INCT Annual Report 2013

157
INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY ANNUAL REPORT ANNUAL REPORT 2013 2013 ISSN 1425-204X

Transcript of INCT Annual Report 2013

Page 1: INCT Annual Report 2013

INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGYINSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY

ANNUAL REPORT ANNUAL REPORT 20132013

ISSN

142

5-20

4X

INSTITUTE OF NUCLEARCHEMISTRY AND TECHNOLOGY

Dorodna 16, 03-195 Warszawa, Polandphone: +48 22 504 12 05, fax: +48 22 811 15 32

e-mail: [email protected]

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ANNUAL REPORT2013

INSTITUTEOF NUCLEAR CHEMISTRY

AND TECHNOLOGY

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© Copyright by the Institute of Nuclear Chemistry and Technology, Warszawa 2014All rights reserved

EDITORSProf. Jacek Michalik, Ph.D., D.Sc.

Wiktor Smułek, Ph.D.Ewa Godlewska-Para, M.Sc.

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CONTENTS

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-ONEK. Skotnicki, K. Bobrowski, J. De la Fuente, A. Cañete 17

FREE RADICAL OXIDATION OF NICOTINE: A PULSE RADIOLYSIS STUDYK. 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 COMPOSITESG. Przybytniak, A. Nowicki, K. Mirkowski 23

PREPARATION OF THE FILMS BASED ON STARCH-PVA SYSTEM. PRELIMINARY STUDIES OF THE GAMMA IRRADIATION EFFECTSK. Cieśla, A. Abramowska, M. Buczkowski, P. Tchórzewski, A. Nowicki, J. Boguski 25

CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 29SYNTHESIS, PHYSICOCHEMICAL AND BIOLOGICAL EVALUATION OF NOVEL TECHNETIUM-99m LABELLED LAPATINIB AS A POTENTIAL TUMOUR IMAGING AGENTE. 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 CARRIERSE. 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 WASTEB. Filipowicz, S. Krajewski, M. Łyczko, M. Pruszyński, A. Bilewicz 39

SORPTION OF AMERICIUM(III) IONS ON THE BENTONITE OF THE VOLCLAY TYPEA. Oszczak, L. Fuks, A. Gładysz-Płaska, M. Majdan 42

THE STUDY OF SORPTION OF COBALT IONS ON THE RED CLAY AND ZEOLITESG. Zakrzewska-Kołtuniewicz, A. Miśkiewicz, W. Olszewska, B. Sartowska 45

ANALYSIS OF THE POSSIBILITY OF URANIUM SUPPLY FROM DOMESTIC RESOURCESG. 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 WASTESD. Wawszczak, A. Deptuła, W. Łada, T. Smoliński, T. Olczak, M. Brykała, P. Wojtowicz, M. Rogowski, M. Miłkowska 52

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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 ASSAYA. 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 DOSES. 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 CELLSI. Grądzka, I. Buraczewska, K. Sikorska, B. Sochanowicz, I. Szumiel, K. Wójciuk, G. Wójciuk 60

LABORATORY OF NUCLEAR ANALYTICAL METHODS 63RADIOLYTIC REMOVAL OF SELECTED PHARMACEUTICALS AND BISPHENOL A FROM WATERS AND WASTESA. Bojanowska-Czajka, S. Borowiecka, M. Trojanowicz 64

DETERMINATION OF URANIUM IN FLOW-INJECTION SYSTEM WITH SPECTROPHOTOMETRIC DETECTIONK. Kołacińska, M. Trojanowicz 67

LABORATORY OF MATERIAL RESEARCH 71STRUCTURAL STUDIES IN Li(I) ION COORDINATION CHEMISTRYW. 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 BEAMSB. 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 TECHNOLOGYJ.J. Kunicki-Goldfinger, I.C. Freestone, I. McDonald, J.A. Hobot, H. Gilderdale-Scott, T. Ayers 78

POLLUTION CONTROL TECHNOLOGIES LABORATORY 79PRELIMINARY MODELLING STUDY OF NOx REMOVAL FROM OIL-FIRED OFF-GAS UNDER ELECTRON BEAM IRRADIATIONY. 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 PLANTA. Pawelec, S. Witman-Zając 82

STABLE ISOTOPE LABORATORY 85DETERMINATION OF SULPHUR ISOTOPIC COMPOSITION OF FOOD PRODUCTSR. Wierzchnicki, K. Malec-Czechowska 86

NEW APPROACH OF THE ISOTOPIC METHOD FOR JUICE AUTHENTICITY CONTROLR. Wierzchnicki, K. Malec-Czechowska 87

LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES 89RECALIBRATION OF DOSIMETER FILMS CTAA. Korzeniowska-Sobczuk, A. Sterniczuk, M. Karlińska 90

LABORATORY FOR DETECTION OF IRRADIATED FOOD 93STABILITY OF THE EPR SIGNAL PRODUCED BY IONIZING RADIATION IN DRIED FRUITSG.P. Guzik, W. Stachowicz 95

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QUANTITY AND QUALITY OF MINERAL FRACTION IN THERMOLUMINESCENCE METHOD FOR THE DETECTION OF IRRADIATION IN ALIMENTARY ARTICLESW. Stachowicz, G. Liśkiewicz 96

LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS 99 DIAGNOSTICS OF BIOGAS INSTALLATION BY GAMMA RADIATIONA. 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

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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

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7GENERAL INFORMATION

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 chem-istry, 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, ra-diation chemistry, nuclear chemical engineering and technology, application of nuclear methods in material engineering and process engineering, radioanalytical techniques, de-sign and production of instruments based on nuclear techniques, environmental research, cellular radiobiology, etc. The results of work at the INCT have been implemented in vari-ous branches of the national economy, particularly in industry, medicine, environmental protection and agriculture. Basic research is focused on: radiochemistry, chemistry of iso-topes, 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 ap-plication, 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 poss-ible 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 coopera-• tion with the Polish Geological Institute – NRI); Development of a multi-parametric triage approach for an assessment of radiation ex-• posure in a large -scale radiological emergency;New generation of electrical wires modified by radiation.•

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8 GENERAL INFORMATION

The INCT is the leading institute in Poland regarding the implementation of nu-clear energy related EU projects. Its expertise and infrastructure was the basis for partici-pation 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 radio-• logical 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 be-• haviors 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 acti-• nide.

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 publica-tions 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 achieve-ments – implementation of new measurement methods related to the tightness of instal-lations 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 or-ganic compounds from gases emitted to the atmospherethird 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 scien-tific meetings.

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9MANAGEMENT OF THE INSTITUTE

MANAGEMENT OF THE INSTITUTE

MANAGING STAFF OF THE INSTITUTE

DirectorProf. Andrzej G. Chmielewski, Ph.D., D.Sc.

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

Deputy Director of FinancesWojciech Maciąg, M.Sc.

Deputy Director of Maintenance and MarketingRoman Janusz, M.Sc.

Accountant GeneralMaria Małkiewicz, M.Sc.

HEADS OF THE INCT DEPARTMENTS

Centre for Radiation Research and Technology• Zbigniew Zimek, Ph.D.

Centre for Radiochemistry and Nuclear • ChemistryProf. Jerzy Ostyk-Narbutt, Ph.D., D.Sc.

Centre for Radiobiology and Biological • DosimetryProf. Marcin Kruszewski, Ph.D., D.Sc.

Laboratory of Nuclear Control Systems • and MethodsJacek Palige, Ph.D.

Laboratory of Material Research• Wojciech Starosta, Ph.D.

Laboratory of Nuclear Analytical Methods• Halina Polkowska-Motrenko, Ph.D., D.Sc, professor in INCT

Stable Isotope Laboratory• Ryszard Wierzchnicki, Ph.D.

Pollution Control Technologies Laboratory• Andrzej Pawelec, Ph.D.

Laboratory for Detection of Irradiated Food• Wacław Stachowicz, Ph.D.

Laboratory for Measurements of Technological• DosesAnna Korzeniowska-Sobczuk, M.Sc.

SCIENTIFIC COUNCIL (2011-2015)

Prof. 1. Grzegorz Bartosz, Ph.D., D.Sc.University of Łódź

2. Prof. Aleksander Bilewicz, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology

Prof. 3. Krzysztof Bobrowski, Ph.D., D.Sc.(Vice-chairman)Institute of Nuclear Chemistry and Technology

4. Marcin Brykała, Ph.D.Institute of Nuclear Chemistry and Technology

5. Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology

6. Andrzej Chwas, M.Sc.Ministry of Economy

7. Jadwiga Chwastowska, Ph.D., D.Sc., professor in INCTInstitute of Nuclear Chemistry and Technology

8. Krystyna Cieśla, Ph.D., D.Sc., professor in INCTInstitute of Nuclear Chemistry and Technology

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9. Jakub Dudek, Ph.D.Institute of Nuclear Chemistry and Technology

Prof. 10. Rajmund Dybczyński, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology

Prof. 11. Zbigniew Florjańczyk, Ph.D., D.Sc.(Chairman)Warsaw University of Technology

Prof. 12. Zbigniew Galus, Ph.D., D.Sc.University of Warsaw

Prof. 13. Henryk Górecki, Ph.D., D.Sc.Wrocław University of Technology

Prof. 14. Leon Gradoń, Ph.D., D.Sc.Warsaw University of Technology

15. Jan Grodkowski, Ph.D., D.Sc., professor in INCTInstitute of Nuclear Chemistry and Technology

16. Edward Iller, Ph.D., D.Sc., professor in NCBJNational Centre for Nuclear Research

17. Adrian Jakowiuk, M.Sc.Institute of Nuclear Chemistry and Technology

Prof. 18. Marcin Kruszewski, Ph.D., D.Sc.(Vice-chairman)Institute of Nuclear Chemistry and Technology

19. Anna Lankoff, Ph.D., D.Sc., professor in INCTInstitute of Nuclear Chemistry and Technology

Prof. 20. Marek Wojciech Lankosz, Ph.D., D.Sc.AGH University of Science and Technology

Prof. 21. Janusz Lipkowski, Ph.D., D.Sc.Institute of Physical Chemistry, Polish Academy of Sciences

22. Zygmunt Łuczyński, Ph.D.Institute of Electronic Materials Technology

Prof. 23. Jacek Michalik, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology

24. Wojciech Migdał, Ph.D., D.Sc., professor in INCTInstitute of Nuclear Chemistry and Technology

Prof. 25. Jarosław Mizera, Ph.D., D.Sc. Warsaw University of Technology

Prof. 26. Jerzy Ostyk-Narbutt, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology

27. Andrzej Pawlukojć, Ph.D., D.Sc., professor in INCTInstitute of Nuclear Chemistry and Technology

28. Dariusz Pogocki, Ph.D., D.Sc., professor in INCTInstitute of Nuclear Chemistry and Technology

29. Halina Polkowska-Motrenko, Ph.D., D.Sc., professor in INCTInstitute of Nuclear Chemistry and Technology

30. Grażyna Przybytniak, Ph.D., D.Sc., professor in INCTInstitute of Nuclear Chemistry and Technology

Prof. 31. Janusz Rosiak, Ph.D., D.Sc.Technical University of Łódź

32. Lech Waliś, Ph.D.Institute of Nuclear Chemistry and Technology

33. Maria Wojewódzka, Ph.D.Institute of Nuclear Chemistry and Technology

34. Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT(Vice-chairman)Institute of Nuclear Chemistry and Technology

35. Zbigniew Zimek, Ph.D.Institute of Nuclear Chemistry and Technology

Prof. 1. Sławomir Siekierski, Ph.D.

Prof. 2. Zbigniew Szot, Ph.D., D.Sc.

Prof. 3. Irena Szumiel, Ph.D., D.Sc.

Prof. 4. Zbigniew Paweł Zagórski, Ph.D., D.Sc.

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

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11MANAGEMENT OF THE INSTITUTE

DIRECTOR

ORGANIZATION SCHEME

Scientific Council

Laboratory of Nuclear Control Systems and Methods

Deputy Director for Research and Development

Centre for Radiobiology and Biological Dosimetry

Centre for Radiochemistry and Nuclear Chemistry

Deputy Director of Maintenance and Marketing

Accountant General

Laboratory of Nuclear Analytical Methods

Stable Isotope Laboratory

Pollution Control Technologies Laboratory

Laboratory for Detection of Irradiated Food

Laboratory of Material Research

Laboratory for Measurements of Technological Doses

Centre for Radiation Research and Technology

Deputy Director of Finances

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SCIENTIFIC STAFF

PROFESSORS

Bilewicz Aleksander1. radiochemistry, inorganic chemistry

Bobrowski Krzysztof2. radiation chemistry, photochemistry, biophysics

Chmielewski Andrzej G.3. chemical and process engineering, nuclear chemical engineering, isotope chemistry

Chwastowska Jadwiga, 4. professor in INCTanalytical chemistry

Cieśla Krystyna, 5. professor in INCTphysical chemistry

Dobrowolski Jan6. spectroscopy and molecular modelling

Dybczyński Rajmund7. analytical chemistry

Grigoriew Helena, 8. professor in INCTsolid state physics, diffraction research of non-crystalline matter

Grodkowski Jan, 9. professor in INCTradiation chemistry

Kruszewski Marcin10. radiobiology

Lankoff Anna, 11. professor in INCTbiology

Leciejewicz Janusz Tadeusz12. crystallography, solid state physics, material science

Michalik Jacek13. radiation chemistry, surface chemistry, radical chemistry

Migdał Wojciech, 14. professor in INCTchemistry, science of commodies

Ostyk-Narbutt Jerzy15. radiochemistry, coordination chemistry

Pawlukojć Andrzej, 16. professor in INCTchemistry

Pogocki Dariusz, 17. professor in INCTradiation chemistry, pulse radiolysis

Polkowska-Motrenko Halina, 18. professor in INCTanalytical chemistry

Przybytniak Grażyna, 19. professor in INCTradiation chemistry

Siekierski Sławomir20. physical chemistry, inorganic chemistry

Szumiel Irena21. cellular radiobiology

Trojanowicz Marek22. analytical chemistry

Zagórski Zbigniew23. physical chemistry, radiation chemistry, electrochemistry

Zakrzewska-Kołtuniewicz Grażyna, 24. professor in INCTprocess and chemical engineering

SENIOR SCIENTISTS (Ph.D.)

Bartłomiejczyk Teresa1. biology

Bojanowska-Czajka Anna2. chemistry

Borowik Krzysztof3. chemistry

Brykała Marcin4. chemistry

Brzóska Kamil5. biochemistry

Buczkowski Marek6. physics

Chajduk Ewelina7. chemistry

Danilczuk Marek8. chemistry

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13SCIENTIFIC STAFF

Deptuła Andrzej9. chemistry

Dobrowolski Andrzej10. chemistry

Dudek Jakub11. chemistry

Fuks Leon12. chemistry

Głuszewski Wojciech13. chemistry

Gniazdowska Ewa14. chemistry

Grądzka Iwona15. biology

Harasimowicz Marian16. technical nuclear physics, theory of elementary particles

Herdzik-Koniecko Irena17. chemistry

Kciuk Gabriel18. chemistry

Kiegiel Katarzyna19. chemistry

Kierzek Joachim20. physics

Kocia Rafał21. chemistry

Kornacka Ewa22. chemistry

Koźmiński Przemysław23. chemistry

Krajewski Seweryn24. chemistry

Kunicki-Goldfinger Jerzy25. conservator/restorer of art

Latek Stanisław26. nuclear physics

Lewandowska-Siwkiewicz Hanna27. chemistry

Łyczko Krzysztof28. chemistry

Łyczko Monika29. chemistry

Majkowska-Pilip Agnieszka30. chemistry

Męczyńska-Wielgosz Sylwia31. chemistry

Mirkowski Jacek32. nuclear and medical electronics

Miśkiewicz Agnieszka33. chemistry

Nowicki Andrzej34. organic chemistry and technology, high-temperature technology

Ostrowski Stanisław35. chemistry

Palige Jacek36. metallurgy

Pawelec Andrzej37. chemical engineering

Pruszyński Marek38. chemistry

Ptaszek Sylwia39. chemical engineering

Rafalski Andrzej40. radiation chemistry

Roubinek Otton41. chemistry

Sadło Jarosław42. chemistry

Samczyński Zbigniew43. analytical chemistry

Sartowska Bożena44. material engineering

Skwara Witold45. analytical chemistry

Sochanowicz Barbara46. biology

Sommer Sylwester47. radiobiology, cytogenetics

Stachowicz Wacław48. radiation chemistry, EPR spectroscopy

Starosta Wojciech49. chemistry

Sterniczuk Macin50. chemistry

Strzelczak Grażyna51. radiation chemistry

Sun Yongxia52. chemistry

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Szreder Tomasz53. chemistry

Waliś Lech54. material science, material engineering

Walo Marta55. chemistry

Warchoł Stanisław56. solid state physics

Wawszczak Danuta57. chemistry

Wierzchnicki Ryszard58. chemical engineering

Wiśniowski Paweł59. radiation chemistry, photochemistry, biophysics

Wojewódzka Maria60. radiobiology

Wójciuk Grzegorz61. chemistry

Wójciuk Karolina62. chemistry

Zimek Zbigniew63. electronics, accelerator techniques, radiation processing

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CENTRE FOR RADIATION RESEARCH

AND TECHNOLOGYElectron 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 tech-nology 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 com-plemented by steady-state radiolysis, stop-flow absorption spectrofluorimetry and product analysis using chromatographic methods. Studies on radiation-induced intermediates are dedi-cated 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 reso-nance (ENDOR), also focused on research problems in nanophase chemistry and radiation-in-duced cross-linking of selected and/or modified polymers and copolymers.

This research has a wide range of potential applications, including creating more environ-mentally 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 ap-plication for: sterilization medical devices, pharmaceutical materials, food products shelf-life extension, polymer advanced materials, air pollution removal technology and others. EB ac-celerators replace frequently thermal and chemical processes for cleaner, more efficient, lower-cost manufacturing. EB accelerators sterilize products and packaging, improve the per-formance of plastics and other materials, and eliminate pollution for industries such as phar-maceutical, 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 sup-ported 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.•

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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.

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17CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY

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, Chile2/ Pontificia Universidad Católica de Chile, Chile

Quinoxalin-2-ones are the class of compounds showing a variety of pharmacological properties, such as antimicrobial [1], antiviral [2], anti-inflam-matory [3], antithrombotic [4, 5], anticancer [6-9] activity.A key factor decisive about their biological activity is a substitution at the carbon-3 in the pyrazine ring and at the carbons 6 and 7 in the benzene ring in a primary quinoxalin-2-one structure (Chart 1). Nearly all biologically active derivatives are sub-stituted in these specific positions.

The structure activity relationship (SAR) studies have revealed that quinoxalin-2-ones derivatives bound to proteins receptors are generally located close to the adenosine triphosphate (ATP) bind-ing pocket [6, 10], e.g. in cyclin-dependent kinases (Cdk). The fact that these compounds are bound in the very specific position in proteins may have serious consequences in their interactions with

either amino acid residues or radicals derived from them. Certain amino acid residues – tyrosine (Tyr), tryptophan (Trp), and cysteine (Cys) are particu-larly vulnerable to oxidation. Therefore, the radical cations derived from quinoxalin-2-ones can modify these amino acids which are reasonably good elec-tron donors and can be oxidized to tyrosyl (TyrO●), tryptophyl (Trp●), and thiyl (Cys●) radicals, respec-tively. On the other hand, these radicals are rea-sonably good electron acceptors and can act po-tentially as oxidants.

Reactive oxygen and nitrogen species (ROS and RNS) are produced in excess during the oxi-dative and nitrosative stress in living organisms. ROS and RNS can react with various biological targets (proteins, DNA, lipids), the most impor-tant of them being proteins and peptides because of their high concentration in cells [11]. In prin-ciple, oxidation and reduction processes in pro-teins can occur everywhere and involve the protein backbone, amino acid residues and also intercalat-ed molecules (e.g. quinoxalin-2-ones). The primary steps leading to these modifications are extremely fast, consist of one electron loss and very often a subsequent one electron capture, resulting in cre-ation of very reactive transients (radicals and radi-cal ions) which are responsible for secondary re-

Chart 1. Structural formula of quinoxalin-2-one.

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.

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actions. For these reasons it is important to char-acterize spectral properties of transients derived from quinoxalin-2-ones (those derived from amino acids are mostly known) and to measure kinetic parameters of the primary and secondary reac-tions involving quinoxalin-2-ones and amino acid residues. These reactions lead to production of various free radicals, including those derived either from amino acids or quinoxalin-2-ones.

Radical oxidation and reduction of 3-methyl-quinoxalin-2-one and kinetics of its reactions with hydroxyl radicals (●OH) and solvated electrons (eaq

−), respectively, were studied by pulse radiolysis technique coupled with the time-resolved UV/Vis spectrophotometric detection system. Reactions were studied in aqueous solutions saturated either with N2O or argon.

Pulse radiolysis studies in N2O-saturated aque-ous solution at pH 8 has been performed in order to check whether 3-methylquinoxalin-2-one is able to scavenge ●OH radicals. ●OH-induced oxidation generally leads to one-electron oxidation prod-ucts. However, it is well known, that the formation of OH adducts is another possible reaction path-way. Transient absorption spectra observed 4 μs

after the pulse are characterized by two distinct absorption maxima located at λ = 370 and 460 nm (Fig.1). The first one is stable within 1.5 ms time domain. Complementry steady-state γ-radiolysis ex-periments revealed that this absorption is stable and is associated with a stable reaction product. The second-order rate constants kQ+OH• were de-termined from the kinetic traces at 370 and 460 nm in pseudo first-order conditions and were found

to be equal to k370 = 4.6 ± 0.2 × 109 M−1s−1 and k460 = 4.4 ± 0.2 × 109 M−1s−1.

Reaction with eaq− has been performed in

Ar-saturated aqueous solution containing tert-bu-tanol at pH 8. One-electron reduction of 3-methyl-quinoxalin-2-one leads to the formation of at least two products, with the respective absorption maxi-ma at λ = 370 and 430 nm (Fig.2). The second--order rate constant kQ+e was determined from the kinetic traces at 720 nm (absorption maximum of solvated electron absorption in water) in pseudo first-order conditions and was found to be equal to k720 = 2.8 ± 0.2 × 1010 M−1s−1.

Additional experiments performed in different pH values and with similar compounds allow to as-sume that one-electron reduction results in the for-

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.

Scheme 1. A proposed mechanism for one-electron reduction of 3-methylquinoxalin-2-one.

N H

N

O

C

N H

N -

O

C

N H

N H

O e solv H +

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19CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY

mation of a radical anion followed by a rapid pro-tonation to a neutral protonated radical. Proposed reaction mechanism is presented in Scheme 1.

Obtained results indicated that quinoxalin-2--ones are able to scavenge OH● radicals with high rate constants (k = 4.5 × 109 M−1s−1) which is a very promising result for their possible medical use. One-electron reductions leads to the formation of radical anion and protonated radical with a rate constant close to a diffusion control (k = 2.8 × 1010 M−1s−1). Further studies concerning interactions of quinoxalin-2-ones with amino acids will be per-formed.

References[1]. Ajani O.O. et al.: Bioorg. Med. Chem., 18(1), 214-221

(2010).[2]. Xu B.L. et al.: Bioorg. Med. Chem., 17(7), 2767-2774

(2009).

[3]. El-Sabbagh O.I. et al.: Med. Chem. Res., 18(9), 782-797 (2009).

[4]. Ries U.J. et al.: Bioorg. Med. Chem. Lett., 13(14), 2297-2302 (2003).

[5]. Willardsen J.A. et al.: J. Med. Chem., 47(16), 4089-4099 (2004).

[6]. Hirai H. et al.: Invest. New Drugs, 29(4), 534-543 (2011).

[7]. Kotb E.R. et al.: Phosphorus, Sulfur Silicon Relat. Elem., 182(5), 1119-1130 (2007).

[8]. Lawrence D.S., Copper J.E., Smith C.D.: J. Med. Chem., 44(4), 594-601 (2001).

[9]. Yuan H.Y. et al.: Med. Chem. Res., 18(8), 671-682 (2009).

[10]. Mori Y. et al.: Chem. Pharm. Bull., 56(5), 682-687 (2008).

[11]. Dean R.T. et al.: Free Radical Biol. Med., 11(2), 161-168 (1991).

FREE RADICAL OXIDATION OF NICOTINE: A PULSE RADIOLYSIS STUDY

Katarzyna Kosno, Monika Celuch, Jacek Mirkowski, Ireneusz Janik, Dariusz Pogocki

Nicotine (3-(1-methyl-2-pyrrolidinyl)pyridine) is a commonly known natural alkaloid present mainly in tobacco plants and is characterized by a stimu-lant action. It interacts with the nicotinic acetyl-choline receptors and cause the release of many neurotransmitters responsible for mood (e.g. nor-adrenaline, serotonin and dopamine). This is the main reason of its strong addictive power. How-ever, nicotinic stimulation has also positive effects as it is used in the therapy of some neurodegen-erative disorders and diseases [1].

Because of its antioxidative properties, nico-tine has the potential to be widely used as a free radical scavenger. It can be used to protect nerve cells in some major neurodegenerative disorders and diseases such as Alzheimer’s and Parkinson’s diseases, Tourette’s syndrome or schizophrenia. Neurodegeneration associated with these diseases is accompanied by an extensive oxidative stress, caused by the imbalance in the production of re-active oxygen species and the biological system’s inability to detoxify them. Nervous tissue is con-tinuously exposed to the presence of toxic oxygen radicals beyond a threshold for proper antioxidant neutralization. Nicotine can easily pass through the blood-brain barrier and prevent this destruc-tive radical action thanks to its antioxidative prop-erties. There are some evidence that nicotine can react with the most dangerous ●OH radical pro-ducing neutral or less aggressive radical products [2]. However, it has not been confirmed so far and more data about the mechanism of nicotine radi-cal processes should be obtained. The knowledge about the reactions kinetic is also important, be-cause the rate of nicotine radical reactions need to be high enough to exclude competitive reactions.

Nicotine molecule is made of two rings: aro-matic pyridine and aliphatic pyrrolidine with chi-ral carbon C2’ atom (Fig.1). The ●OH radical re-

acts through a variety of reaction mechanisms, including direct electron transfer, hydrogen ab-straction, and addition to unsaturated bonds. In case of nicotine every three pathways are possible.

Considering the electron density and favourable energetic effect, substitution occurs mainly at the meta position, the most probable product of hy-drogen abstraction is radical located at a chiral carbon and the cation radical is formed at pyrroli-dine nitrogen. However, nicotine is a weak base with a pKa1 of 8.02 (pKa2 = 3.12) in aqueous solu-tion at 25oC [3] and the protonation state has the influence on its radical reactions. According to DFT calculations, protonation of pyrrolidine ni-trogen increases the dissociation enthalpy of the C2’-H bond. Some reaction pathways can be even blocked in acidic solutions.

The main experimental technique used to study the radical oxidation of nicotine was pulse radio-lysis coupled with a time-resolved UV/Vis detec-tion system, which enables to study molecular processes close to or even beyond the diffusion controlled reaction limit. Experiments were per-formed with the LAE 10 [4] (Institute of Nuclear Chemistry and Technology) and Titan Beta Model TBS-8/16-1 [5] (Notre Dame Radiation Labora-tory) linear accelerators. Analysis was done in the broad range of pH giving data for protonated and unprotonated forms of nicotine. Using pyridine

3

2

4

N1

5

6

2' N1'

3'

5'

4'

CH36'

Fig.1. Structural formula of nicotine.

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20 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY

and N-methylpyrrolidine as nicotine model com-pounds enabled to divide radical reactions into occurring with aromatic and aliphatic part of the molecule.

In order to check if nicotine oxidation can pro-ceed with single-electron transfer, its reaction with azide radical has been studied. Azide radical is a strong one-electron oxidant and it can be read-ily prepared radiolytically by ●OH oxidation of azide anions in aqueous solution (Fig.2A,B). It ex-hibits moderate absorption only in the UV range

with a sharp maximum at 274 nm. Reaction of one-electron oxidation can only occur with the aliphatic nitrogen (Fig.2C). Azide radical will not react with aromatic ring, because according to data obtained by Schuler, the rate of its reaction with pyridine is lower than 3 × 105 M–1s–1 [6]. Al-though there are no reports that azide radicals re-acts by hydrogen abstraction, theoretically in fa-vourable reaction conditions there is such a possi-bility (Fig.2D). The bond dissociation energy for a bond between hydrogen atom and asymmetric car-

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 nico-tine concentration.

300 350 400 450 500 550

2.5x103

5.0x103

7.5x103

1.0x104

1.3x104

0 2 4 6 8 100

1x105

2x105

3x105

4x105

5x105k(Nic + N3.) = 5.23 x 107 M-1s -1

k app (

s-1)

[Nic] (10-3mol dm-3)

1 mM Nic + 10 mM NaN3 pH 10 pH 5.6

G ×

ε [m

2 /J]

λ [nm]

A

B

C

D

Fig.2. Reaction scheme for the oxidation of nicotine by azide radical.

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bon in nicotine molecule is about 25 kJ/mol lower than the N-H bond dissociation energy in hydra-zoic acid.

The reaction of nicotine with azide radical was studied for two protonation states of the pyrro-lidinyl nitrogen. Transients obtained in the reac-tion of unprotonated nicotine at pH 10 gave spec-trum with one distinct absorption band with λmax = 330 nm and a broad absorption band with λmax ca. 460 nm, both growing with the same rate (Fig.3). It is very similar to the spectrum obtained for nico-tine reaction with hydroxyl radicals, what may sug-gest that we also observe here mainly radical at chiral carbon. For the protonated aliphatic nitro-gen at pH 5.6, the absorption at 330 nm is almost 20 times lower and we observed a weak band at

280 nm, which can be assigned to azide radicals. This indicates that azide radical does not react with protonated form of nicotine, because the electron transfer is blocked. Hydrogen abstraction from chiral carbon is also inhibited because of the higher C*–H bond dissociation energy than in un-protonated form. The reaction with the unproto-nated form is second order with a rate constant of 5 × 107 M–1s–1.

To confirm that azide radical can oxidize the pyrrolidinyl nitrogen, we studied its reaction with N-methylpyrrolidine in the presence of trypto-phan. Tryptophan is a natural amino acid existing in proteins. Its reaction with azide radical is well known (Fig.4A). It proceeds with electron trans-fer and generates radicals absorbing at 320 and 520 nm with high extinction coefficients. The rate of this reaction at pH 11.4 is 4.5 × 109 M–1s–1. Azide

radical should react with N-methylpyrrolidine also by electron transfer (Fig.4B). After the pyrrolidinyl nitrogen protonation this way of reaction is block-ed. N-methylpyrrolidine has a pKa of 10.46, so the experiments were done at pH 11.4, where there is about 90% of the unprotonated form.The kinetic studies of the 520 nm absorbance changes have been done using a competition method. N-methylpyrrolidine will compete with tryptophan and react with azide radicals, what causes a decrease in the absorbance with increas-ing alkaloid concentration. The rate constant for the reaction of N-methylpyrrolidine with azide radical was determined to be 5.6 × 107 M–1s–1. Such a low reaction rate suggest that the electron trans-fer will have a minor contribution to the mecha-

nism of nicotine reaction with azide radical. Ob-tained results indicate that azide radical, although is a well-known one-electron oxidant, in energeti-cally favourable conditions it can also abstract hy-drogen atoms.

References[1]. Pogocki D., Ruman T., Danilczuk M., Danilczuk M.,

Celuch M., Wałajtys-Rode E.: Eur. J. Pharm., 563, 18-39 (2007).

[2]. Wang S.-L., Wang M., Sun X.-Y., Li W., Ni Y.: Spec-trosc. Spect. Anal., 23, 481-483 (2003).

[3]. CRC Handbook of Chemistry and Physics on CD-ROM. CRC Press, 2004.

[4]. Bobrowski K.: Nukleonika, 50, 3, 67-76 (2005). [5]. Hug G.L., Wang Y., Schöneich Ch., Jiang P.-Y., Fessen-

den R.W.: Radiat. Phys. Chem., 54, 559-566 (1999). [6]. Schuler R.H., Alfassi Z.B.: J. Phys. Chem., 89, 3359-3363

(1985).

Fig.4. Mechanism of the azide radical reaction with tryptophan and N-methylpyrrolidine.

Removal of radionuclides from aqueous nuclear wastes is a challenging task for the management of waste disposal. Sorbents containing radionu-clides are exposed to high level of radiation dose which generates changes in sorbent structure. It is expected that new sorption materials will be not

only effective and highly selective but also resis-tant to radiation for very long time [1-3].

In this report we present the studies on para-magnetic species formed in γ-irradiated saponite and crystalline sitinakite (Fig.1) containing ex-changeable Ag+ cations. Saponite is a layered clay

RADIATION EFFECTS IN SORPTION MATERIALS WITH Ag+ CATIONS – EPR STUDY

Anna Bugaj, Jarosław Sadło, Marcin Sterniczuk, Grażyna Strzelczak, Jacek Michalik

A

B

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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 syn-thetic titanosilicate IONSIV* IE-911. Both mate-rials are successfully used for sorption of radionu-clides from Fukushima radioactive wastewaters.

Electron paramagnetic resonance (EPR) spec-troscopy is very useful tool for characterization of paramagnetic species like radicals and paramag-netic atoms or cations generated by radiation in sorbent materials.

Fission product radioisotopes can get into re-actor primary cooling system as a result of zirco-nium cladding damage. Silver 110mAg together with 60Co, 137Cs and others belongs to long-lived radio-isotopes which for safety reasons should be re-moved from cooling water. Sorption on micropo-rous materials like zeolites or clays is usually used for that purpose. For model studies of radiation changes of metal valence state by EPR we use silver as an exchangeable cation. Both silver iso-topes 107Ag and 109Ag have nuclear spin ½ and large magnetic moments which usually makes possible to identify paramagnetic silver species like silver atoms, cations and clusters produced by radiation.

Saponite and sitinakite samples after degas-sing on vacuum line at room temperature or dehy-drating at 120oC were irradiated at 77 K with dose of 10 kGy in Co-60 source. EPR spectra were measured using EPR Bruker X-band ESP 300 spectrometer in the temperature range 100-280 K. In all cases samples before irradiation did not show any EPR signals. The EPR spectra of γ-irradiated sitinakite mea-sured at 130 K are presented in Fig.2.

Dehydrated Na-sitinakite shows strong aniso-tropic singlet T with orthorhombic symmetry of g-factor: g1 = 2.003, g2 = 2.011 and g3 = 2.024 (Fig.2a). Hydrated Na-sitinakite sample shows the same signal. Similar EPR signal was recorded in TiO2 colloids and was assigned to the hole trap-ped on the colloidal surface – Ti4+O2–Ti4+O*– [4]. In Ag-sitinakite both in hydrated and dehydrated form, signal T is also recorded but then is accom-panied by strong signals of paramagnetic silver species. In hydrated Ag-sitinakite the most pro-nounced signal is anisotropic doublet with g⊥ = 2.039, gII = 2.242, A⊥ = 3.2 mT, AII = 4.0 mT (Fig.2b). Doublet with similar g-factors and hy-perfine splitting values was earlier observed after irradiation of hydrated zeolite A and was assigned to Ag2+ divalent cation [5]. In dehydrated Ag-siti-nakite perpendicular component of Ag2+ signal shows additional splittings which indicate the over-lapping of Ag2+ EPR line with unknown signal (Fig.2c). We speculate that three lines labelled x with splitting ~10 mT belongs to the same signal but at this moment we are unable to identify its origin. Doublet H with hyperfine splitting equal ~50 mT present in all spectra in Fig.2 represents hydrogen atoms trapped in spectrosil tubings.

Figure 3 shows the EPR spectra of γ-irradiated samples of hydrated saponite synthetized in NIMS, Tsukuba, Japan. The exchangeable cations were in-troduced into gel before synthesis.

In Na-saponite (Fig.3a) three major lines W, Y, Z showing asymmetric shape and additional split-ting represent unidentified radiation-induced para-magnetic defects in clay layers. Moreover, in the

Fig.2. EPR spectra at 130 K of γ-irradiated sitinakite: (a) dehydrated sample with Na+ cations, (b) hydrated sample with Ag+ cations, (c) dehydrated sample with Ag+ cations.

Fig.1. Crystal structure of saponite (A) and sitinakite (B).

B

A

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sample with exchanged Ag+ ions (Fig.3b) appears a weak doublet with hyperfine splitting 64 mT. It represents silver atoms Ag0. In saponite sample

containing Na+, Ag+ and Cs+ cations (Fig.3c) the Ag0 lines clearly shows additional splittings la-belled 1, 2, 3 and 4. They are not only due to the different hyperfine splittings of 107 Ag0 and 109Ag0

because then only two lines should be observed at high magnetic field and two ones at low field. In conrast both field regions show four lines which indicates that Ag0 atoms are stabilized at two dif-ferent 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 re-search project “Technologies supporting develop-ment of safe nuclear power engineering” – task 8 “Study of processes occurring under regular opera-tion 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).[2]. Allard T., Calas G.: Appl. Clay Sci., 43(2), 143-149

(2009).[3]. Anthony R.G. et al.: Ind. Eng. Chem. Res., 33(11),

2702-2705 (1994).[4]. Micic O.I. et al.: J. Phys. Chem., 97(28), 7277-7283

(1993).[5]. Sadlo J., Wasowicz T., Michalik J.: Radiat. Phys.

Chem., 45(6), 909-915 (1995).

Fig.3. EPR spectrum at 160 K of γ-irradiated hydrated sa-ponite with: (a) Na+; (b) Na+ and Ag+; (c) Na+, Ag+ and Cs+.

RADIATON-INDUCED CURING OF EPOXY RESINS AND ITS NANOCARBON COMPOSITES

Grażyna Przybytniak, Andrzej Nowicki, Krzysztof Mirkowski

Recently published papers have reported that cur-ing of epoxy resins might be supported by ionizing radiation and that such a treatment provides ma-terials with high glass transition temperatures. Al-though flexural strength of radiation cured epoxy resin is comparable to thermally cured ones, other mechanical parameters are more advantageous. Enhanced toughness and unusual long-term stabil-

ity make the resins usable under harsh/degradable conditions for many years. In order to obtain good quality material usually a photoinitiator at a con-centration of 1% or more is required. The final product shows better features than the resins based on polyamine hardeners [1-3].

In our studies primary objective was to esti-mate if radiation technique might be applied for the high performance ionizing radiation curable nanocarbon composites based on thermoset. Such products are interesting from the practical point of view as they can be applied in automobile, air-craft and aerospace industry [4].

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 pres-ence 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 sus-pension in epoxy resin were obtained from NA-NOMATERIALS (Warszawa, Poland). Graphene oxide (GO) was synthesized by Hummer’s method at the Institute of Electronic Materials Technology (ITME, Poland), whereas the reduced form of the material (RGO) was obtained at the Institute of Nuclear Chemistry and Technology (INCT) as a suspension in dichloromethane (CH2Cl2). The ini-

Scheme 1. Formulae of DGEBA (1) and cationic initiator used for radiation-induced curing Rhodorsil 2074 (IPB) (2).

(2)

(1)

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tiator was dissolved in DGEBA at 60-65oC in an ultrasonic bath. In the same way carbon based nanofilers were dispersed in the resins.

For irradiation, an Elektronika accelerator gen-erating 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

radiation energy by the walls were observed. In order to estimated these consequences, the ther-mal measurements were conducted for the cham-ber unloaded and loaded with water or epoxy resin free from initiator (Fig.1). The diagrams indicate that even after 6 h temperature in the loaded chamber is less than 45oC and has not reached equilibrium yet. On the basis of these results it was assumed that ionizing radiation effects predomi-nantly initiate cross-linking in the presence of the initiator at the first stage. The conclusion confirms thermogram recorded by the DSC method show-ing intensive thermal curing of the system only above 170oC (Fig.2).

Figure 3 shows the progress of temperature in-crease for the radiation-initiated curing of epoxy resin and its nanocomposites in the presence of cationic initiator – Rhodorsil. The profiles of tem-perature variations related to the radiation-ini-

tiated polymerization are presented for several systems.

For all specimens, except this one comprising RGO (“i” peak), the rapid temperature increase has been confirmed for irradiation lasting less than 60 min, i.e. when temperature in the chamber loaded with the materials free from initiator does not reach 30oC. This reflects an accumulation of the radical centres generated in the presence of the initiator at the first stage of the process. When their population achieves an appropriate level a rapid combination of radicals gives strong exo-thermic effect which initially intensifies curing but upon depletion of the initiator goes out with de-creasing amount of the active centres. Radiation energy has to initiate thermal curing which re-quires about 170oC (Fig.2), as just above this tem-perature thermal effect prevails over radiation-in-duced phenomena. Worth noting that in spite of various dose rates and initiator concentrations maximum temperature of exothermic curing is above 200oC for all comprising IPB systems irra-diated in the GC 5000. High temperature of poly-merization is an unfavourable phenomenon as in such a case significant thermal stress is created within the matrix. For the bulk specimens, the ef-fects 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 irradia-tion. Induction time is very short for exposure to an electron beam (a few minutes) and much long-er for gamma irradiation. In the second case the maximum temperature is achieved after 30 and 45 min at 6.4 kGy/h (3.2 kGy) and 3.2 kGy/h (2.4 kGy), respectively. These discrepancies arise from various phenomena standing behind electron beam and gamma-ray irradiations. In the former case, the temperature does not reach value high enough to begin thermal curing thus polymerization is completely radiation-dependent. Such a course of the processes results from generation in situ a suf-

Fig.1. Thermal effects for the selected materials placed in a Gamma Chamber 5000 at a dose rate of 6.4 kGy/h.

Fig.2. Thermogram of DGEBA in the presence of 1% ini-tiator, heating rate – 5 oC/min.

Fig.3. Temperature changes in the DGEBA-based resin during radiation-induced curing: a – without IPB; b – 1% IPB; c, d – 1% IPB; e – 0.5% IPB; f – 0.25% IPB; g – 0.25% IPB, 0.1% CNT; h – 0.25% IPB, 0.1% GO; i – 0.5% RGO, 1% IPB. b – irradiated EB; a, c-i – irradiated in a Gamma Chamber 5000. a, c – irradiation at 6.4 kGy/h; d-i – irradia-tion at 3.2 kGy/h.

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25CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY

ficient population of intermediates due to the high dose rate what causes fast exhaustion of the initia-tor combined with decay of radicals. Therefore, the system cannot be thermally cured, contrary to gamma-initiated processes.

The presence of graphene derivatives extends the induction time of exothermic polymerization, particularly in the case of RGO, what can results from adsorption of the part of initiator by the de-veloped surface of the filler. On the other hand, carbon nanotubes that have not oxygen contain-ing functional groups do not reveal such phenom-ena. Therefore, it seems that access to polar sub-stituents in GO and RGO facilitates binding of the initiator to the carbon nanostructures what delays curing of the resin.

On the basis of the studies it was found that the temperature profiles recorded during radiation curing of epoxy resins in the presence of cationic photoinitiators and selected carbon nanofillers were determined by the type of radiation and its dose rate, the concentration of initiator and the

nature of nanofillers. The induction time of poly-merization is even twice longer for graphene based composites than for non-filled matrix due to limit-ing access to the initiator absorbed on the surface of dispersed phase.

The work was financially supported by the In-ternational Atomic Energy Agency (IAEA) – CRP contract No. 16666 and the Ministry of Science and Higher Education, Poland – project ID 225404.

References[1]. Degrand H., Cazaux F., Coqueret X., Defoort B.,

Boursereau F., Larnac G.: Radiat. Phys. Chem., 68, 5, 885-891 (2003).

[2]. Alessia S., Parlato A., Dispenza C., De Maria M., Spa-daro G.: Radiat. Phys. Chem., 76, 8-9, 1347-1350 (2007).

[3]. Alessi S., Dispenza C., Fuochi P.G., Corda U., Lavalle M., Spadaro G.: Radiat. Phys. Chem., 76, 8-9, 1308-1311 (2007).

[4]. Sui G., Zhang Z-G., Liang Z-Y., Chen Ch.-Q.: Mater. Sci. Eng. A, 342, 28-37 (2003).

[5]. Rhodorsil photo initiator 2074 – Material Safety Data Sheet. RHODIA Inc. SILICONES (USA).

PREPARATION OF THE FILMS BASED ON STARCH-PVA SYSTEM. PRELIMINARY STUDIES OF THE GAMMA IRRADIATION EFFECTS

Krystyna Cieśla, Anna Abramowska, Marek Buczkowski, Paweł Tchórzewski, Andrzej Nowicki, Jacek Boguski

The increasing problem of the non-degradable plastic waste induces the interest in substitution of traditional packaging by the biodegradable ma-terials. Preparation of the films in the mixed sys-tems composed of variety of natural polymers (polysaccharides or proteins) as well as containing polysaccharide – artificial biodegradable polymer seems to be one of the abilities to obtain better and more friendly for the environment packaging material.

Starch is an abundant and cheap biopolymer with a good film forming ability and therefore it appears to be an appropriate source for prepara-tion of the cheap biodegradable packaging [1-3]. In purpose to improve mechanical and barrier properties of starch films various modification methods are applied for the starch substrate as well as blending starch with the other natural or artificial biodegradable polymer. PVA (polyvinyl alcohol) can be used for packaging purposes, and is known to be the appropriate polymer for blend-ing with starch [3].

The potential application for packing of the products subjected to radiation decontamination and the possibility of radiation modification of its structure and properties makes interesting to ex-amine the effect of ionizing radiation on biode-gradable polymer [4]. Our previous results have already shown that using the irradiated starch en-ables to obtain films with better functional prop-erties as compared to those prepared basing on the native starch [1, 2].

Accordingly, our present studies were focused on the elaboration of method for preparation of

the biodegradable films based on starch and PVA and examination of the effect of gamma irradia-tion on the properties of the obtained materials.

Four PVAs (products of Sigma and of Alfa Aesar) characterized by various molecular masses (Mw; PVA1: 145000, PVA2: 90000, PVA3: 60000, and PVA4: 15000-30000) as well as two corn-starches – SC1 (by Sigma) and SC2 (by Cerestar) and two potato starches – S8 (Sigma product) and S7 (commercial, local market) were selected for the films preparation. Moreover, the starches SC1d and S8d degraded by the way of irradiation with a dose of 10 kGy (in purpose to reduce their viscos-ity [1, 5]) were prepared and applied.

Films were prepared by the solution casting method after addition of glycerol as a plasticizer at a level of 0, 20 and 30% (in relation to the starch-PVA mass). The films were dried, peeled from the substrate and conditioned during couple of days at a relative humidity of 43% before test-ing.

Irradiations were carried out with Co-60 gam-ma radiation in vacuum or in air at ambient tem-perature in a Gamma Chamber 5000 placed in the Centre for Radiation Research and Technology, INCT. Irradiations of the PVA films were con-ducted with a dose of 100 kGy and irradiation of the the starch and starch-PVA were carried out using a dose of 25 kGy.

Mechanical tests were carried out using an Inström testing machine [2]. The average values of tensile strength and elongation at break were calculated on the basis of 6-8 measurements per-formed for each composition. For evaluation of

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26 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY

hydrophilic/hydrophobic properties the capability for water uptake and the wetting angle for water were measured using an instrument constructed in the Laboratory of Material Research, INCT and the method described in [2]. In purpose to evaluate the polymer degradation/crosslinking de-gree gel content in the starch containing films was determined after heating in water [1, 6].

At the beginning, the experimental conditions enabling preparation of PVA and starch films were optimized using all the substrates. Then, op-timization of the conditions for preparation of the starch-PVA films was conducted. The film compo-sitions were based on PVA : starch ratio 1:1. Two sets of syntheses were carried out.

Solubilization of PVAs and preparation of starch gels appear to be the crucial step in the films synthesis. Moreover, phase separation was observed in the starch-PVA films. Therefore, tem-perature and time of the PVA solvation and of the starch gelatinization were adapted, as well as the amount of plastificator and conditions applied for its addition. Glycerol was introduced into the film forming solution before the starch gelatinization or prior to casting. The difficulties arise in obtain-ing homogeneous starch films based on the native starches in regard to the high viscosity of the gels formed at the intermediate step of the syntheses. Accordingly, application of the starches degraded on the way of irradiation were expected to be ad-vantageous [1, 5]. Our present experiments have

shown that the films prepared using the starch ir-radiated with a 10 kGy dose reveal better prop-erties as compared to the films prepared basing on the non-irradiated starch. In result of the opti-mization the experimental procedure homogene-ous starch-PVA films were finally obtained. Basing on these results the PVA1 and cornstarch SC1d (pre-irradiated) were selected for the further more advanced experiments.

Flexible PVA films and stiff starch films were obtained. Elasticity of PVA film was lower when Mw of the substrate was higher (Table 1). The low-est tensile strength values were determined for the films based on the PVA4 characterized by the lowest Mw. Increase in elasticity and decrease in tensile strength were connected with an increase in the glycerol content in the films.

All the PVA and starch films shown limited hy-drophilicity (PVA – contact angle ca. 70o). In the majority of cases the hydrophilicity of PVA films was higher when Mw was smaller and when plasti-ficator content was higher (for example the water uptake determined after 11 days for PVA1 films containing 0, 20 and 30% of glycerol was equal to 28.07, 30.78 and 27.89, respectively, as com-pared to the values of 36.72, 58.71 and 59.05 found for PVA4). Hydrophilicity (shown by the contact angle data) decreases during storage of the films. A contact angle determined for the films contain-ing native starches and 30% of glycerol varied in the range 60-81o. The films obtained basing on

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.

PVA Glycerol content [wt.%]

Dose 0 kGy Dose 100 kGy

tensile strength [MPa]

elongation at break [%]

tensile strength [MPa]

elongation at break [%]

PVA1

0 56.6 119.3 58.3 105.9

20 37.9 168.2 33.9 141.6

30 30.3 133.8 25.6 125.8

PVA2

0 59.2 160.9 53.8 112.3

20 40.8 223.9 33.0 175.0

30 32.4 268.6 39.6 253.8

PVA3

0 53.1 35.0 57.5 29.1

20 31.9 224.9 36.3 218.3

30 30.0 222.0 27.3 162.8

PVA4

0 41.6 296.7 47.8 172.4

20 26.3 211.5 30.2 216.1

30 20.7 278.0 20.5 188.6

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 con-tain 30% of glycerol introduced into the final solution. The samples were conditioned at 20oC.

CompositionDose 0 kGy Dose 25 kGy

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

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27CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY

the pre-irradiated specimens reach higher contact angle value (till 90o) as compared to those ob-tained using the non-irradiated starches.

Starch-PVA films were characterized by the relatively good mechanical properties (Tables 2 and 3). The values of the wetting angle of the

starch-PVA films (77-88o, Table 4) were generally higher as compared to those of pure PVA films (ca. 70o). However, the water uptake by those films (Table 4) were higher as compared to the PVA films. For example, the water uptake of the blends of PVA1 with various starches (20% of glycerol) were in the range of 50.86-61.32% as compared to 30.78% determined for the pure PVA1 under similar conditions.

Mechanical data (Table 1) obtained for the PVA films prepared without glycerol addition or using 20% of glycerol suggest that the application of gamma radiation might result in an increase in tensile strength, in particular in the case of PVAs with a low molecular mass (PVA4 and PVA3). A negligible differences were noticed in the case of the films containing 30% of glycerol. In the cases of the PVA with the high molecular mass a small decrease in tensile strength was noticed and the higher decrease was observed when the samples contained a higher amount of glycerol. In all the cases of the irradiated films a decrease in elonga-

tion at break value occurs as compared to the non--irradiated films. None particular differences were found in the contact angle data determined for the non-irradiated and the irradiated films. How-ever, the moisture uptake was somewhat higher in the majority of the irradiated films.

The effect of irradiation on the mechanical properties of the starch-PVA films depends on their composition and the conditions applied dur-ing synthesis and irradiation. Therefore, none par-ticular differences, a decrease in tensile strength with a simultaneous increase in elasticity as well as decrease in elasticity with negligible effect on strength were found after irradiation (Tables 2 and 3). Degree of radiation effect differs after ir-radiation of the same sample in air and in oxygen free atmosphere, although the directions of the changes are the same. This result suggest that deg-radation of the material is the prevailing process taking place in air.

The increase in the films homogeneity after ir-radiation might be concluded basing on the SEM observation (Fig.1) and the smaller dispersion of the mechanical results.

Hydrophilicity of the majority of the starch--PVA films has increased after irradiation (Tables 4 and 5). However, in some cases these properties became unchanged or even decreases.

Table 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.

CompositionDose 0 kGy Dose 25 kGy, oxygen absence Dose 25 kGy, air

tensile strength [MPa]

elongation at break [%]

tensile strength [MPa]

elongation at break [%]

tensile strength [MPa]

elongation at break [%]

PVA2 + SC1d a) 19.6 57.3 21.3 29.9 20.2 35.3

PVA1 + SC1d a) 18.6 23.2 8.9 49.9 10.4 27.9

PVA1 + SC1d b) 24.4 31.7 26.9 c) 14.0 c) 24.4 25.1

a) Glycerol introduced prior to casting.b) Glycerol introduced before starch gelatinization. c) Measurements carried out after one month.

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 type

Starch sample

Glycerol content [%]

Dose [kGy]

Gel fraction [%]

% of the gel fraction of the initial film

Moisture uptake [%]

Wetting angle [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

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28 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY

Decrease in the gel fraction content was found after irradiation in the majority of the samples (Tables 4 and 5) showing the occurring degrada-tion processes. However, the degree of this de-crease differs in the cases of particular samples. Moreover, it seems to be in some cases insignifi-cant, or at least lower than can be expected after

irradiation performed using a dose of 25 kGy. For example, it reach the value ca. 75% in the case of PVA1-SC1d (pre-irradiated starch, 30% of glycerol) of that obtained for the initial sample (Tables 4 and 5), while the value of ca. 30% was found under the same conditions for the SC1d pure starch. This result suggests that crosslinking accompanies deg-radation in these systems. The last conclusion was supported by thermogravimetry.

These preliminary results show the increase in the compatibility of the components in the PVA--starch-glycerol systems taking place under gamma radiation. The effect of irradiation depends on the sample composition and on the applied conditions. Degradation was found to be the prevailing process taking place in the majority of the films. However, it can be supposed that crosslinking occurs simul-taneously with degradation and in some cases its

particpation might be even more important than that of degradation. None particular effect of ir-radiation on mechanical properties found in some cases suggests that the materials based on the ex-amined system, properly prepared, might appear appropriate for packing products predicted for ra-diation decontamination.

The work was sponsored in the frame of the International Atomic Energy Agency (IAEA) re-search contract No. 17493 (CRP F2206).

References[1]. Cieśla K.: Przekształcenia struktury nadcząsteczkowej

w polimerach naturalnych inicjowane promieniowa-niem jonizującym (Transformation of supramolecular structure initialized in natural polymers by gamma ir-radiation). Institute of Nuclear Chemistry and Tech-nology, Warszawa 2009, 223 p. (in Polish).

[2]. Cieśla K., Nowicki A, Buczkowski M.: Nukleonika, 55, 2, 233-242 (2010).

[3]. Tang X., Alavi S.: Carbohydr. Polym., 85, 1-16 (2011).[4]. Ryzhkova, Jarzak U., Schäffer A., Bämer M., Swiderek

P.: Carbohydr. Polym., 83, 608 (2011). [5]. Cieśla K.: J. Therm. Anal. Calorim., 74, 259-274 (2003).[6]. Cieśla K., Eliasson A-C.: Acta Aliment., 36(1), 111-126

(2007).

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.

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 [%]

PVA2 + SC1d a) 0 47.90 100 35.54

PVA2 + SC1d a) 25 c) 41.39 86 40.84

PVA2 + SC1d a) 25 d) 31.53 66 45.60

PVA1 + SC1d a) 0 41.91 100 55.57

PVA2 + SC1d a) 25 c) 32.90 76 43.28

PVA2 + SC1d a) 25 d) 33.26 79 35.85

PVA1 + SC1d b) 0 49.58 100 25.52

PVA2 + SC1d b) 25 c) 37.34 75 24.79

PVA2 + SC1d b) 25 d) 37.60 76 24.64

a) Glycerol introduced prior to casting.b) Glycerol introduced before starch gelatinization.c) In oxygen absence. d) In air.

A 1000 x B

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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 con-tinued 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 re-search, novel methods were examined for the separation of radionuclides and heavy metal ions, based on hybrid processes (membrane filtration combined with sorption or complex for-mation, and micellar-enhanced ultrafiltration), as the basis for further technologies for radio-active 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, second-ary 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 radiopharmaceu-ticals, 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 and 211At) via 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-

Page 31: INCT Annual Report 2013

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 interna-tional 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 scien-tific 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.

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31CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY

SYNTHESIS, PHYSICOCHEMICAL AND BIOLOGICAL EVALUATION OF NOVEL TECHNETIUM-99m LABELLED LAPATINIB

AS A POTENTIAL TUMOUR IMAGING AGENTEwa Gniazdowska, Przemysław Koźmiński, Leon Fuks, Krzysztof Bańkowski1/,

Wojciech Łuniewski1/, Leszek Królicki2/

1/ Pharmaceutical Research Institute, Warszawa, Poland2/ Nuclear Medicine Department, Medical University of Warsaw, Warszawa, Poland

One of the most important radiopharmaceuticals which selectively distribute within given tissues or organs, are formed by coordination compounds with diagnostic/therapeutic radiometal firmly at-tached to selected biologically active molecule. Lapatinib ditosylate (Fig.1A) is an anticancer drug used for treatment of solid tumours such as breast or lung cancer, because it exhibits high affinity to-

wards Her-2 receptors [1]. It is expected, that lapa-tinib labelled with technetium-99m may also serve as a diagnostic receptor radiopharmaceutical for patients suffering from breast cancer of the Her-2 type.

The aim of this work was to synthesize conju-gate containing technetium-99m complex of the ‘4+1’ type and lapatinib as the biologically active

molecule (Fig.1B) and to determine physicochem-ical and biological properties of the conjugate im-portant from the radiopharmaceutical point of view.

The conjugate (NS3)99mTc(CN-lapatinib) con-sists of 99mTc(III) cation coordinated by the tetra-dentate NS3 tripodal chelator (tris(2-mercapto-

ethyl)-amine; 2,2’,2’’-nitrilotriethanethiol) and a monodentate isocyanide species CN-BFCA (bi-functional coupling agent, isocyanobutyric acid suc-cinimidyl ester) previously coupled with lapatinib molecule. The tetradentate NS3 ligand was pre-pared by reaction of tris(2-chloroethyl)amine hy-drochloride with potassium thioacetate followed by reduction with LiAlH4 [2]. The aliphatic linker CN-BFCA was synthesized according to the pro-

cedure described in [3]. The coupling reaction of the isocyanide linker CN-BFCA with the lapatinib molecule (Scheme 1) was performed according to the procedure described in [4]. Crude product was purified on a semi-preparative HPLC column (sys-tem 1), alkalized and lyophilized, yield ≈ 35%. MS: m/z: calcd. – 675.17; found – 676.17 [M+H+], 698.19 [M+Na+].

IR: (KBr plates), cm–1: 2153 (C≡N), 1814, 1785, 1729 (succinimidyl ester).

The (NS3)99mTc(CN-lapatinib) conjugate was synthesized in n.c.a. scale in two-step procedure according to [4] (Scheme 2). The NS3 molecule coordinates the 99mTc(III) cation and leaves the fifth coordination site available for one monoden-tate isocyanide ligand CN-lapatinib.

The reaction progress was checked by TLC (thin layer chromatography) and HPLC (high performance liquid chromatography; system 2) methods. The radiochemical yield of the synthe-sized conjugate was higher than 97%.

Conditions of HPLC systems were the follow-ing:

System 1: Phenomenex Jupiter Proteo semi-pre-parative column (4 μm, 90 Å, 250 x 10 mm), UV/Vis detector (220 nm); elution conditions: solvent A – water with 0.1% TFA (v/v), solvent B – ace-tonitrile with 0.1% TFA (v/v); gradient – 0-20 min 20 to 80% solvent B, 20-35 min 80% solvent B; 2 ml/min.System 2: Phenomenex Jupiter Proteo analytical column (4 μm, 90 Å, 250 x 4.6 mm), gamma radia-

NS

S S

CNLapatinib

O

99mTc

B

(NS3)99mTc(CN-BFCA-Lapatinib)

NH

O

N

N

NH Cl

OF

SOO

SOH O

O

SOH O

O

A

Fig.1. Lapatinib molecule (A) and 99mTc-labelled lapatinib using the ‘4+1’ approach (B).

NH

O

N

N

NH Cl

OF

SOO

CN

O

O

N

O

O CN

O

N

O

N

N

NH Cl

OF

SOO

O

O

OH++

Scheme 1. Coupling reaction of CN-BFCA with lapatinib.

Scheme 2. Two-step synthesis of (NS3)99mTc(CN-lapatinib) conjugate in n.c.a. scale.

99mTcO4-

EDTA-kit

room temp. 20 min

99mTc-EDTA 70oC, 30 min

(NS3)99mTc(CN-lapatinib)NS3, CN-lapatinib, MeOH

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32 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY

tion detector; elution conditions: solvent A – water with 0.1% TFA (v/v), solvent B – acetonitrile with 0.1% TFA (v/v); gradient – 0-20 min 20 to 80% solvent B, 20-35 min 80% solvent B; 1 ml/min.

TLC analyses were performed using Merck 60 F254 aluminum sheets. All radioactive substances were placed on the strip, developed with appro-priate solutions and dried. Distribution of radio-activity on the strip was determined using a home--made automatic TLC analyser SC-05 (INCT).

The synthesized conjugate was characterized by determination of the logarithm of its partition coefficient, log P, in the n-octanol/PBS (pH 7.40) system. Stability of the isolated conjugate was in-vestigated both as a function of time (HPLC) and in challenge experiments (in the presence of excess of histidine or cysteine), as well as in rat serum. The biological properties of the conjugate were char-acterized in vitro by investigations of the conjugate affinity to Her-2 receptor using cell line SKOV-3 and in vivo by the biodistribution studies.

The conjugate (NS3)99mTc(CN-lapatinib) is form-ed with high yield and purity (Fig.2). The small peaks recorded at RT = 3.4 and 7.9 min correspond

to the intermediate complexes 99mTc-EDTA/man-nitol and 99mTc(NS3), respectively.

The determined lipophilicity value of the con-jugate was found to be 1.24 ± 0.04 (n = 3). The studied conjugate exhibited high stability. After 24 h of incubation in 10 mM histidine or cysteine solution and in rat serum the obtained HPLC chromatograms have shown mainly the existence of one radioactive species in the solution, with the retention time characteristic for the studied con-jugate.

Biological studies were performed using the SKOV-3 cell line. The cells were maintained in McCOY’S 5A Medium (Modified), containing 2 mM of L-glutamine, 10% of fetal bovine serum and supplemented with 0.1 IU/ml penicillin and 0.1 mg/ml streptomycin. Cells were cultured at 37oC in a humidified incubator under an atmos-phere containing 5% of CO2. The cells were sub-cultured once a week. Affinity studies were performed on 6-well plates (SARSTEDT) in McCOY’S 5A Medium which contained approximately 4 x 105 adherent cells in

each well. Cell count was determined using hemo-cytometer and microscope. Preliminary affinity studies were performed by incubating SKOV-3 cells together with the studied conjugate, as well as with other 99mTc-species, namely with 99mTcO4

–, 99mTc-EDTA/mannitol and 99mTc(NS3). After 45 min of incubation the binding was stopped, the so-lution from above the cells was quantitatively sep-arated and the cells were washed three times with cold PBS, pH 7.4 (in order to eliminate unbound radioactivity). Then, the cells were solubilized with 1 M NaOH and activity of solution from above the cells and that of solubilized cells was measured in the gamma counter. Affinity of the conjugate was

Fig.2. HPLC chromatogram of the reaction mixture (per-formed in system 2) after completion of the synthesis of the (NS3)99mTc(CN-lapatinib) conjugate.

Fig.3. Cell binding of (NS3)99mTc(CN-lapatinib) conjugate in comparison with other 99mTc species. Cell binding levels are expressed as the percentage of added doses (% ID).

0

10

20

30

40

50

% ID

1 2 3 4

99m

TcO

4

99m

Tc-E

DTA

99m

Tc(N

S3)

(NS

3 )99m

Tc(C

N-la

patin

ib)

Fig.4. (A) The saturation curve for (NS3)99mTc(CN-lapati-nib). The specifically bound radioligand is plotted as a function of increasing concentrations of (NS3)99mTc(CN-la-patinib). (B) Scatchard plot.

0

0,5

1

1,5

2

2,5

3

0 10 20 30 40 50 60

concentration of (NS3)99mTc(CN-lapatinib) [nM]

% S

peci

fic B

ound

[nM

]

Bmax = 2.4 nM

A

0,0

0,2

0,4

0,6

0,8

1,0

1,2

0,00 0,50 1,00 1,50 2,00 2,50 3,00

B [nM]

B/F

Kd = 3,5 nM

B

(NS3)99mTc(CN-lapatinib)

0

20000

40000

60000

0 5 10 15 20 25 30 35

min

cpm

RT = 18.5 min

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calculated as the ratio of activity bound by cells to the sum of activity bound by cells and that which remained in the solution above the cells (Fig.3).

Binding of the (NS3)99mTc(CN-lapatinib) con-jugate to Her-2 receptor of SKOV-3 cells was found to be saturable and specific in the predomi-nant degree (Fig.4A). The non-specific binding determined in the presence of 0.1 μM solution of lapatinib accounts in general for about 0.3% of specific binding. The Bmax value was found to be 2.4 ± 0.3 nM (n = 3), which corresponds to the approximate number of 2 500 000 binding sites per cell. The dissociation constant, Kd, usually used to describe the affinity of the conjugate to its receptor (Fig.4B), was found to be 3.5 ± 0.4 nM (n = 3). The low value of Kd indicates high affinity of the studied conjugate.

In a competitive binding experiment the unla-belled lapatinib molecules inhibited binding of (NS3)99mTc(CN-lapatinib) and the inhibitory con-centration of 50% (IC50) obtained for lapatinib was

found to be 41.2 ± 0.4 nM (Fig.5). This value also confirms satisfactorily high affinity of (NS3)99mTc (CN-lapatinib) conjugate to Her-2 receptors in the SKOV-3 cells.

Biodistribution studies of (NS3)99mTc(CN-lapa-tinib) conjugate (Table, Fig.6) were performed on normal 3 months old male BALB/c mice (of weight

between 23 and 28 g, n = 12), according to the rel-evant national regulations. The mice were injected via tail vein with 3.02-3.66 MBq in 200-210 μL of aqueous solution of (NS3)99mTc(CN-lapatinib) and sacrificed at 30 and 60 min after injection of con-

jugate. Then, tissues were dissected, washed free of blood and weighed. Associated radioactivity was counted using gamma counter. The accumulated radioactivity in the tissue of organs was calculated as the percentage of injected dose per gram (% ID/g) of tissue, as well as the percentage of inject-ed dose per gram of blood. The standard source of 99mTc was also measured simultaneously with the samples in order to perform the decay correction.

The presented data show similar uptake of (NS3)99mTc(CN-lapatinib) conjugate in liver (4-5% ID/g) and in kidney (3-5% ID/g). It points out to the clearance of the conjugate through the renal and through the hepatic route in the comparable degree. The uptake in other organs remained on the level < 1% ID/g.

(NS3)99mTc(CN-lapatinib) conjugate is formed with high yield and presents high stability in solu-tions containing competitive cysteine/histidine li-gands. The biological in vitro and in vivo studies of the conjugate showed its high affinity to Her-2 re-ceptor and the clearance through the renal and hepatic route in comparable degree.

To conclude, (NS3)99mTc(CN-lapatinib) conju-gate may be considered a promising diagnostic radiopharmaceutical for patients suffering from breast cancer of Her-2 type.

The work was carried out within the grant No. N R13 0150 10 (National Centre for Research and Development, Poland).

References[1]. Burris H.A. et al.: Oncologist, 9, 10-15 (2004).[2]. Spies H., Glaser M., Pietzsch H.-J., Hahn F.E., Lueg-

ger T.: Inorg. Chim. Acta, 240, 465-478 (1995).[3]. Kuenstler J.-U., Veerenda B., Figueroa S.D., Sieck-

man G.L., Rold T.L., Hoffman T.J., Smith C.J., Pietzsch H.-J.: Bioconjugate Chem., 18, 1651-1661 (2007).

[4]. Seifert S., Kuenstler J.-U., Schiller E., Pietzsch H.-J., Pawelke B., Bergmann R., Spies H.: Bioconjugate Chem., 15, 856-863 (2004).

Fig.5. Displacement of (NS3)99mTc(CN-lapatinib) by in-creasing concentration of unlabelled lapatinib.

Fig.6. Biodistribution studies of (NS3)99mTc(CN-lapatinib) in BALB/c mice after 30 and 60 min p.i.

Table. Biodistribution studies of (NS3)99mTc(CN-lapatinib) conjugate in BALB/c mice at 30 and 60 min p.i. (n = 6, % ID/g ± SD).

0

20

40

60

80

100

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

log [M]

% S

peci

fic B

ound

OrganUptake in organ, percentage of injected dose per g tissue

[% ID/g ± SD]

Heart 0.10 ± 0.02 0.92 ± 0.04

Kidneys 3.28 ± 0.4 4.98 ± 0.6

Liver 4.89 ± 0.9 4.55 ± 0.8

Lungs 0.77 ± 0.08 0.56 ± 0.09

Spleen 0.44 ± 0.3 0.38 ± 0.02

Blood 0.99 ± 0.01 0.48 ± 0.02

Thyroid 0.94 ± 0.04 0.38 ± 0.02

0

1

2

3

4

5

6

1 2 3 4 5 6 7

%ID

/g

30 min after injection60 min after injection

Hea

rt

Kidn

eys

Live

r

Lung

s

Spl

een

Blo

od

Thyr

oid

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CYCLOTRON PRODUCTION OF 99mTc. SEPARATION OF 99mTc FROM 100Mo TARGET

Magdalena Gumiela, Ewa Gniazdowska, Aleksander Bilewicz

Every day about 70 000 diagnosis procedures us-ing 99mTc-radiopharmaceuticals are performed ren-dering this the most widely used radioisotope in nuclear imaging. 99mTc is commonly easy available from 99Mo/99mTc generators. 99Mo (the mother nu-clide, t1/2 = 66 h) is produced via either thermal neutron irradiation of natural Mo in the reaction 98Mo(n,γ)99Mo or thermal fission of highly en-riched 235U (HEU) in the reaction 235U(n,f)99Mo. Usually, the operation period of research reactors used for the production of 99Mo is about 40-50 years. Most reactors used for the preparation of 99Mo have already reached this age, or they will reach it in the near future. Therefore, there is still growing interest in exploring alternative cyclotron production of 99mTc using 100Mo(p,2n)99mTc reac-tion, the method proposed first by Beaver and

Hupf nearly 40 years ago [1]. In other way, some amounts of 99Mo suitable for the production of 99Mo/99mTc generators can be obtained in the nu-clear reaction 100Mo(p,pn)99Mo [2]. The significant advantage of the direct production of 99mTc using cyclotrons is the less nuclear waste production compared to the fission product method of 99Mo production. On the other hand, due to the rela-tively short half-life of 99mTc, the method of direct 99mTc production can be applied only in hospitals near cyclotron centres.

Natural molybdenum consists of several iso-topes including 92Mo, 94Mo, 95Mo, 96Mo, 97Mo, 98Mo and 100Mo. During proton bombardment of natural Mo, depending on proton energy, several reaction channels may be present and, apart from 99mTc, various isotopes of technetium, such as 96Tc, 95Tc and 94Tc, can be produced. Therefore, the ap-plication of molybdenum target enriched with 100Mo (97.46%) is needed. However, the natural abun-dance of 100Mo is only 9.63%. High cost associated with the isotopic enrichment of 100Mo from natural molybdenum makes necessary to investigate the recycling of the 100Mo target material. So, there is a real necessity to develop separation technologies

suitable for use in novel modes of 99mTc produc-tion. Separation of technetium from irradiated molybdenum may be carried out using either “wet” or “dry” chemical processes. “Wet” separa-tion techniques require dissolving of the metallic target under oxidative conditions and then sep-aration of pertechnetate can be achieved using one of many strategies, e.g. liquid-liquid extraction [3], ion-exchange chromatography [4], aqueous bi-phasic extraction chromatography using ABEC resin [5] and electrochemistry [6].

The aim of our studies was to elaborate a simple and fast method for separation of microquantities of pertechnetate from macroquantities of molyb-date anions in the process of cyclotron produc-tion of 99mTc. The schematic diagram of proposed methods is presented in Fig.1.

Our studies were carried out using natural mo-lybdenum powder. We utilized formation of insol-uble yellow ammonium molybdenum phosphate (AMP) in the reaction of ammonium phosphate with molybdate anions, which takes place accord-ing to the formula:

(NH4)3PO4 · 3H2O + 12MoO42– + 24H+ →

(NH4)3P(Mo3O10)4↓ + 5H2OIn the first step, metallic molybdenum target was

dissolved in 3.5 M HNO3. Next, triammonium phos-phate and ammonium nitrate were added, and AMP was precipitated in the form of yellow solid. We have optimized four parameters of the process: the con-centration of NH4NO3 and of (NH4)3PO4 · 3H2O, temperature and the time of precipitation.

The increase in the concentration of ammo-nium nitrate results in lower solubility of AMP precipitate. In 0.125 M ammonium nitrate solu-tion the solubility of AMP is nearly twice less than in the case when the precipitation was carried out in the absence of ammonium nitrate. We have also found that the concentration of (NH4)3PO4 · 3H2O does not influence the AMP solubility, and no excess of triammonium phosphate is needed. In the next steps, we analysed the influence of tem-

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

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perature and time on the precipitation process (Fig.2). Precipitation process was tested at various temperature (40, 60 and 80oC) and time periods (15 min-1 h). The lowest concentration of Mo in the solution, equal to about 370 μg/ml, was reach-ed in the reaction mixture heated at 80oC. As one can see in Fig.2, the concentration of Mo in the reaction mixture only slightly depends on the time of sample heating.

Based on the performed experiments, the fol-lowing optimal conditions for the separation of microamounts of 99mTc from Mo target have been selected: 25 mg of metallic Mo target is dissolved in 0.5 ml of 3.5 M HNO3, next 400 μl 0.44 M of

(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 pro-cess, under conditions presented above, we found in the filtrate solution 99.6% of the total 99mTc ac-tivity. 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 solution without coprecipitation of 99mTc. After op-timization of the precipitation conditions, the low-est concentration of MoO4

2– was only 0.37 mg/ml. The final solution will be conducted through a col-umn containing one of the Zr-based sorbents.

References[1]. Beaver J., Hupf H.: J. Nucl. Med., 12, 739-41 (1971).[2]. Almeida G.L., Helus F.: Radiochem. Radioanal. Lett.,

28, 205 (1977).[3]. Dallali N., Ghanbari M., Yamini Y., Fateh B., Agrawal

Y.K.: Indian J. Chem. A, 46A, 1615-1617 (2007).[4]. Chattopadhyay S., Das S.S., Das M.K., Goomer N.C.:

Appl. Radiat. Isot., 66, 12, 1814-1817 (2008).[5]. Rogers R.D., Bond A.H., Griffin S.T., Horwitz E.P.:

Solvent Extr. Ion Exch., 14, 919-946 (1996).[6]. Chakravarty R., Dash A., Venkatesh M.: Nucl. Med.

Biol., 37, 21-28 (2010).

Fig.2. Concentration of Mo in solution as a function of time and temperature of precipitation process.

THE STRUCTURES OF BISMUTH(III) COMPLEXES WITH TROPOLONEKrzysztof Łyczko, Monika Łyczko, Krzysztof Woźniak1/, Marcin Stachowicz1/

1/ Department of Chemistry, University of Warsaw, Warszawa, Poland

Tropolone (2-hydroxy-2,4,6-cycloheptatriene-1--one), abbreviated as Htrop, is an aromatic com-pound with a seven-membered carbon ring. It contains two neighbouring functional groups (car-bonyl and hydroxyl) which make possible its coor-dination to various metal ions. The tropolonate anion (trop–) is a bidentate oxygen donor ligand forming a five-membered chelate ring upon com-plexation.

In the 1960s the bismuth(III)-tropolonato complexes, such as [Bi(trop)2Cl] [1], Bi(trop)3 and Na[Bi(trop)4] [2], were synthesized for the first time. In 1995, the preparation and characteriza-tion of new bismuth(III) compounds with tro-polone and its derivatives were presented. Among them, the structures of only nitratobis(tropolona-to)bismuth(III) and aquabis(4,5-benzotropolona-to)bismuth(III) nitrate were published [3]. How-ever, they are not available in the Cambridge Struc-tural Database.

We have previously reported the formation of three polymeric lead(II)-tropolonato complexes – [Pb(trop)(CF3SO3)(H2O)]n, [Pb3(trop)4(ClO4)2]n, [Pb2(trop)2(NO3)2(CH3OH)]n and one dimeric compound – [Pb(trop)2]2, which depends on the pH of solution and the counterion [4].

Bismuth compounds have been extensively studied in respect of their antibacterial properties

and possible usage in cancer therapy [3, 5-8]. Based on our work concerning of lead(II)-tropolonato complexes [4], we decided to investigate the effect of counterion and pH of the solution on the for-mation of bismuth(III)-tropolonato compounds.

The reaction of tropolone with Bi(CF3SO3)3, Bi(ClO4)3 and Bi(NO3)3 in methanol solution in the molar ratios 1:2 and 1:3 led to the formation of three different bismuth(III) complexes: one dimeric and two polymeric. The structures of the [Bi(trop)2(CF3SO3)]2 (1), [Bi2(trop)4(ClO4)2]n (2) and [Bi2(trop)4(NO3)2]n (3) compounds were de-termined by single crystal X-ray diffraction (Figs.1-3). A simple tris(tropolonato)bismuth(III) complex, Bi(trop)3 (4), was obtained from bis-muth(III) acetate salt. In the crystal structure of 1 two Bi(trop)2(CF3SO3) entities are held together in dimeric units (Fig.1). Compounds 2 and 3 have polymeric structures with the Bi2(trop)4(ClO4)2 and Bi2(trop)4(NO3)2 fragments, respectively, re-peated in the polymeric chains (Figs.2-3). Each bismuth(III) ion in the compounds 1-3 is chelated by two tropolonato ligands. It is obvious that the counterions (triflate, perchlorate and nitrate) play an important role in the formation of the studied compounds, through entering their structures. Contrary to the complex 1 which has the bismuth centres of the same kind, the complexes 2 and 3

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comprise two coordinatively different types of Bi atoms. In all the complexes studied, the tropolo-nate ions chelate the bismuth(III) ions in an ani-

sobidentate manner, with one shorter and one longer Bi−O bond. The lengths of the chelating Bi−O bonds are within the range 2.176-2.376 Å. In addition, some tropolonato ligands are also bridg-ing to one (in 1-3) or two (in 2 and 3) neighbour-ing bismuth(III) ions. In the studied structures, the bridging Bi−O(trop) distances are longer than the chelating Bi−O(trop) bonds, and vary in the range 2.630-2.960 Å. The bond distances between

the metal ions and oxygen atoms of counterions (CF3SO3

–, ClO4– and NO3

–), changing in the range 2.652-2.909 Å, are similar to the bridging Bi−O(trop) contacts in respect to distance. The shortest dis-tances 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 neigh-bouring 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 co-ordination 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) and three longer (2.400 Å) Bi−O bond lengths (Fig.4). The arrangement of these six oxygen atoms around the metal centre forms strongly distorted octahedron (or distorted triangle antiprism) with the bismuth(III) ion placed almost on the surface built up of three O atoms [O(2), O(4) and O(6)] (Fig.4B).

The 6s2 lone electron pairs on the bismuth(III) ions seem to be stereochemically active in all com-plexes studied. The presence of distinct empty volumes around the metal ions is the evidence for

Fig.1. The structure of [Bi(trop)2(CF3SO3)]2 (1). Selected bond lengths, distances [Å] and angles [o]: Bi(1)−O(2) 2.279(3), Bi(1)−O(1) 2.231(3), Bi(1)−O(12) 2.266(3), Bi(1)−O(11) 2.164(3), Bi(1)−O(3) 2.870(3), Bi(1)−O(4) 2.862(3), Bi(1)−O(1’) 2.657(3), O(1)−Bi(1)−O(2) 70.31(9), O(11)−Bi(1)−O(12) 72.19(10). The non-hydrogen atoms are shown as the 50% probability ellipsoids.

Fig.2. The structure of [Bi2(trop)4(ClO4)2]n (2). Select-ed bond lengths [Å] and angles [o]: Bi(1)−O(1) 2.304(3), Bi(1)−O(2) 2.226(3), Bi(1)−O(11) 2.306(3), Bi(1)−O(12) 2.176(3), Bi(1)−O(4) 2.823(4), Bi(1)−O(8’) 2.776(3), Bi(1)−O(21) 2.740(3), Bi(1)−O(32) 2.896(3), Bi(2)−O(21) 2.299(3), Bi(2)−O(22) 2.179(3), Bi(2)−O(31) 2.242(3), Bi(2)−O(32) 2.193(3), Bi(2)−O(1) 2.753(3), Bi(2)−O(2’) 2.870(3), Bi(2)−O(11’) 2.894(4), Bi(2)−O(7’) 2.880(4), O(1)−Bi(1)−O(2) 69.32(12), O(11)−Bi(1)−O(12) 71.59(12), O(21)−Bi(2)−O(22) 70.63(12), O(31)−Bi(2)−O(32) 71.29(11). The atoms are shown as the 50% probability ellipsoids. Hy-drogen atoms are omitted.

Fig.3. The structure of [Bi2(trop)4(NO3)2]n (3). Selected bond lengths [Å] and angles [o]: Bi(1)−O(1) 2.360(2), Bi(1)−O(2) 2.309(2), Bi(1)−O(11) 2.269(2), Bi(1)−O(12) 2.189(2), Bi(1)−O(3) 2.652(2), Bi(1)−O(4) 2.746(2), Bi(1)−O(6’) 2.776(2), Bi(1)−O(21) 2.901(2), Bi(1)−O(32) 2.630(2), Bi(2)−O(21) 2.205(2), Bi(2)−O(22) 2.250(2), Bi(2)−O(31) 2.248(2), Bi(2)−O(32) 2.376(2), Bi(2)−O(6) 2.909(2), Bi(2)−O(7) 2.658(2), Bi(2)−O(1) 2.651(2), Bi(2)−O(2”) 2.960(2), Bi(2)−O(11”) 2.875(2), O(1)−Bi(1)−O(2) 67.48(5), O(11)−Bi(1)−O(12) 72.01(6), O(21)−Bi(2)−O(22) 71.26(6), O(31)−Bi(2)−O(32) 67.52(6). The atoms are shown as the 50% probability ellipsoids. Hy-drogen atoms are omitted.

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the stereochemically active 6s2 lone pair in the com-pounds 1 and 4 [11]. In turn, the observed pattern in 2 and 3, with a few adjacent shorter and a few adjacent longer Bi−O distances, can also indicate the active character of this lone electron pair [11].

The formation of studied complexes, similarly as in the case of lead(II)-tropolonato compounds

[4], depends on pH of the solution. The pH of me-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 ob-served. 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-

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).

[8]. Su F-M., Beaumier P., Axworthy D., Atcher R., Fritz-berg A.: Nucl. Med. Biol., 32, 741-747 (2005).

[9]. Mantina M., Chamberlin A.C., Valero R., Cramer C.J., Truhlar D.G.: J. Phys. Chem. A, 113, 5806-5812 (2009).

[10]. Frisch M.J. et al.: Gaussian 09, revision C.01. Gaus-sian, Inc., Wallingford CT, USA 2010.

[11]. Shimoni-Livny L., Glusker J.P., Bock Ch.W.: Inorg. Chem., 37, 1853-1867 (1998).

Fig.4. The calculated molecular structure of tris(tropolo-nato)bismuth(III), Bi(trop)3 (4), in two projections: (A) top view and (B) side view.

211At is one of the most prospective alpha emitters studied so far for cancer therapy. It is produced in the 209Bi(α,2n)211At reaction in cyclotrons. Its half--life of 7.2 h is sufficient for separation, labelling, quality control, shipment and medical application. It decays by double branch pathway with the mean alpha energy of 6.7 MeV.

From chemical point of view, astatine as a heavy halogen has similar properties to other members of the group, but it also exhibits some metallic character. Therefore, its bonds with aromatic and aliphatic moieties are much weaker than those of

iodine [1]. Thus, the labelling of peptides or anti-bodies with 211At is a big challenge. Moreover, bio-conjugates labelled with 211At are usually unstable under physiological conditions, which limits the use of astatinated radiophamaceuticals.

We propose a new type of 211At carriers, based on TiO2 nanoparticles modified with metallic silver. The nanoparticles are nanoscale materials (at least one dimensions below 100 nm). They exhibit some useful properties, e.g. ultra-small size, high specific surface area, high ion exchange properties, possi-bility of attaching organic compounds to the sur-

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, Poland2/ University of Silesia, Katowice, Poland

3/ The Henryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, Poland

A

B

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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 as-tatine, 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 carefully washed with distilled water. The loaded nanoparticles were shaken with solutions of am-monia (25%) and glucose (0.1 M). The adsorbed silver cations were reduced in commonly known reaction – “silver mirror” (Tollens’ reaction). The colour of the particles changed from white to dark brownish grey. The modified nanoparticles were washed with distilled water and ethanol, then dried at 100oC. The obtained nanoparticles differing in size (6-100 nm) and in the amount of adsorbed silver, were then labelled with 211At.

The labelling of TiO2/Ag nanoparticles with 211At was performed in phosphate buffer (pH 7.4). 2 ml PBS with 211At (~0.1 MBq/ml) was added to 5 mg TiO2/Ag nanoparticles, and the mixture was shaken for 1 h. The radiolabelled nanoparticles

were separated from the solution by ultracentrifu-gation (13 000 000 rpm). In all experiments the distribution coefficient of 211At exceeded 104 cm3/g.

The stability of 211At-labelled nanoparticles was assessed by adding the material (~3 mg) to physio-logical salt solution (0.9% NaCl), 0.02 M PBS buffer, 0.001 M cysteine, 0.001 M glutathione and human serum (2 ml each). The labelled nanopar-ticles were incubated from 1 to 14 h at room tem-perature, 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 to agglomerate in aqueous media. In order to sta-bilize them in the dispersed form, the particles were coated with polyethylene glycol (PEG). Me-

thoxyl silane functionalized PEG was used, be-cause it can be easily attached to the surface of metal oxide nanoparticles via the reaction of hy-droxyl groups with trimethoxyl silane. The aim of the surface modification was not only to hamper the agglomeration process, but also to make the nanoparticles more resistant to protein adsorp-tion and to enhance their biocompatibility [4]. Thermal gravimetric analysis (TGA) confirmed that the TiO2/Ag nanoparticles had been success-fully covered with PEG molecules. The images of TiO2/Ag nanoparticles observed under trans-mission electron microscope (TEM) are shown in Fig.2.

Afterwards, the samples of TiO2/Ag nanopar-ticles covered with PEG molecules were examined for labelling with 211At. The results were similar to those obtained for uncoated TiO2/Ag nanoparticles. Also in this case the distribution coefficients were high (>104 cm3/g). The stability of radiolabelled

Fig.1. The leakage of 211At from TiO2/Ag nanoparticles of different diameter in various solutions after 1 h.

Fig.2. TEM images of bare TiO2/Ag nanoparticles (A) and TiO2/Ag nanoparticles covered with PEG (B).

Fig.3. The leakage of 211At from labelled TiO2/Ag nano-particles covered with PEG of different diameter in vari-ous solutions after 1 h.

A B

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NANOTITANATE AS A NEW SORBENT FOR 137Cs SEPARATION FROM RADIOACTIVE WASTE

Barbara Filipowicz, Seweryn Krajewski, Monika Łyczko, Marek Pruszyński, Aleksander Bilewicz

nanoparticles covered with PEG was tested in the same solutions as above. No significant leakage of 211At was detected in any of the samples after 1 h (Fig.3). The highest release of 211At (ca. 6%) was detected in human serum. At the longest incuba-tion time (14 h) the slightly higher leakage of 211At (< 8%) was detected.

In conclusion, the new type of nanoparticles was successfully synthesized and tested. Both types of nanoparticles, TiO2/Ag and TiO2/Ag covered with PEG, exhibited high affinity for 211At and high stability in human serum. Therefore, they are good astatine carriers that can be used in nuclear medi-cine. Further experiments will focus on the modi-

fication of TiO2/Ag nanoparticles by attaching a tumour seeking agent. The stability, cell affinity and radiotoxicity studies with these new nanopar-ticles will be carried out.

References[1]. Vaidyanathan G., Zalutsky M.R.: Curr. Radiopharm.,

3, 177-200 (2008).[2]. Johnson G.L., Leininger R.F., Segrè E.: J. Chem.

Phys., 17, 1-10 (1949).[3]. Kang J., Sohn Y.: J. Mater. Sci., 47, 824-83 (2012).[4]. Eck W., Craig G., Sigdel A., Ritter G., Old L.J., Tang

L., Brennan M.F., Allen P.J., Mason M.D.: ACS Nano, 2, 2263-2272 (2008).

Radionuclides of 134Cs and 137Cs with the half-lives of 2 and 30 years, respectively, belong to the main long-lived fission products of 235U. These radionu-clides undergo radioactive decay with the emission of beta particles and relatively strong gamma ra-diation. Caesium salts, the most common form of the element easily dissolved in water, which causes a serious hazard if an accident appears with a nu-clear reactor. Caesium radionuclides leaked into the environment make a serious threat to the

health of present and future generations. There-fore, serious attention has been paid to the re-moval and separation of radiocaesium, especially 137Cs, from nuclear waste.

Various approaches and technologies such as coprecipitation and ion exchange have been de-veloped for the separation and immobilization of radioactive aqueous wastes generated at different stages of nuclear fuel cycle. Common ion exchange resins are not sufficiently efficient for radiocaesium

Fig.1. SEM images of: (A) nanotubes, (B) nanofibers, (C) nanoribbons, (D) nanowires.

BA

C D

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sorption from the waste. On the other hand, many inorganic and composite sorbents, such as insoluble ferrocyanides [1], zeolites [2], ammonium hetero-polyacid salts [3], titanium dioxide [4] and sodium titanates [5], have been systematically studied for separation of 137Cs from nuclear wastewater and safe disposal of the exchanged cations. The advan-tage of these materials is their ability to withstand intense radiation and elevated temperature in ad-dition to their high selectivity for Cs+ ions.

Nanostructures of titanates play an important role in the process of binding inorganic cations, in-cluding radionuclides, because of their good sorp-tion properties. The advantage of some layered nanotitanates is the collapse of their structure, which occurs during the ion exchange, and results in tight immobilization of targeted cations in the interlayer, thus in irreversible ion exchange [6, 7]. Therefore, the aim of our work was to examine various nanostructured titanates as sorbents for caesium radionuclides.

To prepare nanotitanates we used the method of hydrothermal synthesis (in autoclave). We have obtained four different forms of nanotitanates. The formation mechanism is complex and not clear. Both, the method used and conditions of the syn-thesis play the key role in obtaining the forms of interest. The morphology of various titanate forms is shown in Fig.1. The structures displayed an ag-gregated shape with heterogeneous morphologi-cal distribution of diverse polyhedral forms and

particles diameter that oscillated between 10-100 nm. Hydrothermal reaction of TiO2 (in the form of anatase) with a concentrated NaOH solution at 140oC resulted formation of nanotubes (Fig.1A). Contrary, amorphous TiO2 under the same condi-tions formed nanofibers (Fig.1B). Amorphous TiO2 was also used as a substrate to produce nanoribbons (Fig.1C), when the synthesis was performed with NaOH solution at 200oC, whereas nanowires (Fig.1D) were obtained in KOH solution. The mor-phology and elemental composition of the corre-sponding nanostructures were characterized by SEM (scanning electron microscopy) and TEM (transmission electron microscopy) with EELS (electron energy-loss spectroscopy). The structure and the degree of conversion of the substrate were determined by XRD (X-ray diffraction) spectra. The specific surface area and porosity were mea-sured by the BET method.

Table. The Kd values of 137Cs on nanotitanate and amor-phous TiO2 in 0.1 M solution of NaNO3.

Nanostructure Kd 137Cs (0.1 M NaNO3)

Nanotubes 4 x 102

Nanowires 2 x 102

Nanofibers 3 x 102

Nanoribbons 1 x 102

TiO2 amorphous 1 x 102

Fig.2. Sorption percentages of caesium on: (A) nanotubes, (B) nanofibers, (C) nanoribbons, (D) nanowires, as a function of time.

0 200 400 600 800 1000 1200 14000

10

20

30

40

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tion

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The sorption studies of 137Cs radionuclide were conducted on the all synthesized nanotitanates. The distribution coefficients (Kd) were determined in 0.1 M NaNO3. The results are shown in Table.

Presumably, similarly as in the case of ferrocy-anides and zeolites, Cs+ sorption can occur inside the nanotubes, where cations are dehydrated and the selectivity of adsorption depends on the energy of hydration. The inner sorption of Cs+ is relative-ly easy, since the energy of hydration for the Cs+ is rather small. This conclusion was also supported by the slow kinetics Cs+ the sorption on the nano-tubes, which suggest Cs+ diffusion into the interior.

Kinetics of ion exchange is one of the most im-portant characteristics in defining the efficiency of the sorbent. Na-titanate nanostructures revealed high and fast initial sorption of 137Cs+, followed by apparent saturation, that was especially visible in the case of nanowires and nanotubes (Fig.2). This can be explained by the fast initial sorption on the surface of the nanostructure, and a slower ion ex-change inside the nanopores.

Sorption of 137Cs+ ions on four forms of titanate nanostructures with different size and morphology (nanotubes, nanowires, nanoribbons and nano-fibers) was examined also at different concentra-tions of NaNO3 or KNO3 (10–3-10–1 M). As shown in Fig.3, a linear dependence of log Kd on log Na+ and log K+ confirms ion exchange mechanism of sorption. Again, nanotubes and nanowires struc-tures had the highest values of sorption towards

137Cs+ ions, probably due to their higher surface area compared to other nanostructures.

The Kd values for 137Cs+ ions slowly decreased with increasing the NaNO3 or KNO3 concentra-tions due to the competition and blocking of ac-tive sites on the nanostructures surface. As pre-dicted, the Kd values for K+ are smaller in relation to the values for Na+, what is related to the larger size of the K+ cation, and thus the greater compe-tition with a 137Cs+.The effect of pH on 137Cs sorption was studied in the pH range of 2-13. The results are shown in Fig.4.

The observed dependence of log Kd on pH above pH 9 seems rather unusual for sorption of inorganic cations on oxide sorbents, where the in-crease in pH is usually followed by a simultaneous increase in the Kd values. In the case of nanostruc-tures the highest sorption of 137Cs was reached at pH 7-9, and at higher pH the Kd decreased.

Leaching experiments in NaNO3 solutions show-ed that the release of 137Cs from titanate nano-tubes was negligible. This proves irreversible sorp-tion and suggests that the exchange of Na+ for Cs+ may result in the change of sorbent structure.

The presented results show that nanotitanates, in particular nanotubes, efficiently absorb radiocaes-ium from aqueous solutions, which makes them a prospective material for disposal of nuclear waste.

The work has been carried out within the stra-tegic research project “Technologies for the devel-opment of safe nuclear power engineering” (No. SP/J/4/143 321/11).

References[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.

Tech., 3, 67-70 (2009).[3]. Murthy G.S., Sivaiah M.V., Kumar S.S.: J. Radioanal.

Nucl. Chem., 260, 109-114 (2004).[4]. Bilewicz A., Dybczyński R., Narbutt J.: J. Radioanal.

Nucl. Chem., Articles, 148, 359-371 (1991).[5]. Mishra S.P., Dubey S.S., Tiwari D.: J. Radioanal. Nucl.

Chem., 261, 457 (2004).[6]. Li N., Zhang L., Chen Y., Fang M., Zhang J., Wang H.:

Adv. Funct. Mater., 22, 835-841 (2012).[7]. Yang D.J., Sarina S., Zhu H.Y., Liu H.W., Zheng Z.F.,

Xie M.X., Smith S.V., Komarneni S.: Angew. Chem. Int. Edit., 50, 10594-10598 (2011).

Fig.3. Effect of concentration of: (A) sodium and (B) po-tassium ions on the sorption of 137Cs+.

Fig.4. Effect of pH on the caesium sorption on titanate na-nostructures.

1 2 3 4 5 6 7 8 9 10 11 12 13 14

2,0

2,5

3,0

pH

log(

Kd)

nanotubes nanofibers nanoribbonsnanowires

-3,5 -3,0 -2,5 -2,0 -1,5 -1,0 -0,51,5

2,0

2,5

3,0

3,5

4,0

4,5

nanotubes nanowires nanoribbons nanofibers

log(

Kd)

log[Na+]

A

-3,5 -3,0 -2,5 -2,0 -1,5 -1,0 -0,51,5

2,0

2,5

3,0

3,5

4,0

4,5

nanotubes nanowires nanoribbons nanofibers

log(

Kd)

log[K+]

B

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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 protective barriers against leaching of the stored radionuclides: metal canisters (tanks), buffers made of adsorbent of metal ions, and often the surrounding rocks. On the other hand, humidity from the outside may penetrate the storage tanks. Various biopolymers and naturally occurring inor-ganic adsorbents were examined as inexpensive and abundant materials able to slow down to a sig-nificant degree the velocity of migration of the radionuclides, e.g. [1, 2].

Volclay MX80 bentonite, aluminum silicate clay formed from volcanic ash, was intensively studied for the last 20 years as a compact barrier for nu-clear waste repositories [3], and it has been found suitable for this purpose. Studies performed in the frame of the strategic project “Technologies sup-porting development of safe nuclear power engin-eering” – task 4 “Development of spent nuclear fuel and radioactive waste management techniques and technologies” concerned bentonite easily avail-able in Poland, which has been tested as potential buffer in the National Radioactive Waste Repo-sitory in Różan (Poland), and also as a sorbent for removing of radionuclides potentially contaminat-ing water, in particular drawn in the water supply of the Institute of Nuclear Chemistry and Tech-nology (INCT).

The present work was devoted to the study of this bentonite as adsorbent of trivalent ions of americium-241. This radionuclide is the only acti-nide element which has been used in the house-hold – in smoke detectors. These sensors use 241Am in the form of dioxide as the source of radiation that ionizes air [4], because this alpha emitter in combination with beryllium forms an efficient neu-tron source owing to the large cross-section of be-ryllium-9 for the (α,n) nuclear reaction [5]. Ame-

ricium-241 is also used as a portable source of both gamma rays and alpha particles applied in some medical and industrial uses. The 60-keV gamma-ray emissions from 241Am in these sources can be used for indirect analysis of materials in radiography and X-ray fluorescence spectroscopy, as well as for quality control and nuclear denso-meters. Because of that, americium-241 is a sig-nificant component of radioactive wastes and it is important test efficient barriers for the 241Am con-taining repositories.

To check the possibility of application of the ben-tonite sorbent as the engineering barrier, samples of the granular Volclay bentonite were gamma-ir-radiated in the cobalt bomb at the INCT with the dose of 100 kGy. Some main properties of the ir-radiated bentonite, among them sorption, were compared with these of the non-irradiated mate-rial.

Prior to the studies, the commercial Volclay bentonite (P.W. Structum Ltd, Lublin, Poland) in the granular form was converted to its sodium form (assigned as Na-Vc) by equilibrating 5 g of raw bentonite with 100 mL of 1 mol/dm3 aqueous solution of NaCl. Chemical composition of the Na-Vc is presented in Table 1. Similarity in the composition of the irradiated material with that of the non-irradiated one suggests that no decompo-sition occurs upon gamma radiation.

Porosity of sorbents and their surface size are the fundamental factors for sorption processes of the toxic and/or radioactive metals [6]. Therefore, in separate studies we determined these properties of Na-Vc. They are summarized in Table 2.

Powder X-ray diffraction studies reveal that Na-Vc is the material of layered structure, both in natural and in the irradiated materials (Fig.1). Remarkable shift, however, of the small 2θ angle

ElementConcentration [%]

ElementConcentration [ppm]

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

Table 1. Chemical composition of the Volclay bentonite used in the studies (ED XRF – energy dispersive X-ray fluores-cence) – major components.

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peak from 7.037 to 7.350 deg suggests a decrease in the distance between the layers, from 12.551 to 12.069 Å, which occures upon the irradiation.

The potable water was collected in the INCT. Content of different ions in the water is presented in Table 3 together with the WHO quality stand-ards. Content of all main cations and anions pre-

sent in the drinkable water and in the water shak-en with the bentonite sample indicates that the sorbent is both chemically and mechanically stable.

The only significant difference in the concentra-tions of sodium cations may be explained by the supposed presence of the excess of these cations used for the conversion of the bentonite to its sod-ium form.

Post-decontamination liquids were simulated by dissolving 21 g of citric acid in 100 mL of water to obtain 1 M solution prior to americium-241 ad-dition.

Sorption of americium(III) was studied as a function of contact time, initial pH and mass of the sorbent, respectively. Except the experiments on the time necessary for reaching the equilibrium, all examinations were made in parallel: with normal Na-Vc and with the irradiated material. The latter seems to be of interest because of its possible ap-plication as the engineered barrier in radioactive waste repositories.

As it can be seen from Fig.2, adsorption of Am3+ comprises two stages: a primary rapidly increasing phase and a secondary phase, of slower increment. At the first 1 h, Am3+ removal from the aqueous

solutions was observed in the rapid stage, while from 1 to 6 h, the adsorption increase was slow. It reached an equilibrium at about 4 h of shaking

Table 2. Main physicochemical properties of the Volclay bentonite applied in the presented work [7].

Property Value

Apparent powder density [g/cm3] 1.31

Particle diameter [mm] 0.1

BET surface [m2/g] 54.08

Micropore surface [m2/g] 17.64

Total volume of the pores [cm3/g] 7.36 · 10–2

Volume of the micropores [cm3/g] 0.82 · 10–2

Mean diameter of the pores [Å] 101.74

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.

Table 3. Content of ions [mg/dm3] in the potable water samples.

Fresh water

Content of ion [mg/dm3]

Na+ K+ Mg2+ Ca2+ Fe3+ Zn2+ Cu2+ F– Cl– NO3– SO4

2–

18.50 ± 1.48

4.36 ± 0.35

8.78 ± 0.70

97.2 ± 7.8

0.005 ± 0.001

1.45 ± 0.12

0.21 ± 0.02

0.046 ± 0.004

20.9 ± 1.7

1.58 ± 0.13

144.7 ± 11.6

Agitated water* 30.98 5.24 8.51 82.39 0.005 0.062 0.005 0.007 22.68 1.66 137.04

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.

Lin

(Cou

nts) 900

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with the efficiency of about 99.7%. We may as-sume that initially, the uptake can be attributed to the concentration gradient of Am3+ and to the

greater number of available binding sites. In the second stage of the Am3+ intake, the active bond-ing 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 charge. This negative charge attracts species of the opposite, positive charge, not only heavy/radioac-tive metals, but also toxins, harmful bacteria, dyes and various pathogens [10]. Thus the acidity of the solution is an important factor that must be con-sidered during sorption studies due to the proto-nation and deprotonation properties of the sor-bent surface. The effect of pH on Am(III) removal was studied in the pH range from 2.0 to 10.0 for an adsorbent dose of about 3.5 g L–1.

The results presented in Fig.3 clarify that at pH < ∼5, the removal of Am(III) is lower due to the competition between hydroxonium ions (H3O+) with the metal cations for the adsorption sites of bentonite. In weakly acidic (pH = 5-7) and basic (pH = 7-10) solutions, various hydrolysed poly-meric species of Am(III) may appear in the rela-tive proportions depending on the pH and the total americum concentration. It may be conclud-ed from the plot in Fig.3 that H3O+ and OH– ions in relatively small concentrations do not signifi-cantly compete with americium for the bentonite

binding sites, thus only small increase in the sorp-tion percentage is observed.

The dependence of Am(III) sorption on ratio of the adsorbent mass : decontaminated solution volume was studied by varying the amount of the the sorbent from 0.1 to 2 g L–1, keeping other pa-rameters (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-

ing the greater availability of the adsorption sites. Around 99% of Am(III) was removed when 1 g of the sorbent was put in the solution. After reaching this dose, the plateau in the sorption percent values is observed even with further addition of the ad-sorbent.

An attempt to revitalize of the Am(III)-loaded Na-Vc was done by shaking the material at room temperature with different types of desorbing agents, i.e. 0.01 M NaCl, 0.01 M NaNO3, 0.01 M Na3PO4, 0.01 Na2CO3, 0.01 M Na2SO4, or 1 M CaCl2 in potable water collected at the INCT. Samples of drinking water of different acidities were also tested.

The results presented in Fig.5 show that the percentage of Am(III) desorption with all agents studied does not exceed 0.1%. Experiments with potable water of the pH in the range of 2.5 to 10.5 also show for strong binding of Am(III) by Na-Vc. No more than 0.4% of the adsorbed radioactivity has been removed from the material. So, in the combination with strong affinity toward water, Na-Vc may be proposed as a potential material for protecting barriers in radioactive waste tanks in waste repositories.

We thank Dr. T. Szreder (INCT) for irradiat-ing the bentonite samples, Dr. J. Dudek (INCT) for carrying out the ICP-MS analyses of the ben-tonite and Mr. K. Kulisa (INCT) for analyses of the samples of water.

The work was supported by the National Centre for Research and Development, Poland in the frame of the strategic project “Technologies supporting development of safe nuclear power engineering” – task 4 “Development of spent nuclear fuel and radioactive waste management techniques and technologies” (No. SP/J/4/143 321/11).Fig.3. Effect of pH on sorption of Am(III) by bentonite.

Fig.4. Effect of the sorbent mass on sorption of Am(III) by Na-bentonite.

Fig.2. Effect of time on Am(III) sorption on Na-bento-nite.

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References[1]. Combined methods for liquid radioactive waste treat-

ment. 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 radio-active 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)[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 ben-tonite). 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.naturalnews.com/036972_bentonite_clay_heavy_metals_detox.html#.

Fig.5. Desorption of Am(III) from Na-Vc: (A) by different aqueous solution, (B) effect of pH on the desorption by potable water collected at the INCT.

THE STUDY OF SORPTION OF COBALT IONS ON THE RED CLAY AND ZEOLITES

Grażyna Zakrzewska-Kołtuniewicz, Agnieszka Miśkiewicz, Wioleta Olszewska, Bożena Sartowska

The removal of hazardous heavy metals from aqueous streams represents a significant environ-mental challenge. Cobalt is classified as heavy metal that can cause serious environmental contamina-tion if present at high enough concentration. The agriculture, mining, electronics, metallurgical, and pigment/paint industries are the principal sources of excessive release of cobalt in waste streams.

Zeolites are proven ion exchange materials where the indigenous (typically sodium) charge bal-ancing cations are not fixed rigidly to the hydrated aluminosilicate framework and are readily exchang-ed with cations in solutions [1]. Zeolites were pre-viously applied for water and wastewater treatment [2] as well as for radioactive waste processing [3, 4].

Clay based adsorbents have also emerged as promising adsorbents for wastewater treatment [5]. Clays possess certain properties which make them an ultimate choice for adsorption process such as low cost, high availability, and environ-mentally friendly material. Consequently, clays can substitute expensive activated carbon as well as low-performing biosorbents [6, 7]. The clays can

be used either in their natural form or modified with some chemical agents, depending on the tar-get pollutants [6].

Red clay is one such material that is abundant-ly available and not expensive, so it can also be considered as an adsorbent like other clay mate-rials. Sorption properties of red clay and different types of clay materials have been extensively in-vestigated for the purpose of Brilliant Green dye removal from aqueous solutions [8]. Red clay was also used for sorption of transition metals [9] as well as such radioactive elements as Cs-134, Sr-85 and Zn-65 [10].

In the present work red clay and zeolite 5A were used for cobalt ions removal from aqueous solutions with further perspective of using them for the treatment of radioactive solutions. The idea is to use these materials just as a adsorbents of radio-active species or as binding material in ultrafiltra-tion/sorption hybrid process for radioactive wastes processing. Characteristics of red clay (Pałęga min-ing) with particle size lower than 0.1 mm is col-lected in Table 1. Zeolite 5A (POCH, ACROS OR-

A

B

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GANIC) used in current studies was in the form of powder with particle size lower than 50 μm.

In the first stage, sorption kinetic studies were performed. Furthermore, the effect of pH, ionic

strength as well as the ratio of the reagents on the efficiency of cobalt ions removal was examined in order to select the optimal process parameters.

Kinetic experiments with red clay, carried out with reagent ratio ([Co2+]/[sorbent]) equal to

1/1000, and at pH = 6 showed that sorption effi-ciency of cobalt ions exceeded 80% just after few minutes of the phases contact (Fig.1A). Even high-er sorption efficiency, nearly 90%, was observed in the case of using zeolite 5A as a sorbent of co-balt ions. In this experiment lower excess of sor-bent was applied, namely 1/20, pH was held at the level of 7. However, in the case of zeolite, the equilibrium of sorption of cobalt ions was obtain-ed only after 10 days of process, what is shown in Fig.1B. Generally, zeolite 5A showed ca. 100-times higher sorption capacity than red clay.

Sorption ability of red clay as well as zeolite 5A was dependent on pH. As showed in the ex-periments, the best conditions of binding Co2+ by both sorbents was at pH = 7 (Fig.2).

The studies performed also showed that the most effective reagent ratio was 1/2000 and 1/20 for red clay and zeolite 5A, respectively. Experi-

Fig.1. Kinetics of sorption of cobalt ions on: (A) red clay – pH = 6, [Co2+] 0 = 5 mg/l, [Co2+]/[sorbent] = 1/2000; (B) zeo-lite 5A – pH = 7, [Co2+]0 = 100 mg/l, [Co2+]/[sorbent] = 1/20; ♦ – sorption efficiency, ο – sorption capacity (q).

A B

Table 1. Characteristics of red clay.

Mineralogical composition

mineral content [%]

Illite 23-37

Kaolinite 6-12

Chlorite 3-5

Quartz 30-45

Hematite 3-6

Chemical composition

SiO2 64.79

Al2O3 16.26

Fe2O3 7.22

MgO 2.38

K2O 2.68

CaO 0.4

TiO2 0.91

MnO 0.09

Fig.2. Effect of pH on the sorption efficiency of cobalt ions on: (A) red clay – [Co2+]0 = 5 mg/l, [Co2+]/[sorbent] = 1/2000, teq = 0.5 h; (B) zeolite 5A – [Co2+]0 = 100 mg/l, [Co2+]/[sorbent] = 1/20, teq = 264 h.

A B

Table 2. Sorption efficiency and sorption capacity of two sorbents for different reagent ratio ([Co2+]/[sorbent]). Ex-periments conditions: red clay – pH = 7, [Co2+]0 = 5 mg/l, teq = 0.5 h; zeolite 5Å – pH = 7, [Co2+]0 =100 mg/l, teq = 264 h.

Reagent ratio

Sorption efficiency [%] q [mg/g]

red clay zeolite 5A red clay zeolite 5A

1/10 7.3 43.9 8.5 43

1/20 - 99.0 - 51

1/100 32.1 98.5 3.75 10

1/2000 95.6 - 0.27 -

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mental data showing the relation between sorp-tion efficiency and the amount of sorbents are col-lected in Table 2.

Finally, the effect of the salinity on the sorp-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 re-duction of sorption efficiency: from 43 to 35%.

In order to verify the applicability of a hybrid process for the removal of cobalt ions from the aqueous solutions, the ultrafiltration/sorption pro-cess in dead-end mode was performed. This ex-periment has been conducted using filtration cell (Amicon) with polyethersulphone membrane (Millipore Corporation, NMWL 10 000). Model solution of cobalt ions of 1 mg/l concentration with an appropriate amount of the sorbent was filtered through the membrane. The UF installa-tion worked under 0.3 MPa pressure. The samples of filtrate were collected for analysis every 15 min. The experiment showed high retention of co-balt ions using the hybrid ultrafiltration/sorption process (Fig.4).

After filtration, the whole amount of the prepared solution (1 dm3), which took about 1 h, the mem-brane was removed from the filtration cell, dried and observed through the scanning electron micro-

scope (DSM 942, Zeiss). The sample images of the membrane surface and deposit collected on the membrane are presented in Fig.5. As can be ob-served, clay deposit covers the membrane surface non-uniformly, and the surface of the deposit par-ticle has a rough structure.

The results show that the sorption ability of the red clay and zeolite 5A are satisfactory. Proper se-

Fig.4. Retention of cobalt ions during filtration of the sus-pension of the red clay and cobalt chloride, using Amicon cell with polyethersulphone membrane; cut-off = 10 kDa, p = 0.3 MPar, [Co2+]0 = 1 mg/l, [Co2+]/[sorbent] = 1/4000, pH = 7, teq = 0.5 h.

Fig.3. Effect of salinity on the sorption efficiency of cobalt ions on: (A) red clay – [Co2+]0 = 5 mg/l, [Co2+]/[sorbent] = 1/2000, pH = 7, teq = 0.5 h; (B) zeolite 5A – [Co2+]0 = 100 mg/l, [Co2+]/[sorbent] = 1/10, pH = 7, teq = 23 h.

A B

Fig.5. SEM images of: (A) membrane used in ultrafiltration experiment of filtration of the red clay suspension; (B) de-posit accumulated on the membrane during filtration experiment.

A B

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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

lection of process conditions allows adsorption of cobalt ions with an efficiency greater than 95%. Moreover, by the use of sorption/ultrafiltration hy-brid process it is possible to remove cobalt ions from water solution with high efficiency.

The research was done in the scope of the stra-tegic research project “Technologies supporting development of safe nuclear power engineering” – stage 6 of research task 4 “Development of spent nuclear fuel and radioactive waste management techniques and technologies”.

References[1]. Breck D.W.: Zeolites molecular sieves: structure,

chemistry and use. New Wiley and Sons, New York 1974, pp. 634-637.

[2]. Wang S., Peng Y.: Chem. Eng. J., 156, 11-24 (2010).

[3]. Sharygin L.M., Muromskii A.Y.: Radiochemistry, 46, 2, 185-189 (2004).

[4]. Çiçek E., Cojocaru C., Zakrzewska-Trznadel G., Ha-rasimowicz M., Miskiewicz A.: Environ. Technol., 33, 1, 51-59 (2012).

[5]. Auta M., Hameed B.H.: Chem. Eng. J., 198-199, 219-227 (2012).

[6]. Nassar M.M., El-Geundi M.S., Al-Wahbi A.A.: De-salin. Water Treat., 44, 340-349 (2012).

[7]. Nandi B.K., Goswami A., Purkait M.K.: J. Hazard. Mater., 161, 387-395 (2009).

[8]. Rehman M.S.U., Munir M., Ashfaq M., Rashid N., Nazar M.F., Danish M., Han J.: Chem. Eng. J., 228, 54-62 (2013).

[9]. Takematsu N.: JOSJ (Journal of the Oceanographi-cal Society of Japan), 35, 1, 36-42 (1979).

[10]. Twining J.R., Payne T.E., Itakura T.: J. Environ. Ra-dioact., 71, 71-87 (2004).

One of the objectives of the Polish Nuclear Power Programme [1] is the assessment of domestic uran-ium deposits as a potential source of uranium for Polish nuclear reactors. Presently, mining of Polish low-grade uranium ores appears uneconomic [2]. However, studies on the prospects of recovery of uranium from domestic resources are in progress, keeping in mind the inevitable growing uranium demand and perspectives of the global uranium market.

The most perspective deposits are in the Lower Ordovician Dictyonema shale of Podlasie Depress-ion (North-Eastern Poland) with uranium concen-tration of 75-250 ppm and the Lower and Middle Triassic rocks of the central part of Peribaltic Syne-clise, where concentrations reach even 1.5% U (recent analysis of archive samples).

The main objectives of this research were: to assess the possibility of exploitation of uranium resources in Poland, and to work out methods of uranium extraction from the ores for production of yellow cake – U3O8.

The characteristics of the material originating from uranium ores vary significantly from deposit to deposit. The effect of ore mineralogy and min-eral liberation on the leaching behaviour of uran-ium is not well defined. The procedure of uranium extraction must be designed to fit specific charac-teristics of the ore; however the general scheme of the process is similar for most of the ore mate-rials. The basic steps of processing of uranium ores are: crushing and grinding, leaching, solid-liquid separation, ion exchange or solvent extraction, and

finally precipitation of final product yellow cake – U3O8 [3].

The solid-liquid extraction is a very important stage in the technology of uranium production from the uranium ores. In the present work at the beginning of the extraction process, uranium was leached from the ground ore by using sulphuric acid or carbonate (CO3

2–) solutions [4, 5]. In com-parison with acid processing, alkaline leaching had the advantage of being selective for uranium. The metals associated with uranium in the ores were also present in acidic post-leaching solutions. In the case of alkaline leaching process only three or two metallic components of the ores were detect-ed: U, Mo and V (dictyonemic shales) or U and small amounts of V (sandstones) (Fig.1). The post--leaching solutions were separated from the leach-ed ore by filtering and washing and then concen-trated and purified using solvent extraction or ion exchange chromatography [6].

The helical membrane contactor equipped with rotating part, applied for uranium recovery from uranium ores, was proposed. In this method leach-ing uranium ores combined with solid-liquid sep-aration by filtration in one membrane apparatus can be carried out [7]. Series of experiments were performed using helical contactor for the purpose of testing the leaching uranium and other valuable metals from uranium ores. The process parameters varied according to the experimental plan were as follows: the velocity of the feed flow (in the range from 0.67 to 1.33 L/min) and rotation frequency of the inner cylinder (in the range from 0 to 2500 rpm).

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49CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY

Results of experiments are presented in Fig.2. It can be noticed that by increasing flow velocity the efficiency of uranium leaching can be enlarged but

the influence of the speed of the rotor is rather in-significant.

Efficiency of uranium leaching obtained with acentric membrane contactor was comparable with those obtained by leaching in a stationary reactor with mixing. The concentration of other associat-ed metals like vanadium, molybdenum or lantha-nides 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 sep-aration of solid phase from post-leaching solu-tions. Such an approach results in reduction of total cost of operation with no consequences to the separation efficiency.

Uranium could be recovered from post-leach-ing solutions by using solvent extraction followed by stripping to aqueous phase. The extracting agents, like for example tributylphosphate (TBP), di(2-ethylhexyl)phosphoric acid (DEHPA), trioc-tylphosphine oxide (TOPO), triethylamine (TEA), tri-n-octylamine (TnOA), and other reagents, were tested with the model uranium solutions [8]. The

Fig.1. Minimal and maximal value of efficiencies of leaching of metals from sandstones deriving from Perbaltic Syneclise (various deposits) under different process conditions: (A) 10% H2SO4, MnO2, 60oC, 1 h; (B) 10% HCl, 30% H2O2, 60oC, 1 h; (C) 8% NaOH/18% Na2CO3, 30% H2O2, 60oC, 1 h; (D) 5% Na2CO3/NaHCO3, KMnO4, 60oC, 1 h.

Fig.2. Comparison of the uranium leaching efficiency de-pending on feed flow velocity and velocity of the rotor in the helical membrane contactor.

Fig.3. Extraction and re-extraction efficiencies of metals from: (A) acidic and (B) alkaline post-leaching solution.

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mixture of DEHPA and TBP was found as a good extractant for uranium and the studies of extrac-tion of uranium from ore-leaching liquors (sul-phuric and carbonate) were carried out. The use a different reagents as strip solutions for uranium in organic phase was also investigated. The results are presented in Fig.3.

The technique of membrane extraction with application of the contactors with co-current flow of aqueous and organic phases was also examined as an alternative to traditional methods of extrac-tion [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 mem-brane extraction process. Then the experiments of extraction/re-extraction with real post-leaching

solutions were proceeded and the high value of recovery of uranium (96%), thorium (81%) and ytterbium (67%) was obtained.

The possibility of application of calixarenes (Fig.4) as selective extracting agents for uranium were also considered. The calix[6]arenes act as very

good uranophiles in separation processes [10]. They may be useful for extracting UO2

2+ from solutions after leaching of uranium ores, sea water, radioac-

Fig.4. The structure of calix[6]arene.Fig.5. Set of two columns with: (A) strongly basic anion exchanger (DOWEX1 X8), (B) strongly acidic cation ex-changer (DOWEX50 WX8).

OHOH

OH

OH

OHOH

R R

R

RRR

Feed solution

U

Ln

Other accompanying metals

eluents

eluents

A

B

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.

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tive waste or contaminated soil. Application of such extracting agents enables the use of 10 to 100 times lower ligand concentrations necessary to reach an assumed extraction yield than with the other existing extractants.

The purification of uranium from accompanying metals could be also achieved by the ion exchange chromatography [6]. Two following columns, one by one, were adapted for purification of acidic post--leaching solution. First column was filled with strongly basic anion exchanger (DOWEX1 X8), and the second – with strongly acidic cation exchanger (DOWEX50 WX8) (Fig.5). Feed solution was in-troduced into the first column (Fig.6A). This col-umn did not adsorb cations, which are eluted to the second column (Fig.6B,C). The combination of dif-ferent eluents allowed to obtain pure fractions of valuable metals. Uranium complexes were adsorb-ed on the anion exchanger and next they were elut-ed with 1 M (one molar) sulphuric acid. Behaviour of U and some other metals, when feed solution was poured into the columns is shown in Fig.6.

The precipitation of ammonium diuranate or uranium peroxide forms is the most crucial step in the production of uranium oxide. This is followed by calcination step forming triuranium octoxide (U3O8). The study of the precipitation was carried out for the model uranium solution. The influence of concentration of sulphuric acid, temperature and concentration of uranyl ion in the solution were examined. The representative results are pre-sented in Table.

The present project allowed preparing the set of methods and technologies that will be ready for subsequent implementation in the nuclear fuel production to extract uranium from the ores and other sources. On the basis of these results, the process design of pilot-scale installation was pre-pared [11]. The project was completed with tech-nical and economic analysis [12].

References[1]. Program Polskiej Energetyki Jądrowej (Polish Nu-

clear Power Programme). Ministerstwo Gospodarki, Pełnomocnik Rządu ds. Polskiej Energetyki Jądro-wej, Warszawa, grudzień 2010 (in Polish).

[2]. Miecznik J.B., Strzelecki R., Wolkowicz S.: Prz. Geol., 59, 10, 688-697 (2011), in Polish.

[3]. Edwards C.R, Oliver A.J.: JOM, 12-20 (2000).[4]. Zakrzewska-Trznadel G., Kiegiel K., Frąckiewicz K.,

Gajda D., Chajduk E., Bartosiewicz I., Chwastowska J., Wołkowicz S., Miecznik J.B., Strzelecki R.: Studies on the leaching of uranium from lower Triassic Peri-baltic sandstones. In: INCT Annual Report 2011. In-stitute of Nuclear Chemistry and Technology, Warsza-wa 2012, pp. 47-48.

[5]. Frackiewicz K., Kiegiel K., Herdzik-Konecko I., Chaj-duk E., Zakrzewska-Trznadel G., Wolkowicz S., Chwas-towska J., Bartosiewicz I.: Nukleonika, 58, 4, 451-459 (2012).

[6]. Zakrzewska G., Gajda D., Dybczyński R., Samczyński Z., Herdzik I., Chajduk E., Danko B.: The study on the separation of uranium from associated metals in the post-leaching solution by ion-exchange process. In: INCT Annual Report 2012. Institute of Nuclear Chemistry and Technology, Warszawa 2013, pp. 48-50.

[7]. Zakrzewska-Trznadel G., Jaworska-Sobczuk A., Miś-kiewicz A., Łada W., Dłuska E., Wroński S.: Method of obtaining and separation of valuable metallic ele-ments, specifically from low grade uranium ores and radioactive liquid wastes. European Patent Applica-tion No. 12196071.0-2122.

[8]. Kiegiel K., Zielińska B., Biełuszka P., Zakrzewska--Trznadel G., Chajduk E., Wołkowicz S., Miecznik J.B.: Solvent extraction of uranium from post-leaching so-lutions. In: INCT Annual Report 2012. Institute of Nuclear Chemistry and Technology, Warszawa 2013, pp. 46-48.

[9]. Biełuszka P., Zakrzewska G., Chajduk E., Dudek J.: J. Radioanal. Nucl. Chem., 299, 1, 611-619 (2014).

[10]. Kiegiel K., Steczek L., Zakrzewska-Trznadel G.: J. Chem., Article ID 762819, 16 p. (2013), http://dx.doi.org/10.1155/2013/762819.

[11]. Pochopień H., Szyndler K.: Projekt procesowy instala-cji pozyskiwania uranu z rud uranowych (The process design of pilot-scale installation for uranium recovery from uranium ores). Centrum Projektowe Polimex--Mostostal, Gliwice 2013 (in Polish).

[12]. Sprawozdanie – Tom II. Zadania 5-7. Analiza możliwo-ści pozyskiwania uranu dla energetyki jądrowej z za-sobów krajowych POIG.01.01.02-14-094/09 (Report: Analysis of the possibility of uranium supply from do-mestic resources POIG.01.01.02-14-094/09. Vol. II. Tasks 5-7). Konsorcjum: Instytut Chemii i Techniki Ją-drowej i Państwowy Instytut Geologiczny – Państwo-wy Instytut Badawczy, Warszawa 2013 (in Polish).

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

Precipitated uranium compound

Concentration of uranyl ions [mg/mL] CH2SO4 Temperature [oC]/time [h] Yield [%]

(NH4)2U2O7

0.3 2 M 40oC/4 h 88

0.5 2 M 40oC/4 h 98

0.9 2 M 40oC/4 h 95

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

UO4 ⋅ H2O

1 2 M 60oC/4 h 17

2 2 M 60oC/4 h 28

2 0.5 M 60oC/4 h 85

1 2 M 90oC/4 h 99

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STUDIES ON LEACHING COPPER ORES AND FLOTATION WASTESDanuta 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-tions are increasingly sought for uranium extrac-tion from unconventional sources, including phos-phate rocks, flotation tailings from copper produc-

tion, wastes from phosphoric acid production, and even sea water [1-3]. Studies on uranium leaching from copper ores and tailings were carried out at

the Institute of Nuclear Chemistry and Technology (INCT).

Significant deposits of copper ores exist in Poland. Large amounts of flotation wastes are pro-

duced in the process of extraction from the ores. Many other valuable metals accompany copper in the ores and flotation wastes. Flotation tailings

Table 1. The content of important elements in copper ores and copper flotation wastes [ppm] (ICP-MS analysis).

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

Elements Waste 1 Copper concentrate Waste 3 Waste Gilów KGHM 1 Waste

Gilów 2 PBK

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

Material (initial uranium content)

Concd. H2SO4

Uranium content

samples roasted samples unroasted samples treated with the oxidant – MnO2

[ppm] [%] [ppm] [%] [ppm] [%]

Waste 1(14.7 ppm)

96% 4.3 29.4 5.1 35.0 7.9 53.6

72% 4.0 27.2 1.7 11.3 6.5 44.6

48% 5.4 36.7 7.3 49.7 10.8 73.5

24% 0.0 0.2 6.0 41.3

Copper concentrate (12.9 ppm)

96% 5.4 41.9 14.0 ~100

72% 6.6 51.4 8.1 62.9 13.0 ~100

48% 2.8 21.8 12.1 93.5 2.2 17.1

24% 2.6 19.9 8.4 64.9

Waste 3(15.5 ppm)

96% 6.4 41.2 3.2 20.6 11.0 71.0

72% 9.1 58.8 11.5 74.0

48% 5.7 3.5 5.9 37.8 5.8 37.3

24% - - 5.3 34.3

Waste Gilów(7.3 ppm)

96% 4.0 54.2 5.4 73.4

72% 6.9 93.9 3.6 49.8 4.1 56.4

48% 3.2 44.6 2.0 27.1 1.1 15.1

24% - - 1.2 15.9

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from the enrichment process of copper ore are es-timated as about 90% of the amount of the ore processed. The uranium content in the ore from the copper mine Sieroszowice Lubin is about 60 ppm (the copper content – 2%) [4]. Production of copper in the basin Lubin-Sieroszowice in 2009 was about 569 kilotons. It is estimated that the

amount of uranium discharged in Poland to land-fill waste is about 1700 tons per year.

The main goal of the present work was the analysis of uranium content in a series of indige-nous copper ores and wastes, and the elaboration of procedures for uranium recovery from the raw materials. The study involved two types of ore (KGHM 1 and PBK), copper concentrate, and

four types of flotation wastes (Gilów, Waste 3, Gilów 2, Waste 1). Using ICP-MS (inductively coupled plasma mass spectrometry) analysis, the content of individual elements in the examined samples was determined. It has been found that uranium content in the materials studied varies from 4.5 to 27 ppm. The other elements that have

been determined in these materials are: Cu (4-5% in ores and 0.3-1.7% in the waste), Ag, Re, Mo, lanthanides, Ni, V, etc. (Table 1).

The process of digestion and leaching of uran-ium ores and flotation wastes was carried out by two methods. The “acid-cure” (AC) method con-sisted in direct action of concentrated sulphuric acid (H2SO4) on the sample. After 5 h, the sample

Fig.1. Recovery of uranium from samples of copper concentrate and Waste 3 using AC method, under various condi-tions.

0

2

4

6

8

10

12

14

unroasted roasted roasted+MnO2

U [p

pm]

0102030405060708090

100

unroasted roasted roasted+MnO2

U %

reco

very

Cooper Concentrate - 96% H2SO4Cooper Concentrate - 72% H2SO4

Waste 3 - 96% H2SO4Waste 3 - 72% H2SO4

Table 3. Uranium leaching from the indicated samples (WR method).

Material (initial uranium content) Concd. H2SO4

Uranium content

samples roasted samples unroasted

[ppm] [%] [ppm] [%]

Waste 1(14.7 ppm)

40% 2.6 18.0 1.6 10.6

20% 4.3 29.2 1.2 8.4

10% - - 0.0 0.1

5% - - - -

Copper concentrate (12.9 ppm)

40% 0.7 5.6 1.3 10.3

20% 3.4 26.5 2.2 16.9

10% - - 5.7 43.8

5% - - 4.1 32.1

Waste 3(15.5 ppm)

40% 12.9 83.4 16.1 ~100

20% 1.5 9.4 11.0 71.0

10% - - 4.2 26.8

5% - - 0.1 0.5

Waste Gilów(7.3 ppm)

40% 3.77 51.6 3.0 41.3

20% 1.6 22.2 2.1 28.8

10% - - 5.5 75.8

5% - 18.0 0.0 10.6

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was leached with H2O, either at room tempera-ture (RT) or at 70oC for 5 h, and then filtered. This method was also applied to samples pre-calcined at 900oC for 2 h and to the samples with addition of 2% MnO2 as oxidant [5, 6]. The second method, WR, consisted in digestion of the sample for 5 h with sulphuric acid of various concentrations (40, 20, 10 and 5%) at boiling temperatures [7].

The influence of grinding the samples on leach-ing efficiency, and on the kinetics of leaching was also studied. The optimum leaching conditions have been found. The concentrations of uranium in the final solutions were generally less than 15 ppm. The leaching solutions contained also the other metals.

Table 2 presents the leaching results (AC method) for samples roasted, unroasted, and also treated with the oxidant (MnO2), and selected re-sults have been presented more clearly in Fig.1. The data show that the highest leaching yields of uranium (> 70%) were obtained for samples roast-ed and treated with MnO2, but only for copper concentrate they approached to 100%.

The results of uranium leaching using the WR process are shown in Table 3.

The influence of grinding the samples on uran-ium leaching is shown in Fig.2. In the case of KGHM ore, the effect of grinding on uranium leaching was not significant because for many

fractions the efficiency close to 100% was reached. For the Waste Gilów such high yields were ob-served only for the fraction 0.2-0.5 mm.

For evaluation of the two leaching methods tested, AC and WR, the following parameters were studied: type of material (ore or waste), concen-tration of sulphuric acid, sulphuric acid with a 2% oxidizing agent, additional pre-calcination step, leaching time, grinding of initial material.

In conclusion, the AC method is definitely better than the WR one for the recovery of uran-ium. The highest yields, nearly 100% leaching, have been found for samples initially calcined, and samples treated with oxidizing agent, MnO2. Simultaneous liquid-liquid extraction of uranium and other metals from the leaching solutions is under study. In our opinion, only such a combined procedure could be cost-effective for the recovery of uranium together with the accompanying ele-ments.

The studies were supported from the Opera-tional Programme Innovative Economy (PO IG) – project “Analysis of the possibility of uranium supply from domestic resources”, No. POIG 01.01.02-14-094/09.

References[1]. Afolabi A.S., Muzenda E., Sigwadi R.: Effect of re-

agent parameters on recovery of South Africa uranium ore. Proceedings of the 3rd International Conference on Uranium – 40th Annual Hydrometallurgy Meeting, 15-18 August 2010, Saskatoon, Saskatchewan, Canada, Vol.1, p. 481.

[2]. Habashi F.: Uranium from phosphate rock. An up-date. Proceedings of the 3rd International Conference on Uranium – 40th Annual Hydrometallurgy Meeting, 15-18 August 2010, Saskatoon, Saskatchewan, Canada, Vol.1, p. 631.

[3]. Prasser H.M.: Are the sources of uranium big enough for the nuclear energy industry? Nuclear energy in Poland: Opportunity or necessity? 20-21 October 2008, Warszawa, Poland.

[4]. Ostrowski M., Skłodowska A.: Małe bakterie wielka miedź (The small bacteria great copper). SCI-ART, Warszawa 1996 (in Polish).

[5]. Brejnak E., Pinkas K.: Badania technologiczne nad prze-robem łupków dictyonemowych w skali laboratoryjnej (Technology research on the processing of dictyonema shale on a laboratory scale). Instytut Badań Jądro-wych, Opracowanie wewnętrzne nr 170/Ch-IV/75 (in Polish).

[6]. Brejnak E., Pinkas K., Deptułowa D.: Badania techno-logiczne nad przerobem łupków dictyonemowych w ska-li laboratoryjnej. Prace uzupełniające (Technology re-search on the processing of dictyonema shale on a laboratory scale. Supplementary work). Instytut Badań Jądrowych, Opracowanie wewnętrzne nr 171/Ch-IV/75 (in Polish).

[7]. Szymańska D.: Opracowanie optymalnych parametrów otrzymywania koncentratu torowego z rudy toronośnej “H” (Development of optimal parameters for obtaining concentrated thorium from ore “H”). Instytut Badań Jądrowych, Opracowanie wewnętrzne nr 45/Ch-IV/67 (in Polish).

Fig.2. Influence of grains sizes for uranium leaching from two samples: KGHM ore (A) and Waste Gilów (B).

>1 mm 0,5<d<1mm 0,5<d<0,2mm d<0,2mm

A

0102030405060708090

100

24 48 72 96

Concentration of sulfuric acid %

U %

reco

very

0102030405060708090

100

24 48 72 96

Concentration of sulfuric acid %

U %

reco

very

B

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CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY

Studies carried out in 2013 concentrated on the validation, adaptation and implementation of various biodosimetric methods in the frame of the strategic research project “Technologies sup-porting 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 proceed-ing 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 indus-try, 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 establish-ing 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 radio-logical 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 im-plemented 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 sum-marized 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 radia-tion 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 molecu-lar and cellular mechanisms in mammalian cells exposed to ionizing radiation and/or nano-

Page 57: INCT Annual Report 2013

materials. In particular, differentiation of Lund human mesencephalon (LUHMES) cells to a dopaminergic neuron-like phenotype was examined and found that it leads to a decrease in expression of the mitochondrial PGAM5 phosphatase. Studies of the cellular response to ionizing radiation with a special emphasis on the molecular mechanisms of the oxidative stress are continued: the role of pirin protein and the signalling pathway NRF2/KEAP1 in re-lation 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 de-monstrated 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.

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57CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY

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-cation of radiation-exposed individuals is crucial for triage and optimal medical management. Cur-rent biological dosimetry methods are inadequate for the task, mainly because of their low through-put resulting from the time-consuming procedures and requirement for highly trained and experi-enced personnel. Our objective is to develop simple and fast bioassays for biological dosimetry based on molecular biomarkers such as gene expression signatures. To this end, we analysed the literature data concerning gene expression changes in the blood cells following irradiation. Based on the available literature (e.g. [1-3]), the following genes were chosen as the most promising biomarkers of radiation exposure: GADD45A, CDKN1A, BBC3, BAX, GDF15, DDB2, MDM2, ATF3, PLK3, SESN2, BCL2.

To further analyse the expression patterns of the selected genes in irradiated blood we per-formed the experiments outlined as described be-low. Blood samples were collected from three healthy donors with informed consent from all subjects. A total of 15 ml of blood was collected from each donor into heparin vacutainer tubes. Each sample was aliquoted into three tubes (one tube per dose group) and irradiated with a single dose of X-rays. X-irradiation was carried out at 37oC, with the use of a Smart200 (Yxlon) defecto-scope operating at 200 kV and 4.5 mA, with 3 mm Al filtration, at a dose rate of 1.14 Gy/min. Fol-lowing irradiation, each tube of blood correspond-ing 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

added to each tube at a 2:1 ratio with the whole blood. The samples were incubated at 37oC in a humidified incubator with 5% CO2 for either 6, 12, 24, 48 h. The experimental schedule is shown in Fig.1.

Total RNA was extracted from samples using the RiboPure-Blood Kit (Ambion); 500 ng of total RNA was converted to cDNA in a 20 μl reaction volume using the High Capacity cDNA Reverse Transcription Kit (Life Technologies). Further, cDNA was diluted to 100 μl with de-ionized, nu-clease-free H2O. Real-time PCR was performed in a 20 μl reaction mixture containing 5 μl of di-luted cDNA, 4 μl of de-ionized, nuclease-free H2O, 10 μl of TaqMan Gene Expression Master Mix (Life Technologies) and 1 μl of TaqMan Gene Ex-pression Assay (Life Technologies). All reactions were run in duplicate. PCR amplification was carried out using a 7500 Real-Time PCR System (Life Technologies) with an initial 10-min step at 95oC followed by 40 cycles of 95oC for 15 s and 60oC for 1 min. Relative gene expression was cal-culated using the ΔΔCt method with ITFG1 and DPM1 as reference controls.

Changes in the mRNA levels in the whole blood after X-irradiation for each of the genes studied have shown that mRNA levels of genes such as GADD45A (cf. Fig.2), CDKN1A, BBC3, BAX, GDF15, DDB2 are significantly elevated even 48 h after irradiation, which allows for correct identi-

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 sub-stantial variability in fold changes between donors especially at longer times after irradiation. The mRNA levels of MDM2, ATF3, PLK3, SESN2, BCL2 show only slight changes (less than two-fold in most cases) after irradiation which, together with substantial variability among donors, preclude

Fig.1. Schematic representation of the experimental sched-ule.

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.

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58 CENTRE FOR RADIOBIOLOGY AND 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

their usefulness as a molecular biomarkers in bio-logical dosimetry.

These preliminary data indicate that analysis of expression of selected genes in the whole blood samples may be useful for fast identification of the irradiated individuals and therefore, may consti-tute a promising molecular biomarker for radia-tion biodosimetry. Nevertheless, further research is needed to establish a reliable, gene expression--based test for biological dosimetry.

References [1]. Paul S., Barker C.A., Turner H.C., McLane A., Wolden

S.L., Amundson S.A.: Radiat. Res., 175, 257-265 (2011).[2]. Joiner M.C., Thomas R.A., Grever W.E., Smolinski

J.M., Divine G.W., Konski A.A., Auner G.W., Tucker J.D.: Radiother. Oncol., 101, 233-236 (2011).

[3]. Budworth H., Snijders A.M., Marchetti F., Mannion B., Bhatnagar S., Kwoh E., Tan Y., Wang S.X., Blakely W.F., Coleman M., Peterson L., Wyrobek A.J.: PLoS ONE, 7, e48619 (2012).

The detection, visualization and enumeration of γ-H2AX foci allow the assessment of DNA double strand breaks and DNA repair in cells exposed to chemical, biological and physical factors. γ-H2AX assay has been used as a biodosimeter for radia-tion exposure, drug development, as well as a bio-marker of radiosensitivity, aging, cancer and chronic inflammation (e.g. [1]). Despite the documented ad-vantages of the γ-H2AX assay, there is a consider-able variation between laboratories regarding foci formation in the same cell lines and exposure con-ditions. Automatic or semiautomatic systems sub-stantially increase the productivity of the foci count-ing analysis and are free of the unavoidable op-erator subjectivity. However, it was shown that the number of foci may be markedly affected by the automated quantification method and parameters [2]. Since no criteria and recommendations have been developed to justify the choice of particular parameter values, we investigated the effect of vari-ous cell selection and object features/spot count-ing parameters on the number of scored cells and the slope of the γ-H2AX foci dose-response curve, using the training data files generated by the Me-tafer system (Metasystems, Germany).

Since no criteria and recommendations have been developed to justify the choice of an appro-priate protocol for the γ-H2AX assay, we evaluat-ed the influence of different settings of automated image acquisition and analysis system (classifiers) on the number of scored cells and the slope of the γ-H2AX foci dose-response curve.

Peripheral blood samples were collected from 34 healthy donors (20 females and 14 males, aver-age age 44 ± 12 yrs) into heparinized (10-20 U/ml) Greiner bio-one tubes. None of the donors was previously exposed to radiation. Venous whole blood was processed according to four protocols and irradiated at room temperature with 250 kV X-rays at a dose rate of 1.14 Gy/min with the doses 0, 0.2, 0.4, 0.6, 0.8, 1, 1.5, 2, 3, 4 Gy (Xylon International Smart 200-E irradiator, Xylon, San

Jose, USA). Isolation of lymphocytes and micro-scopic slide preparation was according to stand-ard protocols.

Images of individual cells with γ-H2AX foci were recorded as a training data files with an au-tomated image acquisition and analysis system Metafer. These files were used to test 10 differ-ent classifiers varying in parameters dealing with automated cell selection (minimum object area, maximum object area, maximum concavity depth, maximum aspect ratio and CS object threshold %) and object features/spot counting (minimum and maximum intensity of a spot, mean relative object area, minimum spot distance, maximum spot distance).

Statistical analysis of the obtained data was performed using Statistica 7.1 software (StatSoft. Inc., Tulsa, USA). The data were expressed as mean ± standard deviation (SD). To compare the fre-quencies of γ-H2AX foci in individual experiments as well as in pooled results, two-way analysis of variance followed by post-hoc Tukey’s test was performed. Significant differences were defined at p < 0.05. The dose-response curves were fitted to a linear model:

y = αD + C where: y – the yield of γ-H2AX foci, D – the dose. The coefficients C and α were calculated with the method of iteratively reweighted least squares for curve fitting. The mean numbers of γ-H2AX foci per cell and deviation of the variance for each point of the dose-response curves were calculated to test the distribution of γ-H2AX foci among the analysed lymphocytes according to the Poisson’s law.

The number of γ-H2AX foci obtained by ap-plying various classifiers was used to construct the dose-response curves. Two such curves (out of 10) are presented in Fig. They illustrate the influence of different settings of automated image acquisi-tion and analysis system on the number of scored cells and the slope of the γ-H2AX foci dose-re-

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59CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY

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

sponse curve. The lowest and highest slope values are shown, for classifiers 3 and 10, respectively. These results indicate that the combination of cell selection and spot counting parameters have a sig-nificant impact on the number of scored cells and the slope of dose-response curve for γ-H2AX foci.

References[1]. Rothkamm K., Horn S.: Ann. Ist. Super. Sanita, 45,

265-271 (2009).[2]. Qvarnström O.F., Simonsson M., Johansson K.A., Ny-

man J., Turesson I.: Radiother. Oncol., 72, 311-317 (2004).

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.

Dose [Gy]

γ-H

2AX

foci

per

cel

l

Dose [Gy]

γ-H

2AX

foci

per

cel

l

In the event of a large-scale radiological emergency, biodosimetry tools will be essential that can pro-vide timely assessment of radiation exposure to the general population and enable the identifica-tion of those individuals exposed who should re-ceive medical treatment. A number of biodosi-metric tools are potentially available, but they must be adapted and tested for a large-scale emer-gency 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 bio-dosimetric tools should be applied.

The dicentric chromosome assay is considered to be the best and most reliable (“gold-standard”) assay for accurately estimating unknown radiologi-cal 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-in-tensive 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 QuickScan, i.e. quick scan of dicentric chromo-

somes). It has been accepted as an alternative ra-pid-scoring approach [1-3] that could be of value in the triage and management of people at risk for the acute radiation syndrome [3].

Fig. Frequencies of dicentric chromosomes determined in varying cell numbers. Standard deviation indicated.

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60 CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY

To investigate how the number of metaphase spreads influences dose prediction accuracy in our hands, numbers of dicentrics were analysed in 20, 30, 50 and 100 cells (depending on the dose) in order to find the lowest number of cells enabling to reconstruct the dose properly. In the range of high doses, 2-4 Gy of acute irradiation, even 20 cells were enough to reconstruct the doses properly with the confidence interval sufficient for triage analysis (cf. Fig.). On the other hand, even 100 scored cells may not be enough to recognize whether the per-son was irradiated with a very low dose.

References[1]. Flegal F.N., Devantier Y., McNamee J.P., Wilkins R.C.:

Health Phys., 98, 276-281 (2010).[2]. Flegal F.N., Devantier Y., Marro L., Wilkins R.C.:

Health Phys., 102, 143-153 (2012). [3]. Romm H., Wilkins R.C., Coleman C.N., Lillis-Hearne

P.K., Pellmar T.C., Livingston G.K., Awa A.A., Jenkins M.S., Yoshida M.A., Oestreicher U., Prasanna P.G.: Radiat. Res., 175, 397-404 (2011).

THE EFFECT OF SUPPLEMENTATION WITH CONJUGATED LINOLEIC ACID (CLA)

ON Akt1 KINASE PHOSPHORYLATION IN X-IRRADIATED HT-29 CELLSIwona Grądzka, Iwona Buraczewska, Katarzyna Sikorska, Barbara Sochanowicz,

Irena Szumiel, Karolina Wójciuk, Grzegorz Wójciuk

Conjugated linoleic acids (CLA) are natural com-ponents of human diet. The most abundant isomer, cis-9,trans-11 CLA (c9,t11-CLA) exhibits strong antitumour activity, and therefore its usefulness as an adjuvant in radiotherapy of cancer is worth con-sidering. Previously, we have shown that c9,t11-CLA sensitized human colon cancer HT-29 cells to X-radiation [1]. The 24-hour supplementation with the CLA isomer (70 μM) did not affect the cell cycle progression or expression of DNA-repair-re-lated genes. Nevertheless, it caused disturbances in the rejoining of X-ray inflicted double strand breaks (DSBs), as shown by pulse-field gel electro-phoresis. The transient increase in DSB levels dur-ing repair in CLA-supplemented cells was reflect-ed in DNA repair foci number (histone γ-H2AX), immunocytochemically monitored, and in chro-matid fragmentation frequencies, measured by premature chromosome condensation. The cell

growth inhibition was strengthened by c9,t11-CLA but, interestingly, higher chromosome aberration frequencies were not observed.

The delay in DSB rejoining was associated with a diminished activation of DNA-dependent pro-tein kinase (DNA-PK) – a key enzyme of the non--homologous DNA end joining (NHEJ). At the same time, the nuclear accumulation of epidermal growth factor receptor (EGFR), known to activate DNA-PK under ionizing radiation-induced stress, was restrained.

DNA-PK is also involved in Akt1 (protein ki-nase B) activation in response to ionizing radia-tion-inflicted DNA damage (reviewed in [2]). Ac-tivation proceeds through phosphorylation of serine (Ser473). Akt1 forms nuclear foci and colo-calizes with DNA-PK at DSBs. Akt1 knockout mice resemble the DNA-PK deficiency radiosen-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).

A

B

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61CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY

sponse to DNA damage, supporting the notion that DNA-PK/Akt1 pathway has a marked impact on cell survival after DNA damage. The above re-sults suggest that apart from the role in DSB re-pair, DNA-PK is the source of anti-apoptotic sig-nalling pathway and CLA treatment prevents this function. Therefore, the effect of c9,t11-CLA on Akt1 activation was examined. HT-29 cells were incubated with CLA-supplemented or non-sup-plemented medium as described in [1] and the ex-tent of Akt1 phosphorylation and Akt1 level were determined with specific antibodies by Western blotting in the nuclear and cytoplasmic fractions of HT-29 cells after X-irradiation with 2 Gy X-rays.

X-irradiation induced a pronounced increase in phosphorylation of the nuclear Akt1 with a maximum at 20 min after irradiation, whereas phosphorylation of the cytoplasmic Akt1 was much smaller but more stable. Further, the ratio of Akt1 pSer473 to unphosphorylated Akt1 was determin-ed in the nuclear fraction. Figure presents the Western blots from a representative experiment. It can be seen that X-irradiation induced a pro-nounced phosphorylation of the nuclear Akt1 in

the absence of CLA supplementation, whereas CLA considerably decreased the Akt1 pSer473 content. This effect corresponded with the previ-ously observed lowered DNA-PK activity after X-irradiation of CLA-supplemented cells as com-pared to the non-supplemented ones [1].

This observation explains the decreased sur-vival of X-irradiated CLA-supplemented cells as compared to the non-supplemented ones in spite of the absence of increase in the chromosomal damage that is usually observed in the case of im-paired DNA-PK activity. It also shows that the signalling function of DNA-PK may be affected by composition of the plasma membrane lipids, obvi-ously resulting in a disturbed function of EGFR. Direct measurement of apoptosis should provide a firm basis for this conclusion.

References[1]. Grądzka I., Sochanowicz B., Brzóska K., Wójciuk G.,

Sommer S., Wojewódzka M., Gasińska A., Degen C., Jahreis G., Szumiel I.: Biochim. Biophys. Acta, 1830, 2233-2242 (2013).

[2]. Toker A.: Trends Biochem. Sci., 33, 356-359 (2008).

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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 applica-tion in a nuclear chemical engineering, radiobiological and environmental problems associat-ed with the use of nuclear power (as well as other specific fields of high technology). New pro-cedures 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 absorp-tion 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 chem-ical 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 cer-tification 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 en-vironmental 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).

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64 LABORATORY OF NUCLEAR ANALYTICAL METHODS

RADIOLYTIC REMOVAL OF SELECTED PHARMACEUTICALS AND BISPHENOL A FROM WATERS AND WASTES

Anna Bojanowska-Czajka, Sylwia Borowiecka1/, Marek Trojanowicz1/ Faculty of Chemistry, University of Warsaw, Warszawa, Poland

Increasing presence of human and veterinary phar-maceuticals in the natural environment is since many years a common environmental problem. This concerns not only wastes of various origin and surface waters [1, 2], but also drinking water which is produced in conventional water treat-ment plants for communal use [3, 4]. A limited ef-ficiency of waters and wastes conventional treat-ment is well illustrated by data published about the removal of a large group of popular pharma-ceuticals and hormones in Spain [2]. As it is shown by histogram in Fig.1, among 20 different examin-ed species occurring in wastes at levels from ng/L to μg/L, only five of them were completely decom-posed, and not found in the effluent for treatment plant.

The research studies dealing with that problem are carried out currently in several areas. Their three main fields include development of new analytical methods for efficient monitoring of the presence of pharmaceutical residues in environ-mental samples, toxicological studies on the inter-action of residual pharmaceuticals with human and animal organisms, and studies on the develop-ment of new and more efficient methods of their removal from waters and wastes. Concerning ana-lytical methods, the most powerful for simultane-ous determinations at trace and ultra-trace levels are high-performance separation methods hyphen-ated with mass spectrometry [5], but also flow ana-lysis methods [6], and sensors [7] are being develop-ed mostly for screening purposes and simple use by the end users. Toxicological studies in this area are mostly focused on the combined interactions with living organisms of a large number of pharma-ceuticals, which are present in the environment at trace level [8]. The most advanced studies on the de-velopment of new methods of efficient decomposi-

tion of pharmaceuticals residues in environment involve especially different advanced oxidation processes, based on radical reactions in aqueous media [9]. Surprisingly, even in this relatively re-cent review there is no mention on the application of ionizing radiation as especially effective method of decomposition of pharmaceutical residues.

There are hundreds of papers published in the last three decades on the application of ionizing radiation for decomposition of organic pollutants in aqueous phase dealing with different groups of compounds. In the last decade an increasing amount of such applications concerns decomposi-tion of pharmaceutical residues in waters and wastes. Very recent papers published in the last two years deal, e.g. with a commonly used analge-stic and antipyretic drug paracetamol [10], sali-cylic and methyl substituted salicylic acids [11], popular non-steroidal anti-inflammatory drugs such as ketoprofen [12, 13], diclofenac [13-16], and ibuprofen [13, 17, 18]. Also radiolytic degra-dation using gamma irradiation was reported re-cently for X-ray contrast medium diatriazoate [19], and several other commonly used drugs in waste-water [13].

In the majority of publications, the conducted studies were focused on the elucidation of mecha-nism of radical reactions of the examined species with products of water radiolysis, and the deter-mination of optimum conditions for decomposi-tion of target compounds at mg/L concentration levels. For compounds examined in this study, e.g. for diclofenac it was level from 30 [14] to 296 [16] mg/L, for ibuprofen – from 28 to 59 mg/L [17], while for carbendazim – 1.2 mg/L [17]. On the other hand, the highest levels of ibuprofen found in surface water reach 1 μg/L [3], and in wastes – 4.2 μg/L [2]. Then, for diclofenac, the data collect-

Fig.1. Histogram showing maximum concentrations [ng/L] of selected pharmaceuticals and hormones found in influents and effluents from the sewage treatment plants in Catalonia, in Spain [2].

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65LABORATORY OF NUCLEAR ANALYTICAL METHODS

ed from 16 countries in effluents from wastewater treatment plants the determined values were up to 1.8 μg/L, and in surface waters – up to 0.3 μg/L [20]. The same values for carbendazim were 3.2 and 0.5 μg/L, respectively [20]. Those data show values, which are several orders of magnitude lower than the concentrations examined in the above-mentioned studies on radiolytic decompo-sition of those pharmaceuticals. In this study three pharmaceuticals occurring as water pollutants were examined (diclofenac, ibuprofen, and carbenda-zim), and also one common industrial organic pol-lutant – bisphenol A.

In the coarse of this study the examined stand-ard solutions and environmental samples were gam-ma-irradiated using a 60Co source Gamma Chamber with a dose-rate of 8.0 kGy/h. The reversed-phase HPLC analyses of irradiated samples were car-ried out using a Shimadzu chromatograph with a diode array UV/Vis detector, a Luna ODS2, 5 μm 250 × 4.6 mm analytical column and a guard col-umn from Phenomenex (Torrance, CA, USA).

For simultaneous monitoring of concentrations of target species and products of decomposition, two HPLC procedures with UV detection have been developed, for which example of recorded chromatograms are shown in Fig.2. In both me-thods the base-line separation can be achieved for all analytes, however, in method B the total ana-lysis time to get the elution of all the determined species was about 60 min, while in method A – 12 min. The HPLC determinations with UV detec-tion at μg/L concentration level require an initial

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 ana-lytes 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 de-veloped HPLC methods in determination of the examined species in natural river water samples from the Vistula river are shown in Fig.3. A satis-factory reproducibility of determinations shown in recordings using method A, indicate that the level of target analytes in the example river water samples is below the limits of detection (LOD), which was evaluated as 0.03, 0.06, 0.11 and 0.14 μg/L for carbamazepine, bisphenol A, diclofenac and ibuprofen, respectively. The drawback of HPLC method A is a large signal obtained for matrix components of natural waters, which are simultaneously with analytes retained and eluted in the preconcentration step (Fig.3A). This effect is less important when method B is employed (Fig.3B), although in this case LODs values are about one order of magnitude poorer.

The investigations of efficiency of radiolytic decomposition reported already in the literature for ibuprofen [13, 17, 18], and carbamazepine [13], were broadened in this work by examination of the effect of pH of the irradiated solutions. At

Fig.2. Comparison of HPLC chromatograms for standard mixtures of determined analytes obtained with two devel-oped methods of isocratic elution. A – Eluent composition: 40% 0.2 M formic acid, 60% acetonitrile, pH 4.0; injection – 4 mg/L each analyte (method A). B – Eluent composition: 50% 0.6 mM KH2PO4, 30% acetonitrile, 20% methanol, pH 4.0; injection – 2 mg/L each analyte (method B). In both cases: flow-rate – 1 mL/min, detection UV at 220 nm.

A

B

Fig.3. Comparison of the application of two developed HPLC methods in the determination of investigated ana-lytes in river water samples. A – chromatograms (3 repeti-tions) obtained with method A for river water sample from the Vistula river, collected before treatment plant with marked retention times for determined analytes. B – chro-matograms of river water with added 10 μg/L concentra-tion of each analyte, obtained with method B for sample prior to the irradiation (1), after gamma irradiation with a dose of 100 (2) and 250 Gy (3).

A

Carbamazepine

Bisphenol A

IbuprofenDiclofenac

123

B

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66 LABORATORY OF NUCLEAR ANALYTICAL METHODS

an initial concentration of both compounds 10 mg/L, the pH effect for ibuprofen is observed only at doses 0.2-0.6 kGy, where irradiated compound is only partly decomposed (Fig.4A). In the case of more resistant towards radiation carbamazepine (Fig.3B), the decomposition process in the whole range of employed doses is about 20% less effi-cient than in neutral or acidic media (Fig.4B).

As it is shown by chromatograms in Fig.5, for the irradiation of the hospital effluent with added 10 μg/L each analyte, up to 0.5 kGy irradiation dose was used. One can see, that only in the case of diclofenac and ibuprofen it was sufficient – the complete decomposition was observed at 0.25 kGy. A comparison of the effect of matrix of the irradiated solution on the yield of decomposition of the examined compounds is illustrated by signal changes in recorded chromatograms for river water

samples and hospital effluent (Fig.6). In both cases the monitored samples were irradiated after spik-ing them with 10 μg/L each analyte. The obtained results confirm that especially the decomposition of carbamazepine and bisphenol A requires much larger irradiation doses in the case of hospital ef-fluent than river water samples. In the case of bi-sphenol A the application of 100 Gy absorbed dose allows the decomposition of 95% in river water, while 70% only in hospital effluent. For carbamazepine those yields were 90 and 37%, re-spectively.

Results of this study firmly show a very essen-tial impact of matrix composition of irradiated natural samples on the yield of decomposition of pharmaceutical residues at their examined level, close to real occurring ones in environmental samples. The observed complete decomposition at an absorbed dose level of about 1 kGy indi-cate that this AOP process may be a competitive method for the decomposition of pharmaceutical residues from waters and wastes compared to methods routinely used nowadays.

References[1]. Nikolaou A., Meric S., Fatta D.: Anal. Bioanal. Chem.,

387, 1225-1234 (2007).[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.,

35, 803-814 (2009).[4]. Kleywegt S., Pileggi V., Yang P., Hao C., Zhao X.,

Rocks C., Thach S., Cheung P., Whitehead B.: Sci. Total Environ., 409, 1481-1488 (2011).

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.

Fig.5. HPLC chromatograms recorded for the sample of wastewater from a hospital spiked with 10 μg/L each ana-lyte prior to gamma irradiation (1), after irradiation with doze 100 (2), 250 (3) and 500 Gy (4).

Fig.6. Comparison of the yield of gamma irradiation of the investigated compounds at different irradiation doses in various water matrices for samples spiked with 10 μg/L concentration each: A – river water sample from the Vis-tula river, B – effluent from a hospital.

A

B

Carbamazepine

Bisphenol A

Diclofenac Ibuprofen1

23

4

A

B

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67LABORATORY OF NUCLEAR ANALYTICAL METHODS

DETERMINATION OF URANIUM IN FLOW-INJECTION SYSTEM WITH SPECTROPHOTOMETRIC DETECTION

Kamila Kołacińska, Marek Trojanowicz

[5]. Pitarch E., Portoles T., Marin J.M., Ibanez M., Albar-ran F., Hernandez F.: Anal. Bioanal. Chem., 397, 2763-2776 (2010).

[6]. Trojanowicz M.: Talanta, 96, 3-10 (2012).[7]. Rodriguez-Mozaz S., Lopez de Alda M., Barcelo D.:

Anal. Bioanal. Chem., 386, 1025-1041 (2006).[8]. Fent K., Weston A.A., Caminda D.: Aquat. Toxicol.,

76, 122-159 (2006).[9]. Klavariotti M., Mantzavinos D., Kassinos D.: Environ.

Int., 35, 402-417 (2009).[10]. Szabo L., Toth T., Homlok R., Takacs E., Wojnarovits

L.: Radiat. Phys. Chem., 81, 1503-1507 (2012).[11]. Ayatollahi S., Kalnina D., Song W., Turks M., Cooper

W.J.: Radiat. Phys. Chem., 92, 93-98 (2013).[12]. Illes E., Takacs E., Dombi A., Gajda-Schranz, Gonter

K., Wojnarovits L.: Radiat. Phys. Chem., 81, 1479-1483 (2012).

[13]. Kimura A., Osawa M., Taguchi M.: Radiat. Phys. Chem., 81, 1508-1512 (2012).

[14]. Homolok R., Takacs E., Wojnarovits L.: Chemo-sphere, 85, 603-608 (2011).

[15]. Trojanowicz M., Bojanowska-Czajka A., Kciuk G., Bobrowski K., Gumela M., Koc A., Nałęcz-Jawecki G., Torun M., Ozbay D.S.: Eur. Water, 39, 15-26 (2012).

[16]. Yu H., Nie E., Xu J., Yan S., Cooper W.J., Song W.: Water Res., 47, 1909-1918 (2013).

[17]. Zheng B.G., Zheng Z., Zhang J.B., Luo X.Z., Wang J.Q., Liu Q., Wang L.H., Desalination, 276, 379-385 (2011).

[18]. Illes E., Takacs E., Dombi A., Gajda-Schranz K., Racz G., Gonter K., Wojnarivits L.: Sci. Total Environ., 447, 286-292 (2013).

[19]. Velo-Gala I., Lopez-Penalver J.J., Sanchz-Polo M., Rivera-Utrilla J.: Chem. Eng. J., 195-196, 369-376 (2012).

[20]. Zhang Y., Geissen S., Gal C.: Chemosphere, 73, 1151-1161 (2008).

Flow analysis is considered as a very efficient way of carrying out numerous analytical determina-tions with different detections and on-line sample treatment processes. The essential feature of the flow analysis is the possibility of mechanization of numerous on-line processes and automation of all analytical procedures, which means a full control over the fluid flow, its volumes, flow rates, timing and detection conditions. This improves the effi-ciency of measurements, provides a good repro-ducibility of results and also minimizes the human error influence by mechanization of all the per-formed processes.

The development of the flow analysis labora-tory methods began with the research conducted by Skeggs in the 1950s, who introduced the air segmentation of liquid in analytical systems de-signed to study body fluids (SFA – segmented flow analysis) [1]. A significant technological progress of the method came through inventing the flow injection analysis (FIA) [2]. The operational prin-ciple of FIA technique is based on recording the transient signal in detector, which corresponds to the analyte concentration in the injected sample. A FIA measuring system consists of a pumping device, which provides flow of a liquid, a tubing manifold, an injection valve with an injection loop to load a sample into system and also a detector. After the sample is injected into a flowing carrier stream, it moves downstream and mixes with an introduced reagent in a reactor coil to produce a detectable form by a chemical reaction. In a more complex FIA setups there are also different mod-ules for on-line sample processing incorporated into the flow system. A sequential injection analysis (SIA) is considered to be a new generation of FIA method, which compared to FIA, can be regarded as a more flexible because it introduces flow re-versal; the change of the flow direction is program-med and usually controlled by a computer [3]. The

flow methods in chemical analysis have been de-veloped for over 50 years and also numerous others highly specialized systems were invented. This includes MCFIA – multi-commuted flow in-jection analysis [4], MSFIA – multi-syringe flow in-jection analysis [5], MPFS’s – multi-pumping flow system [6] and the most recent option LOV – Lab-on-Valve systems [7]. Currently, flow analysis has a solid place among other methods of modern analytical chemistry [8, 9], and is widely applied to the chemical analysis of environmental samples as well as geological, industrial or clinical ones.

The implementation of this technique for the determination of radionuclides is a relatively new field of applications; although the first approach of using FIA in radioanalysis was reported for measuring vanadate by passage sample through col-umn with radioisotope of silver [10]. The applica-tions of flow analysis to the determination of radio-nuclides for different purposes have been devel-oped for more than 20 years, which were already a subject of several reviews [11-14]. A choice of a de-tection type depends primarily on the nature of the sample analysed and analytes to be determined. Generally, for radiochemical analysis few kinds of detectors are used, only, such as radiometric, mass spectrometric and also spectrophotometric.

In recent decade several papers were published on the application of flow-injection methods for the determination of uranium [15-29]. Methods which were based on the use of spectrophoto-metric detection [15-22], or amperometric one [23] allow the determination of total content of uranium in analysed samples. The application of inductively coupled plasma mass spectrometry (ICP-MS) can be used in the determination of particular isotopes such as 234U [24], 236U [25] and 238U [26-29], or isotope ratio 235U/238U [27]. Regard-ing the construction of flow systems, a typical FIA systems are most often used [15, 20-24, 26-28].

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68 LABORATORY OF NUCLEAR ANALYTICAL METHODS

Very recently, a design of SIA system was report-ed for simultaneous determination of 236U, 237Np, and Pu isotopes in sea water [25]. Several at-tempts can be found in the literature on design of MSFIA systems [16, 17], recently also employing a more complex construction of rotary injection valves – LOV with built-in a mini-column for ex-traction, preconcentration and separation of ana-lytes [18, 19, 29].

Most commonly in flow injection systems for the determination of uranium is spectrophotometric detection based on the formation of coloured com-plexes of UO2

2+ cation with Arsenazo III [15-20], and also such ligands as Chromazurol S [21] and Chlorphosphonazo III [22]. With the use of Arse-nazo III, limits of detection for different configu-rations of flow system are in a wide range form 40 mg/L [16] down to even 5.9 ng/L [19], at a well op-timized preconcentration procedure. For on-line trace U(VI) preconcentration, various types of sor-bents are employed, including commercially avail-able extraction chromatography resins TRU-Spec [17, 20, 27], UTEVA [18, 19, 24, 25, 29], TEVA [28], strong anion exchanger Amberlite IRA-402 [20], and also, e.g. a laboratory-made styrene-divi-nylbenzene copolymer modified with dodecylami-doxime [22].

In this study, initiated recently in the Institute of Nuclear Chemistry and Technology (INCT), a commercial MSFIA-LOV system from Sciware Systems (Bunyola, Spain) was employed, which was already used in the determination of uranium in environmental samples with spectrophotomet-ric detection [18]. The configuration of flow sys-tem is shown schematically in Fig.1. The spectro-photometric detection was based on the formation of UO2

2+ complex with Arsenazo III (2,2’-(1,8-di-hydroxy-3,6-disulfonapthylene-2,7-bisazo)bisben-zenearsonic acid), whose structure is shown in Fig.2.

The maximum of absorption of U(VI) com-plex with Arsenazo is at 651 nm, and molar ab-sorption coefficient 4 450 M–1cm–1 [30]. Taking into account this absorption maximum, as a source of light in MSFIA-LOV system, seven different light emitting diodes (LED) were examined with the emission maxima from 650 to 660 nm. As the op-timum one, the LED type L-53SRC/F from King-bright (Issum, Germany) was employed, with an emission maximum at 655 nm (Fig.3). Spectro-photometric measurements were carried out with

Fig.2. Structure of UO22+ complex with Arsenazo III.

Fig.1. Schematic diagram of MSFIA-LOV system used for determination of uranium.

Fig.3. Emission spectrum of light emitting diode L-53SRC/F from Kingbright company used as a source of radiation in the MSFIA-LOV system for determination of uranium.

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69LABORATORY OF NUCLEAR ANALYTICAL METHODS

a 100 cm long waveguide capillary cell (LWCC) from World Precision Instruments (Saracota, USA), and with a CCD detector type USB 2000 from Ocean Optics (Dunedin, USA).

Arsenazo III forms also stable complexes with Th, Zr, Cd, Zn, Ca and can be used for spectro-photometric determination of those elements. The selectivity of spectrophotometric determination of U(VI) can be achieved by the application of suit-able masking reagents, as it was shown in the si-multaneous determination of U and Th in FIA system [21], or by the use of the above-mentioned selective sorbents. In this work, for this purpose the extraction resin UTEVA from Triskem (Bruz, France) was used. By the use of diamyl amylphos-phonate as extrahent, this resin allows selective retention of U(VI) and tetravalent actinides as neutral nitrato complexs [31]. The resin (30 mg) was packed into mini-column of LOV injection valve, and all stages of analytical procedure were

carried out according to the programme shown in Table. For spectrophotometric detection, 0.001% Arsenazo III solution in 0.7 M chloroacetic acid – 0.1 M sodium chloroacetate buffer of pH 2.0 was used. In the initial experiments 1 μg/L to 1 mg/L of U(VI) solutions in 3 M HNO3 were injected.

Example of the signals recorded in FIA system are shown in Fig.4. This recording shows that for 1 mL of the injected sample volume, the whole measurement of 1 sample takes about 3 min, which indicates a very efficient way of conducting analytical determination in such a system. The ob-

tained detectability at this initial stage of the work, is far from satisfactory, the whole measuring pro-cedure requires further optimization in order to improve detection level, examination of complete-ness of retention and elution of the analyte from the sorbent bed. In further steps also selectivity of retention/elution process will be examined in flow injection conditions employed, and eventually ad-justed by the modification of the whole procedure. The developed method will be also examined in the determination of total uranium content in en-vironmental samples.

The work was financed by the National Centre for Research and Development, Poland in the frame of the strategic research project “Technologies sup-porting development of safe nuclear power engi-neering” – task 8 “Study of processes occurring under regular operation of water circulation sys-tems in nuclear power plants with suggested ac-tions aimed at upgrade of nuclear safety”.

References [1]. Skeggs L.J.: Am. J. Clin. Pathol., 28, 311-322 (1975).[2]. Ruzicka J., Hansen E.H.: Anal. Chim. Acta, 78,

145-157 (1975). [3]. Ruzicka J., Marshall G.D.: Anal. Chim. Acta, 237,

329-343 (1990).[4]. Reis B.F., Gine M.F., Zagatto E.A.G., Lima J.L.F.C.,

Lapa R.A.: Anal. Chim. Acta, 293, 129-138 (1994).[5]. Cerdá V., Estela J.M., Forteza R., Cladera A., Becerra

E., Altimira P., Sitjar P.: Talanta, 50, 695-705 (1999).[6]. Lapa R.A.S., Lima J.L.F.C., Reis B.F., Santos J.L.M.,

Zagatto E.A.G.: Anal. Chim. Acta, 466, 125-132 (2002).

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

3Elution of interferences

9 M HCl 0.1 2

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

Table. Sequence of operation in flow-injection determination of uranium in MSFIA-LOV system.

Fig.4. Example of flow-injection signals obtained in the MSFIA-LOV system for injection of uranium solutions at differ-ent concentrations.

0

0,2

0,4

0,6

0,8

1

1,2

1,4

2 502 1002 1502 2002 2502

Abs

[a.u

.]

Time [s]

0 ppb

100 ppb

1000 ppb

1 ppb 10 ppb

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70 LABORATORY OF NUCLEAR ANALYTICAL METHODS

[7]. Ruzicka J.: Analyst, 125, 1053-1060 (2000).[8]. Advances in flow analysis. Ed. M. Trojanowicz. Wi-

ley-VCH, Weinheim 2008.[9]. Westmeier W., Siemon K.: J. Environ. Radioact., 117,

25-30 (2013).[10]. Grudpan K., Nacapricha D.: Anal. Chim. Acta, 246,

329-331 (1991).[11]. Grate J.W., Egorov O.B.: Automated radiochemical

separation, analysis and sensing. In: Handbook of radioactivity analysis. 2nd ed. Ed. M. L’Annunziata. Elsevier Science, USA 2003, pp. 1129-1164.

[12]. U M., Tölgyessy J.: J. Radioanal. Nucl. Chem., 191, 413-426 (1995).

[13]. Grate J.W., Egorov O.B., O’Hara J.M., DeVol T.A.: Chem. Rev., 108, 543-562 (2008).

[14]. Fajardo Y., Avivar J., Ferrer L., Gómez E., Casas M., Cerdà V.: Trends Anal. Chem., 29, 1399-1408 (2010).

[15]. De Sousa A.S.F., Ferreira E.M.M., Cassella R.J.: Anal. Chim. Acta, 620, 89-96 (2008).

[16]. Guzmán Mar J.L., López Mertínez L., López de Alba P.L., Ornelas Soto N., Cerdá V.: J. Radioanal. Nucl. Chem., 281, 433-439 (2009).

[17]. Avivar J., Ferrer L., Casas M., Cerdá V.: Anal. Bio-anal. Chem., 397, 871-878 (2010).

[18]. Avivar J., Ferrer L., Casas M., Cerdà V.: Talanta, 84, 1221-1227 (2011).

[19]. Avivar J., Ferrer L., Casas M., Cerdá V.: Anal. Bio-anal. Chem., 400, 3585-3594 (2011).

[20]. Nisa Q., Ali A., Haleem Khan M.: J. Radioanal. Nucl. Chem., 295, 2203-2214 (2013).

[21]. Hirano Y., Ogawa Y., Oguma K.: Anal. Sci., 19, 303-307 (2003).

[22]. Oguma K., Suzuki T., Saito K.: Talanta, 84, 1209-1214 (2011).

[23]. Aguiar M.A.S., Marquez K.S.G., Gutz I.G.R.: Electro-analysis, 12, 742-746 (2000).

[24]. Godoy M.L.D.P., Godoy J.M., Kowsmann R., dos Santos G.M., Petinatti da Cruz R.: J. Environ. Radio-act., 88, 109-117 (2006).

[25]. Qiao J., Hou X., Steier P., Golser R.: Anal. Chem., 85, 11026-11033 (2013).

[26]. Truscott J.B., Bromley L., Jones P., Evans E.H., Tur-ner J., Fairman B.: J. Anal. At. Spectrom., 14, 627-631 (1999).

[27]. Benkhedda K., Epov V.N., Evans R.D.: Anal. Bio-anal. Chem., 381, 1596-1603 (2005).

[28]. Schaumlöffel D., Giusti P., Zoriy M.V., Pickhardt C., Szpunar J., Łobiński R., Becker J.S.: J. Anal. At. Spectrom., 20, 17-21 (2005).

[29]. Avivar J., Ferrer L., Casas M., Cerda V.: J. Anal. At. Spectrom., 27, 327-334 (2012).

[30]. Golmohammadi H., Rashidi A., Safadri S.J.: Chem. Chem. Technol., 6, 245-249 (2012).

[31]. Horwitz E.P., Dietz M.L., Chiarizia R., Gatrone R.C., Esslin A.M., Bane R.W., Graczyk D.: Anal. Chim. Acta, 266, 25-37 (1992).

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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 par-• ticle track membranes as template,modification of surface layer of engineering materials by implantation of lanthanide ele-• ments 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 re-

cent years, as evidenced by the very rapid growth of publications. Particularly, the porous co-ordination 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 pub-lished.

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-contain-ing 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 investi-gate 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.

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72 LABORATORY OF MATERIAL RESEARCH

STRUCTURAL STUDIES IN Li(I) ION COORDINATION CHEMISTRYWojciech Starosta, Janusz Leciejewicz

Like diazine carboxylate, diazole and triazole car-boxylate ligands have a number of multifunctional potential coordination sites involving hetero-ring N and carboxylate O atoms. They are accessible to metal ions and as such can be coordinated as mono-, bi- and tetradentate and act as linkers pro-viding multibridging modes generating different types of coordination polymers. Recent results of our studies are briefly summarized below:

Among 22 new structures determined in course • of this project only three have been observed to be built of discrete molecules. The latest example is represented by the structure of a complex with pyrazole-4-carboxylate and water ligands [1].Dinuclear moiety in which two Li ions and two • ligand molecules related by an inversion centre has been observed as a structural unit in 12 com-plexes studied in the course of the present pro-ject. This unit has been observed to exist either as a separate dimeric molecule or as a build-ing unit of polymeric structures. An example is provided by the structure of a Li complex with triazole carboxylate ligand. A discrete centrosym-metric 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 struc-ture of a complex with pyrazole-3,5-dicarboxy-late and water ligands [3].The molecular pattern observed in the structure• of a Li complex with 5,6-dimethylpyrazine-2,3--dicarboxylate and water ligands composed of molecular ribbons in which Li ions are bridged by both N,O bonding sites [4] has been earlier found in the structures of four Li complexes with pyrazine-2,3-dicarboxylate and water ligands [5, 6]. In the structure of one of them nitrato groups bridge the ribbons giving rise to a three--dimensional framework [6]. In all the above structures an intra-molecular short hydrogen

bond between carbonyl and carboxylato O atoms is operating; in all Li ions show trigonal bipy-ramidal coordination environment.

PART 19. Triaqua(pyrazole-4-carboxylato-κN1)--lithium

The orthorhombic structure of the title com-pound is composed of discrete mononuclear mol-ecules in which Li1+ is coordinated by the non-pro-tonated hetero-ring N atom of the ligand molecule and three aqua O atoms at the apices of distorted tetrahedron. The observed Li–O and Li–N bond distances and bond angles reveal usual values. The carboxylic group is deprotonated. It makes a dihe-dral angle of 10.7(2)o with the almost planar [r.m.s. 0.0014(1) Å] pyrazole ring. Bond distances and bond angles within the latter are close to those ob-served in the structure of the parent acid. Complex

molecules form layers parallel to the unit cell ac plane (Fig.1) and are stacked along the b axis (Fig.2). Coordinated water molecules are active as donors and acceptors in an extended hydrogen bond system in which carboxylate O atoms are as acceptors. The protonated hetero-ring N atom as a donor and a carboxylate O atom as an acceptor are also observed.

Fig.2. A single molecular layer viewed along the [010] direction.

Fig.1. The molecule of the title compound with atom label-ling scheme and 50% probability displacement elipsoids.

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73LABORATORY OF MATERIAL RESEARCH

PART 20. Di-μ-aqua-bis([aqua(5-carboxylato--1H-1,2,3-triazole-4-carboxylic acid-κ2N3,O4) lithium

The triclinic unit cell of the title compound comprises two Li(C4H2N3O4)(H2O)2 molecules re-lated by an inversion centre to form a dimeric moiety in which two Li ions are bridged by an aqua

O atom donated by each molecule (Fig.3). The coordination of the Li ion is distorted square py-ramidal: carboxylate O1, hetero-ring N1, aqua O6 and O5i atoms constitute its base [r.m.s. 0.0798(2) Å], the Li1 ion is 0.1995(2) Å out of it, the aqua O5i is at the apex. Li-O and Li-N bond distances are usual. The ligand triazole ring is almost planar [r.m.s. 0.0006(1) Å]. The carboxylate C6/O1/O2 and C7/O3/O4 groups make with it dihedral angles of 2.0(1)o and 5.5(1)o, respectively. The Fourier map indicates clearly that the O2 atom is proto-nated and acts as a donor in a fairly short intra--molecular hydrogen bond of 2.538(2) Å to the O3 atom as an acceptor. The C7/O3/O4 carboxylic group remains deprotonated and coordination in-active. The bond distances and bond angles within the triazole ring do not differ from those reported in the structures of other complexes. The dimers form molecular sheets (Fig.4) in which they inter-act via an extensive hydrogen bond network; coor-dinated water molecules are as donors a hetero--ring N atom and carboxylate O atoms as accep-tors.

PART 21. catena-Poly[[diaquabis(μ3-5-carboxy-lato-1H-pyrazole-3-carboxylic acid-κ 3O3:O3;O5)dilithium(I)] monohydrate]

The structural unit of the title complex is a centrosymmetric dinuclear moiety composed of two Li ions bridged by two bidentate carboxylato O atoms, each donated by a symmetry related li-

gand (Fig.5). The ligand acts in μ3 bridging mode since apart from the bidentate O1 atom, the O4 atom of its second carboxylate group is chelated to a Livi ion in the adjacent dimer. In this way a Li ion is coordinated by the bridging O1 and O1ii atoms, the O4i from the adjacent dimer and an aqua O5 atom resulting in a distorted tetrahedral geometry. The Li–O bond distances which fall in the range between 1.930(2) Å and 1.980(3) Å are typical of Li complexes with carboxylate and water ligands. The pyrazole ring is planar with r.m.s. of 0.0009(1) Å; the carboxylate group C6/O1/O2 and C7/O3/O4 make with it dihedral angles of 2.4(1)o

and 5.5(1)o, respectively. The carboxylate O2 atom is chelating inactive, the O3 remains protonated and participates as a donor in the short hydrogen bond of 2.516(2) Å to O2vi in an adjacent dimer. Bond distances and bond angles within the pyra-zole ring do not differ from those reported in the structure of the parent acid. The plane of the Li,O1,Liii,O1ii dimer core makes a dihedral angle of 36.1o with the ligand plane. The dimeric units linked by carboxylate O4 atoms form polymeric

Fig.3. A dinuclear molecule of the title compound with 50% probability displacement ellipsoids. Symmetry code: (i) -x+1, -y+1, -z+1.

Fig.4. The packing of the dinuclear molecules with hydrogen bonds shown as dashed lines.

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74 LABORATORY OF MATERIAL RESEARCH

ribbons along [011] crystal direction. A solvate water molecule O6 with 50% site occupancy is present in the asymmetric cell resulting in one molecule per a dimer. Moreover, this water mol-ecule shows 0.5/0.5 positional disorder. The rib-bons are held together by a system of hydrogen bonds involving coordinated and crystal water molecules, the carboxylate groups and pyrazole N ring atoms resulting in a three-dimensional archi-tecture (Fig.6).

PART 22. catena-Poly[[aqualithium(I)]-μ-3-car-boxy-5,6-dimethylpyrazine-2-carboxylato-κ 4O2,N1:O3,N4]

The asymmetric unit of the title compound contains two Li(I) ions and two coordinated to them water molecules, all located on the rotation twofold axis, a Li(I) ion, two ligand molecules and a coordinated to water molecule. Two water coor-dinated Li(I) ions located on the rotation twofold axis are bridged by a ligand via its both N,O bond-

ing sites form type 1 molecular ribbon. The type 2 molecular ribbon is built of units composed of a water coordinated Li(I) cation and a ligand which also uses its both N,O bonding sites (Fig.7). Both ligands act in μ2 bridging mode. All three Li(I) cat-ions show slightly distorted trigonal bipyramidal coordination geometry. The Li11 cation is situat-ed in the equatorial plane composed of O11, O11ii and O13 atoms; N11 and N11ii atoms are in the apical positions. The Li12 coordination is form-

ed by O13, O13iii and O16 atoms, N14 and N14iii

atoms are at the apices; the Li12 is also coplanar with the equatorial plane. On the other hand, the Li21 cation is 0.0142(2) Å out of the equatorial plane formed by O21, O21i and O25 atoms; N22i and N21i are at the apices. The Li-O and Li-N bond distances fall in the range observed in the structures of other Li complexes with diazine car-boxylate ligands. Methyl carbon and pyrazine ring atoms in both ligands are coplanar with r.m.s. of

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.

Fig.6. The packing of molecular ribbons viewed along their propagation direction.

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75LABORATORY OF MATERIAL RESEARCH

0.0062(1) Å in the ligand 1 and 0.0193(2) Å in the ligand 2. The carboxylic groups C17/O11/O12 and C18/O13/O14 form with the ligand 1 ring dihedral angles of 6.1(1)o and 10.9(1)o, respectively. The di-

hedral angles between ligand 2 and carboxyl groups C27/O21/O22 and C28/O23/O24 are 1.2(10)o and 9.0(1)o, respectively. In both ligands the second car-boxyl O atoms remain protonated and act as do-nors in the short intramolecular hydrogen bonds with bond distances of 2.378(2) Å and 2.369(2) Å. Two ribbons of the same type form pairs which

propagate in [001] direction (Fig.8). The planes of ribbon 1 and ribbon 2 pairs are inclined 91.1(1)o each to the other. They are held together by a sys-tem of hydrogen bonds in which water molecules

act as donors and carboxyl O atoms are as accep-tors giving rise to a three-dimensional molecular framework.

References[1]. Starosta W., Leciejewicz J.: Acta Crystallogr., E69,

m438 (2013).

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.

Fig.8. The packing of molecular ribbons viewed along the [001] direction.

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76 LABORATORY OF MATERIAL RESEARCH

[2]. Starosta W., Leciejewicz J.: Acta Crystallogr., E69, m515-m516 (2013).

[3]. Starosta W., Leciejewicz J.: Acta Crystallogr., E69, m593-m594 (2013).

[4]. Starosta W., Leciejewicz J.: Acta Crystallogr., E69, m655-m656 (2013).

[5]. Starosta W., Leciejewicz J.: Acta Crystallogr., E67, m1133-m1134 (2011).

[6]. Starosta W., Leciejewicz J.: Acta Crystallogr., E69, m62 (2013).

FORMATION OF THE SURFACE LAYER WITH IMPROVED TRIBOLOGICAL PROPERTIES

ON AUSTENITIC STAINLESS STEEL BY ALLOYING WITH REE USING HIGH INTENSITY PULSED PLASMA BEAMS

Bożena Sartowska, Marek Barlak1/, Lech Waliś, Jan Senatorski2/, Wojciech Starosta1/ National Centre for Nuclear Research, Otwock-Świerk, Poland

2/ Institute of Precision Mechanics, Warszawa, Poland

Modification of the surfaces of technical materials is applied to change their surface properties. Auste-nitic stainless steels are used in numerous indus-trial applications, mainly due to their corrosion resistance in different environments, for example: nuclear and petrochemical industries and chemi-cal processing. But poor tribological and mechan-ical properties of austenitic stainless steels limited their applications. Improvement of the wear resist-ance of austenitic stainless steels without loss of corrosion resistance can be achieved using differ-ent surface treatment, for example: enrichment of the surface layer with reactive elements or re-so-lidification techniques using laser, electron or ion beams. Rapid solidification process is useful to obtain very fine structure with uniform properties [1-4]. It is also well known that high oxygen affin-ity elements such as Y, Ce, La, Er and other rare earth elements (REE) added to steels in small amounts can improve their resistance for wear and mechanical properties [5, 6]. REE can be alloyed during the steel making process or can be added to the surface region of materials using different surface modification techniques such as: ion im-plantation [7-9], sol-gel coating [9] or using plasma beams [10].

Austenitic stainless steel AISI 316L (Cr – 16.3 wt.%, Ni – 11.5 wt.%, Mo – 2.0 wt.%, Mn – 1.3 wt.% and Fe – balance) was used as the substrate for investigations. As the REE sources, cerium or lanthanum or mischmetal (MM) with a composi-tion: Ce – 65.3 wt.%, La – 34.0 wt.% and balance of Fe, Mg, and Pr were used. REE were incorpo-rated into one surface of steel samples using high intensity pulsed plasma beams – HIPPB (106-108

W/cm2). The plasma pulses were generated in a rod plasma injector (RPI) with its own name IBIS described with details in [11]. The pulse energy was high enough for melting the surface layer of the material. Heating and cooling processes were of non-equilibrium type.

Samples were irradiated with 3 pulses with an energy density of 3.0 J/cm2, in PID (pulsed implan-tation doping), DPE (deposition by pulse erosion) and mixed modes with titanium rods coated with Ce, La or mischmetal tips as electrodes and nitro-gen as the working gas. Samples of initial and modified materials were characterized by: scan-ning electron microscopy (SEM) – DSM 942 (Zeiss, Germany), energy dispersive X-ray spectrometry (EDS) – Quantax 400 (Bruker, Germany), grazing angle X-ray diffraction (GXRD) – diffractometer D8 Advanced (Bruker, Germany). Wear resistance measurements were carried out using the Amsler method.

After the modification process, the initial grain boundaries (Fig.1A) almost disappeared. Features typical of the melted and rapidly solidified mate-rial of the mixed deposit-substrate forms can be seen (Fig.1B-D).

Atomic concentrations of REE incorporated into specimens were in the range of 0.5-1.8 at.%.

GXRD spectra for initial and modified mate-rial analysis confirm the presence of FCC phase – austenitic structure with Fm-3m symmetry. Auste-nitic peaks (111) present in the spectra of modified materials are shifted towards bigger angles, what means that lattice parameters were decreased (Fig.2). Austenite lattice parameters calculated using the computer program Topas3 are presented

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.

A B C D

Page 77: INCT Annual Report 2013

77LABORATORY OF MATERIAL RESEARCH

Fig.2. Details of (111) peak analysis obtained for the surface layer of initial and modified with HIPPB with a single REE incorporation.

in Table. Austenite lattice parameters decreased significantly as a result of remelting and rapid so-lidification of the surface layer.

HIPPB modified AISI 316L steel reveals small-er value of linear wear and this means higher wear resistance – as compared with the initial material (Fig.3). Final value of the linear wear were of about 80% lower for the samples modified with HIPPB with a single REE incorporation and about 60% for the samples modified with HIPPB with Ce + La incorporation as compared with the initial material.

Results obtained from GXRD investigations and wear tests showed an interesting fact. Prac-tically no differences were observed in the results between alloying AISI 316L steel with Ce or La. Differences between alloying using MM or a single REE were observed. MM consists not only of 65% Ce + 34% La, it is a mixture of other elements. These elements can be accepted as impurities with an unknown role in modification processes.

Conclusions are the following:Austenitic phases (FCC) were identified in the • modified surface layer with decreased lattice pa-rameters as compared with the initial material.Modified surface layers showed improvement • of the tribological properties as compared with the initial material.The present authors suppose that improvement • of the tribological properties of the modified sur-faces is connected with the fine grains forma-tion and enrichment of grain boundaries with REE.

References[1]. Piekoszewski J., Werner Z., Szymczyk W.: Vacuum,

63, 475-581 (2001).[2]. Pereira A. et al.: Thin Solid Films, 453-454, 16-21

(2004). [3]. Sartowska B. et al.: Plasma Process. Polym., 4,

S314-S318 (2007).[4]. Wang, X., Lei M.K., Zhang J.S.: Surf. Coat. Technol.,

201, 5884-5890 (2007). [5]. Cheng X.H., Xie C.Z.: Wear, 254, 415-420 (2003).[6]. Liu H., Yan M.F., Wu D.L.: J. Mater. Process. Tech-

nol., 210, 784-790 (2010).[7]. Abreu C.M., Cristobal M.J., Novoa X.R.: Surf. Coat.

Technol., 158, 1, 582-587 (2002).[8]. Cleugh D. et al.: Surf. Coat. Technol., 142-144,

392-396 (2001).[9]. Riffard F. et al.: Appl. Surf. Sci., 199, 107-122 (2002). [10]. Piekoszewski J. et al.: Surf. Coat. Technol., 206,

854-858 (2011).[11]. Werner Z., Piekoszewski J., Szymczyk W.: Vacuum,

63, 701-708 (2001).

0

500

1000

1500

2000

2500

3000

3500

4000

42,5 43 43,5 44 44,5 45 45,5

2 Theta (deg)

Inten

sity (

coun

ts)

316L316L+Ce316L+La

0

1

2

3

4

5

6

0 500 1000 1500 2000 2500Sliding distance (m)

Linea

r wea

r (um

)

316L316L+Ce 316L+La 316L+REE

Fig.3. Linear wear of initial material and modified up to 0.8-1.1 at.% REE concentration.

Table. Lattice parameter of austenitic structure identified in the initial and modified surface layer.

Material Lattice parameter [A]

Lattice parameter change [%]

316L 3.6016 -

316L+Ce 3.5591 -15.3

316L+La 3.5457 -15.5

316L+REE 3.5373 -17.9

Page 78: INCT Annual Report 2013

78 LABORATORY OF MATERIAL RESEARCH

TECHNOLOGY, PRODUCTION AND CHRONOLOGY OF RED WINDOW GLASS IN THE MEDIEVAL PERIOD – REDISCOVERY

OF A LOST TECHNOLOGYJerzy J. Kunicki-Goldfinger, Ian C. Freestone1/, Iain McDonald2/, Jan A. Hobot3/,

Heather Gilderdale-Scott4/, Tim Ayers4/

1/ Institute of Archaeology, UCL, London, United Kingdom2/ School of Earth and Ocean Sciences, Cardiff University, Cardiff, United Kingdom

3/ Electron Microscopy Unit, School of Medicine, Cardiff University, Cardiff, United Kingdom4/ Department of History of Art, University of York, Heslington, United Kingdom

SEM-EDXA (scanning electron microscope with energy dispersive X-ray analysis) of 132 examples of medieval red window glass reveals the presence of around 1% copper oxide in all cases. SEM and TEM (transmission electron microscopy) of se-lected samples confirm the presence of Cu nano-particles. Two structural categories of red glass sheet are identified. Sheets comprising a single layer of red glass from a few tens to around 300 μm thick overlying a supporting substrate of white glass, with or without a protective cover of white glass, are typically found from the 14th century on-wards. However, in the 12th-14th century England, France and Spain, and perhaps elsewhere, typical red glass sheets have a complex microstructure comprising multiple coloured striae about 1 μm thick in a white background. SEM-EDXA, TEM and LA-ICP-MS (laser ablation inductively coupled plasma mass spectrometry) have been used to characterize and investigate the technologies of the two types in detail. The single-layered glasses were produced using an approach analogous to that of copper red glass in the modern period, where a red glass is flashed onto a colourless base.

In contrast, the multi-layered glasses were formed by the incomplete mixing of an oxidized high-Cu and a reduced low-Cu glass. The red colour forms due to the diffusion of oxidized copper into the reduced glass and the nucleation and growth of metallic copper during heat-treatment. This repre-sents a previously unrecognized medieval glass technology, where red was created by mixing two weakly coloured glasses, a complex, arcane and mysterious procedure which must have reinforced the exclusivity of the craft. The occurrence of the technique has implications for dating windows and the identification of glass which has been inserted in early restorations and repairs, for the trade in coloured glass and for the transfer of glassmaking technologies in medieval times. This provides a link between stained glass window technology of the high medieval period and the glass-colouring practices of the late first millennium CE [1].

References [1]. Kunicki-Goldfinger J.J., Freestone I.C., MacDonald I.,

Hobot J.A., Gilderdale-Scott H., Ayers T.: J. Archaeol. Sci., 41(1), 89-105 (2014).

Page 79: INCT Annual Report 2013

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 elec-• tron 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 SO• 2 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) (NO• x, SO2, CO, O2, etc.).The following projects were realized in 2013 in the Laboratory:“Attracting investments in plasma-based air and water cleaning technologies – PlasTEP+” • (international project co-financed by ERDF). The project is continuation of the previous one “Dissemination and fostering of plasma-based technological innovation for environ-ment 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);•

Page 80: INCT Annual Report 2013

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).•

Page 81: INCT Annual Report 2013

81POLLUTION CONTROL TECHNOLOGIES LABORATORY

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-ants to be controlled. It is expected that by 2020 the emissions from international shipping around Europe are forcasted to exceed the emissions of these pollutants from all other sources in the Euro-pean Union (EU). Although NOx removal from off-gases was widely studied, most of them were focused on NOx emission control from off-gases generated from power plants, chemical industry and car engine. Fewer investigations were conduct-ed on NOx emission from diesel engine of cargo ship. Heavy fuel oil (HFO) is the main fuel used in the diesel engine of the ship with a high sulphur content up to 4.0 wt.% [1]. In this work we theore-tically studied NOx removal from oil-fired off-gas under electron beam (EB) irradiation with the aid of computer simulation.

The computer simulation of NOx removal in oil-fired off-gas under EB irradiation was carried out by using the computer code “KINETIC” and GEAR method. 200 reactions involving 55 species were considered for 700 ppm SO2 + (74.3% N2 + 16.2% O2 + 9.5% H2O) + NOx (200 ppm, 1500 ppm). Five main groups of reactions were includ-ed, the rate constants of reactions were mostly taken from the literatures [2-4]. The units of rate constant are 1/s, m3/mole·s and m6/mole2·s for first-, second and third-order reactions, respectively. When fast electrons from electron beams are ab-sorbed in the carrier gas, they cause ionization and excitation process of the nitrogen, oxygen and H2O molecules in the carrier gas. Primary species and secondary electrons are formed. The second-ary electrons are fast thermalized within 1 ns in air at a 1 bar pressure. The G-values (molecules/100 eV) of main primary species are simplified as fol-lows [4]:4.43N2 → 0.29N2* + 0.885N(2D) + 0.295N(2P) +

1.87N + 2.27N2+ + 0.69N+ + 2.96e (1)

5.377O2 → 0.077O2* + 2.25O(1D) + 2.8O +0.18(O*) + 2.07O2

+ + 1.23O+ + 3.3e (2)7.33H2O → 0.51H2 + 0.46O(3P) + 4.25OH +

4.15H + 1.99(H2O+) + 0.01(H2+) +

0.57(OH+) + 0.67(H+) + 0.06(O+) + 3.3e (3)The generation of active species under the elec-tron beam is described in [4]:

(4)

where: ni – concentration of the i-th component [mole/m3], Gni

– radiation yield of the i-th compo-nent of the gas [mole/J], xi – mole fraction of the i-th component, D

. – dose rate [J/(kg·s)], ρ – gas

density [kg/m3].Kinetics of chemical reactions of species formed during gas irradiation with molecules of the gas

medium and with one another is described by dif-ferential equations:

(5)

For given initial concentrations:ni(0) = ni0 (6)

where: ni – concentration of the i-th component [mole/m3], ki

(n) – rate constant for n-order chemical reaction between the i-th and the k-th components of gas, nk – concentration of the k-th component, ni0 – initial concentration of the i-th component.

Calculations were made at 8.8 kGy absorbed dose with two different temperatures, 70 and 90oC, re-spectively: 700 ppm SO2 + (74.3% N2 + 16.2% O2 + 9.5% H2O) + NOx (200 and 1500 ppm, respec-tively).Calculation results of NOx removal from oil-fired off-gas under EB irradiation at the absorbed dose of 8.8 kGy are presented in Fig.1, and the corre-sponding experimental results are presented in Fig.2 [5]. It is seen that NOx removal efficiency is slightly improved with increasing temperature. The key reactions are listed below:

i

in i

dn G Dxdt

= ρ

0%

2%

4%

6%

8%

10%

70°C 90°CInlet gas temperature

Rem

oval

effi

cien

cy o

f NO

x

200ppm 1500ppm

0%

5%

10%

15%

20%

25%

70°C 90°CInlet gas temperature

Rem

oval

effi

cien

cy o

f NO

x

200ppm 1500ppm

Fig.1. Calculation results of NOx removal from oil-fired off-gases under EB irradiation.

Fig.2. Experimental results of NOx removal from oil-fired off-gases under EB irradiation.

n(n)i

i i kn k 1

dn n k ndt =

= ∑ ∏

Page 82: INCT Annual Report 2013

82 POLLUTION CONTROL TECHNOLOGIES LABORATORY

ANALYSIS OF THE CONSTRUCTION POSSIBILITY OF A LARGE ELECTRON BEAM FLUE GAS TREATMENT PLANT

Andrzej Pawelec, Sylwia Witman-Zając

N + NO = O + N2 (R1)O2 + 2NO = 2NO2 (R2)

O + NO = NO2 (R3)NO + O4

– = NO3– + O2 (R4)

OH + NO + M = HNO2 (R5)NO2 + OH + M = HNO3 + M

(M is the third body in the reaction system) (R6)HO2 + NO = OH + NO2 (R7)

NO2 + O = O2 + NO (R8)The oxidation-reduction cycle between NO2 and NO is toward the oxidation path.

Comparing calculation results with experimen-tal results, we drew the following conclusions:

Removal efficiency of NO• x is increased with in-creasing temperature.

Removal efficiency of NO• x is decreased with in-creasing initial inlet concentration of NOx. At 8.8 kGy of the absorbed dose less than about 1% NOx was removed from flue gas for 1500 ppm a high inlet concentration of NOx without ammonia added.

References[1]. Basfar A.A. et al.: Fuel, 87, 8-9, 1446-1452 (2008). [2]. Albritton D.L.: At. Data Nucl. Data, 22, 1-101 (1978).[3]. http://kinetics.nist.gov/kinetics/index.jsp.[4]. Mätzing H.: Advances in chemical physics.Vol. LXXX.

John Wiley & Sons, Inc., New Jersey 1991, pp. 315-402.[5]. Chmielewski A.G. et al.: Radiat. Phys. Chem., 81, 8,

1036-1039 (2012).

Electron beam flue gas treatment (EBFGT) process was invented in Japan in the 1970s. At the beginning, the process was elaborated for SO2 re-moval from ore sintering plants, however soon the possibility of simultaneous removal of both of SO2 and NOx was observed. During the next twenty years processes of the intensive development were undertaken resulting in the construction of three industrial EBFGT plants at Chengdu and Hangz-hou Power Plants (China) and the Pomorzany Power Plant in Szczecin (Poland). All of the plants were designed for treatment up to 300 000 Nm3/h of flue gas that corresponds to a rather small (up to 100 MWth) energy generation unit.

In the recent years a new phase of EBFGT tech-nology development began. New implementation of the technology in the TPP Sviloza in Svishtov (Bulgaria) was undertaken. The plant was planned to purify up to 608 000 Nm3/h of flue gas from coal fired boilers, that is twice more than the existing EBFGT plant. However, nowadays, the most im-portant direction of technology development is the application of EBFGT technology for treatment of flue gas from heavy fuel oil combustion. This application is dedicated to Middle East countries using liquid fuels as the main source of energy. Laboratory and pilot research on this topic were performed with satisfactory results. Dependences of SO2 and NOx removal efficiency on main process parameters as well as process optimization were elaborated. With regard to the experiences gather-ed during construction and exploitation of the Pomorzany industrial EBFGT facility, the tech-nology is ready for design and construction of in-dustrial plant to be applied for liquid fuel fired boilers. However, in the most cases large energy generation units are applied and previously con-structed electron beam flue gas treatment facilities are too small for practical application. Therefore, analysis of the possibility of application of EBFGT technology for large energy generation units was undertaken.

For the purpose of the elaboration, a 1 000 000 Nm3/h flue gas flow rate unit was selected as a basic unit for large plant application. A typical composition and parameters of flue gas for heavy fuel oil fired boilers were assumed. Oxygen con-tent was assumed to be 3.2% vol., humidity – 12.6% vol. and a temperature of 360oC. Pollutants con-centrations were taken respectively: SO2 – 1900 ppmv, NOx – 240 ppmv and dust – 170 mg/Nm3. Required removal rates according to Saudi Arabian standards were 45% removal of SO2 for general rules (82% for special industrial zones) and 22% removal of NOx. For the purpose of technology demonstration 90% of SO2 removal and 50% of NOx removal were assumed.

Typical construction of the EBFGT plant may be used in this case. Raw flue gas from boilers shall be directed to a gas conditioning unit in order to decrease its temperature and increase humidity. The gas out coming from the oil fired boilers has too high temperature to be properly cooled down in one stage by water evaporation. Therefore, two--stage gas conditioning unit composed of heat ex-changer and spray cooler shall be applied. In the next step ammonia shall be injected into flue gas. Ammonia shall be stored in the liquid form in pressurized tanks and added to the flue gas up-stream reactors. Such a prepared gas is directed to the reaction unit, which is the main unit of the EBFGT plant. Reaction unit is composed of such parts as reactors, accelerators, radiation shielding, cooling and ventilation system, etc. In this unit flue gas is being irradiated by electron beam from accelerators that initiate chemical reactions lead-ing to SO2 and NOx conversion into ammonium sulphate and ammonium nitrate. Due to reliability of the EBFGT plant, at least two parallel reaction chambers shall be constructed. The by-product – a mixture of ammonium salts formed in the process of SO2 and NOx removal shall be collected and shipped to a receiver. According to experiences from other EBFGT installations, electrostatic pre-

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83POLLUTION CONTROL TECHNOLOGIES LABORATORY

cipitator is the most appropriate apparatus for by-product collection. The purified flue gas is re-leased to atmosphere. In order to compensate pressure drop in the plant, auxiliary fan shall be in-stalled upstream the stack. The conceptual scheme of a large-scale EBFGT installation is presented in Fig.

As most of the equipment is used in conven-tional flue gas treatment technologies, selection of the reliable, high power electron accelerators is crucial for the large-scale EBFGT facility construc-tion. However, nowadays intensive development of electron accelerators is observed and 1 MW, 1.5 MeV accelerators may be offered by the manufac-turers. Application of four pieces of such equip-

ment for irradiation of two independent reactors (double stage irradiation system) makes the con-struction of 1 000 000 Nm3/h unit feasible.

The performed analysis showed that the con-struction of 1 000 000 Nm3/h electron beam flue gas treatment unit for SO2 and NOx removal from flue gas emitted during combustion of heavy fuel oil is fully feasible from the technical point of view. Assumed removal efficiencies 90% for SO2 and 50% for NOx can be achieved by the use of EBFGT facility.

The 1 000 000 Nm3/h EBFGT facility may be constructed as a basic unit for the treatment of flue gas from large combustion plants. For larger amounts of flue gas, this unit may be multiplied.

Fig. Conceptual scheme of a large-scale EBFGT facility.

Page 84: INCT Annual Report 2013

STABLE ISOTOPE LABORATORYBasic 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, envi-• ronmental protection and origin identification.The Laboratory is equipped with the following instruments: mass spectrometer – DELTA• plus (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 (N• 2O, 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 – profi-• ciency testing scheme).

Specific activity: industrial emission control of greenhouse gases by the use of isotopic compo-sition 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 composi-tion. 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 spectro-metry (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).•

Page 85: INCT Annual Report 2013

86 STABLE ISOTOPE LABORATORY

DETERMINATION OF SULPHUR ISOTOPIC COMPOSITION OF FOOD PRODUCTS

Ryszard Wierzchnicki, Kazimiera Malec-Czechowska

Sulphur is one of the popular elements in living organisms: C, H, N, P, O, S. In food product sul-phur isotopic composition δ34S is strongly influ-enced by its origin: geology of the region, feed diet of animal, fertilization of plant, climate and close-ness to the sea.

Typically δ34S values of the food samples ranged from -2 to +12‰. The variation in δ34S values ob-served within a single region could be due to the different production systems (conventional and organic). Rich products into sulphur mostly con-tain proteins: meat, poultry, eggs, dairy product, cabbage, fish, legumes, cauliflower, broccoli, garlic and onion (Table 1).

Sulphur have a four stable isotopes: 32S (95.02 at.%), 34S (4.21 at.%), 33S (0.75 at.%), 36S (0.02 at.%) and three radioisotopes: 31S (3.2 s), 35S (87.1 day), 37S (5.04 min half-life).

Sulphur in chemical composition occur in on few oxidation steps. Bacterial reduction of sul-phate (sulphur cycle) to sulphide. For sulphur is the lack of the enrichment effect in the nutritional cycle (chain).

Our interest in the study of sulphur isotopic compostition it is a result of differentiation δ34S in the environment (Table 2) and possibility of ap-plying this parameter to food origin control. Aim of this study is to explore this isotopic parameter for differentiate of food origin, method of pro-duction and food composition in the field of food authenticity control.

The following instruments were used in sulphur isotopic measurements: isotope ratio mass spectro-meter DELTAplus, FinniganMAT (Bremen, Ger-many); elemental analyser Flash 1112NC, Thermo-Finnigan (Italy); Parr Bomb oxidation, Parr In-strument Company (Illinois, USA); ConFloIII – interface for EA and IRMS connecting, Finnigan, (Bremen, Germany).

Basic problem which we have with sulphur iso-topic measurement is a low content of sulphur in organic matter. For extraction sulphur from or-ganic samples without isotopic effects we can use the method of Parr Bomb oxidation. The mass of the samples is connected with sulphur content in the sample. For sample powder 2 mg and 3-5 drops

of bidestilled water for one pill is used. Every sample should be prepared two times – two pills.

After burning the samples a special chemical procedure for BaSO4 preparation from the pro-duced SO2 dissolved in water is used. Finally the sulphur can be precipitated as BaSO4 using a 10% BaCl2 solution. To obtain BaSO4 for sulphur iso-topic measurements by the use elemental analyser--isotope ratio mass spectrometer (EA-IRMS). For sulphur isotopic measurements with EA-IRMS we use a special procedure of food samples con-version to BaSO4 (Fig.).

The elemental analyser for sulphur measure-ments is specially equipped with: teflon tubes (connection), GC column and special quartz reac-tor for sulphur.

Samples and references materials are loaded into an autosampler AS200 on elemental analyser Flash 1112. Mass of sulphur in the measured ma-terials should be 30 μg per sample or more. To rich protein product the mass of samples should be 15-20 mg; for pure protein the mass of samples can be 3-5 mg (for casein 5 mg). Sulphur isotope ratio is expresed using conventional notation:

[‰]

where: Rsp – measured isotopic ratio between abundance of isotope 34S and isotope 32S in sample, RCDT – isotopic ratio between abundance of iso-tope 34S and isotope 32S in international standard CDT (Canyon Diablo Troilite) – actual in use standard VCDT (Vienna Canyon Diablo Troilite) with RCDT = 0.0450045.

Reference materials for sulphur isotopic mea-surements were the following: barium sulphate NBS-127, barium sulphate IAEA-SO-5 (IAEA), silver sulphide IAEA-S-1 (IAEA).

Table 1. Proteins concentration in food products.

Food products The protein content in the dry matter [%]

Legumes 40

Vegetable 3

Fruit 1

Meat 20

Milk 5

Fish 15

Table 2. Examples of isotopic variability of sulphur in envi-ronmental samples.

sp34 34 32CDT CDT

CDT

RS S/ S 1 1000

R⎡ ⎤

δ ≡ δ = − ∗⎢ ⎥⎣ ⎦

δ34S [‰]

Environment marine:

- marine sediments 10÷33

- atmosferic sulphate -30÷30

Environment terrestrial:

- fossil fuels -10÷30

- soil -30÷30

- plants 0÷14

- meat -10÷20

- milk 0÷6

- fish -5÷25

- vegetable 0÷6

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87STABLE ISOTOPE LABORATORY

For improve oxidation condition to every weighted sample the V2O5 (1:1 or more) is added.

Typically the standard deviation for measure-ments was ± 0.3‰

Problems with sulphur measurements in food samples are the following:

low concentration of sulphur in food,• high memory effect of measurements connect-• ed with the SO2 reactivity,high concentration of carbon in food sample.• The first stage of the project was concerning an

implementation of method of sulphur isotopic measurement and two methods of sample prepa-ration. A further approach in our study will be testing the possibility to discriminating different methods of food production and different regions of its origin.

Stable isotope ratios of sulphur of food prod-uct can be used as a good indicator of geographi-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-trol.

This study was supported by the Ministry of Science and Higher Education, Poland in the frame of statutory work.

References[1]. Boner M., Förstel H.: Anal. Bioanal. Chem., 378, 2,

301-310 (2004).[2]. Molkentin J., Giesemann A.: Anal. Bioanal. Chem.,

388(1), 297-305 (2007).[3]. Rossmann A.: Food Rev. Int., 17(3), 347-381 (2001).

Fig. The steps of chemical treatment for BaSO4 prepara-tion.

NEW APPROACH OF THE ISOTOPIC METHOD FOR JUICE AUTHENTICITY CONTROL

Ryszard Wierzchnicki, Kazimiera Malec-Czechowska

The subject of our study was the authenticity of fruit juice originated from the Polish market. Nowadays in Europe, origin and authenticity is probably one of the most important characteristic features of food. This is connected with economic politics of European Commission in agriculture sector (Table 1). Adulteration is as an addition of

the artificial (prohibited) components to natural products, a cheaper product put into a place ex-pensive one and mislabelling of products.Fruit juice can be adulterated by:

undeclared addition of sugar/pectin,• undeclared addition of water,• undeclared addition of organic acids,• undeclared addition of vitamin C,• undeclared addition of flavour compounds.• Important limitation of the application of iso-

topic method for food authenticity control is the

lack of database of stable isotope composition in juice of different origin. Stable Isotope Laboratory of the Institute of Nuclear Chemistry and Tech-nology (INCT) since many years is carring out a

Table 1. Standard methods accepted by the European Union for juice authenticity control.

a) IRMS – isotope ratio mass spectrometry.b) SNIF-NMR – site specific natural isotope fractionation determined by nuclear magnetic resonance.

Method Fraction Technique Isotope ratio

CEN (ENV 12140) sucrose IRMS a) 13C/12C

AOAC method 995.17 ethanol (from fermentation) SNIF-NMR b) (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

Pills preparation

Burning pills in Parr Bomb

NH4OH addition (pink to yellow)

Filtration

H2O2 2.5 ml

HCl (yellow to red)

Boiling

Filtration

HCl 2ml

Washing and roasting at 800oC

(overnight) filters with sediment

5 ml BaCl2

Page 87: INCT Annual Report 2013

88 STABLE ISOTOPE LABORATORY

study of isotopic composition of food by IRMS method (Table 2) implementation and by database for some food from the Polish market. These instruments were used in the multielement method in control of fruit juices:

GasBench II (GB) for oxygen in water;• H/Device (HD) for hydrogen in water;• elemental analyser (EA) for organic C, N, S;• mass spectrometer DELTA• plus with dual inlet system (IRMS);HPLC preparative + multicollector;• Parr Bomb for sulphur from organic product • preparation.An actual problem encountered in the area of

fruit juice authentication is in the detection of un-declared sugar added to a juice. The sugar can be added in the form of a beet or cane sucrose or as a high fructose corn syrup (HFCS). Other impor-tant topic in fruit juice analysis is the detection of adulteration by L-ascorbic acid. For this reason, the method of internal standard with malic acid

was proposed [1]. Carbon stable isotope ratio δ13C analysis to multicomponent method for juice au-thenticity control is applicable.

We try to use different method of comparison of isotopic composition between components of juice: sugars and acids (Table 3). Minimal sample preparation, rapid separation and good recovery support for these procedures is a promising for the sugars and acids isotope composition determi-nation in fruits.Trends in isotopic analyses of juice are the follow-ing:

Insoluble solids (pulp) of the whole fruit can be • used as internal standard [2].

Internal carbon isotopes of acids: malic, citric • and ascorbic, can be used to detect the addition of synthetic organic acids. Ratios between bulk sugars and individual acids • by IRMS, to detect sugars or acid addition [3] can be applied.Specific stable isotope analysis (CSIA) of juice by• the use of a gas chromatograph or a liquid chro-matograph connected with combustion and mass spectrometer: GC-C-IRMS and LC-C-IRMS can be applied.We look for a rapid and precise method for

juice authenticity control. Most isotope techniques require the use of the database of isotopic compo-sition or original fruits as a reference for compari-son with the composition of analysed product. The database can be substituted by the isotope analysis of an internal standard. The application of inter-nal component reduces measurement errors which is depending on the isotope variability of raw ma-terials. In our study, no clear conclusions were

possible with a still limited number of samples in-vestigated.

This research work was supported by the Mi-nistry of Science and Higher Education, Poland under grant No. 12-0043-10/2010.

References[1]. Jamin E., Martin F., Santamaria-Fernandez R., Lees

M.: J. Agric. Food Chem., 53, 5130-5133 (2005).[2]. Figueira R., Venturini Filho W.G., Ducatti C., Nogueira

A.M.P. : Ciênc. Tecnol. Aliment., 31, 3, 660-665 (2011).[3]. Tremblay P., Paquin R.: J. Agric. Food Chem., 55,

197-203 (2007).

Table 2. Multielement analysis for the control of juice origin.

a) IRMS – isotope ratio mass spectrometry.b) Py – pyrolise.c) ICP-MS – inductively coupled plasma mass spectrometry.d) TIMS – thermal ionization mass spectrometry.

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)

Table 3. Carbon isotopic composition of juice components and some artificial juice components for multicomponent method of juice control.

Juice components Apple Strawberry Black currant Commercial product

Sugars -26.5, -25.0 -24.0 -25.6 beet -24.5HFCS -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

Page 88: INCT Annual Report 2013

LABORATORY FOR MEASUREMENTS

OF TECHNOLOGICAL DOSESThe Laboratory for Measurements of Technological Doses (LMTD) was created in 1998 and accredited as testing laboratory in February 2004 (Polish Centre of Accreditation, accredita-tion 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 de-• fined doses,irradiation of dosimeters or other small objects with 10 MeV electron beams to strictly de-• fined 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).

Page 89: INCT Annual Report 2013

90 LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES

RECALIBRATION OF DOSIMETER FILMS CTAAnna Korzeniowska-Sobczuk, Aneta Sterniczuk, Magdalena Karlińska

The responses of most films used in routine dosi-metry are usually influenced by the environmental conditions such as temperature during irradiation, dose rate and post-irradiation storage [1]. Many problems may be encountered in the routine dosi-metry for radiation processing applications, be-cause the conditions in irradiation facilities may differ considerably from the conditions in which dosimeter films were calibrated. These differences may lead to expected systematic errors in dose es-timation. The advantage of the CTA film is its linear response to the dose and the dose-inde-

pendent post-irradiation signal change. However, its low sensitivity to ionizing radiation restricts its use to high and very high doses [2].

Implementation issues related to research the CTA film dosimeter results from the need to con-tinually monitor the quality of services provided [3]. In the Laboratory for Measurments of Techno-logical Doses (LMTD) of the Institute of Nuclear Chemistry and Technology (INCT) is the accredita-tion method for measuring the absorbed dose based

on a CTA film dosimeter. CTA dosimeter, produc-tion Fujifilm, was purchased in 2005 and then made the first calibration purchased batch with this dosi-meter. Currently, the LMTD owns approximately 40% of the originally purchased amount of the

CTA film dosimeter, so it is advisable to redo re-calibration the dosimeter. the LMTD having ac-creditation of the Polish Centre for Accreditation in accordance with the requirements of PN-EN ISO/EIC 17025:2005 [4] imposed on the LMTD im-plementation of improvement activities, preven-tive as well as quality control tests. The implemen-tation of this subject allows for comprehensive requirements according to a previous experimen-tal data and archival film samples after irradiation of the CTA film dosimeter which will allow to trace the changes in the long term.

The film dosimeters CTA was irradiated with 10-MeV electron beams from an industrial 10-kW linear accelerator radiation in the range of 10-40 kGy dose (accelerator Elektronika 10/10) and the gamma radiation 10-80 kGy in the gamma field of a reference 60Co source Issledovatel (~0.5 kGy/h) having the dose rate traceable to a primary stand-ard maintained by the National Physical Labora-tory – NPL (Teddington, UK). In the experiments the film dosimeters CTA were used, with an opti-

cal signal detection. The absorbance was measur-ed by using a JASCO-V650 spectrophotometer UV/Vis (λmax = 280 nm). The wavelength and ab-sorbance scales were checked before each experi-ment by a calibrated reference standard.

Fig.1. The physicochemical parameters of the dosimeter films CTA.

0,115

0,120

0,125

0,130

0,135

0,140

0,145

0,150

0,155

0 10 20 30 40 50 60 70

Sample number

The

aver

age

thic

knes

s [m

m]

A

0,115

0,120

0,125

0,130

0,135

0,140

0,145

0,150

0,155

0 10 20 30 40 50 60 70

Sample number

Abs

orba

nce

Ao

B

Table. Change of the parameters of the CTA dosimetric film with time after irradiation (post-effects).

Dose [kGy]

Time after irradiation

30 min 24 h 7 days 30 days 6 months

A – 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

Page 90: INCT Annual Report 2013

91LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES

In 2013, the first stage of the study was to verify the physicochemical parameters of unexposed film and comparison with the data contained on the score sheet dosimeter (after the first calibration). A comparison of the absorbance, A0, and an aver-age thickness of 60 samples revealed no radiation of the CTA film (Fig.1).

Parameters determined for the calibration curves take into account the changes in absorbance (post--effects) after 30 min, 24 h, 7 and 30 days, 3 and 6 months after the irradiation. Details are present-ed in Table. Compilation of all annual calibrations, 30 min after irradiation, taking into account also the aging of the CTA film is presented in Fig.2.

On the basis of these results the following con-clusions can be drawn (scientific and practical ap-plications):

The absorbance of unexposed film CTA in-• creases during storage, this factor should be taken into account when determining the dosi-metric signal for each sample.Differences in thickness within one series • (spool) CTA film are negligible.Answer the CTA film dosimetry test is linear in • the full range of doses and increased with stor-age time after irradiation. Using the CTA dosi-meter as the transfer dosimeter should take into account the passage of time between irra-diation and spectrophotometric measurement. Adapting the measuring points to the calibra-tion curve, in many cases R2 > 0.99.

References[1]. McLaughlin W.L., Boyed A.W., Chadwick K.H., McDo-

nald J.C., Miller A.: Dosimetry for Radiation Process-ing. Taylor & Francis, Ltd., London 1989, 251 p.

[2]. Peimel-Stuglik Z., Fabisiak S.: Appl. Radiat. Isot., 66, 346-352 (2008).

[3]. ISO/ASTM Standard 51650-20052, Standard practice for use of cellulose aceteate dosimetry system.

[4]. PN-EN ISO/IAC 17025:2005. Ogólne wymagania doty-czące kompetencji laboratoriów badawczych i wzorcu-jących (General requirements for the competence of testing and calibration laboratories).

Fig.2. Summary of calibration curves for CTA films made in different years from the date of purchase of the film.

y = 0,0056x + 0,0182R2 = 0,991

y = 0,0063x + 0,0053R2 = 0,9854

y = 0,0062x + 0,0073R2 = 0,9939

y = 0,0064x - 0,0053R2 = 0,9915

0,00

0,05

0,10

0,15

0,20

0,25

0,30

0 10 20 30 40 50 60

2013

2012

2010

2008

Dose [kGy]

Ab

sorb

an

ce

A –

A0

Page 91: INCT Annual Report 2013

LABORATORY FOR DETECTION OF IRRADIATED FOOD

Typical groups of products controlled in the Laboratory.

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 ac-creditation 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 en-larged assortment of food products. Currently, the Laboratory offers analytical service to do-mestic 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 supple-ment 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 para-• magnetic 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 spec-• troscopy based on analytical procedure given by the CEN European standard EN-1787;method for the detection of irradiated food containing crystalline sugars with EPR spec-• troscopy 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 stand-ard EN-13751.

The application of five standardized and vali-dated 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 ana-lytical and measuring procedures suitable for the detection of irradiation in complex food articles which typically contain low concentra-tion of irradiated ingredient admixed to unir-radiated product which appears in abundance.

Page 92: INCT Annual Report 2013

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 iso-lated 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, ferment-ed 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 irradi-ated component.

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95LABORATORY FOR DETECTION OF IRRADIATED FOOD

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-tion in dried fruits EN-13708:2003 issued by the CEN (European Committee for Standardization) in Brussels in 2002 [1] is currently widely used for irradiation control of raisins, dates, figs, mangos, papaya, etc. in Europe and over the world. The method is based on the identification of a specific EPR (electron paramagnetic resonance) signal in irradiated food articles which is never observed in dried fruits not exposed to the action of ionizing radiation. It is suggested that this signal originates from free radicals produced by ionizing radiation in crystalline domains of dried fruits [2]. The ef-forts were undertaken to identify these radicals [3, 4]. The important feature of any EPR signal which is used for the detection of irradiation is its stability at room temperature. The EPR signal re-corded in irradiated fruits is stable several months after irradiation, but decays slowly during pro-longed storage. Dried fruits belong to this assort-ment of food commodities which are allowed to be stored safely for a relatively long time. In order to ascertain the reliability of the identification of the EPR signal observed in radiation treated dried fruits during their storage for several months the model experiments have been performed.

The following fruits purchased in the market were chosen: cranberry, papaya, pineapple, date, fig, rowan berry, banana and raisins. The fruits were divided into three parts each irradiated with

different dose of 60Co gamma rays: 0.5, 1 and 3 kGy, respectively. The adapted doses correspond to technological doses as announced to be used for radiation disinfestation and pasteurization of dried fruits. After radiation treatment, the samples were stored at room temperature with the access of air. The EPR measurements were conducted with each of the samples after one day, and subse-quently after 30, 90, 180 and 360 days of storage. All measurements were done with the samples handled similarly under the same EPR spectro-meter settings and operational conditions. The recorded EPR signals were doubly integrated within the same range of magnetic field – 7 mT. The scans were centred at g = 2.003. The inte-grated signal areas are in proportion to the over-all signal intensity. The EPR signals of raisins un-irradiated and irradiated with 0.5, 1 and 3 kGy are shown as an example in Fig.1. The upper record represents the EPR spectrum of unirradi-ated raisins. A weak, not specific signal is seen which is easily distinguished from multicompo-nent signals typical for irradiated samples (shown below). Such weak, so-called “native” EPR sig-nals appear in some of irradiated fruits and origi-nate from stable paramagnetic impurities or trace components present. The integrated EPR signal areas related to irradiated samples and measured as a function of prolonged storage time were used to construct the kinetic decay curves for each of the sample.

In Fig.2, the time-dependent decay curves of the EPR signals intensity recorded with the samples of dried dates, raisins, rowan berries and cran-berries are presented. The decrease of the EPR signal intensity does not fit to a classic first- or second-order kinetics. The decay process of radi-cals in dried fruits exposed to ionizing radiation

Fig.1. EPR signal of dried raisins irradiated with 0.5, 1 and 3 kGy of 60Co gamma rays. The upper graph refers to unir-radiated sample. The numbers in the right denote to the attenuation of the recorded signals.

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

Magnetic fi eld [G]

1 kGy

3 kGy

0.5 kGy

0 kGy

x 4

x 2.4

x 1.3

x 1

A

A

B

B 3420 3440 3460 3480 3500 3520 3540 3560 3580

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96 LABORATORY FOR DETECTION OF IRRADIATED FOOD

QUANTITY AND QUALITY OF MINERAL FRACTION IN THERMOLUMINESCENCE METHOD

FOR THE DETECTION OF IRRADIATION IN ALIMENTARY ARTICLESWacław Stachowicz, Grażyna Liśkiewicz

can be divided at least in two phases. The first easily distinguished phase of radical decay lasting about 50 days proceeds relatively fast, resulting in the decrease of initial EPR signal intensity by about 30%. The annihilation of less temperature resistant shallow radical traps might be respon-sible.

The second phase of temperature-dependent radical decay in dried fruits treated with ionizing radiation is markedly slower. The EPR measure-ments have been done between the 50th day of storage to one year (360 days). Although the re-cording time was ca. 6 times longer than in the first phase, the decreases of the EPR signal inten-sity did not exceed 20%. It is clear that at this stage thermal annihilation of radical traps is less effec-tive. In general, the radiation-induced radical de-cay in eight kinds of dried fruits studied was found similar. It means that in all fruits two described phases of radical decay can be distinguished. How-ever, distinct individual differences do appear be-tween some of them which are seen in Fig.2 and in the Table.

The highest stability of radiation-induced EPR signal after one year of storage at room tempera-ture was found in cranberry resulting in 88.2% survival of EPR signal what means that it de-creased by 11.8% only. The lowest stability, in turn, was demonstrated by raisins resulting in 43.2% survival of the EPR signal and the decrease of the EPR signal intensity by 56.8%.

The general conclusion drawn from the above experiments is that the stability of the EPR signals utilized for the detection of radiation treatment in dried fruits according to EN-13708 European standard is high and facilitates the reliable detec-tion of radiation treatment in any kind of dried fruits after one year of storage at room tempera-ture with free access of air oxygen to the product. It is concluded from the analysis of the decay curves after 200 days of storage (Fig.2) that the

decrease of the signal by storing dried fruits much longer than for one year (two or more years) will not influence negatively on the detection of radia-tion treatment in this product. As to our knowl-edge, long-lasting kinetic studies on the stability of radiation-induced radicals in food had not been performed so far. From the practical point of view the obtained results can be useful for the control of food reserves and for accidental dosi-metry.

References[1]. EN-13708:2001 Foodstuffs – Detection of irradiated

food containing crystalline sugar by ESR spectroscopy. European Committee for Standardization (CEN), Brussels.

[2]. Raffi J., Angel J.P.: Radiat. Phys. Chem., 34, 891-894 (1989).

[3]. Guzik G., Stachowicz W., Michalik J.: Nukleonika, 57, 4, 545-549 (2012).

[4]. Guzik G., Stachowicz W.: Nukleonika, 58, 3, 425-428 (2013).

Table. Decrease of the EPR signal intensity in dried fruits irradiated with 3 kGy of 60Co gamma rays after 360 days of storage.

Dried fruitDecrease

of the EPR signal intensity [%]

Intensity of remaining

EPR signal [%]

Cranberry 11.8 88.2

Papaya 18.0 82.0

Pineapple 26.9 73.1

Date 28.3 71.7

Fig 40.8 59.2

Rowan berry 40.9 59.1

Banana 43.0 57.0

Raisin 56.8 43.2

Thermoluminescence (TL) is a method success-fully used for the detection of irradiation in dif-ferent alimentary articles from which crystalline minerals can be isolated. Dried spices and herbs belong to this group, while those imported from tropical countries are usually highly contaminated with microorganisms, parasites and pests being often dried in the opened air. For that reason, these products undergo disinfection processing. A very effective method for the neutralization of biological contaminates in food is radiation pas-teurization with gamma rays or beams of acceler-ated electrons. Aromatic spices and herbs under-going this processing do not lose their aroma or flavour as it is the case by applying the elevated

temperature or pressure, for example. Presently dried spices, herbs and seasonings belong to this category of food products which are treated quite frequently with ionizing radiation. Thermolumin-escence method for the detection of irradiated spices and herbs is currently adapted for the iden-tification of radiation treatment in very different food assortments containing only negligible flavour admixtures of spices as souses, cheese or dinner compositions. The method is also successfully used for the detection of irradiated components in diet supplements and herbal pharmaceuticals.

The essential problem of the method is effec-tive isolation of mineral fraction based on general procedure recommended in European standard

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97LABORATORY FOR DETECTION OF IRRADIATED FOOD

EN-1788 [1], as discussed in our earlier study [2], and the content and quality of isolated minerals. In the proceeding study it has been shown [3] that the weight of mineral fraction isolated from differ-ent commodities (samples weighing 20 g) varied from 0.1 do 2.5 mg while the corresponding TL intensity differs from sample to sample even by the factor of 500. It has been also observed that the correlation between the weight of mineral and the intensity of thermoluminescence was not proven. The explanation lies in different geographical ori-gin of the investigated vegetal products and con-sequently in a very different composition of soils in which the plants giving the products were culti-vated [4].

In order to throw more light on this problem a new experimental approach has been undertaken. In addition to the weight of isolated mineral frac-tion before the TL measurement the weight of this

fraction was determined but after heating to 500oC. The number of 28 samples delivered to the Lab-oratory for Detection of Irradiated Food, INCT for testing whether irradiated was used to perform the study. The experiment delivers the information concerning the stability of mineral fraction isolat-ed from food at elevated temperature. This kind of study has not been done, as to our knowledge, so far.

The samples were organized in the Table ac-cording to the increasing loss of weight by heating (column 3). As is seen from the Table, the weight losses of the mineral fraction isolated from the most of the samples heated to 500oC are surpris-ingly high, proving a low temperature stability of mineral fraction separated. The source of the thermoluminescene released from mineral con-stituents of food are structural imperfections in the crystalline lattice of minerals – suitable traps

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

Product samples 100 g ± 0.2 g each Weight of isolated mineral fraction [mg]

Mineral loss by heating to 500oC [%]

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

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98 LABORATORY FOR DETECTION OF IRRADIATED FOOD

for radiation energy during the irradiation pro-cessing. This kind of stable energy traps appear in crystalline minerals such as quartz, quartzite, feld-spar defined as silicate minerals [5]. The isolation procedure of mineral fraction recommended in European Standard EN-1788 eliminates efficient-ly limestone and ground chalk from mineral de-posit separated from organic pulp but does not eliminate amorphous loams, clay stones, shale, etc. which may appear in the form of hard, rigid par-ticles and accompany the crystalline minerals. Amorphous components of soil contain a lot of structural water which is easily freed by heating. The heating can also stimulate the decomposition of organic constituents which are always contained in amorphous rocks appearing in mineral fraction. Both dehydration and decomposition of amor-phous soil originated solid deposits separated from food can be responsible for the observed effect of significat loss of the weight of mineral fraction iso-lated from food.

References[1]. EN-1788:2001 Foodstuffs – Detection of irradiated

food from which silicate minerals can be isolated. Euro-pean Committee for Standardization (CEN), Brussels.

[2]. Sadowska M., Stachowicz W.: Effectiveness of differ-ent procedures of mineral isolation from irradiated spices suitable for thermoluminescence detection me-thod. In: INCT Annual Report 2011. Institute of Nu-clear Chemistry and Technology, Warszawa 2012, pp. 102-105.

[3]. Sadowska M, Stachowicz W.: Luminescence of silicate minerals and sensitivity of thermoluminescnce method for detection of food irradiation. In: INCT Annual Re-port 2012. Institute of Nuclear Chemistry and Tech-nology, Warszawa 2013, pp. 97-99.

[4]. Sanderson D.C.W., Carmichael L.A.. Naylor J.D.: Food Sci. Technol. Today, 7, 150-154 (1995).

[5]. Sanderson D.C.W., Slater C., Cairns V.J.: Radiat. Phys. Chem., 34, 915-920 (1989).

Page 97: INCT Annual Report 2013

LABORATORY OF NUCLEAR CONTROL SYSTEMS

AND METHODSThe main subject of the Laboratory activity in 2012 was the development of methods and ap-paratus, based generally on the application of ionizing radiation, and process engineering for measurements and diagnostic purposes. The research programme of the Laboratory was fo-cused 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 installa-• tions;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 de-tection 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, develop-ment 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 trans-mission 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.

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100 LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS

DIAGNOSTICS OF BIOGAS INSTALLATION BY GAMMA RADIATIONAdrian 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 technologi-cal 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 installa-tion (gamma scanning) [4] and on the basis of the measurements locate the place and type of dam-age. Examination of such kind were designed and carried out on an average lab installation for ob-taining biogas.

The initial studies were performed using two radiation sources: 137Cs (activity – 550 MBq) and 60Co (activity – 300 MBq). Source and probe were placed at a distance of 90 cm from each other. The test system including the located measuring system is shown in Fig.1. Installation was tested in its middle part. For each source, have been made three runs measuring with a moving set of source-probe

from the bottom up. The obtained results are shown in Fig.2. Then, the obtained values were converted to density according to the formula:

Fig.1. Installation for obtaining biogas. The measuring system probe-source.

Fig.2. Scan results [imp/s].

Page 99: INCT Annual Report 2013

101LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS

where: N0 – number of pulses at the open area source-probe [imp/s], Nx – measured number of pulses [imp/s], μ – average mass attenuation coef-ficient [cm2/g], d – distance between probe and source [cm].

Assuming average mass attenuation coefficient for radiation 137Cs as 0.062 cm2/g and for 60Co value 0.049 cm2/g the average densities in the ex-amined cross section were calculated. The densities are shown in Fig.3. From the graph, we can read with a certain approximation the current level of factor (of biomass) used in the system (≈14 cm). Also a frame surrounding the tank in the central part is visible.

The obtained results of initial tests will serve as a benchmark for testing the installation of biogas plants at a later data. Installation tests will be compared with those obtained earlier and on that basis the changes in the installation can be noticed (e.g. change of level, density factor).

References[1]. Charakterystyka technologiczna rafinerii ropy i gazu

w Unii Europejskiej (Technological characteristics of oil and gas refineries in the European Union). Ed. M. Mihułek. Ministerstwo Środowiska, Warszawa 2003 (in Polish).

[2]. Kraś J., Waliś L., Myczkowski S.: Doświadczenia z izo-topowej kontroli szczelności obiektow technologicz-nych – aspekty techniczne i ekonomiczne (Experience in isotope leak-proof control of engineering objects – technical and economical aspects). In: Technika jądro-wa w przemyśle, medycynie, rolnictwie i ochronie śro-dowiska. T.2. Instytut Chemii i Techniki Jądrowej, War-szawa 2002, pp. 373-379. Raporty IChTJ. Seria A nr 2/2002 (in Polish).

[3]. Strategia rozwoju atomistyki w Polsce (Nuclear strategy development in Poland). Rada do Spraw Atomistyki, Warszawa 2006 (in Polish).

[4]. Jakowiuk A., Kowalska E., Pieńkos J., Filipiak P., Mo-dzelewski Ł., Palige J., Kraś J.: The radiometric probes for industrial measuring systems. In: INCT Annual Re-port 2011. Institute of Nuclear Chemistry and Tech-nology, Warszawa 2012, pp. 108-109.

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

0

x

NlnNd

⎛ ⎞⎜ ⎟⎝ ⎠ρ =μ

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102 PUBLICATIONS IN 2013

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ARTICLES

Arabski M., Lisowska H., Lankoff A., Davydova V.N., Drulis-Kawa Z., Augustyniak D., Yermak 1. 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).

Baran M., Zhydachevskii Ya., Suchocki A., Reszka A., Warchoł S., Diduszko R., Pajączkowska A.2. Sol-gel synthesis and luminescent properties of nanocrystalline YAP:Mn. Optical Materials, 34, 604-608 (2013).

Bartłomiejczyk T., Lankoff A., Kruszewski M., Szumiel I. 3. Silver nanoparticles – allies or adversaries? Annals of Agricultural and Environmental Medicine, 20, 1, 48-54 (2013).

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Bator G., Sobczyk L., Sawka-Dobrowolska W., Wuttke J., Pawlukojć A., Grech E., Nowicka-Schei-5. 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).

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Calinescu I., Chmielewski A., Ighigeanu D. 8. E-beam SO2 and NOx removal from flue gas in the presence of fine water droplets. Radiation Physics and Chemistry, 85, 130-138 (2013).

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Dispenza C., Grimaldi N., Sabatino M.-A., Todaro S., Bulone D., Giacomazza D., Przybytniak G.,10. 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).

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Georgantzopoulou A., Balachandran Y.L., Rosenkranz P., Dusinska M., Lankoff A., Wojewódz-12. 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 evalua-tion with NanoSIMS. Nanotoxicology, 7, 7, 1168-1178 (2013).

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Głuszewski W. 13. Napromieniowany czy promieniotwórczy? (Irradiated or radioactive?). Postępy Techniki Jądrowej, 56, 2, 22-23 (2013).

Głuszewski W. 14. Nowe możliwości medycyny nuklearnej w Polsce (New possibilities of the nuclear medicine in Poland). Postępy Techniki Jądrowej, 56, 4, 27-29 (2013).

Głuszewski W. 15. Porozumienie o współpracy między SFEN i PTN (Agreement on the cooperation between SFEN and PTN). Postępy Techniki Jądrowej, 56, 4, 9-11 (2013).

Głuszewski W. 16. Techniki radiacyjne w konserwacji obiektów o znaczeniu historycznym (Radiation techniques in preser-vation of objects of historical importance). Postępy Techniki Jądrowej, 56, 3, 29-32 (2013).

Głuszewski W., Zagórski Z.P., Rajkiewicz M. 17. Efekty ochronne w radiolizie elastomerów (Protective effects in the radiolysis of elastomers). Tworzywa Sztuczne w Przemyśle, 6, 23-24 (2013).

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Gniazdowska E., Koźmiński P., Fuks L.19. Synthesis, radiochemistry and stability of the conjugates of technetium-99m complexes with Substance P. Journal of Radioanalytical and Nuclear Chemistry, 298, 1171-1177 (2013).

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Houée-Levin Ch., Bobrowski K. 22. The use of the methods of radiolysis to explore the mechanisms of free radical modifications in proteins. Journal of Proteomics, 92, 51-62 (2013).

Iller E., Wawszczak D., Konior M., Polkowska-Motrenko H., Milczarek J.J., Górski L. 23. Synthesis and structural investigations of gel metal oxide composites WO3-ZrO2, WO3-TiO2, WO3-ZrO2--SiO2, and their evaluation as materials for the preparation of 188W/188Re generator. Applied Radiation and Isotopes, 75, 115-127 (2013).

Jagadeesh S., Ravi Shankar A., Kamachi Mudali U., Nowicki A., Raj B. 24. Characterisation of pyrolitic graphite exposed to molten LiCl-KCl salt. Surface Engineering, 29, 1, 28-33 (2013).

Kacprzak J., Kuszewski T., Lankoff A., Müller W.-U., Wójcik A., Lisowska H. 25. Individual variations in the micronucleous assay for biological dosimetry after high dose exposure. Mutation Research/Genetic Toxicology and Environmental Mutagenesis, 756, 196-200 (2013).

Kamiński A., Komender J., Michalik J. 26. 50 lat bankowania i sterylizacji radiacyjnej tkanek w Polsce (50 years of banking and radiation steriliza-tion of tissues in Poland). Postępy Techniki Jądrowej, 56, 3, 13-17 (2013).

Kapka-Skrzypczak L., Niedźwiecka J., Skrzypczak M., Kruszewski M. 27. Udział składników diety w modulacji procesów zapalnych (Nutrients as inflamatory state modulators). Pediatric Endocrinology, Diabetes and Metabolism, 19, 1, 39-43 (2013).

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Kiegiel K., Starosta W., Leciejewicz J. 28. Pyrimidine-4-carboxylic acid. Acta Crystallographica Section E, 69, o885 + [4] p. (2013), doi:10.1107/S1600536813012610, www.jour-nals.iucr.org.

Kiegiel K., Steczek Ł., Zakrzewska-Trznadel G. 29. 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).

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Kruszewski M., Grądzka I., Bartłomiejczyk T., Chwastowska J., Sommer S., Grzelak A., Zu-32. berek M., Lankoff A., Dusińska M., Wojewódzka M. Oxidative DNA damage corresponds to the long term survival of human cells treated with silver nano-particles. Toxicology Letters, 219, 151-159 (2013).

Lankoff A., Arabski M., Węgierek-Ciuk A., Kruszewski M., Lisowska H., Banasik-Nowak A., 33. Rozga-Wijas K., Wojewódzka M., Słomkowski S. Effect of surface modification of silica nanoparticles on toxicology and cellular uptake by human periph-eral blood lymphocytes in vitro. Nanotoxicology, 7, 3, 235-250 (2013).

Latek S. 34. 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).

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Latek S. 36. 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).

Latek S. 37. Nobel za „boską cząstkę” (Nobel prize for the “divine particle”). Postępy Techniki Jądrowej, 56, 3, 2-6 (2013).

Leciejewicz J. 38. 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).

Leciejewicz J. 39. 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).

Lewandowska H. 40. Coordination chemistry of nitrosyls and its biochemical implications. Structure and Bonding, [70] p. (2013), doi: 10.1007/430_2013_102.

Lewandowska H. 41. Spectroscopic characterization of nitrosyl complexes. Structure and Bonding, [51] p. (2013), doi: 10.1007/430_2013_109.

Lisowska H., Węgierek-Ciuk A., Banasik-Nowak A., Braziewicz J., Wojewódzka M., Wójcik A., 42. Lankoff A.

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The dose-response relationship for chromosomes and γ-H2AX foci in human peripheral blood lym-phocytes: Influence of temperature during exposure and intra- and inter-individual variability of donors. International Journal of Radiation Biology, 89, 3, 191-199 (2013).

Łuczyńska-Szymczak K., Starosta W., Drużbicki K. 43. Solid-state DFT-assisted Raman study of titanate nanostructures. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 116, 646-650 (2013).

Łyczko K. 44. 1,5-Dimethyl-2-phenyl-1H-pyrazol-3(2H)-one-4,4’-(propane-2,2-diyl)bis[1,5-dimethyl-2-phenyl-1H-pyra-zol-3(2H)-one] (1/1). Acta Crystallographica Section E, 69, o127-o128 + [11] p. (2013).

Łyczko K., Łyczko M. 45. 2-Hydroxy-7-nitrocyclohepta-2,4,6-trien-1-one. Acta Crystallographica Section E, 69, o536 + [5] p.

Malec-Czechowska K., Wierzchnicki R. 46. A study of stable isotope composition of chosen foodstuffs from the Polish market. Nukleonika, 58, 2, 323-327 (2013).

Migdał W., Gryczka U. 47. Radiacyjna metoda higienizacji i utrwalania żywności (Radiation method of the food products hygieni-zation and preservation). Postępy Techniki Jądrowej, 56, 1, 8-14 (2013).

Mioduski T., Gumiński C., Zeng D., Voigt H. 48. 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).

Miśkiewicz A., Zakrzewska-Trznadel G. 49. 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).

Miśkiewicz A., Zakrzewska-Trznadel G. 50. 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.

Niesteruk A., Lewandowska H., Golub Ż., Świsłocka R., Lewandowski W. 51. 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).

Pignalosa D., Lee R., Hartel C., Sommer S., Nikoghosyan A., Debus J., Ritter S., Durante M. 52. Chromosome inversions in lymphocytes of prostate cancer patients treated with X-rays and carbon ions. Radiotherapy and Oncology, 109, 256-261 (2013).

Piotrowska A., Leszczuk E., Brucherfseifer F., Morgenstern A., Bilewicz A. 53. 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.

Połosak M., Piotrowska A., Krajewski S., Bilewicz A. 54. Stability of 47Sc-complexes with acylic polyamino-polycarboxylate ligands. Journal of Radioanalytical and Nuclear Chemistry, 295, 1867-1872 (2013).

Rewerski B., Mielnicki S., Bartosiewicz I., Polkowska-Motrenko H., Skłodowska A. 55. Uranium post-mining wastes as a potential reverse source of uranium for nuclear energy plants. Physicochemical Problems of Mineral Processing, 1, 5-11 (2013).

Romm H., Ainsbury E., Barnard S., Barrios L., Barquinero J.F., Beinke C., Deperas M., Gre-56. 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).

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Romm H., Ainsbury E., Barnard S., Barrios L., Barquinero J.F., Deperas M., Gregoire E., Koi-57. 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).

Sartowska B., Starosta W., Apel P., Orelovitch O., Blonskaya I. 58. Polymeric track etched membranes – application for advanced porous structures formation. Acta Physica Polonica A, 123, 5, 819-821 (2013).

Sartowska B., Waliś L., Starosta W., Barlak M., Pochrybniak C., Kowalska E. 59. Enrichment of AISI 316L steel surface layer with rare earth elements using ion beams. Acta Physica Polonica A, 123, 5, 822-824 (2013).

Shkrob I.A., Marin T.W., Hatcher J.L., Cook A.R., Szreder T., Wishart J.F. 60. 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).

Skowron K., Olszewska H., Paluszak Z., Zimek Z., Kałuska I., Skowron K.J. 61. Radiation hygienization of cattle and swine slurry with high energy electron beam. Radiation Physics and Chemistry, 87, 88-96 (2013).

Sobczyk L., Pawlukojć A., Grech E., Huczyński A., Brzeziński B. 62. Extremely different structures and vibrational spectra of tetramethylpyrazine nitrate dihydrate in solid and solutions. Journal of Molecular Structure, 1037, 264-270 (2013).

Stachowicz W. 63. Identyfikacja napromieniowania produktów spożywczych w IChTJ (Identification of the irradiated food products in the INCT). Postępy Techniki Jądrowej, 56, 2, 20-21 (2013).

Starosta W., Leciejewicz J. 64. 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.

Starosta W., Leciejewicz J. 65. catena-Poly[[diaquabis(μ3-5-carboxylato-1H-pyrazole-3-carboxylic acid-κ3O3:O3;O5)dilithium(I)] mono-hydrate]. Acta Crystallographica Section E, 69, m593-m594 + [5] p. (2013), doi:10.1107/S1600536813026408, www.journals.iucr.org.

Starosta W., Leciejewicz J. 66. 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.

Starosta W., Leciejewicz J. 67. Poly[(μ4-3-carboxypyrazine-2-carboxylato)(μ4-nitrato)dilithium]. Acta Crystallographica Section E, 69, m62 + [7] p. (2013).

Starosta W., Leciejewicz J. 68. Triaqua(pyrazole-4-carboxylato-κN1)-lithium. Acta Crystallographica Section E, 69, m438 + [5] p. (2013).

Starosta W., Leciejewicz J., Kiegiel K. 69. Tetraaqua(pyridine-4,6-dicarboxylato-κ2N1,O6)magnesium monohydrate. Acta Crystallographica Section E, 69, m189 + [5] p.

Strzelczak G., Sterniczuk M., Sadło J., Kowalska M., Michalik J. 70. EPR study of γ-irradiated feather keratin and human fingernails concerning retrospective dose assessment. Nukleonika, 58, 4, 505-509 (2013).

Sun Y., Chmielewski A.G., Bułka S., Zimek Z. 71. Toluene and 4-chlorotoluene decomposition in air mixture in electron beam generated non-thermal plasma reactor and their by-products identification.

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BOOKS

Surface & Coatings Technology, 234, 104-113 (2013).

Trojanowicz M., Koc M. 72. Recent developments in methods for analysis of perfluorinated persistent pollutants. Microchimica Acta, 180, 957-971 (2013), doi: 10.1007/s00604-013-1046-z.

Tymiński Z., Miśta E., Kalbarczyk P. 73. 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).

Walo M., Przybytniak G., Akkas Kavakh P., Güven O. 74. Radiation-induced graft polymerization of N-vinylpyrrolidone onto segmented polyurethane based on isophorone diisocyanate. Radiation Physics and Chemistry, 84, 85-90 (2013).

Walo M., Przybytniak G., Sadło J. 75. Radiation-induced radicals in aliphatic poly(ester urethane)s studied by EPR spectroscopy. Journal of Molecular Structure, 1036, 488-493 (2013).

Zakrzewska G., Biełuszka P., Chajduk E., Wołkowicz S. 76. Recovery of uranium(VI) from water solutions by membrane extraction. Advanced Materials Research, 704, 66-71 (2013).

Zakrzewska-Trznadel G. 77. Advances in membrane technologies for the treatment of liquid radioactive waste. Desalination, 321, 119-130 (2013).

Zalewska E., Rabiński M., Latek S. 78. Jubileusz 20-lecia nowej edycji PTJ (Jubilee of the “Postępy Techniki Jądrowej” new edition). Postępy Techniki Jądrowej, 56, 3, 40-42 (2013).

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 tech-nological study.Institute of Nuclear Chemistry and Technology, Warszawa 2013, 75 p.

CHAPTERS IN BOOKS

Chmielewska D.K. 1. 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.

Cieśla K. 2. 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 packag-ing materials for food products, 22 to 26 April 2013, Vienna. Working material. IAEA, Vienna 2013, pp. 88-99.

Dybczyński R.S., Polkowska-Motrenko H. 3. 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.

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INCT Annual Report 2012.1. Institute of Nuclear Chemistry and Technology, Warszawa 2013, 164 p.

Sun Y.2. Degradation of air pollutants in non-thermal plasma generated by electron beam. Experimental and theoretical study.Institute of Nuclear Chemistry and Technology, Warszawa 2013, 75 p.

Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych (Analysis 3. of the possibility of uranium supply from domestic resources).Instytut Chemii i Techniki Jądrowej, Warszawa 2013, 30 p.

Recommendations for broader and sustainable participation of New Member States in H2020.4. Institute of Nuclear Chemistry and Technology, Warszawa 2013, 67 p.

Chajduk E., Polkowska-Motrenko H., Pyszynska M., Skwara W., Dudek J., Szaniawska E.5. 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.

THE INCT PUBLICATIONS

Nowicki A., Przybytniak G., Mirkowski K. 4. 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.

Samczyński Z. 5. 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.

Zakrzewska-Trznadel G.6. 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.

Zakrzewska-Trznadel G.7. 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.

Zakrzewska-Trznadel G.8. 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.

Zakrzewska-Trznadel G.9. 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.

Zakrzewska-Trznadel G.10. 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.

Zakrzewska-Trznadel G.11. 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.

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Biełuszka P., Zakrzewska-Trznadel G. 1. 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.

Chmielewski A.G., Palige J., Urbaniak A., Zalewski M.K., Roubinek O., Dobrowolski A., Wawryniuk K. 2. Wzbogacanie biogazu ze składowiska odpadów komunalnych i miejskiej oczyszczalni ścieków w metan w procesie membranowym (Methane enrichment of biogas from municipal waste landfill and waste-water treatment plant in membrane process). XI Konferencja „Dla miasta i środowiska – problemy unieszkodliwiania odpadów”, Warszawa, Poland, 25.11.2013. Materiały konferencyjne, [6] p.

Chmielewski A.G., Pawelec A., Witman-Zając S. 3. 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.

Chmielewski A.G., Pawelec A., Witman-Zając S., Dobrowolski A. 4. 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.

Dybczyński R., Polkowska-Motrenko H., Samczyński Z. 5. 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.

Głuszewski W., Zimek Z. 6. 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.

Głuszewski W., Zimek Z., Cieśla K. 7. 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.

Sartowska B. 8. 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).

Starosta W., Sartowska B., Barlak M., Waliś L., Michalik J. 9. 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).

Trojanowicz M., Gumiela M., Koc A., Bojanowska-Czajka A., Kciuk G., Bobrowski K., Nałęcz-Ja-10. 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.

Zakrzewska-Trznadel G., Kiegiel K., Abramowska A., Zielińska B., Biełuszka P., Steczek Ł., 11. Chajduk E., Wołkowicz S. Recovery of uranium from post-leaching solutions by solvent extraction: state of the art and new tech-nological 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.

CONFERENCE PROCEEDINGS

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Abramowska A., Kiegiel K., Gajda D., Szczygłów K., Zakrzewska-Trznadel G., Chajduk E., 1. 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.

Abramowska A., Kiegiel K., Zakrzewska G., Samczyński Z., Skwara W. 2. Precypitacja prekursorów oktatlenku triuranu do produkcji paliwa jądrowego (Precipitation of precur-sors of triuranium octa-oxide for nuclear power engineering). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium nau-kowe w ramach projektu POIG.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera-tów, p. 17.

Antoniak M., Chmielewska D. 3. 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.

Barnard S., Ainsbury E.A., Al-hafidh J., Hadjidekova V., Hristova R., Lindholm C., Monteiro 4. 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.

Bartłomiejczyk T., Grądzka I., Kruszewski M. 5. 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.

Bartosiewicz I., Chajduk E., Chwastowska J., Dudek J., Pyszynska M., Polkowska-Motrenko H.6. Oznaczanie całkowitych zawartości oraz analiza specjacyjna uranu i pierwiastków towarzyszących w pol-skich 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 nau-kowe w ramach projektu POIG.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera-tów, p. 10.

Bartosiewicz I., Chwastowska J., Polkowska-Motrenko H. 7. 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.

Bartosiewicz I., Chwastowska J., Polkowska-Motrenko H. 8. 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.

Bartosiewicz I., Skwara W., Dudek J., Chwastowska J., Polkowska-Motrenko H. 9. 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 oznacza-nia śladowych ilości pierwiastków”, Poznań, Poland, 4-5.04.2013, p. 43.

CONFERENCE ABSTRACTS

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Biełuszka P., Zakrzewska G. 10. 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 nau-kowe w ramach projektu POIG.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera-tów, p. 13.

Biełuszka P., Zakrzewska G., Chajduk E. 11. 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 nau-kowe w ramach projektu POIG.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera-tów, p. 15.

Biełuszka P., Zakrzewska-Trznadel G. 12. 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.

Biełuszka P., Zakrzewska-Trznadel G. 13. 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.

Biełuszka P., Zakrzewska G., Harasimowicz M. 14. 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 nau-kowe w ramach projektu POIG.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera-tów, p. 19.

Bobrowski K. 15. 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.

Bobrowski K. 16. 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.

Bobrowski K., Filipiak P., Hug G.L., Marciniak B., Pędziński T., Pogocki D., Schöneich C. 17. 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.

Boguski J., Przybytniak G., Łyczko K. 18. 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.

Bojanowska-Czajka A., Kołacińska K., Trojanowicz M. 19. 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.

Brykała M., Deptuła A., Rogowski M. 20. 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.

Brykała M., Deptuła A., Rogowski M., Łada W., Olczak T. 21. Process IChTJ – method for preparation of spherical particles of ceramic nuclear fuels.

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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.

Brykała M., Deptuła A., Rogowski M., Olczak T., Łada W., Smoliński T., Wawszczak D., Wojto-22. 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.

Brykała M., Deptuła A., Rogowski M., Olczak T., Łada W., Smoliński T., Wawszczak D., Wojto-23. 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.

Brykała M., Deptuła A., Walczak R., Rogowski M., Olczak T., Łada W., Smoliński T., Waw-24. 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.

Brykała M., Rogowski M., Deptuła A., Olczak T., Łada W., Smoliński T., Wawszczak D., Wojto-25. 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.

Brykała M., Rogowski M., Deptuła A., Wawszczak D., Łada W., Smoliński T. 26. Badania nad otrzymywaniem węglika uranu i azotku uranu za pomocą CSGP (Research on the prepara-tion of uranium carbide and uranium nitride by CSGP). ChemSession’13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 17.05.2013. Streszczenia, p. 186.

Brzóska K., Kruszewski M. 27. 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.

Brzóska K., Stępkowski T., Kruszewski M. 28. Regulation of pirin expression as a mechanism enabling cross-talk between NRF2 and other transcrip-tion factors. 13th Young Scientists’ Forum, Saint Petersburg, Russia, 3-6.07.2013. Book of abstracts, p. 44.

Brzóska K., Stępkowski T., Kruszewski M. 29. Regulation of pirin expression as a mechanism enabling cross-talk between NRF2 and other transcrip-tion factors. FEBS Journal, 280, Suppl. 1, 218 (2013).

Brzóska K., Wojewódzka M., Stępkowski T., Kruszewski M. 30. 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.

Bugaj A., Sadło J., Sterniczuk M., Strzelczak G., Michalik J. 31. 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.

Bugaj A., Sadło J., Sterniczuk M., Strzelczak G., Michalik J. 32. Paramagnetic centres generated radioanalytically in molecular sieves TiAlMCM type – EPR study.

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Porous and Powder Materials Symposium and Exhibition PPM 2013, Cesme Izmir, Turkey, 3-6.09.2013, p. 343.

Bugaj A., Sadło J., Sterniczuk M., Strzelczak G., Michalik J. 33. 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.

Bugaj A., Sadło J., Sterniczuk M., Strzelczak G., Michalik J. 34. 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.

Celuch M., Mirkowski J., Bojanowska-Czajka A., Kulisa K., Kisała J., Pogocki D. 35. 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.

Celuch M., Skotnicki K., Bobrowski K., Masłowska A., Kisała J., Pogocki D. 36. 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.

Chajduk E., Bartosiewicz I., Pyszynska M., Chwastowska J., Polkowska-Motrenko H. 37. 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 oznacza-nia śladowych ilości pierwiastków”, Poznań, Poland, 4-5.04.2013, p. 41.

Chajduk E., Danko B., Pańczyk E., Dudek J., Skłodowska A., Polkowska-Motrenko H. 38. Complementary application of ICP MS and INAA in microanalysis of elemental composition of histori-cal samples. XVII EuroAnalysis: Analytical Chemistry for Human Well-Being and Sustainable Development, Warsaw, Poland, 25-29.08.2013. Book of abstracts, p. 243.

Chajduk E., Dudek J., Polkowska-Motrenko H. 39. Program Rośliny – Wnioski z dziesięciu lat badań (PT scheme Plants – lessons from the decade of ex-perience). Ogólnopolska konferencja naukowa: Jakość w chemii analitycznej, Mory k/Warszawy, Poland, 27-29.11.2013, p. 37.

Chajduk E., Polkowska-Motrenko H., Bilewicz A. 40. 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.

Chajduk E., Witman-Zając S., Polkowska-Motrenko H. 41. Determination of low level 99Tc in the primary coolant water by ICP-MS. Analysis of potential inter-ferences. 5th Asia-Pacific Symposium on Radiochemistry, APSORC 13, Kanazawa, Japan, 22-27.09.2013, p. 224.

Chajduk E., Zuba M., Skwara W., Dudek J., Polkowska-Motrenko H. 42. Sorpcja 226Ra na jonitach z wytrąconych MnO2 i jego oznaczanie w próbkach środowiskowych za pomocą ICP-MS (Sorption of 226Ra 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.

Chmielewska D., Sartowska B. 43. 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.

Chmielewski A.G. 44. 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.

Chmielewski A.G. 45. Działania IChTJ na rzecz Polskiego Programu Energetyki Jądrowej (Activity of the INCT for the Polish Nuclear Power Programme).

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Konferencja naukowo-techniczna: „Nauka i technika wobec wyzwania budowy elektrowni jądrowej – Mądralin 2013”, Warszawa, Poland, 13-15.02.2013, pp. 22-24.

Chmielewski A.G. 46. Radiation processing for rich and poor, experts and beginners. 17th International Meeting on Radiation Processing, Shanghai, China, 4-8.10.2013, p. 230.

Chmielewski A.G. 47. Radiation processing technology – now & in the future. 17th International Meeting on Radiation Processing, Shanghai, China, 4-8.10.2013, p. 109.

Chmielewski A.G., Pawelec A., Licki J., Sun Y., Zimek Z. 48. 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.

Chmielewski A.G., Sartowska B., Jakowiuk A., Ptaszek S., Modzelewski Ł., Sommer S. 49. Analiza potencjału polskich firm pod kątem możliwości wykonywania dostaw systemów dozymetrycz-nych dla bezpiecznej eksploatacji elektrowni jądrowej (Analysis of potential of the Polish firms concern-ing 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.

Cieśla K. 50. Modification of the structure and the functional properties of the starch based films by radiation treat-ment and addition of lipids/surfactant. 4th International Conference on Biodegradable Polymers and Suistance Composites BIOPOL-2013, Rome, Italy, 1-3.10.2013, [2] p.

Cieśla K., Nowicki A., Buczkowski M., Sartowska B., Łyczko K. 51. 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].

Cieśla K., Rahier H., Łyczko K. 52. 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.

Deptuła A., Brykała M., Rogowski M., Olczak T., Łada W., Wawszczak D., Smoliński T. 53. 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.

Deptuła A., Wawszczak D., Łada W., Miłkowska M., Brykała M., Olczak T., Chmielewski A.G., 54. Laskowska R., Gorzałczyński J. Analiza możliwości pozyskiwania uranu z krajowych zasobów rud miedzionośnych i odpadów poflota-cyjnych (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 nau-kowe w ramach projektu POIG.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera-tów, p. 20.

Dybczyński R.S. 55. 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.

Dybczyński R.S. 56. 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.

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Dybczyński R.S. 57. 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.

Dybczyński R., Polkowska-Motrenko H., Samczyński Z. 58. 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 qual-ity assurance). Ogólnopolska konferencja naukowa: Jakość w chemii analitycznej, Mory k/Warszawy, Poland, 27-29.11.2013, p. 7.

Filipiak P., Hug G.L., Bobrowski K., Pędziński T., Kozubek H., Marciniak B. 59. 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.

Filipowicz B. 60. 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.

Filipowicz B. 61. Porównanie sorpcji 137Cs na nanostrukturach TiO2-ZrO2 i TiO2 (Comparison of sorption of 137Cs in the TiO2-ZrO2 and TiO2 nanostructures). ChemSession’13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 17.05.2013. Streszczenia, p. 82.

Filipowicz B., Krajewski S., Bilewicz A. 62. 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.

Gajda D., Danko B., Zakrzewska-Trznadel G., Kiegiel K., Chajduk E., Bartosiewicz I., Sam-63. 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=AAGCxfLuvo7qYmacTG0LiAZxEE9F6p-3CShNZYS3tlmNO.

Gajda D., Zakrzewska G., Danko B., Samczyński Z., Dybczyński R., Chajduk E., Bartosiewicz I.64. 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 nau-kowe w ramach projektu POIG.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera-tów, p. 16.

Gajda D., Zakrzewska G., Kiegiel K., Frąckiewicz K., Szczygłów K., Chajduk E., Bartosiewicz 65. 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 nau-kowe w ramach projektu POIG.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera-tów, p. 11.

Gajda D., Zakrzewska-Trznadel G., Kiegiel K., Danko B., Chajduk E., Bartosiewicz I. 66. 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).

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ChemSession’13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 17.05.2013. Streszczenia, p. 83.

Głuszewski W., Rajkiewicz M., Zagórski Z.P.67. Radiacyjna modyfikacja elastomerów (Radiation modification of elastomers). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, 23-26.09.2013. Materiały konferencyjne, p. 91.

Głuszewski W., Rajkiewicz M., Zagórski Z.P.68. 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.

Głuszewski W., Rajkiewicz M., Zagórski Z.P., Kubacki R. 69. 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.

Głuszewski W., Tran Q.K., Cortella L. 70. 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.

Głuszewski W., Zagórski Z.P., Rajkiewicz M. 71. Protective effects in radiation modification of elastomers. 17th International Meeting on Radiation Processing, Shanghai, China, 4-8.10.2013, p. 149.

Gniazdowska E., Koźmiński P., Fuks L., Bańkowski K., Łuniewski W., Królicki L. 72. 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).

Graupner A., Gutzkow K.B., Collins A.R., Shaposhikov S., Štetina R., Kruszewski M., Sirota 73. 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.

Grądzka I., Sochanowicz B., Męczyńska-Wielgosz S. 74. 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.

Gryczka U., Migdał W., Chmielewska D., Buttafava A., Dondi D. 75. Study on the radiolytic transformation of willow biomass. 17th International Meeting on Radiation Processing, Shanghai, China, 4-8.10.2013, p. 128.

Gumiela M., Gniazdowska E., Koźmiński P., Bilewicz A. 76. 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.

Gumiela M., Gniazdowska E., Koźmiński P., Bilewicz A. 77. 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.

Gumiela M., Gniazdowska E., Koźmiński P., Bilewicz A. 78. 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.

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Ignasiak M.T., Scuderi D., Houée-Levin Ch., Pędziński T., Filipiak P., Rusconi F., Kciuk G., 79. 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.

Jakowiuk A., Modzelewski Ł., Ptaszek S., Sartowska B. 80. Systemy detekcji skażeń izotopami promieniotwórczymi dla obiektów jądrowych / Radioisotopes con-tamination detection systems for the nuclear facilities. I Międzynarodowa Konferencja Ochrony Radiologicznej, Cerna Hora, Czech Republic, 19-22.09.2013, [2] p.

Janowicz M., Buraczewska I., Kruszewski M., Sommer S., Wasyk I., Wojewódzka M., Lankoff A.81. 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.

Janowicz M., Buraczewska I., Kruszewski M., Sommer S., Wasyk I., Wojewódzka M., Lankoff A.82. DOSE-MATIC: a multiparametric computational tool for dose estimation and data analysis in biologi-cal dosimetry and biomonitoring. 40th Annual Meeting of the European Radiation Research Society, Dublin, Ireland, 1-5.09.2013, W-72.

Kalbarczyk P., Chajduk E., Pyszynska M., Fuks L., Polkowska-Motrenko H., Zuba M. 83. 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.

Kapka-Skrzypczak L., Brzóska K., Niedźwiecka J., Sawicki K., Czajka M., Popek S., Skrzypczak84. M., Kruszewski M. DNA damage and genetic polymorphisms: assessment of individual sensitivity of children environmen-tally 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.

Kapka-Skrzypczak L., Niedźwiecka J., Sawicki K., Cyranka M., Wasak M., Turski W.A., Krusze-85. 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.

Kapka-Skrzypczak L., Posobkiewicz M., Hołownia P., Niedźwiecka J., Sawicki K., Cyranka M., 86. 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.

Kasperek A., Leszczuk E., Bilewicz A. 87. 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).

Kaźmierczak U., Banaś D., Braziewicz J., Choiński J., Czub J., Jaskóła M., Korman A., Krusze-88. 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.

Kiegiel K., Abramowska A., Biełuszka P., Zielińska B., Chajduk E., Zakrzewska G. 89. 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 fol-lowed by reextraction into the aqueous phase). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium nau-kowe w ramach projektu POIG.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera-tów, p. 14.

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Kiegiel K., Steczek Ł., Zakrzewska G. 90. 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 nau-kowe w ramach projektu POIG.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera-tów, p. 21.

Kołacińska K. 91. 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.

Kołacińska K., Koncki R. 92. 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.

Kornacka E.M., Przybytniak G.K., Mirkowski K. 93. 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.

Kornacka E.M., Zagórski Z.P. 94. 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.

Kosno K., Celuch M., Janik I., Pogocki D. 95. Kinetyka rodnikowego utleniania nikotyny w roztworach wodnych (Kinetics of nicotine radical oxida-tion in aqueous solutions). XVII Mikrosympozjum: Kinetyczne metody badania mechanizmów reakcji w roztworach, Poznań, Poland, 24.05.2013, K-8.

Kosno K., Celuch M., Janik I., Pogocki D. 96. Mechanism and kinetics of nicotine radical oxidation. 6th European Young Investigator Conference, Słubice, Poland, 26-30.06.2013. Book of abstracts, p. 28.

Kosno K., Celuch M., Janik I., Pogocki D. 97. Mechanism of nicotine radical reactions. 28th Miller Conference on Radiation Chemistry, Dead Sea, Israel, 14-19.03.2013, p. 36.

Kosno K., Celuch M., Janik I., Pogocki D. 98. Mechanizm i kinetyka rodnikowych reakcji nikotyny (Mechanism and kinetics of nicotine radical reac-tions). ChemSession’13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 17.05.2013. Streszczenia, p. 125.

Kosno K., Celuch M., Janik I., Pogocki D. 99. Radioliza impulsowa wodnych roztworów nikotyny i jej związków modelowych (Pulse radiolysis of nico-tine and its model compounds aqueous solutions). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, 23-26.09.2013. Materiały konferencyjne, p. 49.

Kowalska M., Węgierek-Ciuk A., Lisowska H., Kruszewski M., Sommer S., Wojewódzka M., 100. 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.

Koźmiński P., Gniazdowska E. 101. 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).

Kruszewski M., Buraczewska I., Lankoff A., Sommer S., Wójciuk K., Wójciuk G., Wojewódzka M.102. Dozymetria biologiczna dla potrzeb energetyki jądrowej (Biological dosimetry for nuclear power engi-neering).

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Konferencja naukowo-techniczna: „Nauka i technika wobec wyzwania budowy elektrowni jądrowej – Mądralin 2013”, Warszawa, Poland, 13-15.02.2013, p. 49.

Kruszewski M., Dziendzikowska K., Oczkowski M., Krawczyńska A., Gromadzka-Ostrowska J.,103. 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.

Kruszewski M., Grądzka I., Bartłomiejczyk T., Chwastowska J., Sommer S., Grzelak A., Zu-104. 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.

Kubacki R., Brzóska K., Buraczewska I., Lankoff A., Sikorska K., Sommer S., Wojewódzka M., 105. 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.

Kulka U., Ainsbury E.A., Atkinson M., Barquinero J.F., Bassinet C., Barrios L., Beinke C., 106. 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.

Kulka U., Ainsbury E.A., Atkinson M., Barquinero J.F., Bassinet C., Barrios L., Beinke C., 107. 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.

Kulka U., Ainsbury E.A., Atkinson M., Barquinero J.F., Bassinet C., Barrios L., Beinke C., 108. 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.

Kunicki-Goldfinger J.J. 109. 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.

Kużelewska I., Chajduk E., Polkowska-Motrenko H. 110. 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.

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Leszczuk E., Piotrowska A., Bilewicz A., Morgenstern A., Bruchertseifer F. 111. Modyfikowane polietylenoglikolem nanocząstki TiO2 jako nośniki radionuklidów 225Ac i 212Pb dla ce-lowanej radioterapii (TIO2 nanoparticles modified with polyethylene glycol as carriers for 225Ac and 212Pb for targeted radiotherapy). II Ogólnopolska Konferencja Radiofarmaceutyczna, Łódź, Poland, 9-10.05.2013, p. 65.

Leszczuk E., Piotrowska A., Bilewicz A., Morgenstern A., Bruchertseifer F. 112. TiO2 nanoparticles as carries of 225Ac/213Bi in vivo generator. 8th International Symposium on Targeted Alpha Therapy, Oak Ridge, Tennessee, USA, p. 30.

Lisowska H., Fortuna B., Fendrych Ż., Nowakowska J., Stankiewicz M., Węgierek-Ciuk A., Bra-113. 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.

Łada W., Wawszczak D., Deptuła A., Brykała M., Olczak T., Smoliński T., Wojtowicz P., Rogowski 114. 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.

Łada W., Wawszczak D., Deptuła A., Narbutt J., Iller E., Królicki L. 115. Nowa technologia otrzymywania sferycznych ziaren tlenku itru dla medycyny nuklearnej (New tech-nology 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.

Łuczyńska-Szymczak K., Starosta W. 116. 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.

Łyczko M., Bilewicz A., Krajewski S., Wąs B., Choiński J., Jastrzębski J., Stolarz A., Chudyka J.,117. 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.

Męczyńska-Wielgosz S., Wojewódzka M., Lankoff A., Iwaneńko T., Kruszewski M. 118. 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.

Migdał W., Gryczka U., Bertrandt J., Nowicki T., Pytlak R. 119. Radiation methods in decision support system for food safety. 17th International Meeting on Radiation Processing, Shanghai, China, 4-8.10.2013, p. 169.

Miloch J., Kciuk G., Kocia R., Rak J. 120. 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.

Miśkiewicz A., Zakrzewska G., Jaworska-Sobczak A. 121. 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 nau-kowe w ramach projektu POIG.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera-tów, p. 12.

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Miśkiewicz A., Zakrzewska-Trznadel G., Niesłuchowska W., Harasimowicz M. 122. Hybrid UF/sorption and MF/sorption processes using inorganic sorbents for radioactive waste treat-ment. 6th Membrane Conference of Visegrad Countries PERMEA 2013, Warsaw, Poland, 15-19.09.2013. Proceedings. J. Krzysztoforski, M. Szwast (eds.), p. 18.

Modzelewski Ł., Jakowiuk A., Kowalska E., Pieńkos J., Sartowska B. 123. Urządzenia do pomiaru promieniowania i kontroli zagrożenia radiacyjnego opracowane w Instytucie Chemii i Techniki Jadrowej. / Devices for radiation measurements and control of radiation risk devel-oped 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.

Narbutt J., Ozimiński W.P., Wodyński A. 124. Teoretyczna ocena przyczyn selektywności ligandów bis-triazynylobipirydynowych w procesie oddziela-nia 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 lantha-nides – a theoretical approach). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, 21-24.04.2013. Streszczenia, K29.

Niesłuchowska W., Miśkiewicz A., Zakrzewska-Trznadel G., Kulisa K. 125. 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.

Nowicki T., Pytlak R., Waszkowski R., Zawadzki T., Migdał W., Bertrandt J. 126. Creating and calibrating models of food-borne epidemics. Annals of Nutrition & Metabolism, 63, Suppl. 1, 1027 (2013).

Nyga M., Grodkowski J., Mirkowski J., Szreder T. 127. 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.

Olszewska W., Kiegiel K., Gajda D., Zakrzewska G., Abramowska A., Wołkowicz S. 128. 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 nau-kowe w ramach projektu POIG.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera-tów, p. 23.

Oszczak A., Fuks L., Rejnis M. 129. 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.

Oszczak A., Fuks L., Sartowska B., Sternik D. 130. 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.

Oszczak A., Zakrzewska G. 131. Fosforyty jako potencjalne źródła uranu (Phosphites as a potential source of uranium). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium nau-kowe w ramach projektu POIG.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera-tów, p. 18.

Pędziński T., Bobrowski K., Ignasiak M., Kciuk G., Hug G.L., Lewandowska-Andralojc A., 132. Marciniak B. 3-Carboxybenzophenone (3CB) as a new sensitizer in the photooxidation of sulfur-containing peptides in aqueous solution. Spectral, kinetic and acid-base properties of selected benzophenone derivatives.

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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.

Polkowska-Motrenko H., Fuks L., Kalbarczyk P., Chajduk E., Dudek J., Pyszynska M., Zuba 133. 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 ap-proaches). VI Krajowa Konferencja Radiochemii i Chemii Jądrowej, Kraków-Przegorzały, Poland, 21-24.04.2013. Streszczenia, P28.

Polkowska-Motrenko H., Smolik M., Danko B., Jakóbik-Kolon A. 134. Analiza wysokiej czystości cyrkonu metodą NAA (Analysis of high purity zirconium by NAA). XXII Poznańskie Konwersatorium Analityczne „Nowoczesne metody przygotowania próbek i oznacza-nia śladowych ilości pierwiastków”, Poznań, Poland, 4-5.04.2013, p. 44.

Przybytniak G. 135. Fizykochemiczne i strukturalne efekty radiacyjne w polimerach (Physicochemical and structural radia-tion affects in polymers). XVI Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Białowieża, Poland, 23-26.09.2013. Materiały konferencyjne, p. 30.

Przybytniak G., Boguski J. 136. 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.

Ptaszek S., Chmielewski A., Sartowska B., Jakowiuk A., Modzelewski Ł., Sommer S. 137. Analiza potencjału polskich firm pod kątem możliwości wykonywania dostaw systemów ochrony radio-logicznej 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.

Rejnis M., Herdzik-Koniecko I., Narbutt J. 138. 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 pre-vent 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.

Romm H., Ainsbury E., Barnard S., Barquinero J.F., Barrios L., Beinke C., Deperas M., Gre-139. 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 irradia-tion scenarios. Global Conference on Radiation Topics – ConRad 2013, Munich, Germany, 13-16.05.2013. Abstracts, [1] p.

Romm H., Bajinskis A., Oestreicher U., Thierens H., Vral A., Rothkamm K., Ainsbury E., Ben-140. 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.

Samczyński Z. 141. Oznaczanie uranu metodą UV/VIS. Eliminacja wpływu jonów interferujących (Determination of ura-nium by means of UV/Vis. Elimination of the influence of interfering ions). Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium nau-kowe w ramach projektu POIG.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera-tów, p. 9.

Sartowska B., Barlak M., Waliś L., Starosta W., Senatorski J. 142. 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).

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Konferencja naukowo-techniczna: „Nauka i technika wobec wyzwania budowy elektrowni jądrowej – Mądralin 2013”, Warszawa, Poland, 13-15.02.2013, p. 67.

Sartowska B., Barlak M., Waliś L., Starosta W., Senatorski J., Starosta W. 143. 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.

Sartowska B., Barlak M., Waliś L., Starosta W., Senatorski J. 144. 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.

Sartowska B., Starosta W., Pieniążek A., Orelovitch O., Apel P. 145. 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.

Sartowska B., Waliś L., Pańczyk E., Dudek J., Weker W., Widawski M. 146. Skład pierwiastkowy w mikroobszarach średniowiecznych denarów krzyżowych (Elemental composi-tion in microareas of the mediaeval denars). XIII Konferencja: „Analiza chemiczna w ochronie zabytków”, Warszawa, Poland, 5-6.12.2013, p. 52.

Sikorska K., Buraczewska I., Wasyk I., Bartłomiejczyk T., Sommer S., Lankoff A., Wojewódzka 147. 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.

Skotnicki K. 148. Badanie pochodnych chinoksalinonu przy użyciu radiolizy impulsowej (Studies of the quinoxaline de-rivatives by means of pulse radiolysis). ChemSession’13. X Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 17.05.2013. Streszczenia, p. 192.

Skotnicki K. 149. Badanie pochodnych chinoksalinonu przy użyciu radiolizy impulsowej (Studies of the quinoxaline de-rivatives by means of pulse radiolysis). XVII Mikrosympozjum: Kinetyczne Metody Badania Mechanizmów Reakcji w Roztworach, Poznań, Poland, 24.05.2013, K-5.

Skotnicki K. 150. 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.

Skotnicki K., de La Fuente J., Bobrowski K. 151. 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.

Smoliński T., Deptuła A., Łada W., Wawszczak D., Olczak T., Brykała M., Rogowski M., Wojto-152. 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.

Smoliński T., Deptuła A., Łada W., Wawszczak D., Olczak T., Brykała M., Wojtowicz P., Rogo-153. wski M., Zaza F. Metoda zestalania odpadów radioaktywnych w perowskicie (Method for the solidification of radioac-tive wastes in perovskite). Konferencja naukowo-techniczna: „Nauka i technika wobec wyzwania budowy elektrowni jądrowej – Mądralin 2013”, Warszawa, Poland, 13-15.02.2013, p. 65.

Smoliński T., Deptuła A., Łada W., Wawszczak D., Olczak T., Brykała M., Wojtowicz P., Rogo-154. wski M., Zaza F.

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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.

Sommer S., Montero Gil O., Jaworska A., Kulka U., Oestreicher U., Ugletveit F., Vas P., Romm H.155. 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.

Sommer S., Wewiór I., Buraczewska I., Bartłomiejczyk T., Szumiel I., Kruszewski M. 156. 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.

Steczek Ł., Narbutt J. 157. 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 nau-kowe w ramach projektu POIG.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera-tów, p. 22.

Sterniczuk M., Sadło J., Bugaj A., Strzelczak G., Michalik J.158. 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.

Sterniczuk M., Sadło J., Strzelczak G., Bugaj A., Michalik J. 159. 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.

Stępień K., Wylazowska A., Konarska A., Wolszczak M., Węgierek-Ciuk A., Kruszewski M., 160. 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.

Sulich A., Grodkowski J., Mirkowski J., Kocia R. 161. 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.

Sulich A., Grodkowski J., Mirkowski J., Kocia R. 162. 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.

Sulich A., Grodkowski J., Mirkowski J., Kocia R., Foreman M.R.St.J., Hudson M.J. 163. 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.

Sulich A., Grodkowski J., Mirkowski J., Kocia R., Foreman M.R.St.J., Hudson M.J. 164. 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.

Szczygłów K. 165. Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych (Analysis of the possibilities of obtaining uranium from domestic resources for nuclear engineering).

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Analiza możliwości pozyskiwania uranu dla energetyki jądrowej z zasobów krajowych. Seminarium nau-kowe w ramach projektu POIG.01.01.02-14-094/09, Warszawa, Poland, 19.11.2013. Streszczenia refera-tów, p. 24.

Trojanowicz M. 166. Recent developments in miniaturization of flow analysis. 18th International Conference on Flow Injection Analysis (18th ICFIA), Porto, Portugal, 15-20.09.2013, p. 37.

Walo M., Przybytniak G. 167. 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.

Walo M., Przybytniak G. 168. 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.

Walo M., Przybytniak G. 169. Grafting of N-isopropylacrylamide onto polyurethane surface by gamma initiated RAFT polymeriza-tion. 17th International Meeting on Radiation Processing, Shanghai, China, 4-8.10.2013, pp. 146-147.

Wasyk I., Buraczewska I., Lankoff A., Sommer S., Wojewódzka M., Kruszewski M. 170. 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.

Wawszczak D., Łada W., Miłkowska M., Deptuła A., Olczak T., Brykała M., Smoliński T. 171. 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.

Węgierek-Ciuk A., Arabski M., Lisowska H., Kędzierawski P., Florek A., Góźdź S., Wójcik A., 172. 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.

Węgierek-Ciuk A., Lisowska H., Wójcik A., Kędzierawski P., Florek A., Góźdź S., Lankoff A. 173. 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.

Wojewódzka M., Sommer S., Sikorska K., Lankoff A., Kruszewski M. 174. 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.

Wojtowicz P., Deptuła A., Łada W., Wawszczak D., Olczak T., Smoliński T., Brykała M., Rogo-175. 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.

Wójcik A., Romm H., Oestreicher U., Thierens H., Vral A., Rothkamm K., Ainsbury E., Bender-176. 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.

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Wójciuk G., Wójciuk K., Kruszewski M. 177. Pentapeptydowa pochodna DTPA znakowana izotopem lutetu-177 i jej potencjalne zastosowanie w diag-nostyce 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.

Wójciuk K., Wójciuk G., Kruszewski M. 178. 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.

Zakrzewska-Trznadel G., Kiegiel K., Abramowska A., Zielińska B., Biełuszka P., Steczek Ł., 179. Chajduk E., Wołkowicz S. Recovery of uranium from post-leaching solutions by solvent extraction: state of the art and new tech-nological 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.

Zakrzewska-Trznadel G., Kiegiel K., Frąckiewicz K., Herdzik I., Zielińska B., Biełuszka P., Gaj-180. 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.

Zakrzewska-Trznadel G., Miśkiewicz A., Harasimowicz M., Niesłuchowska W., Nieścior P., 181. 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.

Zakrzewska-Trznadel G., Miśkiewicz A., Jaworska A., Kiegiel K., Gajda D., Bilewicz A., Sar-182. towska B., Kruszewski M. Włączanie nowych krajów członkowskich Unii Europejskiej w struktury zaawansowanych badań w ra-mach 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.

Zakrzewska-Trznadel G., Miśkiewicz A., Mysłek-Laurikainen B. 183. 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.

Zimek Z., Duch P., Roman K. 184. 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.

Zuba M., Chajduk E., Polkowska-Motrenko H. 185. 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.

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SUPPLEMENT LIST OF THE PUBLICATIONS IN 2012

Chajduk E. 1. 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.

Eppard E., Pruszyński M., Mikołąjczak R., Koumarianou E., Miederer M., Baum R., Roesch F.2. 44Sc-labelled octreotides: Synthesis, stability, in vitro, ex vivo, and in vivo behaviour. Journal of Nuclear Medicine, 53, Suppl. 1, 458 (2012).

Kasperek A., Bilewicz A. 3. Nieorganiczne nanocząstki w medycynie nuklearnej (Inorganic nanoparticles in nuclear medicine). Wiadomości Chemiczne, 66, 7-8, 697-714 (2012).

Leszek P., Sochanowicz B., Brzóska K., Komuda-Leszek E., Danko B., Kuśmierski K., Piotro-4. 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).

Leszek P., Sochanowicz B., Brzóska K., Komuda-Leszek E., Kraj L., Danko B., Kolsut P., Pio-5. 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).

Leszek P., Sochanowicz B., Brzóska K., Komuda-Leszek E., Kuśmierczyk M., Piotrowski W., 6. Rywik T., Różański J., Kruszewski M. Heart failure remodeling – could the failing myocytes be the additional source of endogenous erythro-poietin? Congress of the European Society of Cardiology, Munchen, Germany, 25-29.08.2012. European Heart Journal, 33, Suppl. 1, 1102 (2012).

Leszek P., Sochanowicz B., Brzóska K., Piotrowski W., Danko B., Kuśmierczyk M., Różański J., 7. 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).

Leszek P., Sochanowicz B., Szperl M., Kolsut P., Brzóska K., Piotrowski W., Rywik T., Danko B., 8. 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).

Pruszyński M., Majkowska-Pilip A., Loktionowa N.S., Eppart E., Roesch F. 9. Radiolabelling of DOTATOC with the long-lived positron emitter 44Sc. Applied Radiation and Isotopes, 70, 974-979 (2012).

Przybytniak G., Kornacka E., Sadło J., Michalik J., Buczkowski M., Sartowska B., Starosta W. 10. 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.

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NUKLEONIKATHE 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, Poland1. 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

4. 155Gd isomer shifts. The case study: GdT2Si2 K. Łątka

5. Mössbauer study of vacuum annealed Fe100–xGax (10 ≤ x ≤ 35) thin films T. Szumiata, B. Górka, K. Brzózka, M. Gawroński, M. Gzik-Szumiata, A. Javed, N.A. Morley, M.R.J. Gibbs

6. Crystal electric field parameters determination for 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

11. Hyperfine interactions in x·Bi0.95Dy0.05FeO3-(1–x)·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 solutionsK. 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

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129NUKLEONIKA

15. Hyperfine interactions in (Cr0.9957Fe0.01)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-41Z. Surowiec, M. Wiertel, M. Budzyński, W. Gac

19. Thermodynamic properties of Au-Fe alloys studied with 57Fe Mössbauer spectroscopyR. 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 expresswayT. 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 ma-terials Z. Surowiec, M. Wiertel, A. Marynowska, W. Gac, W. Zawadzki

29. Structure and hyperfine interactions of multiferroic Bim+1Ti3Fem–3O3m+3 ceramics prepared by mechani-cal 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 alloysW. 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 diffractionM. 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

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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 spectros-copy 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 experimentsG. 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 measurementsJ. Chrzanowski, Yu.A. Kravtsov

6. Correction methods for pulsed neutron source reactivity measurement in accelerator driven systems P. Gajda, J. Janczyszyn, W. Pohorecki

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131NUKLEONIKA

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-mag-

netic 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

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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 phos-phorylated 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 radia-tion 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 biode-gradable 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-oxidaseW. 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 assess-ment 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, PolandK.W. Fornalski, L. Dobrzyński

14. In memoriam – Professor Janusz Z. Beer

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133NUKLEONIKA

InformationINSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY

NUKLEONIKADorodna 16, 03-195 Warszawa, Poland

phone: +48 22 504 11 32; fax: +48 22 811 15 32; e-mail: [email protected] and full texts are available on-line at http://www.nukleonika.pl

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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. 1/20131. 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 hygieniza-tion and preservation)W. Migdał, U. Gryczka

3. Raport z eksploatacji reaktora badawczego MARIA w 2012 roku (Report on the operation of the re-search 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 radio-logical 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

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135POSTĘPY TECHNIKI JĄDROWEJ

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 steriliza-tion 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 preser-vation 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

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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

InformationINSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY

POSTĘPY TECHNIKI JĄDROWEJDorodna 16, 03-195 Warszawa, Poland

phone: +48 22 504 12 48; fax: +48 22 811 15 32; e-mail: [email protected]

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137INTERVIEWS IN 2013

INTERVIEWS IN 2013

Łada W. 1. Fober I.: Meganadzieja w mikrosferach (Megahope in microspheres). Przegląd Techniczny, 3-4, 14 (2013).

Gajda D.2. 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).

Gajda D.3. 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).

Gajda D.4. 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).

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138 THE INCT PATENTS AND PATENT APPLICATIONS IN 2013

THE INCT PATENTS AND PATENT APPLICATIONS IN 2013

PATENTS

PATENT APPLICATIONS

Urządzenie do radiacyjnego oczyszczania przemysłowych gazów odlotowych (Device for the radiation 1. purification of industrial flue gases)A.G. Chmielewski, A. Pawelec, A. Dobrowolski, N.N. Dutskinov, K.L. Nikolov, L.K. Stamatov, Y.G. Pelovski Polish Patent (with TPP Svilosa JSCo., Sofia, Bulgaria)

Sposób otrzymywania opatrunków hydrożelowych zawierających kompleks radiacyjnie degradowanego 2. polisacharydu i srebra (Method for the preparation of hydrogel wound dressings containing complex of radiation-degraded polysaccharide with silver)D. Chmielewska, W. Migdał, A.G. Chmielewski, U. Gryczka, P. Kik Polish Patent (with KIK Mirosław Przedsiębiorstwo Produkcyjno-Handlowe KIK, Poland)

Sposób degradacji usieciowanych odpadowych żywic epoksydowych oraz zastosowanie produktu degra-3. dacji usieciowanych odpadowych żywic epoksydowych (Method of degradation of cross-linked epoxy resin wastes and utilization of the degradation products of epoxy resin wastes)I. Legocka, E. Wierzbicka, G. Przybytniak, A. Nowicki Polish Patent (with the Industrial Chemistry Research Institute, Warszawa, Poland)

Sposób unieszkodliwiania odpadów promieniotwórczych w szkłach krzemionkowych (Method for the dis-4. posal of radioactive wastes in structures of silica glasses)A.G. Chmielewski, A. Deptuła, M. Miłkowska, W. Łada, T. Olczak Polish Patent

Sposób rozpuszczania tlenku toru (Method of dissolution of thorium oxide)5. K. Łyczko, M. Łyczko, I. Herdzik, B. Zielińska Polish Patent

Radiofarmaceutyk terapeutyczny znakowany radionuklidami radu oraz sposób jego wytwarzania (Thera-6. peutic radiopharmaceutical labelled with radionuclides of radium and method for its obtaining)A. Kasperek, A. Bilewicz, T. Olczak Polish Patent

Process for the preparation of uranium dioxide with spherical and irregular grains 7. A. Deptuła, M. Brykała, W. Łada, D. Wawszczak, T. Olczak, A.G. ChmielewskiBelarus Patent

Method for the preparation of hydrogel wound dressings8. D. Chmielewska, W. Migdał, A.G. Chmielewski, U. Gryczka, P. Kik Belarus Patent (with KIKGEL, Poland)

Sposób otrzymywania sferycznych ziaren ditlenku uranowo-neodymowego metodą dwustopniowej eks-1. trakcji (Method for producing of spherical particles of uranium-neodymium dioxide by double extrac-tion process)

M. Brykała, A. Deptuła, W. Łada, T. Olczak, M. Rogowski, A.G. Chmielewski Polish Patent Application P-403817

Prekursor radiofarmaceutyku, sposób jego wytwarzania, radiofarmaceutyk oraz jego zastosowanie (Pre-2. cursor of the radiopharmaceutical, the method for its production, radiopharmaceutical and its applica-tions)

G. Wójciuk, M. Kruszewski Polish Patent Application P-404564

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139THE INCT PATENTS AND PATENT APPLICATIONS IN 2013

Sposób wytwarzania stabilizowanego ditlenku cyrkonu w postaci matrycy inertnej do transmutacji ak-3. 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

Sposób jednorodnego sieciowania wykonanych z poliolefin izolacji i osłon przewodów i kabli elektrycz-4. nych 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

Prekursor radiofarmaceutyku oraz sposób jego wytwarzania (Precursor of a radiopharmaceutical and 5. the method for its production)

A. Bilewicz, M. Łyczko, A. Piotrowska, E. Leszczuk Polish Patent Application P-405251

Sposób oddzielania ameryku(III) i ewentualnie kiuru od lantanowcowych produktów rozszczepienia 6. 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

Prekursor radiofarmaceutyku i radiofarmaceutyk oparty na analogach dezacylogreliny, sposób ich wy-7. twarzania 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

Sposób otrzymywania diagnostycznych ilości radionuklidu 8. 99mTc (Method for the obtaining of diagnostic amounts of the 99mTc radionuclide)

A. Bilewicz, M. Gumiela Polish Patent Application P-406594

Sposób unieszkodliwiania odpadów radioaktywnych w „syntetycznej skale” (Method of the disposal of 9. radioactive wastes in the “synthetic rock”)

T. Smoliński, A.G. Chmielewski, A. Deptuła, W. Łada, T. Olczak European Patent Application EP-13176463.1

Sposób otrzymywania opatrunków hydrożelowych (Method for the preparation of hydrogel wound dress-10. ings)

D. Chmielewska, W. Migdał, A.G. Chmielewski, U. Gryczka, P. Kik European Patent Application EP-12461532.9 (with KIKGEL, Poland)

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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

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141CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2013

“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.

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142 Ph.D. THESES IN 2013

Ph.D. THESES IN 2013

Macin Brykała, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)1. 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

Izabela Cydzik, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)2. Radiolabelling of nanoparticles for biological studiessupervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology, 07.03.2013

Rafał Kocia, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)3. 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 INCTInstitute of Nuclear Chemistry and Technology, 14.06.2013

Seweryn Krajewski, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)4. 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

Agnieszka Miśkiewicz, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)5. Nowe znaczniki promieniotwórcze fazy ciekłej i stałej do zastosowań w badaniach procesów membrano-wych (New radiotracers of liquid and solid phases for applications in researches of membrane processes)supervisor: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCTInstitute of Nuclear Chemistry and Technology, 10.09.2013

Macin Sterniczuk, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)6. 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

Marta Walo, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)7. 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 INCTInstitute of Nuclear Chemistry and Technology, 19.12.2013

Grzegorz Wójciuk, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)8. Analog des-acyl greliny jako nowy nośnik radionuklidów i potencjalny radiofarmaceutyk (Des-acyl ghre-lin 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

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143EDUCATION

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 r• esearch, material science and pro-tection of historical heritage.The candidates accepted for the mentioned programme will be employed at the Institute. The can-

didates 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

Institution Country Number of participants Period

International Atomic Energy Agency Egypt 1 3 months

International Atomic Energy Agency Ghana 1 2 months

Technical University of Łódź, Faculty of Chemistry, Institute of Applied Radiation Chemistry Poland 9 one-day course

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144 EDUCATION

Institution Country Number of participants Period

University of Warsaw, Faculty of Chemistry

Poland 8 3 weeks

Poland 1 2 months

Poland 1 6 months

University of Waterloo Canada 1 3 months

Warsaw University of Technology, Faculty of Chemistry Poland 6 1 month

Warsaw University of Technology, Faculty of Physics Poland1 1 month

25 one-day course

Warsaw University of Technology,Faculty of Power and Aeronautical Engineering Poland 1 2 months

WAT Military University of Technology,Department of Chemistry and New Technologies Poland 3 1.5 month

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145RESEARCH PROJECTS AND CONTRACTS

RESEARCH PROJECTS AND CONTRACTS

RESEARCH PROJECTS GRANTED BY THE NATIONAL SCIENCE CENTRE

IN 2013

Provenance and chronology studies of selected silver coins minted in the Polish and Central 1. Europe coinages by means of chemical composition, sources of raw materials and technology.supervisor: Lech Waliś, Ph.D.

Radiochemical separation of arsenic from selenium and its potential usage in the generator 2. 72Se/72As construction.supervisor: Ewelina Chajduk, Ph.D.

Glass in Central Europe from the late-medieval times to the end of the pre-industrial era. 3. Chemical composition.supervisor: Jerzy Jakub Kunicki-Goldfinger, Ph.D.

Participation of radiation chemistry in systems chemistry, especially in prebiotic chemistry.4. supervisor: Prof. Zbigniew P. Zagórski, Ph.D., D.Sc.

Functionalization of polyurethane surface by radiation-induced grafting (Preludium).5. supervisor: Marta Walo, Ph.D.

Nanozeolites as a carrier for radium in targeted therapy.6. supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc.

Paramagnetic centres generated radiolytically in molecular sieves exposed to carbon oxides.7. supervisor: Marcin Sterniczuk, Ph.D.

Des-acyl ghrelin analog as a new carrier of radionuclides and a potential radiopharmaceutical.8. supervisor: Grzegorz Wójciuk, Ph.D.

Physicochemical and biochemical studies of selected biological conveyers of nitrogen oxide. 9. 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

Formation of the data bank on original products for the juice sector, to supply requirements of 1. the Polish market and producers, basing on the method of stable isotopes.supervisor: Ryszard Wierzchnicki, Ph.D.

Elaboration of the synthesis procedure of a receptor diagnostic radiopharmaceutical for breast 2. 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

A mobile membrane installation for the enrichment of gas in methane (project INITECH).1. supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

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146 RESEARCH PROJECTS AND CONTRACTS

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

IN 2013

Radiation supporting synthesis and curing of nanocomposites suitable for practical applications.1. supervisor: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT

Ageing diagnostics and prognostics of low-voltage I&C cables (ADVANCE).2. supervisor: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT

Multi-disciplinary biodosimetric tools to manage high scale radiological casualties (MULTI-3. BIODOSE).supervisor: Sylwester Sommer, Ph.D.

Implementing public participation approaches in radioactive waste disposal (IPPA).4. supervisor: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT

PGAM5 protein as a signalling factor in the crosstalk between the oxidative stress protective 5. pathway NRF2/KEAP1 and apoptosis and autophagy related to the activation of ASK1 kinase. The testing of the hypothesis and implications in Parkinson’s disease (Iuventus Plus).supervisor: Tomasz Stępkowski, M.Sc.

Advanced fuels for generation IV reactors: reprocessing and dissolution (ASGARD).6. supervisor: Andrzej Deptuła, Ph.D.

Upgrading the capacities and capabilities in nuclear and radiation processing technology and 7. applications by increasing the proficiency level in national nuclear institutions.supervisor: Dagmara Chmielewska-Śmietanko, M.Sc.

Formation, investigations and characterization of advanced nanoporous materials.8. supervisor: Bożena Sartowska, Ph.D.

Safety of actinide separation processes (SACSESS).9. supervisor: Prof. Jerzy Narbutt, Ph.D., D.Sc.

Transnational access to large infrastructure for a safe management of actinide (TALISMAN).10. supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

Characterization of modified surface layer of austenitic stainless steel enriched with rare earth 11. elements (REE) formed using ions and plasma beams with RBS measurements.supervisor: Bożena Sartowska, Ph.D.

Based on starch-PVA system and cellulose reinforced active packaging materials for food pre-12. pared using of radiation modification (PackRad).supervisor: Krystyna Cieśla, Ph.D., D.Sc., professor in INCT

Studies on the methods of synthesis of hybrid porous metallo-organic nanomaterials of separa-13. tion and sorption properties (NANOSYNT).supervisor: Wojciech Starosta, Ph.D.

APPLIED RESEARCH PROGRAMME OF THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT

IN 2013

Optimization of two stages bioreactor for biogas with high methane contents production - elab-1. oration of biostarters and biomarkers of methane fermentation. Task 2.1. Construction in lab-oratory scale of two stages bioreactors for biogas production with high methane concentration.supervisor: Jacek Palige, Ph.D.

Alternative methods for technetium-99m production. Task 8. Isolation of Tc-99m 2. using zirconium modified TiO2 nanotubes and by extraction method with HDEHP.supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc.

Elaboration and certification of new reference materials needed for obtaining European accred2. i-tation by Polish laboratories involved in industrial analytics (project INNOTECH, MODAS). supervisor: Halina Polkowska-Motrenko, Ph.D., D.Sc., professor in INCT

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147RESEARCH PROJECTS AND CONTRACTS

STRATEGIC PROJECT “ADVANCED TECHNOLOGIES FOR GAINING ENERGY”

Scientific problem no. 4: Elaboration of integrated technologies for production of fuels and 1. 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

Radiation supporting synthesis and curing of nanocomposites suitable for practical applications 1. (NANO-RAD).No. 16666principal investigator: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT

Laboratory and feasibility study for industrial waste water effluent treatment by radiation.2. No. 16454principal investigator: Zbigniew Zimek, Ph.D.

Application of hybrid nuclear techniques in the multiphases flows investigations in wastewater 3. treatment and biogases production plants.No. 17366principal investigator: Jacek Palige, Ph.D.

Based on starch-PVA system and cellulose reinforced active packaging materials for food pre-4. pared using of radiation modification (PackRad).No. 17493principal investigator: Krystyna Cieśla, Ph.D., D.Sc., professor in INCT.

STRATEGIC PROJECT “TECHNOLOGIES SUPPORTING DEVELOPMENT

OF SAFE NUCLEAR POWER ENGINEERING”

Scientific problem no. 3: Principles to secure fuel needs for the Polish nuclear energy. 1. supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

Scientific problem no. 4: Development of spent nuclear fuel and radioactive waste management 2. techniques and technologies.supervisor: Leon Fuks, Ph.D.

Scientific problem no. 5: Participation criteria of the Polish industry in the development of nuclear3. energy. Study of the case.supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

Scientific problem no. 6: Development of methods securing nuclear safety and radiological pro-4. tection for the current and future needs of nuclear energy.supervisor: Prof. Marcin Kruszewski, Ph.D., D.Sc.

Scientific problem no. 7: Analysis of hydrogen generation processes in nuclear reactor during 5. normal exploitation and nuclear accidents in order to increase safety standards.supervisor: Prof. Jacek Michalik, Ph.D., D.Sc.

Scientific problem no. 8: Study of processes occurring under regular operation of water circula-6. tion systems in nuclear power plants with suggested actions aimed at upgrade of nuclear safety.supervisor: Anna Bojanowska-Czajka, Ph.D.

Attracting investments in plasma-based air and water cleaning technologies (PlasTEP+).14. supervisor: Andrzej Pawelec, Ph.D.

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148 RESEARCH PROJECTS AND CONTRACTS

PROJECTS WITHIN THE FRAME OF EUROPEAN UNION FRAME PROGRAMMES

IN 2013

FP7 – EURATOM, Fission: Multi-disciplinary biodosimetric tools to manage high scale radio-1. logical casulaties (MULTIBIODOSE).principal investigator: Sylwester Sommer, Ph.D.

FP7 – EURATOM, Fission: Ageing diagnostics and prognostics of low-voltage I&C cables 2. (ADVANCE).principal investigator: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT

FP7 – EURATOM, Fission: Implementing public participation approaches in radioactive waste 3. disposal (IPPA).principal investigator: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT

FP7 – EURATOM, Fission: New MS linking for an advanced cohesion in Euratom research 4. (NEWLANCER).principal investigator: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT

FP7 – EURATOM, Fission: Advanced fuels for generation IV reactors: reprocessing and dis-5. solution (ASGARD).principal investigator: Andrzej Deptuła, Ph.D.

FP7 – EURATOM, Fission: Realizing the European Network in Biodosimetry (RENEB) 6. principal investigator: Sylwester Sommer, Ph.D.

FP7 – Transnational access to large infrastructure for a safe management of actinide (TALIS-7. MAN).principal investigator: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

FP7 – Safety of actinide separation processes (SACSESS).8. principal investigator: Prof. Jerzy Narbutt, Ph.D., D.Sc.

FP7 – Assessment of regional capabilities for new reactors development through an integrated 9. approach (ARCADIA).principal investigator: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT

FP7 – Enhancing education, training and communication processes for informed behaviors and 10. decision-making related to ionizing radiation risks (EAGLE).principal investigator: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT

IAEA TECHNICAL AND REGIONAL CONTRACTS IN 2013

Developing of an advanced industrial gamma scanning system with wireless data acquisition.1. POL/0/010

Regional Training on IAEA Validation and Process Control for Electron Beam Radiation Process-2. ing.RER/1/011

Supporting radiation synthesis and the characterization of nanomaterials for health care, envi-3. ronmental protection and clean energy applications.RER/8/014

Using nuclear techniques for the characterization and preservation of cultural heritage artefacts 4. in the European Region.RER/8/015

Enhancing quality control methods and procedures for radiation technology.5. RER/8/017

The study of the influence of the environmental factors on the isotopic compositions of dairy 5. products.No. 18056principal investigator: Ryszard Wierzchnicki, Ph.D.

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149RESEARCH PROJECTS AND CONTRACTS

STRUCTURAL FUNDS:OPERATIONAL PROGRAMME INNOVATIVE ECONOMY

Analysis of the possibilities of uranium supply from domestic resources.1. supervisor: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCTPOIG.01.01.02-14-094/09

New generation of electrical wires modified by radiation.2. supervisor: Zbigniew Zimek, Ph.D.POIG.01.03.01-14-052/09

Development of a multi-parametric triage approach for an assessment of radiation exposure in 3. a large -scale radiological emergency.supervisor: Prof. Marcin Kruszewski, Ph.D., D.Sc.POIG.01.03.01-14-054/09

OTHER INTERNATIONAL RESEARCH PROGRAMMES IN 2013

European cooperation in the field of scientific and technical research. COST CM0703 Systems 1. 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.

Formation, investigations and characterization of advanced nanoporous materials 2. (with Joint Institute for Nuclear Research, Dubna, Russia).supervisor: Bożena Sartowska, Ph.D.

Studies on synthesis methods of nanoscale metal organic framework type materials 3. (with Joint Institute for Nuclear Research, Dubna, Russia).supervisor: Wojciech Starosta, Ph.D.

Support of public and industrial research using ion beam technology (SPIRIT)4. .supervisor: Bożena Sartowska, Ph.D.

Electron beam flue gas treatment pilot test 5. (for ARAMCO Overseas Company B.V.).supervisor: Andrzej Pawelec, Ph.D.

FP7 – Building a platform for enhanced societal research related to nuclear energy in Central 11. and Eastern Europe (PLATENSO).principal investigator: Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., professor in INCT

EUROPEAN REGIONAL DEVELOPMENT FUND: BALTIC SEA REGION PROGRAMME

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

Attracting investments in plasma-based air and water cleaning technologies2. (PlasTEP+).supervisor: Andrzej Pawelec, Ph.D.

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150 LIST OF VISITORS TO THE INCT IN 2013

LIST OF VISITORS TO THE INCT IN 2013

Abel Trixie1. , International Atomic Energy Agency (IAEA), Austria, 18-20.10.2013

Armah Jonathan Okai2. , International Atomic Energy Agency (IAEA), Ghana, 28.04.-29.06.2013

Avivar Cerezo Jessica3. , Department of Chemistry, University of the Balearic Islands, Spain, 15-19.04.2013

Bonifacic Marija4. , Ruđer Bošković Institute, Zagreb, Croatia, 08-15.12.2013

Cerdà Victor5. , Department of Chemistry, University of the Balearic Islands, Spain, 15-19.04.2013

Dzeba Eva6. , Ruđer Bošković Institute, Zagreb, Croatia, 14-25.10.2013

Erdogan Huriye7. , ETH Zurich, Switzerland, 30.06.-04.07.2013

Etoom Mohammad Amer8. , International Atomic Energy Agency (IAEA), Jordan, 26-30.08.2013

Fuente Julio De la9. , Universidad de Chile, Santiago de Chile, Chile, 26.08.-25.09.2013

Humbert D.10. , University of Paris, France, 18-20.10.2013

Kattan Munzer11. , International Atomic Energy Agency (IAEA), Syria, 26-30.08.2013, 24-30.11.2013

Lazunik Valentin12. , V.N. Karazin Kharkiv National University, Ukraine, 21-26.04.2013

Maalouf Manale13. , ETH Zurich Switzerland, 30.06.-04.07.2013

Mahmoudi Leila14. , ETH Zurich, Switzerland, 30.06.-04.07.2013

Maspoch Daniel15. , Catalan Institute of Nanotechnology, Bellatera, Spain, 15-19.04.2013

Miranda Enrigue Francisco16. , International Atomic Energy Agency (IAEA), Cuba, 10-23.11.2013

Molina Christian17. , ETH Zurich, Switzerland, 30.06.-04.07.2013

Mothersill Carmel18. , McMaster University, Hamilton, Canada, 12-15.09.2013

Orelovitch Oleg L.19. , Joint Institute for Nuclear Research (JINR), Dubna, Russia, 07-19.05.2013

Popov Genadii20. , V.N. Karazin Kharkiv National University, Ukraine, 21-26.04.2013

Seymour Colin21. , McMaster University, Hamilton, Canada, 12-15.09.2013

Soliman Yasser Shaaban22. , International Atomic Energy Agency (IAEA), Egypt, 05.08.-04.11.2013

Tietze-Jaensch Holger23. , Institute of Energy and Climate Research – IEK-6, Forschungszentrum Jülich GmbH, Germany, 08-12.04.2013, 17-19.06.2013

Terzidis Michael24. , Institute of Organic Synthesis and Photoreactivity (ISOF), National Research Council, Bolonia, Italy, 01-08.10.2013

Vajda Nora25. , RadAnal. Ltd., Budapest, Hungary, 05-13.10.2013

Wordman Peter26. , University of Oxford, United Kingdom, 22-27.09.2013

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151THE INCT SEMINARS IN 2013

THE INCT SEMINARS IN 2013

Dr. Jessica Avivar Cerezo (Department of Chemistry, University of the Balearic Islands, Spain)1. How to automate radiochemical analysis exploiting flow techniques

Paweł Biełuszka, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)2. Zastosowanie kontaktorów membranowych w procesach ekstrakcji uranu z rud uranowych (Application of membrane contactors in processes of uranium extraction from uranium ores)

Jacek Boguski, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)3. Dobór kryteriów oceny degradacji radiacyjnej i termicznej kabli (Criteria for the evaluation of radiation and thermal degradation of cables)

Arkadiusz Bonna, Ph.D. (Institute of Biochemistry and Biophysics, Polish Academy of Sciences, 4. Warszawa, Poland)Zastosowanie peptydów w badaniach procesów biochemicznych (Application of peptides in studies of biochemical processes)

Prof. dr. Victor Cerdà (Department of Chemistry, University of the Balearic Islands, Spain)5. Automation of analytical methods by flow techniques: history and new trends

Prof. Rajmund Dybczyński, Ph.D., D.Sc. (Institute of Nuclear Chemistry and Technology, War-6. szawa, Poland)50 lat przygód z neutronową analizą aktywacyjną (Fifty years with neutron activation analysis)

Maciej Jarzębski, Ph.D. (NanoBioMedical Centre (NBMC), Adam Mickiewicz University, Poznań,7. Poland)Modelowanie systemów nanocząstek i układów koloidowych w potencjalnych aplikacjach medycznych, systemach dostarczania leków i diagnostyce (Modelling of systems of nanoparticles and colloidal sets in potential medical applications, in systems of supplying medicines and in diagnosis)

Prof. Jerzy Jastrzębski, Ph.D., D.Sc., Jarosław Choiński, Ph.D. (Heavy Ion Laboratory, University8. of Warsaw, Warszawa, Poland)Ośrodek Produkcji i Badania Radiofarmaceutyków w ŚLCJ (Radiopharmaceuticals Production and Re-search Centre, HIL)

Prof. Leszek Królicki, Ph.D., D.Sc. (Medical University of Warsaw, Warszawa, Poland)9. Terapia i diagnostyka chorób nowotworowych (Therapy and diagnosis of tumour diseases)

Prof. Daniel Maspoch (Catalan Institute of Nanotechnology, Bellaterra (Barcelona), Spain)10. Nanochemistry is in the air and on surfaces: synthesis and assembly of nanoscale metal-organic frame-works

Adam Mieczkowski, Ph.D. (Institute of Biochemistry and Biophysics, Polish Academy of Sciences,11. Warszawa, Poland)Nukleozydy i benzodiazepiny jako struktury uprzywilejowane (“privileged structures”), wykorzystywane w projektowaniu i poszukiwaniu nowych leków (Nucleosides and benzodiazepines as the privileged structures used in the designing and searching for new medicines)

Prof. Carmel Mothersill (McMaster University, Hamilton, Ontario, Canada)12. Radiation-induced non-targeted effects – adaptive responses or damaging low dose effects?

Paweł Ochman, Ph.D. (Maria Skłodowska Curie Memorial Cancer Centre and Institute of 13. Oncology, Warszawa, Poland)Substancje biologicznie czynne znakowane radionuklidami w diagnostyce i terapii onkologicznej (Active biological substances labelled with radionuclides in diagnosis and oncological theraphy)

Prof. Colin Seymour (McMaster University, Hamilton, Ontario, Canada)14. Why is radiotherapy not delivering the expectations of radiobiology?

Yongxia Sun, Ph.D. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)15. Degradation of air pollutants in non-thermal plasma generated by electron beam. Experimental and theoretical study

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152 THE INCT SEMINARS IN 2013

Prof. Peter Wardman (emeritus professor, formerly with the University of Oxford, United King-16. dom)Redox properties of free radicals and their effects on the rates of reactions

Prof. Kazimierz Piotr Zaleski, Ph.D. (Paris-Dauphine University, France)17. Przyszłość energetyki jądrowej na świecie (The future of nuclear power in the world)

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153LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2013

LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2013

LECTURES

Bilewicz A.1. 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.

Bilewicz A. 2. Własności chemiczne pierwiastków transaktynowych (Chemical properties of transactinides). II Letnia Szkoła Energetyki i Chemii Jądrowej, Warszawa, Poland, 16-20.09.2013.

Boguski J., Przybytniak G. 3. Changes in thermal properties of radiation aged cables. Symposium on Ageing Management of Nuclear Plant Cables, Moret sur Loing, France, 17-19.09.2013.

Brykała M., Deptuła A., Rogowski M., Modolo G., Schreinemachers Ch.4. 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.

Brzóska K.5. Classical and modern methods in biological dosimetry.Regional Worshop on Regulatory Control of Radioactive Discharges to the Environment, Warszawa, Poland, 17-21.06.2013.

Chmielewski A.G. 6. European energy mix tomorrow. CEE Meeting “Sustainable Energy for Europe”, Warszawa, Poland, 12-15.09.2013.

Chmielewski A.G. 7. 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 ap-plications).II Letnia Szkoła Energetyki i Chemii Jądrowej, Warszawa, Poland, 16-20.09.2013.

Chmielewski A.G. 8. 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.

Chmielewski A.G.9. Environmental applications of ionizing radiation.International Meeting on Radiation Processing IMRP 17, Shanghai, China, 04-08.11.2013.

Kunicki-Goldfinger J.J.10. 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.

Lewandowska H., Stępkowski T., Sadło J., Kruszewski M.11. Formation of glutationyl dinitrosyl iron complexes does not alleviate iron genotoxicity.International Conference on Bioinorganic Chemistry ICBIC 16, Grenoble, France, 22-26.07.2013.

Ostyk-Narbutt J. 12. Rozdzielanie jonów metali metodą ekstrakcji ciecz-ciecz. Podstawy termodynamiczne (Solvent extrac-tion separations of metal ions. Thermodynamics).

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154 LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2013

II Letnia Szkoła Energetyki i Chemii Jądrowej, Warszawa, Poland, 16-20.09.2013.

Ostyk-Narbutt J.13. 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.

Sartowska B., Starosta W., Pieniążek A., Orelovitch O., Apel P. 14. 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.

Schlegel-Zawadzka M., Gryczka U., Migdał W., Bertrandt J., Siegień F.15. 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.

Stępkowski T., Wasyk I., Kruszewski M.16. 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.

Trojanowicz M. 17. Pharmaceutical residues in the environment – importance, analysis and removal. International Conference on Environmental Pollution and Remediation, Toronto, Canada, 15-17.07.2013.

Zimek Z.18. Technology solutions: accelerators for sludge treatment.HEPTech Academia meets Industry: Environmental Applications of Accelerators, Warrington, United Kingdom, 08-09.07.2013.

Zimek Z.19. Technology solutions: accelerators for treating water.HEPTech Academia meets Industry: Environmental Applications of Accelerators, Warrington, United Kingdom, 08-09.07.2013.

SEMINARS

Gajda D. 1. 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.

Lewandowska-Siwkiewicz Hanna 2. 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.

Polkowska-Motrenko Halina3. 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.

Polkowska-Motrenko Halina4. Procedury przygotowania certyfikowanego materiału (Procedures of preparation of certified reference material).Faculty of Chemistry, University of Warsaw, Warszawa, Poland, 13.04.2013.

Trojanowicz M. 5. 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.

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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 fermenterSilver 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, 18-19.09.2013Institute of Nuclear Chemistry and Technology

6. The IMRP 17 Laureate Award for Science – Life Time Award in recognition of the outstanding contri-bution to the development of the irradiation processing industryAndrzej G. Chmielewski

7. The Hevesy Medal Award 2013 in recognition of the outstanding contributions to the field of radio-chemical neutron activation analysis (RNAA), in particular for proposing the idea of “definitive” methods by RNAA, and to the certification of reference materialsRajmund 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 researchKrzysztof 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 EducationInstitute 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 EducationInstitute 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 ozna-czania śladowych ilości pierwiastków”, Poznań, Poland, 04-05.04.2013

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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 ex-change 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, 17.05.2013Dorota 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, 17.05.2013Magdalena 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 con-ference “Nauka i technika wobec wyzwania budowy elektrowni jądrowej” Mądralin 2013, Warszawa, Poland, 13-15.02.2013Dorota 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 con-ference “Nauka i technika wobec wyzwania budowy elektrowni jądrowej” Mądralin 2013, Warszawa, Poland, 13-15.02.2013Marcin 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 systemsKrzysztof 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 radiosensi-tivityMaria 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 membrano-wych (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 sciencesAgnieszka Miśkiewicz

19. New type of track membranes with asymmetric pores for a wide spectrum of nanotechnology applicationsThe 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 peopleStanisław 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 enrich-ment 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

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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 pipelinesJanusz 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 InstituteAgata 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 InstituteKamila 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 InstituteKonrad 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

Page 156: INCT Annual Report 2013

158 INDEX OF THE AUTHORS

INDEX OF THE AUTHORS

A

Abramowska Anna 25, 48Ayers Tim 78

B

Barlak Marek 76 Bańkowski Krzysztof 31 Bartłomiejczyk Teresa 58, 59 Bartosiewicz Iwona 48 Biełuszka Paweł 48Bilewicz Aleksander 34, 37, 39Bobrowski Krzysztof 17Bojanowska-Czajka Anna 64Boguski Jacek 25Borowiecka Sylwia 64Brykała Marcin 52Brzóska Kamil 57Bugaj Anna 21Bułka Sylwester 81Buczkowski Marek 25Buraczewska Iwona 57, 58, 59, 60

C

Cañete Alvaro 17 Celuch Monika 19 Chajduk Ewelina 48Chmielewski Andrzej G. 81Choiński Jarosław 37 Chwastowska Jadwiga 48 Cieśla Krystyna 25

D

Danko Bożena 48Deptuła Andrzej 52Dudek Jakub 48 Dybczyński Rajmund 48

F

Filipowicz Barbara 39Frąckiewicz Kinga 48 Freestone Ian C. 78Fuente Julio De la 17 Fuks Leon 31, 42

G

Gajda Dorota 48Gilderdale-Scott Heather 78 Gładysz-Płaska Agnieszka 42 Gniazdowska Ewa 31, 34Grądzka Iwona 57, 60Gumiela Magdalena 34

Guzik Grzegorz P. 95

H

Harasimowicz Marian 48 Herdzik-Koniecko Irena 48Hobot Jan A. 78

I

Iwaneńko Teresa 57, 58

J

Jakowiuk Adrian 100 Janik Ireneusz 19 Jastrzębski Jerzy 37Jaworska Agnieszka 48

K

Karlińska Magdalena 90Kiegiel Katarzyna 48 Kołacińska Kamila 67 Korzeniowska-Sobczuk Anna 90Kosno Katarzyna 19 Kowalska Ewa 100Koźmiński Przemysław 31Krajewski Seweryn 39Królicki Leszek 31 Kruszewski Marcin 57, 58, 59 Kunicki-Goldfinger Jerzy J. 78

L

Lankoff Anna 58, 59Leciejewicz Janusz 72Leszczuk Agata 37Liśkiewicz Grażyna 96

Ł

Łada Wiesława 52Łuniewski Wojciech 31 Łyczko Krzysztof 35Łyczko Monika 35, 37, 39

M

Majdan Marek 42 Malec-Czechowska Kazimiera 86, 87McDonald Iain 78Michalik Jacek 21Miecznik Jerzy B. 48Miłkowska Magdalena 52 Mirkowski Jacek 19Mirkowski Krzysztof 23Miśkiewicz Agnieszka 45, 48

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159INDEX OF THE AUTHORS

Modzelewski Łukasz 100

N

Nichipor Henrietta 81Nowicki Andrzej 23, 25

O

Olczak Tadeusz 52 Olszewska Wioleta 45, 48Oszczak Agata 42

P

Palige Jacek 100Pawelec Andrzej 82Pieńkos Jan 100Piotrowska Agata 37Polkowska-Motrenko Halina 48Pogocki Dariusz 19 Pruszyński Marek 39Przybytniak Grażyna 23

R

Rogowski Marcin 52

S

Sadło Jarosław 21Samczyński Zbigniew 48Sartowska Bożena 45, 76Senatorski Jan 76 Sikorska Katarzyna 58, 59, 60Smoliński Tomasz 52Skotnicki Konrad 17Sochanowicz Barbara 57, 60Sommer Sylwester 58, 59Stachowicz Marcin 35 Stachowicz Wacław 95, 96

Starosta Wojciech 72, 76Sterniczuk Aneta 90Sterniczuk Marcin 21Stępkowski Tomasz 57Stolarz Anna 37 Strzelczak Grażyna 21Sun Yongxia 81Szczygłów Katarzyna 48 Szkliniarz Katarzyna 37 Szumiel Irena 58, 60

T

Tchórzewski Paweł 25 Trojanowicz Marek 64, 67 Trzcińska Agnieszka 37

W

Waliś Lech 76Wasyk Iwona 58, 59 Wawszczak Danuta 52Wąs Bogdan 37 Wierzchnicki Ryszard 86, 87Witman-Zając Sylwia 82Wojewódzka Maria 57, 58, 59Wojtowicz Patryk 52 Wołkowicz Stanisław 48 Woźniak Krzysztof 35Wójciuk Grzegorz 57, 60 Wójciuk Karolina 58, 60

Z

Zakrzewska-Kołtuniewicz Grażyna 45, 48Zielińska Barbara 48Zimek Zbigniew 81 Zipper Wiktor 37 Zwolińska Ewa 81