rate [J/(kg·s)], ρ – gas Inlet gas temperature density [kg/m3]. 200ppm 1500ppm

Kinetics of chemical reactions of species formed Fig.2. Experimental results of NOx removal from oil-fired during gas irradiation with molecules of the gas off-gases under EB irradiation. 82 POLLUTION CONTROL TECHNOLOGIES LABORATORY

N + NO = O + N2 (R1) • Removal efficiency of NOx is decreased with in- O2 + 2NO = 2NO2 (R2) creasing initial inlet concentration of NOx. At O + NO = NO2 (R3) 8.8 kGy of the absorbed dose less than about – – NO + O4 = NO3 + O2 (R4) 1% NOx was removed from flue gas for 1500 OH + NO + M = HNO2 (R5) ppm a high inlet concentration of NOx without NO2 + OH + M = HNO3 + M ammonia added. (M is the third body in the reaction system) (R6) References HO2 + NO = OH + NO2 (R7) et al. NO2 + O = O2 + NO (R8) [1]. Basfar A.A. : Fuel, 87, 8-9, 1446-1452 (2008). [2]. Albritton D.L.: At. Data Nucl. Data, 22, 1-101 (1978). The oxidation-reduction cycle between NO2 and NO is toward the oxidation path. [3]. http://kinetics.nist.gov/kinetics/index.jsp. Comparing calculation results with experimen- [4]. Mätzing H.: Advances in chemical physics.Vol. LXXX. tal results, we drew the following conclusions: John Wiley & Sons, Inc., New Jersey 1991, pp. 315-402. [5]. Chmielewski A.G. et al.: Radiat. Phys. Chem., 81, 8, • Removal efficiency of NOx is increased with in- 1036-1039 (2012). creasing temperature.

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) For the purpose of the elaboration, a 1 000 000 process was invented in Japan in the 1970s. At the Nm3/h flue gas flow rate unit was selected as a beginning, the process was elaborated for SO2 re- basic unit for large plant application. A typical moval from ore sintering plants, however soon the composition and parameters of flue gas for heavy possibility of simultaneous removal of both of SO2 fuel oil fired boilers were assumed. Oxygen con- and NOx was observed. During the next twenty tent was assumed to be 3.2% vol., humidity – 12.6% years processes of the intensive development were vol. and a temperature of 360oC. Pollutants con- undertaken resulting in the construction of three centrations were taken respectively: SO2 – 1900 3 industrial EBFGT plants at Chengdu and Hangz- ppmv, NOx – 240 ppmv and dust – 170 mg/Nm . hou Power Plants (China) and the Pomorzany Required removal rates according to Saudi Arabian Power Plant in Szczecin (Poland). All of the plants standards were 45% removal of SO2 for general were designed for treatment up to 300 000 Nm3/h rules (82% for special industrial zones) and 22% of flue gas that corresponds to a rather small (up removal of NOx. For the purpose of technology to 100 MWth) energy generation unit. demonstration 90% of SO2 removal and 50% of In the recent years a new phase of EBFGT tech- NOx removal were assumed. nology development began. New implementation Typical construction of the EBFGT plant may of the technology in the TPP Sviloza in Svishtov be used in this case. Raw flue gas from boilers shall (Bulgaria) was undertaken. The plant was planned be directed to a gas conditioning unit in order to to purify up to 608 000 Nm3/h of flue gas from coal decrease its temperature and increase humidity. fired boilers, that is twice more than the existing The gas out coming from the oil fired boilers has EBFGT plant. However, nowadays, the most im- too high temperature to be properly cooled down portant direction of technology development is the in one stage by water evaporation. Therefore, two- application of EBFGT technology for treatment -stage gas conditioning unit composed of heat ex- of flue gas from heavy fuel oil combustion. This changer and spray cooler shall be applied. In the application is dedicated to Middle East countries next step ammonia shall be injected into flue gas. using liquid fuels as the main source of energy. Ammonia shall be stored in the liquid form in Laboratory and pilot research on this topic were pressurized tanks and added to the flue gas up- performed with satisfactory results. Dependences stream reactors. Such a prepared gas is directed to of SO2 and NOx removal efficiency on main process the reaction unit, which is the main unit of the parameters as well as process optimization were EBFGT plant. Reaction unit is composed of such elaborated. With regard to the experiences gather- parts as reactors, accelerators, radiation shielding, ed during construction and exploitation of the cooling and ventilation system, etc. In this unit Pomorzany industrial EBFGT facility, the tech- flue gas is being irradiated by electron beam from nology is ready for design and construction of in- accelerators that initiate chemical reactions lead- dustrial plant to be applied for liquid fuel fired ing to SO2 and NOx conversion into ammonium boilers. However, in the most cases large energy sulphate and ammonium nitrate. Due to reliability generation units are applied and previously con- of the EBFGT plant, at least two parallel reaction structed electron beam flue gas treatment facilities chambers shall be constructed. The by-product – a are too small for practical application. Therefore, mixture of ammonium salts formed in the process analysis of the possibility of application of EBFGT of SO2 and NOx removal shall be collected and technology for large energy generation units was shipped to a receiver. According to experiences undertaken. from other EBFGT installations, electrostatic pre- POLLUTION CONTROL TECHNOLOGIES LABORATORY 83

Fig. Conceptual scheme of a large-scale EBFGT facility. cipitator is the most appropriate apparatus for ment for irradiation of two independent reactors by-product collection. The purified flue gas is re- (double stage irradiation system) makes the con- leased to atmosphere. In order to compensate struction of 1 000 000 Nm3/h unit feasible. pressure drop in the plant, auxiliary fan shall be in- The performed analysis showed that the con- stalled upstream the stack. The conceptual scheme struction of 1 000 000 Nm3/h electron beam flue of a large-scale EBFGT installation is presented gas treatment unit for SO2 and NOx removal from in Fig. flue gas emitted during combustion of heavy fuel As most of the equipment is used in conven- oil is fully feasible from the technical point of view. tional flue gas treatment technologies, selection Assumed removal efficiencies 90% for SO2 and of the reliable, high power electron accelerators is 50% for NOx can be achieved by the use of EBFGT crucial for the large-scale EBFGT facility construc- facility. tion. However, nowadays intensive development The 1 000 000 Nm3/h EBFGT facility may be of electron accelerators is observed and 1 MW, 1.5 constructed as a basic unit for the treatment of MeV accelerators may be offered by the manufac- flue gas from large combustion plants. For larger turers. Application of four pieces of such equip- amounts of flue gas, this unit may be multiplied. STABLE ISOTOPE LABORATORY

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

• portable gas analyser (N2O, CO2, CH4, H2S), (Nanosens, Poland). Research staff of the Laboratory is involved in the following projects: • “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 under- take any research and development task within the scope of our activity. Especially, we offer our measurement experience, precision and proficiency in the field of stable isotope composition. Besides, we are open for any service in the area of food authenticity control by stable isotope methods supported by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) methods. Our Laboratory cooperates with the following national partners: • Inspekcja Jakości Handlowej Artykułów Rol- no-Spożywczych, • 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). 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 Table 2. Examples of isotopic variability of sulphur in envi- organisms: C, H, N, P, O, S. In food product sul- ronmental samples. 34 phur isotopic composition δ S is strongly influ- 34 enced by its origin: geology of the region, feed diet δ S [‰] of animal, fertilization of plant, climate and close- Environment marine: ness to the sea. Typically δ34S values of the food samples ranged - marine sediments 10÷33 from -2 to +12‰. The variation in δ34S values ob- - atmosferic sulphate -30÷30 served within a single region could be due to the Environment terrestrial: different production systems (conventional and organic). Rich products into sulphur mostly con- - fossil fuels -10÷30 tain proteins: meat, poultry, eggs, dairy product, - soil -30÷30 cabbage, fish, legumes, cauliflower, broccoli, garlic and onion (Table 1). - plants 0÷14 Table 1. Proteins concentration in food products. - meat -10÷20

The protein content in the dry matter - milk 0÷6 Food products [%] - fish -5÷25 Legumes 40 - vegetable 0÷6 Vegetable 3 of bidestilled water for one pill is used. Every Fruit 1 sample should be prepared two times – two pills. Meat 20 After burning the samples a special chemical procedure for BaSO preparation from the pro- Milk 5 4 duced SO2 dissolved in water is used. Finally the Fish 15 sulphur can be precipitated as BaSO4 using a 10% BaCl2 solution. To obtain BaSO4 for sulphur iso- Sulphur have a four stable isotopes: 32S (95.02 topic measurements by the use elemental analyser- at.%), 34S (4.21 at.%), 33S (0.75 at.%), 36S (0.02 at.%) -isotope ratio mass spectrometer (EA-IRMS). For and three radioisotopes: 31S (3.2 s), 35S (87.1 day), sulphur isotopic measurements with EA-IRMS 37S (5.04 min half-life). we use a special procedure of food samples con- Sulphur in chemical composition occur in on version to BaSO4 (Fig.). few oxidation steps. Bacterial reduction of sul- The elemental analyser for sulphur measure- phate (sulphur cycle) to sulphide. For sulphur is ments is specially equipped with: teflon tubes the lack of the enrichment effect in the nutritional (connection), GC column and special quartz reac- cycle (chain). tor for sulphur. Our interest in the study of sulphur isotopic Samples and references materials are loaded compostition it is a result of differentiation δ34S in into an autosampler AS200 on elemental analyser the environment (Table 2) and possibility of ap- Flash 1112. Mass of sulphur in the measured ma- plying this parameter to food origin control. Aim terials should be 30 μg per sample or more. To of this study is to explore this isotopic parameter rich protein product the mass of samples should for differentiate of food origin, method of probe 15-20 mg; for pure protein the mass of samples duction and food composition in the field of food can be 3-5 mg (for casein 5 mg). Sulphur isotope authenticity control. ratio is expresed using conventional notation: The following instruments were used in sulphur ⎡⎤Rsp isotopic measurements: isotope ratio mass spectro- δ≡δ=34S 34 S/ 32 S −∗ 1 1000 [‰] meter DELTAplus, FinniganMAT (Bremen, Ger- CDT CDT ⎢⎥ ⎣⎦RCDT many); elemental analyser Flash 1112NC, Thermo-

Finnigan (Italy); Parr Bomb oxidation, Parr In- where: Rsp – measured isotopic ratio between strument Company (Illinois, USA); ConFloIII – abundance of isotope 34S and isotope 32S in sample, interface for EA and IRMS connecting, Finnigan, RCDT – isotopic ratio between abundance of iso- (Bremen, Germany). tope 34S and isotope 32S in international standard Basic problem which we have with sulphur iso- CDT (Canyon Diablo Troilite) – actual in use topic measurement is a low content of sulphur in standard VCDT (Vienna Canyon Diablo Troilite) organic matter. For extraction sulphur from or- with RCDT = 0.0450045. ganic samples without isotopic effects we can use Reference materials for sulphur isotopic mea- the method of Parr Bomb oxidation. The mass of surements were the following: barium sulphate the samples is connected with sulphur content in NBS-127, barium sulphate IAEA-SO-5 (IAEA), the sample. For sample powder 2 mg and 3-5 drops silver sulphide IAEA-S-1 (IAEA). STABLE ISOTOPE LABORATORY 87 • low concentration of sulphur in food, Pills preparation HCl • high memory effect of measurements connect- (yellow to red) ed with the SO2 reactivity, • high concentration of carbon in food sample. The first stage of the project was concerning an Burning pills HCl 2ml implementation of method of sulphur isotopic in Parr Bomb measurement and two methods of sample preparation. A further approach in our study will be Boiling testing the possibility to discriminating different NH4OH addition (pink to yellow) methods of food production and different regions of its origin. 5 ml BaCl2 Stable isotope ratios of sulphur of food product can be used as a good indicator of geographi- Filtration Filtration cal 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 con- H2O2 2.5 ml Washing and trol. roasting at 800oC This study was supported by the Ministry of (overnight) Science and Higher Education, Poland in the filters with sediment frame of statutory work. Fig. The steps of chemical treatment for BaSO prepara- 4 References tion. [1]. Boner M., Förstel H.: Anal. Bioanal. Chem., 378, 2, For improve oxidation condition to every 301-310 (2004). [2]. Molkentin J., Giesemann A.: Anal. Bioanal. Chem., weighted sample the V2O5 (1:1 or more) is added. Typically the standard deviation for measure- 388(1), 297-305 (2007). ments was ± 0.3‰ [3]. Rossmann A.: Food Rev. Int., 17(3), 347-381 (2001). Problems with sulphur measurements in food samples are the following:

NEW APPROACH OF THE ISOTOPIC METHOD FOR JUICE AUTHENTICITY CONTROL Ryszard Wierzchnicki, Kazimiera Malec-Czechowska

The subject of our study was the authenticity of • undeclared addition of sugar/pectin, fruit juice originated from the Polish market. • undeclared addition of water, Nowadays in Europe, origin and authenticity is • undeclared addition of organic acids, probably one of the most important characteristic • undeclared addition of vitamin C, features of food. This is connected with economic • undeclared addition of flavour compounds. politics of European Commission in agriculture Important limitation of the application of iso- sector (Table 1). Adulteration is as an addition of topic method for food authenticity control is the Table 1. Standard methods accepted by the European Union for juice authenticity control.

Method Fraction Technique Isotope ratio CEN (ENV 12140) sucrose IRMS a) 13C/12C

b) AOAC method 995.17 ethanol (from fermentation) SNIF-NMR (D/H)I, (D/H)II, R CEN (ENV 12141) water IRMS 18O/16O CEN (ENV 12142) water IRMS 2H/1H AOAC method 2004.01 ethanol (from fermentation) IRMS 13C/12C CEN (ENV 13075) pulp IRMS 13C/12C 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 lack of database of stable isotope composition in products, a cheaper product put into a place ex- juice of different origin. Stable Isotope Laboratory pensive one and mislabelling of products. of the Institute of Nuclear Chemistry and Tech- Fruit juice can be adulterated by: nology (INCT) since many years is carring out a 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 2H/1H water precipitation – geographical altitude H/Device – IRMS a) Oxygen 18O/16O water precipitation – geographical altitude GasBench – IRMS Nitrogen 15N/14N solid fertilizer (organic or synthetic) EA – IRMS Carbon 13C/12C solid C3, CAM, C4 metabolism EA – IRMS Hydrogen 2H/1H solid precipitation, climate Py b) – IRMS Oxygen 18O/16O solid precipitation, climate Py – IRMS Sulphur 34S/32S solid fertilizer, distance to the sea, bacterial processes EA – IRMS, ICP-MS c) Strontium 87Sr/86Sr 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 • Internal carbon isotopes of acids: malic, citric method (Table 2) implementation and by database and ascorbic, can be used to detect the addition for some food from the Polish market. of synthetic organic acids. These instruments were used in the multielement • Ratios between bulk sugars and individual acids method in control of fruit juices: by IRMS, to detect sugars or acid addition [3] • GasBench II (GB) for oxygen in water; can be applied. • H/Device (HD) for hydrogen in water; • Specific stable isotope analysis (CSIA) of juice by • elemental analyser (EA) for organic C, N, S; the use of a gas chromatograph or a liquid chro- • mass spectrometer DELTAplus with dual inlet matograph connected with combustion and mass system (IRMS); spectrometer: GC-C-IRMS and LC-C-IRMS • HPLC preparative + multicollector; can be applied. • Parr Bomb for sulphur from organic product We look for a rapid and precise method for preparation. juice authenticity control. Most isotope techniques An actual problem encountered in the area of require the use of the database of isotopic compo- fruit juice authentication is in the detection of un- sition or original fruits as a reference for compari- declared sugar added to a juice. The sugar can be son with the composition of analysed product. The added in the form of a beet or cane sucrose or as database can be substituted by the isotope analysis a high fructose corn syrup (HFCS). Other impor- of an internal standard. The application of inter- tant topic in fruit juice analysis is the detection of nal component reduces measurement errors which adulteration by L-ascorbic acid. For this reason, is depending on the isotope variability of raw ma- the method of internal standard with malic acid terials. 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 beet -24.5 Sugars -26.5, -25.0 -24.0 -25.6 HFCS -9.7 Malic acid -24.5, -23.0 -23.2 Citric acid -25.5, -23.5 -24.2/-24.4 -24.7 Ascorbic acid -26.0, -25.0 -20.5 -10, -12 was proposed [1]. Carbon stable isotope ratio δ13C possible with a still limited number of samples in- analysis to multicomponent method for juice au- vestigated. thenticity control is applicable. This research work was supported by the Mi- We try to use different method of comparison nistry of Science and Higher Education, Poland of isotopic composition between components of under grant No. 12-0043-10/2010. juice: sugars and acids (Table 3). Minimal sample References preparation, rapid separation and good recovery support for these procedures is a promising for [1]. Jamin E., Martin F., Santamaria-Fernandez R., Lees the sugars and acids isotope composition determi- M.: J. Agric. Food Chem., 53, 5130-5133 (2005). nation in fruits. [2]. Figueira R., Venturini Filho W.G., Ducatti C., Nogueira Trends in isotopic analyses of juice are the follow- A.M.P. : Ciênc. Tecnol. Aliment., 31, 3, 660-665 (2011). ing: [3]. Tremblay P., Paquin R.: J. Agric. Food Chem., 55, 197-203 (2007). • Insoluble solids (pulp) of the whole fruit can be used as internal standard [2]. 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 (20-400 Gy), • gamma radiation dose measurement by means of a CTA film dosimeter (10-80 kGy), • electron radiation dose measurement by means of a CTA film dosimeter (15-40 kGy), • electron radiation dose measurement by means of graphite and polystyrene calorimeters, • irradiation of dosimeters or other small objects with Co-60 gamma radiation to strictly defined doses, • irradiation of dosimeters or other small objects with 10 MeV electron beams to strictly defined doses. The secondary standard of the dose rate using by the LMTD is a Co-60 gamma source “Issle- dovatel” and a Gamma Chamber 5000. 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). 90 LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES RECALIBRATION OF DOSIMETER FILMS CTA Anna Korzeniowska-Sobczuk, Aneta Sterniczuk, Magdalena Karlińska

The responses of most films used in routine dosi- CTA film dosimeter, so it is advisable to redo re- metry are usually influenced by the environmental calibration the dosimeter. the LMTD having ac- conditions such as temperature during irradiation, creditation of the Polish Centre for Accreditation dose rate and post-irradiation storage [1]. Many in accordance with the requirements of PN-EN problems may be encountered in the routine dosi- ISO/EIC 17025:2005 [4] imposed on the LMTD im- metry for radiation processing applications, be- plementation of improvement activities, preven- cause the conditions in irradiation facilities may tive as well as quality control tests. The implemen- differ considerably from the conditions in which tation of this subject allows for comprehensive dosimeter films were calibrated. These differences requirements according to a previous experimen- may lead to expected systematic errors in dose es- tal data and archival film samples after irradiation timation. The advantage of the CTA film is its of the CTA film dosimeter which will allow to linear response to the dose and the dose-inde- trace the changes in the long term.

0,155 A 0,155 B

0,150 0,150

0,145 0,145

0,140 0,140

0,135 0,135

0,130 0,130 Absorbance Ao 0,125 0,125 The average thickness [mm] 0,120 0,120

0,115 0,115 0 10203040506070 0 10203040506070 Sample number Sample number Fig.1. The physicochemical parameters of the dosimeter films CTA. pendent post-irradiation signal change. However, The film dosimeters CTA was irradiated with its low sensitivity to ionizing radiation restricts its 10-MeV electron beams from an industrial 10-kW use to high and very high doses [2]. linear accelerator radiation in the range of 10-40 Implementation issues related to research the kGy dose (accelerator Elektronika 10/10) and the CTA film dosimeter results from the need to con- gamma radiation 10-80 kGy in the gamma field of tinually monitor the quality of services provided a reference 60Co source Issledovatel (~0.5 kGy/h) [3]. In the Laboratory for Measurments of Techno- having the dose rate traceable to a primary stand- logical Doses (LMTD) of the Institute of Nuclear ard maintained by the National Physical Labora- Chemistry and Technology (INCT) is the accredita- tory – NPL (Teddington, UK). In the experiments tion method for measuring the absorbed dose based the film dosimeters CTA were used, with an opti- Table. Change of the parameters of the CTA dosimetric film with time after irradiation (post-effects).

Time after irradiation Dose 30 min 24 h 7 days 30 days 6 months [kGy] % A – A0 A – A0 % A – A0 % A – A0 % A – A0 9.35 0.0487 0.0489 0.3 0.0657 34.8 0.0752 54.3 0.0927 90.3 15.01 0.1009 0.1063 5.4 0.1224 21.4 0.1257 24.6 0.1539 52.6 18.7 0.1140 0.1185 3.9 0.1422 24.7 0.1425 24.9 0.1642 44.0 26.3 0.1679 0.1752 4.4 0.1942 15.6 0.2014 20.0 0.2386 42.1 28.49 0.1684 0.1718 2.0 0.1960 16.4 0.2061 22.4 0.2432 44.4 34.4 0.2195 0.2273 3.6 0.2494 13.6 0.2563 16.7 0.2993 36.4 39.64 0.2490 0.2601 4.4 0.2812 12.9 0.2908 16.8 0.3347 34.4 Parameters of calibration curves Y=0.0064X – 0.0053 Y=0.0067X – 0.0063 Y=0.0069X + 0.0101 Y=0.0070X + 0.0137 Y=0.0079X + 0.0242 R2 = 0.9915 R2 = 0.9874 R2 = 0.9913 R2 = 0.9961 R2 = 0.9930 on a CTA film dosimeter. CTA dosimeter, produc- cal signal detection. The absorbance was measur- tion Fujifilm, was purchased in 2005 and then made ed by using a JASCO-V650 spectrophotometer the first calibration purchased batch with this dosi- UV/Vis (λmax = 280 nm). The wavelength and ab- meter. Currently, the LMTD owns approximately sorbance scales were checked before each experi- 40% of the originally purchased amount of the ment by a calibrated reference standard. LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES 91 In 2013, the first stage of the study was to verify On the basis of these results the following con- the physicochemical parameters of unexposed film clusions can be drawn (scientific and practical ap- and comparison with the data contained on the plications): score sheet dosimeter (after the first calibration). • The absorbance of unexposed film CTA in- A comparison of the absorbance, A0, and an aver- creases during storage, this factor should be age thickness of 60 samples revealed no radiation taken into account when determining the dosi- of the CTA film (Fig.1). metric signal for each sample. • Differences in thickness within one series 0,30 (spool) CTA film are negligible. 0,25 • Answer the CTA film dosimetry test is linear in 0 the full range of doses and increased with stor- 0,20 y = 0,0064x - 0,0053 2013 age time after irradiation. Using the CTA dosi- R2 = 0,9915 0,15 meter as the transfer dosimeter should take y = 0,0062x + 0,0073 2012 R2 = 0,9939 into account the passage of time between irra- 0,10 y = 0,0063x + 0,0053 diation and spectrophotometric measurement. 2 2010 Absorbance A – R = 0,9854 0,05 Adapting the measuring points to the calibra- y = 0,0056x + 0,0182 2 2008 R = 0,991 tion curve, in many cases R2 > 0.99. 0,00 0 102030405060References Dose [kGy] [1]. McLaughlin W.L., Boyed A.W., Chadwick K.H., McDo- Fig.2. Summary of calibration curves for CTA films made nald J.C., Miller A.: Dosimetry for Radiation Process- in different years from the date of purchase of the film. ing. Taylor & Francis, Ltd., London 1989, 251 p. Parameters determined for the calibration curves [2]. Peimel-Stuglik Z., Fabisiak S.: Appl. Radiat. Isot., 66, take into account the changes in absorbance (post- 346-352 (2008). [3]. ISO/ASTM Standard 51650-20052, Standard practice -effects) after 30 min, 24 h, 7 and 30 days, 3 and 6 for use of cellulose aceteate dosimetry system. months after the irradiation. Details are present- [4]. PN-EN ISO/IAC 17025:2005. Ogólne wymagania doty- ed in Table. Compilation of all annual calibrations, czące kompetencji laboratoriów badawczych i wzorcu- 30 min after irradiation, taking into account also jących (General requirements for the competence of the aging of the CTA film is presented in Fig.2. testing and calibration laboratories). 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 1999. 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 re- newed after passing positively by the Laboratory the PCA expert audit. Present accreditation certificate was received in 2010 and is valid until 24.10.2014. 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 unir- radiated. 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-13751. The application of five standardized and validated detection methods addressed to speci- fied groups of foods validated in the Labora- tory guarantees an accurate analysis and classi- fication 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 unir- radiated product which appears in abundance. Typical groups of products controlled in the Laboratory. 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 2013. 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. 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 irradia- different dose of 60Co gamma rays: 0.5, 1 and 3 tion in dried fruits EN-13708:2003 issued by the kGy, respectively. The adapted doses correspond CEN (European Committee for Standardization) to technological doses as announced to be used in Brussels in 2002 [1] is currently widely used for for radiation disinfestation and pasteurization of irradiation control of raisins, dates, figs, mangos, dried fruits. After radiation treatment, the samples papaya, etc. in Europe and over the world. The were stored at room temperature with the access method is based on the identification of a specific of air. The EPR measurements were conducted EPR (electron paramagnetic resonance) signal in with each of the samples after one day, and subse- irradiated food articles which is never observed in quently after 30, 90, 180 and 360 days of storage. dried fruits not exposed to the action of ionizing All measurements were done with the samples radiation. It is suggested that this signal originates handled similarly under the same EPR spectro- from free radicals produced by ionizing radiation meter settings and operational conditions. The in crystalline domains of dried fruits [2]. The ef- recorded EPR signals were doubly integrated forts were undertaken to identify these radicals within the same range of magnetic field – 7 mT. [3, 4]. The important feature of any EPR signal The scans were centred at g = 2.003. The inte- which is used for the detection of irradiation is its grated signal areas are in proportion to the over- stability at room temperature. The EPR signal re- all signal intensity. The EPR signals of raisins un- corded in irradiated fruits is stable several months irradiated and irradiated with 0.5, 1 and 3 kGy after irradiation, but decays slowly during pro- are shown as an example in Fig.1. The upper longed storage. Dried fruits belong to this assort- record represents the EPR spectrum of unirradi- ment of food commodities which are allowed to ated raisins. A weak, not specific signal is seen be stored safely for a relatively long time. In order which is easily distinguished from multicompo- to ascertain the reliability of the identification of nent signals typical for irradiated samples (shown the EPR signal observed in radiation treated dried below). Such weak, so-called “native” EPR sig- fruits during their storage for several months the nals appear in some of irradiated fruits and origi- model experiments have been performed. nate from stable paramagnetic impurities or trace The following fruits purchased in the market components present. The integrated EPR signal were chosen: cranberry, papaya, pineapple, date, areas related to irradiated samples and measured fig, rowan berry, banana and raisins. The fruits as a function of prolonged storage time were used were divided into three parts each irradiated with to construct the kinetic decay curves for each of 0 kGy the sample.

x 4

0.5 kGy

x 2.4

1 kGy

x 1.3

A 3 kGy

B Fig.2. Decay of the EPR signal intensity in dried fruits (dates, raisins, rowan berries and cranberries) during one A x 1 year of storage. The result refers to the samples irradiated with 3 kGy of 60Co gamma rays.

B In Fig.2, the time-dependent decay curves of 3420 3440 3460 3480 3500 3520 3540 3560 3580 the EPR signals intensity recorded with the samples Magnetic ﬁ eld [G] of dried dates, raisins, rowan berries and cran- Fig.1. EPR signal of dried raisins irradiated with 0.5, 1 and berries are presented. The decrease of the EPR 3 kGy of 60Co gamma rays. The upper graph refers to unir- signal intensity does not fit to a classic first- or radiated sample. The numbers in the right denote to the second-order kinetics. The decay process of radi- attenuation of the recorded signals. cals in dried fruits exposed to ionizing radiation 96 LABORATORY FOR DETECTION OF IRRADIATED FOOD can be divided at least in two phases. The first Table. Decrease of the EPR signal intensity in dried fruits easily distinguished phase of radical decay lasting irradiated with 3 kGy of 60Co gamma rays after 360 days of about 50 days proceeds relatively fast, resulting storage. in the decrease of initial EPR signal intensity by Decrease Intensity about 30%. The annihilation of less temperature Dried fruit of the EPR signal of remaining resistant shallow radical traps might be respon- intensity [%] EPR signal [%] sible. The second phase of temperature-dependent Cranberry 11.8 88.2 radical decay in dried fruits treated with ionizing Papaya 18.0 82.0 radiation is markedly slower. The EPR measurements have been done between the 50th day of Pineapple 26.9 73.1 storage to one year (360 days). Although the re- Date 28.3 71.7 cording time was ca. 6 times longer than in the Fig 40.8 59.2 first phase, the decreases of the EPR signal intensity did not exceed 20%. It is clear that at this stage Rowan berry 40.9 59.1 thermal annihilation of radical traps is less effec- Banana 43.0 57.0 tive. In general, the radiation-induced radical decay in eight kinds of dried fruits studied was found Raisin 56.8 43.2 similar. It means that in all fruits two described phases of radical decay can be distinguished. How- decrease of the signal by storing dried fruits much ever, distinct individual differences do appear be- longer than for one year (two or more years) will tween some of them which are seen in Fig.2 and in not influence negatively on the detection of radia- the Table. tion treatment in this product. As to our knowl- The highest stability of radiation-induced EPR edge, long-lasting kinetic studies on the stability signal after one year of storage at room tempera- of radiation-induced radicals in food had not ture was found in cranberry resulting in 88.2% been performed so far. From the practical point survival of EPR signal what means that it de- of view the obtained results can be useful for the creased by 11.8% only. The lowest stability, in control of food reserves and for accidental dosi- turn, was demonstrated by raisins resulting in metry. 43.2% survival of the EPR signal and the decrease References of the EPR signal intensity by 56.8%. The general conclusion drawn from the above [1]. EN-13708:2001 Foodstuffs – Detection of irradiated experiments is that the stability of the EPR signals food containing crystalline sugar by ESR spectroscopy. utilized for the detection of radiation treatment European Committee for Standardization (CEN), in dried fruits according to EN-13708 European Brussels. standard is high and facilitates the reliable detec- [2]. Raffi J., Angel J.P.: Radiat. Phys. Chem., 34, 891-894 (1989). tion of radiation treatment in any kind of dried [3]. Guzik G., Stachowicz W., Michalik J.: Nukleonika, 57, fruits after one year of storage at room tempera- 4, 545-549 (2012). ture with free access of air oxygen to the product. [4]. Guzik G., Stachowicz W.: Nukleonika, 58, 3, 425-428 It is concluded from the analysis of the decay (2013). curves after 200 days of storage (Fig.2) that the

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 success- temperature or pressure, for example. Presently fully used for the detection of irradiation in dif- dried spices, herbs and seasonings belong to this ferent alimentary articles from which crystalline category of food products which are treated quite minerals can be isolated. Dried spices and herbs frequently with ionizing radiation. Thermolumin- belong to this group, while those imported from escence method for the detection of irradiated tropical countries are usually highly contaminated spices and herbs is currently adapted for the iden- with microorganisms, parasites and pests being tification of radiation treatment in very different often dried in the opened air. For that reason, food assortments containing only negligible flavour these products undergo disinfection processing. admixtures of spices as souses, cheese or dinner A very effective method for the neutralization of compositions. The method is also successfully used biological contaminates in food is radiation pas- for the detection of irradiated components in diet teurization with gamma rays or beams of acceler- supplements and herbal pharmaceuticals. ated electrons. Aromatic spices and herbs under- The essential problem of the method is effec- going this processing do not lose their aroma or tive isolation of mineral fraction based on general flavour as it is the case by applying the elevated procedure recommended in European standard LABORATORY FOR DETECTION OF IRRADIATED FOOD 97

Table. Weight and temperature simulated luminescence of minerals isolated from aromatic and flavour components of alimentary articles.

Weight of isolated mineral fraction Mineral loss by heating to 500oC Product samples 100 g ± 0.2 g each [mg] [%] Chondroitin porcine 0.34 0 Cumin seeds 3.51 1 Eyebright powder 21.25 1 Hawthorn extract 10.50 1 Paprika flakes 2.14 3 Leek flakes 4.03 4 Paprika flowers sharp 10.35 4 Garlic powder 6.44 5 Apple powder 2.40 5 Paprika flowers sharp 2.74 6 Fermented rice Angkak 2.14 7 Horsetail powder 0.60 7 Garlic flakes 0.38 9 Chondroitin bovine 0.64 9 Chilli powder 4.25 9 Chilli flakes 7.11 10 Chilli needles 11.56 10 Golden rot powder 4.75 10 Millet powder 3.90 11 Paprika powder 5.15 18 Garlic flakes 0.38 18 Ginkgo biloba extract 3.15 20 Chilli rolls 2.82 20 Gingko biloba extract 0.58 24 Leek sliced 1.43 35 Protein Erbse powder 1.54 37 Chondroitin marine 38.2 52 Protein Erbse powder 0.45 62

EN-1788 [1], as discussed in our earlier study [2], fraction was determined but after heating to 500oC. and the content and quality of isolated minerals. The number of 28 samples delivered to the Lab- In the proceeding study it has been shown [3] that oratory for Detection of Irradiated Food, INCT the weight of mineral fraction isolated from differ- for testing whether irradiated was used to perform ent commodities (samples weighing 20 g) varied the study. The experiment delivers the information from 0.1 do 2.5 mg while the corresponding TL concerning the stability of mineral fraction isolat- intensity differs from sample to sample even by the ed from food at elevated temperature. This kind factor of 500. It has been also observed that the of study has not been done, as to our knowledge, correlation between the weight of mineral and the so far. intensity of thermoluminescence was not proven. The samples were organized in the Table ac- The explanation lies in different geographical ori- cording to the increasing loss of weight by heating gin of the investigated vegetal products and con- (column 3). As is seen from the Table, the weight sequently in a very different composition of soils losses of the mineral fraction isolated from the in which the plants giving the products were culti- most of the samples heated to 500oC are surpris- vated [4]. ingly high, proving a low temperature stability of In order to throw more light on this problem a mineral fraction separated. The source of the new experimental approach has been undertaken. thermoluminescene released from mineral con- In addition to the weight of isolated mineral frac- stituents of food are structural imperfections in tion before the TL measurement the weight of this the crystalline lattice of minerals – suitable traps 98 LABORATORY FOR DETECTION OF IRRADIATED FOOD for radiation energy during the irradiation pro- References cessing. This kind of stable energy traps appear in [1]. EN-1788:2001 Foodstuffs – Detection of irradiated crystalline minerals such as quartz, quartzite, feld- food from which silicate minerals can be isolated. Euro- spar defined as silicate minerals [5]. The isolation pean Committee for Standardization (CEN), Brussels. procedure of mineral fraction recommended in [2]. Sadowska M., Stachowicz W.: Effectiveness of differ- European Standard EN-1788 eliminates efficient- ent procedures of mineral isolation from irradiated ly limestone and ground chalk from mineral de- spices suitable for thermoluminescence detection me- posit separated from organic pulp but does not thod. In: INCT Annual Report 2011. Institute of Nu- eliminate amorphous loams, clay stones, shale, etc. clear Chemistry and Technology, Warszawa 2012, pp. which may appear in the form of hard, rigid par- 102-105. ticles and accompany the crystalline minerals. [3]. Sadowska M, Stachowicz W.: Luminescence of silicate minerals and sensitivity of thermoluminescnce method Amorphous components of soil contain a lot of for detection of food irradiation. In: INCT Annual Re- structural water which is easily freed by heating. port 2012. Institute of Nuclear Chemistry and Tech- The heating can also stimulate the decomposition nology, Warszawa 2013, pp. 97-99. of organic constituents which are always contained [4]. Sanderson D.C.W., Carmichael L.A.. Naylor J.D.: in amorphous rocks appearing in mineral fraction. Food Sci. Technol. Today, 7, 150-154 (1995). Both dehydration and decomposition of amor- [5]. Sanderson D.C.W., Slater C., Cairns V.J.: Radiat. Phys. phous soil originated solid deposits separated from Chem., 34, 915-920 (1989). food can be responsible for the observed effect of significat loss of the weight of mineral fraction isolated from food. 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 222Rn decay products in air or water was elaborated and tested in laboratory conditions. In the frame of realized R&D project, development of a new generation of mining radiometers was undertaken. The radiometer 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. 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 in- terference in the structure of the installation by dismounting it [1]. Such kind of approach entails considerable financial losses. Then, it becomes de- liberate 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: 137Cs (activity – 550 MBq) and 60 Co (activity – 300 MBq). Source and probe were Fig.1. Installation for obtaining biogas. The measuring placed at a distance of 90 cm from each other. The system probe-source. test system including the located measuring system is shown in Fig.1. Installation was tested in its from the bottom up. The obtained results are middle part. For each source, have been made three shown in Fig.2. Then, the obtained values were runs measuring with a moving set of source-probe converted to density according to the formula:

Fig.2. Scan results [imp/s]. LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS 101

Fig.3. Scan results – density [g/cm3].

References ⎛⎞N0 ln⎜⎟ [1]. Charakterystyka technologiczna rafinerii ropy i gazu N ρ= ⎝⎠x w Unii Europejskiej (Technological characteristics of μd oil and gas refineries in the European Union). Ed. M. where: N – number of pulses at the open area Mihułek. Ministerstwo Środowiska, Warszawa 2003 (in 0 Polish). source-probe [imp/s], Nx – measured number of [2]. Kraś J., Waliś L., Myczkowski S.: Doświadczenia z izo- pulses [imp/s], μ – average mass attenuation coef- topowej kontroli szczelności obiektow technologicz- 2 ficient [cm /g], d – distance between probe and nych – aspekty techniczne i ekonomiczne (Experience source [cm]. in isotope leak-proof control of engineering objects – Assuming average mass attenuation coefficient technical and economical aspects). In: Technika jądro- for radiation 137Cs as 0.062 cm2/g and for 60Co wa w przemyśle, medycynie, rolnictwie i ochronie śro- value 0.049 cm2/g the average densities in the ex- dowiska. T.2. Instytut Chemii i Techniki Jądrowej, War- amined cross section were calculated. The densities szawa 2002, pp. 373-379. Raporty IChTJ. Seria A nr are shown in Fig.3. From the graph, we can read 2/2002 (in Polish). with a certain approximation the current level of [3]. Strategia rozwoju atomistyki w Polsce (Nuclear strategy development in Poland). Rada do Spraw Atomistyki, factor (of biomass) used in the system (≈14 cm). Warszawa 2006 (in Polish). Also a frame surrounding the tank in the central [4]. Jakowiuk A., Kowalska E., Pieńkos J., Filipiak P., Mo- part is visible. dzelewski Ł., Palige J., Kraś J.: The radiometric probes The obtained results of initial tests will serve as for industrial measuring systems. In: INCT Annual Re- a benchmark for testing the installation of biogas port 2011. Institute of Nuclear Chemistry and Tech- plants at a later data. Installation tests will be nology, Warszawa 2012, pp. 108-109. compared with those obtained earlier and on that basis the changes in the installation can be noticed (e.g. change of level, density factor). 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, 284-292 (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, 604-608 (2013). 3. Bartłomiejczyk T., Lankoff A., Kruszewski M., Szumiel I. Silver nanoparticles – allies or adversaries? Annals of Agricultural and Environmental Medicine, 20, 1, 48-54 (2013). 4. Bartoś B., Łyczko K., Kasperek A., Krajewski S., Bilewicz A. Search of ligands suitable for 212Pb/212Bi in vivo generators. Journal of Radioanalytical and Nuclear Chemistry, 295, 205-209 (2013). 5. Bator G., Sobczyk L., Sawka-Dobrowolska W., Wuttke J., Pawlukojć A., Grech E., Nowicka-Schei- be J. Structural spectroscopic and theoretical studies on 3,4,7,8-tetramethyl-1,10-phenantroline complex with pictric acid. Chemical Physics, 410, 55-65 (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, 9859-9862 (2013). 7. Blicharska M., Bartoś B., Krajewski S., Bilewicz A. Separation of fission produced 106Ru from simulated high level nuclear wastes for production of brachy- therapy sources. Journal of Radioanalytical and Nuclear Chemistry, 298, 1713-1716 (2013). 8. Calinescu I., Chmielewski A., Ighigeanu D.

E-beam SO2 and NOx removal from flue gas in the presence of fine water droplets. Radiation Physics and Chemistry, 85, 130-138 (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, 1913-1919 (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, 1349-1353 (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, 2359-2368 (2013). 12. Georgantzopoulou A., Balachandran Y.L., Rosenkranz P., Dusinska M., Lankoff A., Wojewódz- ka 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, 1168-1178 (2013). PUBLICATIONS IN 2013 103 13. Głuszewski W. Napromieniowany czy promieniotwórczy? (Irradiated or radioactive?). Postępy Techniki Jądrowej, 56, 2, 22-23 (2013). 14. Głuszewski W. Nowe możliwości medycyny nuklearnej w Polsce (New possibilities of the nuclear medicine in Poland). Postępy Techniki Jądrowej, 56, 4, 27-29 (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, 29-32 (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, 23-24 (2013). 18. Głuszewski W., Zimek Z., Zagórski Z.P., Rajkiewicz M. Radiacyjna modyfikacja polimerów (Radiation modification of polymers). Tworzywa Sztuczne w Przemyśle, 1, 56-59 (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, 1171-1177 (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 adeno- carcinoma HT-29 cells to X-radiation. Biochimica et Biophysica Acta, 1830, 2233-2242 (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, 308-318 (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, 51-62 (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 WO3-ZrO2, WO3-TiO 2, WO3-ZrO2- 188 188 -SiO2, and their evaluation as materials for the preparation of W/ Re generator. Applied Radiation and Isotopes, 75, 115-127 (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, 28-33 (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, 196-200 (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, 13-17 (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, 39-43 (2013). 104 PUBLICATIONS IN 2013 28. Kiegiel K., Starosta W., Leciejewicz J. Pyrimidine-4-carboxylic acid. Acta Crystallographica Section E, 69, o885 + [4] p. (2013), doi:10.1107/S1600536813012610, www.journals.iucr.org. 29. 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/10.1155/2013/762819 (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, 151-156 (2013). 31. Krajewski S., Cydzik I., Abbas K., Bulgheroni A., Simonelli F., Holzwarth U., Bilewicz A. Cyclotron production of 44Sc for clinical application. Radiochimica Acta, 101, 333-338 (2013). 32. Kruszewski M., Grądzka I., Bartłomiejczyk T., Chwastowska J., Sommer S., Grzelak A., Zu- berek 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, 151-159 (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, 235-250 (2013). 34. Latek S. 20 lat współczesnej edycji „Postępów Techniki Jądrowej” (20 years of the new edition of “Postępy Tech- niki Jądrowej” journal). Postępy Techniki Jądrowej, 56, 3, 35-37 (2013). 35. Latek S. Co dalej po IPPA? (What to do next after finishing IPPA?). Postępy Techniki Jądrowej, 56, 4, 19-22 (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, 32-34 (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, 12-16 (2013). 40. Lewandowska H. Coordination chemistry of nitrosyls and its biochemical implications. Structure and Bonding, [70] p. (2013), doi: 10.1007/430_2013_102. 41. Lewandowska H. Spectroscopic characterization of nitrosyl complexes. Structure and Bonding, [51] p. (2013), doi: 10.1007/430_2013_109. 42. Lisowska H., Węgierek-Ciuk A., Banasik-Nowak A., Braziewicz J., Wojewódzka M., Wójcik A., Lankoff A. PUBLICATIONS IN 2013 105

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, 191-199 (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, 646-650 (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, 323-327 (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, 013101-1 – 013101-35 (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, 160-162 (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/20135001005. 51. Niesteruk A., Lewandowska H., Golub Ż., Świsłocka R., Lewandowski W. Zainteresujmy się rokitnikiem. Preparaty z rokitnika zwyczajnego (Hippophae rhumnoides L.) jako do- datki 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, 571-581 (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, 256-261 (2013). 53. Piotrowska A., Leszczuk E., Brucherfseifer F., Morgenstern A., Bilewicz A. Functionalized NaA nanozeolites labeled with 224,225Ra for targeted alpha therapy. Journal of Nanoparticles Research, 15, 11, 11 p. (2013), doi: 10.1007/s1051-013-2082-7. 54. Połosak M., Piotrowska A., Krajewski S., Bilewicz A. Stability of 47Sc-complexes with acylic polyamino-polycarboxylate ligands. Journal of Radioanalytical and Nuclear Chemistry, 295, 1867-1872 (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., Gre- goire E., Koivistoinen A., Lindholm C., Moquet J., Oestreicher U., Puig R., Rothkamm K., Som- mer 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, 174-183 (2013). 106 PUBLICATIONS IN 2013 57. Romm H., Ainsbury E., Barnard S., Barrios L., Barquinero J.F., Deperas M., Gregoire E., Koi- vistoinen A., Lindholm C., Moquet J., Oestreicher U., Puig R., Rothkamm K., Sommer S., Thie- rens 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, 174-183 (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, 819-821 (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, 822-824 (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 delocaliza- tion in 1-benzylpyridinium. The Journal of Physical Chemistry B, 117, 14385-14399 (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, 88-96 (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, 264-270 (2013). 63. Stachowicz W. Identyfikacja napromieniowania produktów spożywczych w IChTJ (Identification of the irradiated food products in the INCT). Postępy Techniki Jądrowej, 56, 2, 20-21 (2013). 64. Starosta W., Leciejewicz J. catena-Poly[[aqualithium(I)]-μ-3-carboxy-5,6-dimethylpyrazine-2-carboxylato-κ4O2,N1:O3,N4]. Acta Crystallographica Section E, 69, m655-m656 + [8] p. (2013), doi:10.1107/S1600536813030493, www.journals.iucr.org. 65. Starosta W., Leciejewicz J. catena H 3O3 O3 O5 -Poly[[diaquabis(μ3-5-carboxylato-1 -pyrazole-3-carboxylic acid-κ : ; )dilithium(I)] monohydrate]. Acta Crystallographica Section E, 69, m593-m594 + [5] p. (2013), doi:10.1107/S1600536813026408, www.journals.iucr.org. 66. Starosta W., Leciejewicz J. Di-μ-aqua-bis[aqua(5-carboxylato-1H-1,2,3-triazole-4-carboxylic acid-κ2N3,O4)lithium]. Acta Crystallographica Section E, 69, m515-m516 + [5] p. (2013), doi:10.1107/S1600536813023167, www.journals.iucr.org. 67. Starosta W., Leciejewicz J.

Poly[(μ4-3-carboxypyrazine-2-carboxylato)(μ4-nitrato)dilithium]. Acta Crystallographica Section E, 69, m62 + [7] p. (2013). 68. Starosta W., Leciejewicz J. Triaqua(pyrazole-4-carboxylato-κN1)-lithium. Acta Crystallographica Section E, 69, m438 + [5] p. (2013). 69. Starosta W., Leciejewicz J., Kiegiel K. Tetraaqua(pyridine-4,6-dicarboxylato-κ2N1,O6)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, 505-509 (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. PUBLICATIONS IN 2013 107

Surface & Coatings Technology, 234, 104-113 (2013). 72. Trojanowicz M., Koc M. Recent developments in methods for analysis of perfluorinated persistent pollutants. Microchimica Acta, 180, 957-971 (2013), doi: 10.1007/s00604-013-1046-z. 73. Tymiński Z., Miśta E., Kalbarczyk P. Pomiary radionuklidów kosmogenicznych w meteorycie z Oslo i interpretacja wyników (The Oslo mete- orite research for cosmogenic radionuclides and the interpretation of the results). Acta Societaris Metheoriticae Polonorum, 4, 115-120 (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, 85-90 (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, 488-493 (2013). 76. Zakrzewska G., Biełuszka P., Chajduk E., Wołkowicz S. Recovery of uranium(VI) from water solutions by membrane extraction. Advanced Materials Research, 704, 66-71 (2013). 77. Zakrzewska-Trznadel G. Advances in membrane technologies for the treatment of liquid radioactive waste. Desalination, 321, 119-130 (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, 40-42 (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

1. 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. 465-478. 2. 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. 88-99. 3. 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. 75-101. 108 PUBLICATIONS IN 2013 4. 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 2013. Praca zbiorowa pod red. R. Stellera i D. Żuchowskiej. Wydawnictwo TEMPO s.c., Wrocław 2013, pp. 382-385. 5. 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. 505-508. 6. 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: 10.1007/SpringerReference_349215. 7. 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: 10.1007/SpringerReference_349214. 8. 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: 10.1007/SpringerReference_349216. 9. 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: 10.1007/SpringerReference_349218. 10. 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: 10.1007/SpringerReference_349217. 11. 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: 10.1007/SpringerReference_349219.

THE INCT PUBLICATIONS

1. INCT Annual Report 2012. Institute of Nuclear Chemistry and Technology, Warszawa 2013, 164 p. 2. 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. 3. 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. 4. Recommendations for broader and sustainable participation of New Member States in H2020. Institute of Nuclear Chemistry and Technology, Warszawa 2013, 67 p. 5. 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 2013. Raporty IChTJ. Seria B nr 1/2013, 32 p. PUBLICATIONS IN 2013 109 CONFERENCE PROCEEDINGS

1. 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, 29-31.05.2013. Conference proceedings, VII-423-VII-432. 2. 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, 25.11.2013. Materiały konferencyjne, [6] p. 3. Chmielewski A.G., Pawelec A., Witman-Zając S. Możliwości zastosowanie radiacyjnej technologii oczyszczania spalin w praktyce przemysłowej (Possibil- ities of EBFGT technology application in industrial practice). XI Konferencja „Dla miasta i środowiska – problemy unieszkodliwiania odpadów”, Warszawa, Poland, 25.11.2013. 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, 25.11.2013. 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, Eka- terinburg, Russia, 10-14.10.2013. Conference proceedings, pp. 138-143. 6. 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. 7-18. 7. 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. 31-44. 8. 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, 19-21.10.2013, 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, 19-21.10.2013, 18 p. (CD edition). 10. Trojanowicz M., Gumiela M., Koc A., Bojanowska-Czajka A., Kciuk G., Bobrowski K., Nałęcz-Ja- wecki 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, 15-17.07.2013. 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, 22-24.05.2013. Book of abstract, pp. 161-167. 110 PUBLICATIONS IN 2013 CONFERENCE ABSTRACTS

1. 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, 21-24.04.2013. Streszczenia, P1. 2. 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.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera- tów, p. 17. 3. 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, 17.05.2013. Streszczenia, p. 47. 4. 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, 24-28.03.2013. Abstracts of lectures and poster presentations, p. 149. 5. 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, 23-26.09.2013. Materiały konferencyjne, p. 76. 6. 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.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera- tów, p. 10. 7. Bartosiewicz I., Chwastowska J., Polkowska-Motrenko H. Badanie składu i wpływu na środowisko pouranowych odpadów kopalnianych w bloku Karkonosko-Izer- skim (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, 16-20.09.2013. Materiały zjazdowe, pp. 358-359. 8. 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, 27-29.11.2013, p. 36. 9. 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, 4-5.04.2013, p. 43. PUBLICATIONS IN 2013 111 10. 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.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera- tów, p. 13. 11. 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.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera- tów, p. 15. 12. 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, 21-24.04.2013. Streszczenia, K2. 13. 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, 9-13.06.2013, [1] p. 14. 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.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera- tów, p. 19. 15. 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 Meet- ing, Bologna, Italy, 5-7.05.2013, p. 32-33. 16. 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, 17-20.10.2013. Abstract book, p. 24. 17. 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, 14-19.03.2013, p. 44. 18. 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, 13-15.02.2013, p. 13. 19. 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, 22-27.09.2013, p. 223. 20. 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, 13-15.02.2013, p. 20. 21. Brykała M., Deptuła A., Rogowski M., Łada W., Olczak T. Process IChTJ – method for preparation of spherical particles of ceramic nuclear fuels. 112 PUBLICATIONS IN 2013

13th Conference under auspices of E-MRS: Composites and Ceramic Materials – Technology, Applica- tion and Testing, Białowieża, Poland, 13-15.05.2013. Book of abstracts, p. 27. 22. Brykała M., Deptuła A., Rogowski M., Olczak T., Łada W., Smoliński T., Wawszczak D., Wojto- wicz P. Synteza za pomocą kompleksowej metody zol-żel (CSGP) stablizowanego ditlenku cyrkonu jako po- tencjalnej 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, 21-24.04.2013. Streszczenia, P3. 23. Brykała M., Deptuła A., Rogowski M., Olczak T., Łada W., Smoliński T., Wawszczak D., Wojto- wicz 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, 21-24.04.2013. Streszczenia, K4. 24. Brykała M., Deptuła A., Walczak R., Rogowski M., Olczak T., Łada W., Smoliński T., Waw- szczak 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, 17.05.2013. Streszczenia, p. 60. 25. Brykała M., Rogowski M., Deptuła A., Olczak T., Łada W., Smoliński T., Wawszczak D., Wojto- wicz 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, 21-24.04.2013. Streszczenia, K34. 26. 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, 17.05.2013. Streszczenia, p. 186. 27. Brzóska K., Kruszewski M. Gene expression signatures in blood as a biomarker for biological dosimetry. XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, 23-26.09.2013. Materiały konferencyjne, p. 36. 28. 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, 3-6.07.2013. Book of abstracts, p. 44. 29. 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). 30. 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, 13-16.05.2013. Abstracts, [1] p. 31. 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, 23-26.09.2013. Materiały konferencyjne, p. 95. 32. Bugaj A., Sadło J., Sterniczuk M., Strzelczak G., Michalik J. Paramagnetic centres generated radioanalytically in molecular sieves TiAlMCM type – EPR study. PUBLICATIONS IN 2013 113

Porous and Powder Materials Symposium and Exhibition PPM 2013, Cesme Izmir, Turkey, 3-6.09.2013, p. 343. 33. 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, 17.05.2013. Streszczenia, p. 63. 34. 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, 26-30.06.2013. Book of abstracts, p. 52. 35. 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, 24.05.2013, P-37. 36. 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, 23-26.09.2013. Materiały konferencyjne, p. 68. 37. Chajduk E., Bartosiewicz I., Pyszynska M., Chwastowska J., Polkowska-Motrenko H. Analiza złóż uranonośnych z Obniżenia Podlaskiego i syneklizy perybałtyckiej metodą ICP-MS (Ana- lysis of Polish dictyonema shales and sandstones by ICP-MS). XXII Poznańskie Konwersatorium Analityczne „Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków”, Poznań, Poland, 4-5.04.2013, p. 41. 38. 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, 25-29.08.2013. Book of abstracts, p. 243. 39. 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, 27-29.11.2013, p. 37. 40. Chajduk E., Polkowska-Motrenko H., Bilewicz A. Novel radiochemical separation of arsenic from selenium for 72Se/72As generator. 5th Asia-Pacific Symposium on Radiochemistry, APSORC 13, Kanazawa, Japan, 22-27.09.2013, p. 182. 41. Chajduk E., Witman-Zając S., Polkowska-Motrenko H. Determination of low level 99Tc in the primary coolant water by ICP-MS. Analysis of potential interferences. 5th Asia-Pacific Symposium on Radiochemistry, APSORC 13, Kanazawa, Japan, 22-27.09.2013, p. 224. 42. Chajduk E., Zuba M., Skwara W., Dudek J., Polkowska-Motrenko H. 226 Sorpcja Ra na jonitach z wytrąconych MnO2 i jego oznaczanie w próbkach środowiskowych za pomocą 226 ICP-MS (Sorption of Ra on ionites from precipitated MnO2 and its determination with ICP-MS). XVIII Konferencja: Zastosowanie metod AAS, ICP-OES i ICP-MS w analizie środowiskowej, Kraków, Poland, 10-11.12.2013, p. 45. 43. 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, 4-8.10.2013, p. 129. 44. 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, 16-20.09.2013. Materiały zjazdowe, p. 96. 45. Chmielewski A.G. Działania IChTJ na rzecz Polskiego Programu Energetyki Jądrowej (Activity of the INCT for the Polish Nuclear Power Programme). 114 PUBLICATIONS IN 2013

Konferencja naukowo-techniczna: „Nauka i technika wobec wyzwania budowy elektrowni jądrowej – Mądralin 2013”, Warszawa, Poland, 13-15.02.2013, pp. 22-24. 46. Chmielewski A.G. Radiation processing for rich and poor, experts and beginners. 17th International Meeting on Radiation Processing, Shanghai, China, 4-8.10.2013, p. 230. 47. Chmielewski A.G. Radiation processing technology – now & in the future. 17th International Meeting on Radiation Processing, Shanghai, China, 4-8.10.2013, p. 109. 48. 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, 4-8.10.2013, pp. 230-231. 49. Chmielewski A.G., Sartowska B., Jakowiuk A., Ptaszek S., Modzelewski Ł., Sommer S. Analiza potencjału polskich firm pod kątem możliwości wykonywania dostaw systemów dozymetrycz- nych 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, 13-15.02.2013, p. 25. 50. 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, 1-3.10.2013, [2] p. 51. 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, 3-7.03.2013, [1] p. [A.3.10.3]. 52. 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, 21-24.10.2013. Book of abstracts, p. 328. 53. 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, 13-15.02.2013, p. 28. 54. 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.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera- tów, p. 20. 55. 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, 22-27.09.2013, p. 2. 56. 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, 21-24.04.2013. Streszczenia, W1. PUBLICATIONS IN 2013 115 57. 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 sub- stancji o charakterze jonowym, Toruń, Poland, 7-9.04.2013, p. 17. 58. 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, 27-29.11.2013, p. 7. 59. 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, 14-19.03.2013, p. 76. 60. 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, 13-15.02.2013, p. 31. 61. Filipowicz B. 137 137 Porównanie sorpcji Cs na nanostrukturach TiO2-ZrO2 i TiO2 (Comparison of sorption of Cs in the TiO2-ZrO2 and TiO2 nanostructures). ChemSession’13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 17.05.2013. Streszczenia, p. 82. 62. Filipowicz B., Krajewski S., Bilewicz A. Nanostruktury tytanianowe jako nowe sorbenty wykorzystywane do separacji Cs+ i Sr2+ z odpadów promieniotwórczych (Titanate nanostructures as new sorbents used for separation of Cs+ and Sr2+ from radioactive waste). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, 21-24.04.2013. Streszczenia, P10. 63. Gajda D., Danko B., Zakrzewska-Trznadel G., Kiegiel K., Chajduk E., Bartosiewicz I., Sam- czyński Z. The study of sandstone rocks as a potential source of uranium from domestic deposits. European Nuclear Young Generation Forum, Stockholm, Sweden, 17-20.06.2013, [2] p., https://dl.drop- boxusercontent.com/s/hpmgeolg1rqogbg/press%20release%20April.pdf?token_hash=AAGCxfLuvo7 qYmacTG0LiAZxEE9F6p-3CShNZYS3tlmNO. 64. 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.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera- tów, p. 16. 65. 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 łup- ków 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.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera- tów, p. 11. 66. Gajda D., Zakrzewska-Trznadel G., Kiegiel K., Danko B., Chajduk E., Bartosiewicz I. Oddzielenie związków uranu od metali towarzyszących z roztworów otrzymanych po ługowaniu pias- kowców pochodzących z polskich złóż, metodą chromatografii jonowymiennej (Separation of uranium compounds from accompanying metals from solutions after leaching of sandstones from the Polish deposits). 116 PUBLICATIONS IN 2013

ChemSession’13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 17.05.2013. Streszczenia, p. 83. 67. Głuszewski W., Rajkiewicz M., Zagórski Z.P. Radiacyjna modyfikacja elastomerów (Radiation modification of elastomers). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, 23-26.09.2013. Materiały konferencyjne, p. 91. 68. 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 / Elasto- mery 2013 “Science and Industry” XV International Science and Technology Conference, Warszawa, Poland, 23-25.10.2013, [2] p. 69. 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, 13-15.02.2013, p. 36. 70. 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, 23-26.09.2013. Materiały konferencyjne, p. 47. 71. Głuszewski W., Zagórski Z.P., Rajkiewicz M. Protective effects in radiation modification of elastomers. 17th International Meeting on Radiation Processing, Shanghai, China, 4-8.10.2013, p. 149. 72. 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 12-17 May 2013, ICC JEJU, Jeju, Korea. Journal of Labelled Compounds and Radiopharmaceuticals, 56, Suppl. 1, S435 (2013). 73. 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, 18-20.09.2013. Book of abstracts, p. 61. 74. 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, 23-26.09.2013. Materiały konferencyjne, p. 43. 75. 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, 4-8.10.2013, p. 128. 76. Gumiela M., Gniazdowska E., Koźmiński P., Bilewicz A. Otrzymywanie 99mTc na cyklotronach medycznych (Cyclotron production of 99mTc). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, 21-24.04.2013. Streszczenia, P12. 77. Gumiela M., Gniazdowska E., Koźmiński P., Bilewicz A. Wydzielanie Tc-99m z aktywowanej w cyklotronie tarczy molibdenowej (Tc-99m separation from iso- topically enriched 100Mo via proton bombardment). II Ogólnopolska Konferencja Radiofarmaceutyczna, Łódź, Poland, 9-10.05.2013, p. 43. 78. Gumiela M., Gniazdowska E., Koźmiński P., Bilewicz A. Wydzielanie Tc-99m z aktywowanej w cyklotronie tarczy molibdenowej (Tc-99m separation from iso- topically enriched 100Mo via proton bombardment). ChemSession’13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 17.05.2013. Streszczenia, p. 94. PUBLICATIONS IN 2013 117 79. 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, 14-19.03.2013, p. 29. 80. 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, 19-22.09.2013, [2] p. 81. 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, 23-26.09.2013. Materiały konferencyjne, p. 81. 82. 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, 1-5.09.2013, W-72. 83. 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, 13-15.02.2013, p. 42. 84. 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 Con- gress of ALAMCTA, Foz do Iguaçu, Brazil, 3-8.11.2013, p. 226. 85. Kapka-Skrzypczak L., Niedźwiecka J., Sawicki K., Cyranka M., Wasak M., Turski W.A., Krusze- wski 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 Min- erals: Trace Elements in Avignon. Bridging Between New Advances and Public Health Issues, Avignon, France, 22-24.05.2013, p. 140. 86. 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, 2-6.11.2013, [1] p. 87. Kasperek A., Leszczuk E., Bilewicz A. Bioconjugated nanozeolites labeled with 223,224,225Ra. The 20th International Symposium on Radiopharmaceutical Sciences 12-17 May 2013, ICC JEJU, Jeju, Korea. Journal of Labelled Compounds and Radiopharmaceuticals, 56, Suppl. 1, S243 (2013). 88. Kaźmierczak U., Banaś D., Braziewicz J., Choiński J., Czub J., Jaskóła M., Korman A., Krusze- wski 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, 23-26.09.2013. Materiały konferencyjne, p. 44. 89. 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 reeks- trakcją 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.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera- tów, p. 14. 118 PUBLICATIONS IN 2013 90. 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.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera- tów, p. 21. 91. 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, 17.05.2013. Streszczenia, p. 120. 92. 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, 15-20.09.2013, p. 97. 93. 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, 14-19.03.2013, p. 87. 94. 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, 23-26.09.2013. Materiały konferencyjne, p. 93. 95. 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, 24.05.2013, K-8. 96. Kosno K., Celuch M., Janik I., Pogocki D. Mechanism and kinetics of nicotine radical oxidation. 6th European Young Investigator Conference, Słubice, Poland, 26-30.06.2013. Book of abstracts, p. 28. 97. Kosno K., Celuch M., Janik I., Pogocki D. Mechanism of nicotine radical reactions. 28th Miller Conference on Radiation Chemistry, Dead Sea, Israel, 14-19.03.2013, p. 36. 98. 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, 17.05.2013. Streszczenia, p. 125. 99. 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, 23-26.09.2013. Materiały konferencyjne, p. 49. 100. 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, 9-12.07.2013, p. 129. 101. Koźmiński P., Gniazdowska E. Ghrelin peptide labelled with technetium-99m complexes a potential diagnostic radiopharmaceuticals. The 20th International Symposium on Radiopharmaceutical Sciences 12-17 May 2013, ICC JEJU, Jeju, Korea. Journal of Labelled Compounds and Radiopharmaceuticals, 56, Suppl. 1, S433 (2013). 102. 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). PUBLICATIONS IN 2013 119

Konferencja naukowo-techniczna: „Nauka i technika wobec wyzwania budowy elektrowni jądrowej – Mądralin 2013”, Warszawa, Poland, 13-15.02.2013, p. 49. 103. 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 Min- erals: Trace Elements in Avignon. Bridging Between New Advances and Public Health Issues, Avignon, France, 22-24.05.2013, p. 174. 104. Kruszewski M., Grądzka I., Bartłomiejczyk T., Chwastowska J., Sommer S., Grzelak A., Zu- berek 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 Con- gress of ALAMCTA, Foz do Iguaçu, Brazil, 3-8.11.2013, p. 237. 105. 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, 23-26.09.2013. Materiały konferencyjne, p. 69. 106. 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, 7-10.10.2013, [2] p. 107. 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, 1-5.09.2013, [1] p. 108. 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., Vander- sickel 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, 13-16.05.2013. Abstracts, [1] p. 109. 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, 1-5.07.2013. Vydavatelstvi Ceske sklarske spolecnosti, Teplice 2013, p. 152. 110. 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 (Elabora- tion 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, 17.05.2013. Streszczenia, p. 135. 120 PUBLICATIONS IN 2013 111. Leszczuk E., Piotrowska A., Bilewicz A., Morgenstern A., Bruchertseifer F. 225 212 Modyfikowane polietylenoglikolem nanocząstki TiO2 jako nośniki radionuklidów Ac i Pb dla ce- 225 lowanej radioterapii (TIO2 nanoparticles modified with polyethylene glycol as carriers for Ac and 212Pb for targeted radiotherapy). II Ogólnopolska Konferencja Radiofarmaceutyczna, Łódź, Poland, 9-10.05.2013, p. 65. 112. Leszczuk E., Piotrowska A., Bilewicz A., Morgenstern A., Bruchertseifer F. 225 213 in vivo TiO2 nanoparticles as carries of Ac/ Bi generator. 8th International Symposium on Targeted Alpha Therapy, Oak Ridge, Tennessee, USA, p. 30. 113. Lisowska H., Fortuna B., Fendrych Ż., Nowakowska J., Stankiewicz M., Węgierek-Ciuk A., Bra- ziewicz 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, 23-26.09.2013. Materiały konferencyjne, p. 51. 114. 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, 21-24.04.2013. Streszczenia, P20. 115. 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, 21-24.04.2013. Streszczenia, K22. 116. 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, 21-24.04.2013. Streszczenia, K24. 117. 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, 9-10.05.2013, p. 68. 118. 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, 23-26.09.2013. Materiały konferencyjne, p. 82. 119. 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, 4-8.10.2013, p. 169. 120. 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, 27-31.05.2013, L19. 121. Miśkiewicz A., Zakrzewska G., Jaworska-Sobczak A. Ługowanie uranu z rud uranowych z separacją faz w membranowym aparacie z przepływem helikoidal- nym (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.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera- tów, p. 12. PUBLICATIONS IN 2013 121 122. 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, 15-19.09.2013. Proceedings. J. Krzysztoforski, M. Szwast (eds.), p. 18. 123. 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, 19-22.09.2013, [4] p. 124. 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-tri- azinyl-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, 21-24.04.2013. Streszczenia, K29. 125. Niesłuchowska W., Miśkiewicz A., Zakrzewska-Trznadel G., Kulisa K. Zastosowanie biosorbentów w procesach hybrydowych UF/sorpcja do usuwania wybranych radionukli- dów 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, 21-24.04.2013. Streszczenia, P23. 126. 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). 127. Nyga M., Grodkowski J., Mirkowski J., Szreder T. •– Generowanie rodnika utleniającego I2 i jego reaktywność w cieczach jonowych (Generation of an •– oxidation radical I2 and its reactivity in ionic liquids). XVII Mikrosympozjum: Kinetyczne Metody Badania Mechanizmów Reakcji w Roztworach, Poznań, Poland, 24.05.2013, P-19. 128. 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.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera- tów, p. 23. 129. 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, 13-15.02.2013, pp. 57-58. 130. 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, 21-24.04.2013. Streszczenia, P26. 131. 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.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera- tów, p. 18. 132. 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Radiolytic and photolytic oxidation of methionine-containing peptides. 28th Miller Conference on Ra- diation Chemistry, Dead Sea, Israel, 14-19.03.2013, p. 81. 133. 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, 21-24.04.2013. Streszczenia, P28. 134. 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, 4-5.04.2013, p. 44. 135. Przybytniak G. Fizykochemiczne i strukturalne efekty radiacyjne w polimerach (Physicochemical and structural radiation affects in polymers). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, 23-26.09.2013. Materiały konferencyjne, p. 30. 136. 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, 13-15.02.2013, p. 62. 137. 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, 19-22.09.2013, [2] p. 138. Rejnis M., Herdzik-Koniecko I., Narbutt J. Kompleksowanie produktów rozszczepienia w fazie wodnej, zapobiegające ich współekstrakcji z akty- nowcami 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, 21-24.04.2013. Streszczenia, P30. 139. Romm H., Ainsbury E., Barnard S., Barquinero J.F., Barrios L., Beinke C., Deperas M., Gre- goire 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, 13-16.05.2013. Abstracts, [1] p. 140. Romm H., Bajinskis A., Oestreicher U., Thierens H., Vral A., Rothkamm K., Ainsbury E., Ben- deritter 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, 17-19.09.2013, p. 222. 141. 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.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera- tów, p. 9. 142. 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). PUBLICATIONS IN 2013 123

Konferencja naukowo-techniczna: „Nauka i technika wobec wyzwania budowy elektrowni jądrowej – Mądralin 2013”, Warszawa, Poland, 13-15.02.2013, p. 67. 143. 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, 2-5.09.2013, p. 102. 144. 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, 18-21.09.2013, p. 82. 145. 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, 3-7.03.2013, [1] p. 146. 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, 5-6.12.2013, p. 52. 147. 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 esti- mate the absorbed dose). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, 23-26.09.2013. Materiały konferencyjne, p. 54. 148. 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, 17.05.2013. Streszczenia, p. 192. 149. 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, 24.05.2013, K-5. 150. Skotnicki K. Pulse radiolysis study of quinoxalin-2-one in aqueous solutions. 6th European Young Investigator Conference, Słubice, Poland, 26-30.06.2013. Book of abstracts, p. 31. 151. 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, 23-26.09.2013. Materiały konferencyjne, p. 58. 152. Smoliński T., Deptuła A., Łada W., Wawszczak D., Olczak T., Brykała M., Rogowski M., Wojto- wicz 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, 17.05.2013. Streszczenia, p. 195. 153. Smoliński T., Deptuła A., Łada W., Wawszczak D., Olczak T., Brykała M., Wojtowicz P., Rogo- wski 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, 13-15.02.2013, p. 65. 154. Smoliński T., Deptuła A., Łada W., Wawszczak D., Olczak T., Brykała M., Wojtowicz P., Rogo- wski M., Zaza F. 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, 21-24.04.2013. Streszczenia, P38. 155. 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, 13-16.05.2013. Abstracts, [2] p. 156. 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, 13-16.05.2013. Abstracts, [1] p. 157. 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.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera- tów, p. 22. 158. 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, 3-6.09.2013, p. 344. 159. 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, 26-30.06.2013. Book of abstracts, p. 37. 160. 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, 23-26.09.2013. Materiały konferencyjne, p. 62. 161. 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, 24.05.2013, P-43. 162. 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, 21-24.04.2013. Streszczenia, K39. 163. 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, 23-26.09.2013. Materiały konferencyjne, p. 40. 164. 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, 17.05.2013. Streszczenia, p. 204. 165. 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). PUBLICATIONS IN 2013 125

Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium naukowe w ramach projektu POIG.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera- tów, p. 24. 166. Trojanowicz M. Recent developments in miniaturization of flow analysis. 18th International Conference on Flow Injection Analysis (18th ICFIA), Porto, Portugal, 15-20.09.2013, p. 37. 167. 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, 23-26.09.2013. Materiały konferencyjne, p. 65. 168. Walo M., Przybytniak G. Functionalization of poly(ester-urethane) surface by radiation-induced grafting. 28th Miller Conference on Radiation Chemistry, Dead Sea, Israel, 14-19.03.2012, p. 70. 169. Walo M., Przybytniak G. Grafting of N-isopropylacrylamide onto polyurethane surface by gamma initiated RAFT polymerization. 17th International Meeting on Radiation Processing, Shanghai, China, 4-8.10.2013, pp. 146-147. 170. Wasyk I., Buraczewska I., Lankoff A., Sommer S., Wojewódzka M., Kruszewski M. Automatyczny test mikrojądrowy w komórkach ludzkiej osteosarkomy i limfocytach kurzych (Auto- matic micronuclei test in human osteosarcoma cells and chicken lymphocytes). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, 23-26.09.2013. Materiały konferencyjne, p. 87. 171. 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, 21-24.04.2013. Streszczenia, K43. 172. 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, 1-5.09.2013, M-66. 173. 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 – ko- relacja 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, 23-26.09.2013. Materiały konferencyjne, p. 59. 174. 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, 18-20.09.2013. Book of abstracts, p. 47. 175. Wojtowicz P., Deptuła A., Łada W., Wawszczak D., Olczak T., Smoliński T., Brykała M., Rogo- wski 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, 21-24.04.2013. Streszczenia, P45. 176. Wójcik A., Romm H., Oestreicher U., Thierens H., Vral A., Rothkamm K., Ainsbury E., Bender- titter 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, 13-16.05.2013. Abstracts, [1] p. 126 PUBLICATIONS IN 2013 177. 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, 23-26.09.2013. Materiały konferencyjne, p. 89. 178. 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, 23-26.09.2013. Materiały konferencyjne, p. 90. 179. 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, 22-24.05.2013. Book of abstract, p. 13. 180. Zakrzewska-Trznadel G., Kiegiel K., Frąckiewicz K., Herdzik I., Zielińska B., Biełuszka P., Gaj- da 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, 13-15.02.2013, pp. 84-85. 181. 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 promie- niotwórczymi: 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, 13-15.02.2013, p. 83. 182. Zakrzewska-Trznadel G., Miśkiewicz A., Jaworska A., Kiegiel K., Gajda D., Bilewicz A., Sar- towska 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, 13-15.02.2013, p. 82. 183. Zakrzewska-Trznadel G., Miśkiewicz A., Mysłek-Laurikainen B. Wdrażanie polityki współuczestnictwa społeczeństwa w procesach decyzyjnych związanych ze składo- waniem 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, 13-15.02.2013, p. 81. 184. 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, 5-8.08.2013, pp. 66-67. 185. Zuba M., Chajduk E., Polkowska-Motrenko H. Wydzielanie 226Ra z próbek środowiskowych dla pomiarów przy użyciu spektrometrii mas z jonizacją w plazmie indukcyjnie sprzężonej (ICP-MS) i spektrometrii promieniowania gamma (Separation of 226Ra from environmental samples for measurements with the use of ICP-MS and gamma radiation spectrometry). ChemSession’13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 17.05.2013. Streszczenia, p. 240. PUBLICATIONS IN 2013 127 SUPPLEMENT LIST OF THE PUBLICATIONS IN 2012

1. 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. 183-202. 2. Eppard E., Pruszyński M., Mikołąjczak R., Koumarianou E., Miederer M., Baum R., Roesch F. 44Sc-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, 697-714 (2012). 4. Leszek P., Sochanowicz B., Brzóska K., Komuda-Leszek E., Danko B., Kuśmierski K., Piotro- wski 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, 25-29.08.2012. European Heart Journal, 33, Suppl. 1, 1102-1103 (2012). 5. Leszek P., Sochanowicz B., Brzóska K., Komuda-Leszek E., Kraj L., Danko B., Kolsut P., Pio- trowski 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, 25-29.08.2012. 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, 25-29.08.2012. 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, 23-26.07.2012. 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 – Fron- tiers in Cardiovascular Biology, London, England, 30.03 – 1.04.2012. 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 44Sc. Applied Radiation and Isotopes, 70, 974-979 (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, 26-30 November 2012. Working material. IAEA, Vienna 2012, pp. 205-218. 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, 10-13 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

155 4. Gd isomer shifts. The case study: GdT2Si2 K. Łątka x 5. Mössbauer study of vacuum annealed Fe100–xGax (10 ≤ ≤ 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 R2Fe14B 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 Fe2O3 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 x x 11. Hyperfine interactions in ·Bi0.95Dy0.05FeO3-(1– )·Pb(Fe2/3W1/3)O3 multiferroics P. Zachariasz, A. Stoch, P. Stoch, J. Maurin

12. X-ray diffraction, Mössbauer spectroscopy, and magnetoelectric effect studies of (BiFeO3)x-(BaTiO3)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 60P2O5-40Fe2O3 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 NUKLEONIKA 129

57 15. Hyperfine interactions in (Cr0.99 Fe0.01)3+xSi1–x D. Satuła, K. Szymański, W. Olszewski, B. Kalska-Szostko, J. Waliszewski, K. Rećko

16. Hydrogen ordering effects in Laves-phase YFe2 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 57Fe 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 Nd10Fe83Zr1B6 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 LaFe11.0Co0.8(Si0.4Al0.6)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 Tb0.27–xYxDy0.73Fe2 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 Bim+1Ti3Fem–3O3m+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 mechano- synthesized CoxFeyNiz alloys T. Pikula 32. Characterization of phase constitution and magnetic properties of the hard magnetic nanocrystalline Nd9.5Fe63.65B21.85Nb5 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 Mn2–xFexP0.5As0.5 V.I. Mitsiuk, T.M. Tkachenka, M. Budzyński, Z. Surowiec, V.I. Valkov

35. Structural and magnetic properties of Sc(Fe1–xCux)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(Co0.4–xNixFe0.6)2 compounds at 295 K A. Zwoźniak, A. Krawczyk, P. Stoch, P. Guzdek, P. Zachariasz, J. Suwalski, J. Pszczoła 130 NUKLEONIKA Proceedings of the 40th Polish Seminar on Positron Annihilation PSPA'2012, 13-14 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 1.4307 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. 2/2013

1. 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)-[123I]- and (2S,3S)-[123I]-trans-2-hydroxy-5-((E)-3-(io- do)allyloxy)-3-(4-phenyl-1-piperazinyl) tetralin as SPECT radiotracer T. Assaad, A.H. Al Rayyes 3. Synthesis and biodistribution of both (±)-5-[18F]-fluoroethoxy and (±)-5-[18F]-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 NUKLEONIKA 131

7. 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, 16-18 May 2012, Często- chowa-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 Fe2+(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 Cu2+ and Mn2+ 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 Fe3+ 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 125-275 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 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. 4/2013 1. 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 per- oxidase 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 NUKLEONIKA 133 Information INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY NUKLEONIKA Dorodna 16, 03-195 Warszawa, Poland phone: +48 22 504 11 32; fax: +48 22 811 15 32; e-mail: [email protected] Abstracts and full texts are available on-line at http://www.nukleonika.pl 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. 1/2013 1. Nowe możliwości pomiarowe Śląskiego Centrum Radiometrii Środowiskowej Głównego Instytutu Gór- nictwa (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 numeri- cal 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. 2/2013 1. 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 POSTĘPY TECHNIKI JĄDROWEJ 135

7. Analiza 23. cyklu aktywności Słońca w oparciu o pomiary Be-7 w przyziemnej warstwie powietrza atmos- ferycznego (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. 3/2013 1. 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 heavi- est 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 4. 50 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 5. 100-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 9. 20 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. 4/2013 1. 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 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: “Absol- vents”. 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, 03-195 Warszawa, Poland phone: +48 22 504 12 48; fax: +48 22 811 15 32; e-mail: [email protected] INTERVIEWS IN 2013 137

INTERVIEWS IN 2013

1. Łada W. Fober I.: Meganadzieja w mikrosferach (Megahope in microspheres). Przegląd Techniczny, 3-4, 14 (2013). 2. 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. http://biotechnologia.pl/biotechnologia/aktualnosci/ mamy-uran-w-polsce-nowe-spojrzenie-na-sprawe,12737 (19.11.2013). 3. Gajda D. Szwed M.: Mamy uran w Polsce – nowe spojrzenie na sprawę (We have got uranium in Poland – a new look at the issue). http://www.swiadomieoatomie.pl/aktualnosci/aktualnosci-z-polski/082013/mamy-uran- -w-polsce-nowe-spojrzenie-na-sprawe.html (19.11.2013). 4. Gajda D. Szwed M.: Mamy uran w Polsce – nowe spojrzenie na sprawę (We have got uranium in Poland – a new look at the issue). http://www.poznajatom.pl/polska_z_energia/mamy_uran_w_polsce_nowe_spoj,560/ (19.11.2013). 138 THE INCT PATENTS AND PATENT APPLICATIONS IN 2013

THE INCT PATENTS AND PATENT APPLICATIONS IN 2013

PATENTS

1. 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) 2. 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) 3. 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) 4. 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 5. Sposób rozpuszczania tlenku toru (Method of dissolution of thorium oxide) K. Łyczko, M. Łyczko, I. Herdzik, B. Zielińska Polish Patent 6. Radiofarmaceutyk terapeutyczny znakowany radionuklidami radu oraz sposób jego wytwarzania (Thera- peutic radiopharmaceutical labelled with radionuclides of radium and method for its obtaining) A. Kasperek, A. Bilewicz, T. Olczak Polish Patent 7. 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 8. 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

1. 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-403817 2. Prekursor radiofarmaceutyku, sposób jego wytwarzania, radiofarmaceutyk oraz jego zastosowanie (Pre- cursor of the radiopharmaceutical, the method for its production, radiopharmaceutical and its applications) G. Wójciuk, M. Kruszewski Polish Patent Application P-404564 THE INCT PATENTS AND PATENT APPLICATIONS IN 2013 139

3. Sposób wytwarzania stabilizowanego ditlenku cyrkonu w postaci matrycy inertnej do transmutacji ak- tynowców 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-404947 4. 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-405025 5. 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-405251 6. 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-405294 7. 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-405451 8. Sposób otrzymywania diagnostycznych ilości radionuklidu 99mTc (Method for the obtaining of diagnostic amounts of the 99mTc radionuclide) A. Bilewicz, M. Gumiela Polish Patent Application P-406594 9. 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-13176463.1 10. 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-12461532.9 (with KIKGEL, Poland) 140 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2013

CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2013

1. 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, Agniesz- ka 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, Ka- tarzyna 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), 21-24 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 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2013 141 “PRESENTATION AND PARTICIPATION IN DEBATES”, 24-25 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, Agniesz- ka 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, Agniesz- ka Miśkiewicz, Ph.D., Dorota Gajda, M.Sc., Wioleta Niesłuchowska, M.Sc., Paulina Niescior-Bro- wińska, 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), 17-18 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, Agniesz- ka 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, Kata- rzyna 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, Agniesz- ka Miśkiewicz, Ph.D., Wioleta Niesłuchowska, M.Sc. 142 Ph.D. THESES IN 2013

Ph.D. THESES IN 2013

1. 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, 19.12.2013 2. 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, 07.03.2013 3. 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-Ter- phenyl 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, 14.06.2013 4. Seweryn Krajewski, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Metaloorganiczne i chelatowe kompleksy 105Rh i 103mRh jako potencjalne prekursory radiofarmaceutyków terapeutycznych (Organometallic and chelate complexes of 105Rh and 103mRh as potential precursors of therapeutic radiopharmaceuticals) supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, 19.12.2013 5. 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, 10.09.2013 6. 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, 10.09.2013 7. 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, 19.12.2013 8. 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, 19.12.2013 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 guest- house for Ph.D. students not living in Warsaw. During the four-year Ph.D. programme, the students participate in lectures given by senior staff from the INCT, University of Warsaw and the Polish Academy of Sciences. In the third year, the Ph.D. students are obliged to prepare a seminar related to the various aspects of nuclear energy. Each year the Ph.D. students are obliged to deliver a lecture on topic of his/her dissertation at a seminar. The final requirements for the Ph.D. programme graduates, consistent with the regulation of the Ministry of Science and Higher Education, are: • submission of a formal dissertation, summarizing original research contributions suitable for publica- tion; • final examination and public 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. (Forschungs- zentrum 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: +48 22 504 13 57, e-mail: [email protected]); • secretary: Dr. Ewa Gniazdowska (phone: +48 22 504 11 78, e-mail: [email protected]).

TRAINING OF STUDENTS

Number Institution Country Period of participants International Atomic Energy Agency Egypt 1 3 months International Atomic Energy Agency Ghana 1 2 months Technical University of Łódź, Faculty of Chemistry, Poland 9 one-day course Institute of Applied Radiation Chemistry 144 EDUCATION

Number Institution Country Period of participants Poland 8 3 weeks University of Warsaw, Faculty of Chemistry 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

1 1 month Warsaw University of Technology, Faculty of Physics Poland 25 one-day course Warsaw University of Technology, Poland 1 2 months Faculty of Power and Aeronautical Engineering WAT Military University of Technology, Poland 3 1.5 month Department of Chemistry and New Technologies RESEARCH PROJECTS AND CONTRACTS 145

RESEARCH PROJECTS AND CONTRACTS

RESEARCH PROJECTS GRANTED BY THE NATIONAL SCIENCE CENTRE IN 2013

1. 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. 2. Radiochemical separation of arsenic from selenium and its potential usage in the generator 72Se/72As construction. supervisor: Ewelina Chajduk, Ph.D. 3. 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. 4. Participation of radiation chemistry in systems chemistry, especially in prebiotic chemistry. supervisor: Prof. Zbigniew P. Zagórski, Ph.D., D.Sc. 5. Functionalization of polyurethane surface by radiation-induced grafting (Preludium). supervisor: Marta Walo, Ph.D. 6. Nanozeolites as a carrier for radium in targeted therapy. supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc. 7. Paramagnetic centres generated radiolytically in molecular sieves exposed to carbon oxides. supervisor: Marcin Sterniczuk, Ph.D. 8. Des-acyl ghrelin analog as a new carrier of radionuclides and a potential radiopharmaceutical. supervisor: Grzegorz Wójciuk, Ph.D. 9. 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 2013

1. 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. 2. 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 2013

1. A mobile membrane installation for the enrichment of gas in methane (project INITECH). supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. 146 RESEARCH PROJECTS AND CONTRACTS 2. Elaboration and certification of new reference materials needed for obtaining European accreditation 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 2013

1. 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 TiO2 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 2013

1. Radiation supporting synthesis and curing of nanocomposites suitable for practical applications. supervisor: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT 2. Ageing diagnostics and prognostics of low-voltage I&C cables (ADVANCE). supervisor: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT 3. Multi-disciplinary biodosimetric tools to manage high scale radiological casualties (MULTI- BIODOSE). supervisor: Sylwester Sommer, Ph.D. 4. Implementing public participation approaches in radioactive waste disposal (IPPA). supervisor: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT 5. 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. 6. Advanced fuels for generation IV reactors: reprocessing and dissolution (ASGARD). supervisor: Andrzej Deptuła, Ph.D. 7. 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. 8. Formation, investigations and characterization of advanced nanoporous materials. supervisor: Bożena Sartowska, Ph.D. 9. Safety of actinide separation processes (SACSESS). supervisor: Prof. Jerzy Narbutt, Ph.D., D.Sc. 10. Transnational access to large infrastructure for a safe management of actinide (TALISMAN). supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. 11. 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. 12. 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 13. Studies on the methods of synthesis of hybrid porous metallo-organic nanomaterials of separation and sorption properties (NANOSYNT). supervisor: Wojciech Starosta, Ph.D. RESEARCH PROJECTS AND CONTRACTS 147 14. 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”

1. Scientific problem no. 3: Principles to secure fuel needs for the Polish nuclear energy. supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. 2. Scientific problem no. 4: Development of spent nuclear fuel and radioactive waste management techniques and technologies. supervisor: Leon Fuks, Ph.D. 3. Scientific problem no. 5: Participation criteria of the Polish industry in the development of nuclear energy. Study of the case. supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. 4. Scientific problem no. 6: Development of methods securing nuclear safety and radiological protection for the current and future needs of nuclear energy. supervisor: Prof. Marcin Kruszewski, Ph.D., D.Sc. 5. 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. 6. 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 2013

1. Radiation supporting synthesis and curing of nanocomposites suitable for practical applications (NANO-RAD). No. 16666 principal investigator: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT 2. Laboratory and feasibility study for industrial waste water effluent treatment by radiation. No. 16454 principal investigator: Zbigniew Zimek, Ph.D. 3. Application of hybrid nuclear techniques in the multiphases flows investigations in wastewater treatment and biogases production plants. No. 17366 principal investigator: Jacek Palige, Ph.D. 4. Based on starch-PVA system and cellulose reinforced active packaging materials for food prepared using of radiation modification (PackRad). No. 17493 principal investigator: Krystyna Cieśla, Ph.D., D.Sc., professor in INCT. 148 RESEARCH PROJECTS AND CONTRACTS 5. The study of the influence of the environmental factors on the isotopic compositions of dairy products. No. 18056 principal investigator: Ryszard Wierzchnicki, Ph.D.

IAEA TECHNICAL AND REGIONAL CONTRACTS IN 2013

1. Developing of an advanced industrial gamma scanning system with wireless data acquisition. POL/0/010 2. Regional Training on IAEA Validation and Process Control for Electron Beam Radiation Process- ing. RER/1/011 3. Supporting radiation synthesis and the characterization of nanomaterials for health care, environmental protection and clean energy applications. RER/8/014 4. Using nuclear techniques for the characterization and preservation of cultural heritage artefacts in the European Region. RER/8/015 5. Enhancing quality control methods and procedures for radiation technology. RER/8/017

PROJECTS WITHIN THE FRAME OF EUROPEAN UNION FRAME PROGRAMMES IN 2013

1. FP7 – EURATOM, Fission: Multi-disciplinary biodosimetric tools to manage high scale radiological casulaties (MULTIBIODOSE). principal investigator: Sylwester Sommer, Ph.D. 2. 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 3. FP7 – EURATOM, Fission: Implementing public participation approaches in radioactive waste disposal (IPPA). principal investigator: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT 4. 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 5. FP7 – EURATOM, Fission: Advanced fuels for generation IV reactors: reprocessing and dissolution (ASGARD). principal investigator: Andrzej Deptuła, Ph.D. 6. FP7 – EURATOM, Fission: Realizing the European Network in Biodosimetry (RENEB) principal investigator: Sylwester Sommer, Ph.D. 7. FP7 – Transnational access to large infrastructure for a safe management of actinide (TALIS- MAN). principal investigator: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. 8. FP7 – Safety of actinide separation processes (SACSESS). principal investigator: Prof. Jerzy Narbutt, Ph.D., D.Sc. 9. 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 10. 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 RESEARCH PROJECTS AND CONTRACTS 149 11. 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. 2. Attracting investments in plasma-based air and water cleaning technologies (PlasTEP+). supervisor: Andrzej Pawelec, Ph.D.

OTHER INTERNATIONAL RESEARCH PROGRAMMES IN 2013

1. European cooperation in the field of scientific and technical research. COST CM0703 Systems chemistry – Chemistry and molecular sciences and technologies. Participation of radiation chemistry in systems chemistry, especially in prebiotic chemistry (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

1. Analysis of the possibilities of uranium supply from domestic resources. supervisor: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT POIG.01.01.02-14-094/09 2. New generation of electrical wires modified by radiation. supervisor: Zbigniew Zimek, Ph.D. POIG.01.03.01-14-052/09 3. 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.01.03.01-14-054/09 150 LIST OF VISITORS TO THE INCT IN 2013

LIST OF VISITORS TO THE INCT IN 2013

1. Abel Trixie, International Atomic Energy Agency (IAEA), Austria, 18-20.10.2013 2. Armah Jonathan Okai, International Atomic Energy Agency (IAEA), Ghana, 28.04.-29.06.2013 3. Avivar Cerezo Jessica, Department of Chemistry, University of the Balearic Islands, Spain, 15-19.04.2013 4. Bonifacic Marija, Ruđer Bošković Institute, Zagreb, Croatia, 08-15.12.2013 5. Cerdà Victor, Department of Chemistry, University of the Balearic Islands, Spain, 15-19.04.2013 6. Dzeba Eva, Ruđer Bošković Institute, Zagreb, Croatia, 14-25.10.2013 7. Erdogan Huriye, ETH Zurich, Switzerland, 30.06.-04.07.2013 8. Etoom Mohammad Amer, International Atomic Energy Agency (IAEA), Jordan, 26-30.08.2013 9. Fuente Julio De la, Universidad de Chile, Santiago de Chile, Chile, 26.08.-25.09.2013 10. Humbert D., University of Paris, France, 18-20.10.2013 11. Kattan Munzer, International Atomic Energy Agency (IAEA), Syria, 26-30.08.2013, 24-30.11.2013 12. Lazunik Valentin, V.N. Karazin Kharkiv National University, Ukraine, 21-26.04.2013 13. Maalouf Manale, ETH Zurich Switzerland, 30.06.-04.07.2013 14. Mahmoudi Leila, ETH Zurich, Switzerland, 30.06.-04.07.2013 15. Maspoch Daniel, Catalan Institute of Nanotechnology, Bellatera, Spain, 15-19.04.2013 16. Miranda Enrigue Francisco, International Atomic Energy Agency (IAEA), Cuba, 10-23.11.2013 17. Molina Christian, ETH Zurich, Switzerland, 30.06.-04.07.2013 18. Mothersill Carmel, McMaster University, Hamilton, Canada, 12-15.09.2013 19. Orelovitch Oleg L., Joint Institute for Nuclear Research (JINR), Dubna, Russia, 07-19.05.2013 20. Popov Genadii, V.N. Karazin Kharkiv National University, Ukraine, 21-26.04.2013 21. Seymour Colin, McMaster University, Hamilton, Canada, 12-15.09.2013 22. Soliman Yasser Shaaban, International Atomic Energy Agency (IAEA), Egypt, 05.08.-04.11.2013 23. Tietze-Jaensch Holger, Institute of Energy and Climate Research – IEK-6, Forschungszentrum Jülich GmbH, Germany, 08-12.04.2013, 17-19.06.2013 24. Terzidis Michael, Institute of Organic Synthesis and Photoreactivity (ISOF), National Research Council, Bolonia, Italy, 01-08.10.2013 25. Vajda Nora, RadAnal. Ltd., Budapest, Hungary, 05-13.10.2013 26. Wordman Peter, University of Oxford, United Kingdom, 22-27.09.2013 THE INCT SEMINARS IN 2013 151

THE INCT SEMINARS IN 2013

1. Dr. Jessica Avivar Cerezo (Department of Chemistry, University of the Balearic Islands, Spain) How to automate radiochemical analysis exploiting flow techniques 2. 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) 3. 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) 4. 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) 5. Prof. dr. Victor Cerdà (Department of Chemistry, University of the Balearic Islands, Spain) Automation of analytical methods by flow techniques: history and new trends 6. Prof. Rajmund Dybczyński, Ph.D., D.Sc. (Institute of Nuclear Chemistry and Technology, War- szawa, Poland) 50 lat przygód z neutronową analizą aktywacyjną (Fifty years with neutron activation analysis) 7. 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) 8. 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 Re- search Centre, HIL) 9. Prof. Leszek Królicki, Ph.D., D.Sc. (Medical University of Warsaw, Warszawa, Poland) Terapia i diagnostyka chorób nowotworowych (Therapy and diagnosis of tumour diseases) 10. 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 11. 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) 12. Prof. Carmel Mothersill (McMaster University, Hamilton, Ontario, Canada) Radiation-induced non-targeted effects – adaptive responses or damaging low dose effects? 13. 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) 14. Prof. Colin Seymour (McMaster University, Hamilton, Ontario, Canada) Why is radiotherapy not delivering the expectations of radiobiology? 15. 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 152 THE INCT SEMINARS IN 2013 16. Prof. Peter Wardman (emeritus professor, formerly with the University of Oxford, United King- dom) Redox properties of free radicals and their effects on the rates of reactions 17. Prof. Kazimierz Piotr Zaleski, Ph.D. (Paris-Dauphine University, France) Przyszłość energetyki jądrowej na świecie (The future of nuclear power in the world) LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2013 153

LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2013

LECTURES

1. Bilewicz A. Emitery promieniowania korpuskularnego w celowanej terapii radionuklidowej (Emitters of corpus- cular radiation for target radiotherapy). II Letnia Szkoła Energetyki i Chemii Jądrowej, Warszawa, Poland, 16-20.09.2013. 2. Bilewicz A. Własności chemiczne pierwiastków transaktynowych (Chemical properties of transactinides). II Letnia Szkoła Energetyki i Chemii Jądrowej, Warszawa, Poland, 16-20.09.2013. 3. Boguski J., Przybytniak G. Changes in thermal properties of radiation aged cables. Symposium on Ageing Management of Nuclear Plant Cables, Moret sur Loing, France, 17-19.09.2013. 4. 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, 14-18.01.2013. 5. Brzóska K. Classical and modern methods in biological dosimetry. Regional Worshop on Regulatory Control of Radioactive Discharges to the Environment, Warszawa, Poland, 17-21.06.2013. 6. Chmielewski A.G. European energy mix tomorrow. CEE Meeting “Sustainable Energy for Europe”, Warszawa, Poland, 12-15.09.2013. 7. 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, 16-20.09.2013. 8. 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, 22-23.10.2013. 9. Chmielewski A.G. Environmental applications of ionizing radiation. International Meeting on Radiation Processing IMRP 17, Shanghai, China, 04-08.11.2013. 10. 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, 09.04.2013. 11. 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, 22-26.07.2013. 12. Ostyk-Narbutt J. Rozdzielanie jonów metali metodą ekstrakcji ciecz-ciecz. Podstawy termodynamiczne (Solvent extraction separations of metal ions. Thermodynamics). 154 LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2013

II Letnia Szkoła Energetyki i Chemii Jądrowej, Warszawa, Poland, 16-20.09.2013. 13. Ostyk-Narbutt J. Wydzielanie aktynowców mniejszościowych z odpadów jądrowych metodą ekstrakcji ciecz-ciecz (Sep- aration of minor actinides from nuclear waste by solvent extraction). II Letnia Szkoła Energetyki i Chemii Jądrowej, Warszawa, Poland, 16-20.09.2013. 14. 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, 03-07.03.2013. 15. 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, 15-20.09.2013. 16. 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, 05-07.05.2013. 17. Trojanowicz M. Pharmaceutical residues in the environment – importance, analysis and removal. International Conference on Environmental Pollution and Remediation, Toronto, Canada, 15-17.07.2013. 18. Zimek Z. Technology solutions: accelerators for sludge treatment. HEPTech Academia meets Industry: Environmental Applications of Accelerators, Warrington, United Kingdom, 08-09.07.2013. 19. Zimek Z. Technology solutions: accelerators for treating water. HEPTech Academia meets Industry: Environmental Applications of Accelerators, Warrington, United Kingdom, 08-09.07.2013.

SEMINARS

1. Gajda D. Dlaczego potrzebujemy nowego składowiska odpadów promieniotwórczych (Why do we need a new repository for radioactive wastes). Maria Skłodowska-Curie Museum, Warszawa, Poland, 21.09.2013. 2. 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, 27.05.2013. 3. 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, War- szawa, Poland, 12.04.2013. 4. Polkowska-Motrenko Halina Procedury przygotowania certyfikowanego materiału (Procedures of preparation of certified reference material). Faculty of Chemistry, University of Warsaw, Warszawa, Poland, 13.04.2013. 5. 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, 17.05.2013. AWARDS IN 2013 155

AWARDS IN 2013

1. Method for the disposal of radioactive wastes in structures of silica glasses (authors: Andrzej G. Chmie- lewski, Andrzej Deptuła, Magdalena Miłkowska, Wiesława Łada, Tadeusz Olczak) Gold Medal at the XVI Moscow International Salon of Inventions and Innovation Technologies “Archi- medes-2013”, Moscow, Russia, 02-05.04.2013 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 “Archi- medes-2013”, Moscow, Russia, 02-05.04.2013 Institute of Nuclear Chemistry and Technology 3. Method for the disposal of radioactive wastes in structures of silica glasses (authors: Andrzej G. Chmie- lewski, 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, 30.10.-03.11.2013 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, 30.10.-03.11.2013 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, 18-19.09.2013 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, 04-05.04.2013 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 pias- kowców 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, 17.05.2013 Dorota Gajda 13. Wydzielanie Tc-99m z aktywowanej w cyklotronie tarczy molibdenowej (Tc-99m separation from iso- topically enriched 100Mo via proton bombardment) Second award for the most interesting work presented at the X Warszawskie Seminarium Doktorantów Chemików ChemSession’13, Warszawa, Poland, 17.05.2013 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, 13-15.02.2013 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, 13-15.02.2013 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 Bra- ziewicz, 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, An- drzej 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 AWARDS IN 2013 157

23. 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 105Rh i 103mRh jako potencjalne prekursory radiofarmaceutyków terapeutycznych” (Organometallic and chelate complexes of 105Rh and 103mRh as potential precursors of therapeutic radiopharmaceuticals) Seweryn Krajewski 158 INDEX OF THE AUTHORS

INDEX OF THE AUTHORS

A Guzik Grzegorz P. 95 25, 48 Abramowska Anna H Ayers Tim 78 Harasimowicz Marian 48 B Herdzik-Koniecko Irena 48 Hobot Jan A. 78 Barlak Marek 76 31 Bańkowski Krzysztof I Bartłomiejczyk Teresa 58, 59 Bartosiewicz Iwona 48 Iwaneńko Teresa 57, 58 Biełuszka Paweł 48 J Bilewicz Aleksander 34, 37, 39 Bobrowski Krzysztof 17 Jakowiuk Adrian 100 Bojanowska-Czajka Anna 64 Janik Ireneusz 19 Boguski Jacek 25 Jastrzębski Jerzy 37 Borowiecka Sylwia 64 Jaworska Agnieszka 48 Brykała Marcin 52 Brzóska Kamil 57 K 21 Bugaj Anna Karlińska Magdalena 90 81 Bułka Sylwester Kiegiel Katarzyna 48 25 Buczkowski Marek Kołacińska Kamila 67 57, 58, 59, 60 Buraczewska Iwona Korzeniowska-Sobczuk Anna 90 19 C Kosno Katarzyna Kowalska Ewa 100 Cañete Alvaro 17 Koźmiński Przemysław 31 Celuch Monika 19 Krajewski Seweryn 39 Chajduk Ewelina 48 Królicki Leszek 31 Chmielewski Andrzej G. 81 Kruszewski Marcin 57, 58, 59 Choiński Jarosław 37 Kunicki-Goldfinger Jerzy J. 78 Chwastowska Jadwiga 48 Cieśla Krystyna 25 L 58, 59 D Lankoff Anna Leciejewicz Janusz 72 Danko Bożena 48 Leszczuk Agata 37 Deptuła Andrzej 52 Liśkiewicz Grażyna 96 Dudek Jakub 48 Dybczyński Rajmund 48 Ł 52 F Łada Wiesława Łuniewski Wojciech 31 Filipowicz Barbara 39 Łyczko Krzysztof 35 Frąckiewicz Kinga 48 Łyczko Monika 35, 37, 39 Freestone Ian C. 78 Fuente Julio De la 17 M 31, 42 Fuks Leon Majdan Marek 42 86, 87 G Malec-Czechowska Kazimiera McDonald Iain 78 Gajda Dorota 48 Michalik Jacek 21 Gilderdale-Scott Heather 78 Miecznik Jerzy B. 48 Gładysz-Płaska Agnieszka 42 Miłkowska Magdalena 52 Gniazdowska Ewa 31, 34 Mirkowski Jacek 19 Grądzka Iwona 57, 60 Mirkowski Krzysztof 23 Gumiela Magdalena 34 Miśkiewicz Agnieszka 45, 48 INDEX OF THE AUTHORS 159

Modzelewski Łukasz 100 Starosta Wojciech 72, 76 Sterniczuk Aneta 90 N Sterniczuk Marcin 21 Nichipor Henrietta 81 Stępkowski Tomasz 57 Nowicki Andrzej 23, 25 Stolarz Anna 37 Strzelczak Grażyna 21 O Sun Yongxia 81 48 Olczak Tadeusz 52 Szczygłów Katarzyna 37 Olszewska Wioleta 45, 48 Szkliniarz Katarzyna 58, 60 Oszczak Agata 42 Szumiel Irena

P T 25 Palige Jacek 100 Tchórzewski Paweł 64, 67 Pawelec Andrzej 82 Trojanowicz Marek 37 Pieńkos Jan 100 Trzcińska Agnieszka 37 Piotrowska Agata W Polkowska-Motrenko Halina 48 Pogocki Dariusz 19 Waliś Lech 76 Pruszyński Marek 39 Wasyk Iwona 58, 59 Przybytniak Grażyna 23 Wawszczak Danuta 52 Wąs Bogdan 37 R Wierzchnicki Ryszard 86, 87 Rogowski Marcin 52 Witman-Zając Sylwia 82 Wojewódzka Maria 57, 58, 59 S Wojtowicz Patryk 52 48 Sadło Jarosław 21 Wołkowicz Stanisław 35 Samczyński Zbigniew 48 Woźniak Krzysztof 57, 60 Sartowska Bożena 45, 76 Wójciuk Grzegorz 58, 60 Senatorski Jan 76 Wójciuk Karolina 58, 59, 60 Sikorska Katarzyna Z Smoliński Tomasz 52 Skotnicki Konrad 17 Zakrzewska-Kołtuniewicz Grażyna 45, 48 Sochanowicz Barbara 57, 60 Zielińska Barbara 48 Sommer Sylwester 58, 59 Zimek Zbigniew 81 Stachowicz Marcin 35 Zipper Wiktor 37 Stachowicz Wacław 95, 96 Zwolińska Ewa 81