Annual Report 2006

ANNUAL REPORT 2006

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

PRINTING Sylwester Wojtas

GENERAL INFORMATION 9

MANAGEMENT OF THE INSTITUTE 11

MANAGING STAFF OF THE INSTITUTE 11 HEADS OF THE INCT DEPARTMENTS 11 SCIENTIFIC COUNCIL (2003-2007) 11

SCIENTIFIC STAFF 14

PROFESSORS 14 ASSOCIATE PROFESSORS 14 SENIOR SCIENTISTS (Ph.D.) 14

RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 17

REACTIONS OF SUPEROXIDE RADICAL ANION WITH METHIONINE-ENKEPHALIN AND ITS TERT-BUTOXYCARBONYL DERIVATIVE. PULSE AND GAMMA RADIOLYSIS STUDIES O. Mozziconacci, J. Mirkowski, K. Bobrowski, Ch. Houée-Levin 19 REACTIONS OF HYDROGEN ATOM WITH METHIONINE-ENKEPHALIN AND RELATED PEPTIDES. PULSE RADIOLYSIS STUDY O. Mozziconacci, K. Bobrowski, C. Ferreri, Ch. Chatgilialoglu 21 PULSE RADIOLYSIS GENERATION OF THE RADICAL ANION DERIVED FROM 2,3-DIHYDRO-OXOISOAPORPHINE IN ORGANIC SOLVENTS K. Bobrowski, G. Kciuk, E. Sobarzo-Sanchez, J.R. De la Fuente 22 PULSE RADIOLYSIS STUDY OF THE INTERMEDIATES FORMED IN IONIC LIQUIDS. NATURE OF INTERMEDIATES IN PULSE IRRADIATED p-TERPHENYL SOLUTION IN THE IONIC LIQUID METHYLTRIBUTYLAMMONIUM BIS[(TRIFLUOROMETHYL)SULFONYL]IMIDE J. Grodkowski, R. Kocia, J. Mirkowski 23 STEREOELECTRONIC CONTROL OVER THE MECHANISM OF SINGLET OXYGEN-INDUCED DECARBOXYLATION IN ALKYLTHIOCARBOXYLIC ACIDS M. Celuch, M. Enache, D. Pogocki 25 OXIDATION OF THIOETHERS BY ORGANIC COMPLEXES OF COPPER M. Celuch, K. Serdiuk, J. Sadło, M. Enache, D. Pogocki 27 ORGANOSILVER RADICALS IN ZEOLITES J. Turek, J. Sadło, J. Michalik 28 EPR STUDY ON RADIATION-INDUCED RADICAL DISTRIBUTION IN MASSIVE BONE GRAFTS J. Sadło, J. Michalik, G. Strzelczak, A. Dziedzic-Gocławska , A. Kamiński 30 RADIATION CHEMISTS VIEW ON PANSPERMIA HYPOTHESIS Z.P. Zagórski 31 MODIFIED BENTONITE FILLERS IN POLYMER COMPOSITES Z. Zimek, G. Przybytniak, A. Nowicki, K. Mirkowski 33 POLY(SILOXANEURETHANE) UREAS BASED ON ALIPHATIC AND AROMATIC DIISOCYANATES MODIFIED BY IONIZING RADIATION E.M. Kornacka, G. Przybytniak, J. Kozakiewicz, J. Przybylski 36 RADIATION EFFECTS IN POLYPROPYLENE/POLYSTYRENE BLENDS W. Głuszewski, Z.P. Zagórski 39 APPLICATION OF GAS CHROMATOGRAPHY TO STUDY POSTIRRADIATION PROCESSES OF POLYMER OXIDATION W. Głuszewski, Z.P. Zagórski 41 CHEMICAL-RADIATION DEGRADATION OF NATURAL POLYSACCHARIDES (CHITOSAN) A.G. Chmielewski, W. Migdał, U. Gryczka, W. Starosta 42 DSC STUDIES OF GAMMA IRRADIATION EFFECT ON INTERACTION OF POTATO STARCH WITH THE SELECTED FATTY ACIDS AND THEIR SODIUM SALTS K. Cieśla, H. Rahier 44 SURFACE TENSION STUDIES OF BINDING CETYLTRIMETHYLAMMONIUM BROMIDE TO GAMMA IRRADIATED AND NON-IRRADIATED POTATO AMYLOPECTIN K. Cieśla, H. Lundqvist, A.-C. Eliasson 47 GAMMA IRRADIATION INFLUENCE ON STRUCTURE OF POTATO STARCH GELS STUDIED BY SEM K. Cieśla, B. Sartowska, E. Królak, W. Głuszewski 49 RADIOLYTIC DEGRADATION OF FUNGICIDE CARBENDAZIM BY GAMMA RADIATION FOR ENVIRONMENTAL PROTECTION A. Bojanowska-Czajka, P. Drzewicz, Z. Zimek, B. Szostek, H. Nichipor, M. Trojanowicz 52 COMPARISON OF PPSL AND TL METHODS FOR THE DETECTION OF IRRADIATED FOOD AND FOOD COMPONENTS G.P. Guzik, W. Stachowicz 56 DEVELOPMENT AND ACCREDITATION OF EPR METHOD FOR DETECTION OF IRRADIATED FOOD CONTAINING SUGAR K. Lehner, W. Stachowicz 58 DETECTION OF IRRADIATION IN HERBAL PHARMACEUTICALS WITH THE USE OF THERMOLUMINESCENCE AND ELECTRON PARAMAGNETIC RESONANCE SPECTROMETRY M. Laubsztejn, K. Malec-Czechowska, G. Strzelczak, W. Stachowicz 60 ACTIVITY OF THE LABORATORY FOR DETECTION OF IRRADIATED FOOD IN 2006 W. Stachowicz, K. Malec-Czechowska, K. Lehner, G.P. Guzik, M. Laubsztejn 63

RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 65

103Ru/103mRh GENERATOR B. Bartoś, E. Kowalska, A. Bilewicz, G. Skarnemark 67 ZOLEDRONIC ACID LABELED WITH 47Sc AND 177Lu FOR BONE PAIN THERAPY M. Neves, I. Antunes, A. Majkowska, A. Bilewicz 67 Rh[16aneS4]211At AND Ir[16aneS4]211At COMPLEXES AS PRECURSORS FOR ASTATINE RADIOPHARMACEUTICALS M. Pruszyński, A. Bilewicz, M.R. Zalutsky 69 FORMATION KINETICS AND STABILITY OF SOME TRI- AND TETRAAZA DERIVATIVE COMPLEXES OF SCANDIUM A. Majkowska, A. Bilewicz 70 IN VITRO STABILITY OF TRICARBONYLTECHNETIUM(I) COMPLEXES WITH N-METHYL-2-PYRIDINECARBOAMIDE AND N-METHYL-2-PYRIDINECARBOTHIOAMIDE – HISTIDINE CHALLENGE M. Łyczko, J. Narbutt 71

99m + ION EXCHANGE STUDIES ON THE ORGANOMETALLIC AQUA-ION fac-[ Tc(CO)3(H2O3] IN ACIDIC AQUEOUS SOLUTIONS Z. Samczyński, M. Łyczko, R. Dybczyński, J. Narbutt 73 SYNERGISTIC EFFECT OF NEUTRAL BIDENTATE N-HETEROCYCLIC LIGANDS ON THE SEPARATION OF Am(III) FROM Eu(III) BY SOLVENT EXTRACTION WITH TETRADENTATE 6,6’-BIS-(DIETHYL-1,2,4-TRIAZIN-3-YL)-2,2’-BIPYRIDINE J. Narbutt, J. Krejzler 75 ESTIMATION OF CYTOSTATIC AND ANTIMICROBIAL ACTIVITY OF PLATINUM(II) COMPLEXES WITH THIOUREA DERIVATIVES E. Anuszewska, B. Gruber, H. Kruszewska, L. Fuks, N. Sadlej-Sosnowska 77 TRANSITION METAL SORPTION BY ALGINATE BIOSORBENT D. Filipiuk, L. Fuks, M. Majdan 79 GALLIUM AND INDIUM ISOTOPE EFFECTS IN THE DOWEX 1-X8/HCl SYSTEM I. Herdzik, W. Dembiński , W. Skwara, E. Bulska, A. Wysocka 81 PROFICIENCY TESTING SCHEME PLANTS 6 – DETERMINATION OF As, Cd, Cu, Hg, Pb, Se and Zn IN DRY MUSHROOM POWDER (Suillus bovinus) H. Polkowska-Motrenko, E. Chajduk, J. Dudek, M. Sadowska-Bratek, M. Sypuła 82 NEW POLISH CERTIFIED REFERENCE MATERIALS FOR INORGANIC TRACER ANALYSIS: CORN FLOUR (INCT-CF-3) AND SOYA BEAN FLOUR (INCT-SBF-4) H. Polkowska-Motrenko, R. Dybczyński, E. Chajduk, B. Danko, K. Kulisa, Z. Samczyński, M. Sypuła, Z. Szopa 85 DETERMINATION OF CADMIUM, LEAD AND COPPER IN FOOD PRODUCTS AND ENVIRONMENTAL SAMPLES BY ATOMIC ABSORPTION SPECTROMETRY AFTER SEPARATION BY SOLID PHASE EXTRACTION J. Chwastowska, W. Skwara, E. Sterlińska, J. Dudek, L. Pszonicki 89 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LIX. THE CRYSTAL AND MOLECULAR STRUCTURE OF A ZINC(II) COMPLEX WITH PYRIDAZINE-3,6-DICARBOXYLATE AND WATER LIGANDS M. Gryz, W. Starosta, J. Leciejewicz 91 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LX. THE CRYSTAL AND MOLECULAR STRUCTURES OF MAGNESIUM(II) AND ZINC(II) COMPLEXES WITH IMIDAZOLE-4-CARBOXYLATE AND WATER LIGANDS M. Gryz, W. Starosta, J. Leciejewicz 92 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXI. THE CRYSTAL AND MOLECULAR STRUCTURE OF A MANGANESE(II) COMPLEX WITH PYRAZOLE-3,5-DICARBOXYLATE AND WATER LIGANDS T. Premkumar, S. Govindarajan, W. Starosta, J. Leciejewicz 93 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXII. THE CRYSTAL STRUCTURE AND MOLECULAR DYNAMICS OF 2-AMINOPYRIDINE-3-CARBOXYLIC ACID A. Pawlukojć, W. Starosta, J. Leciejewicz, I. Natkaniec, D. Nowak 94 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXIII. THE CRYSTAL AND MOLECULAR STRUCTURE OF A CALCIUM(II) COMPLEX WITH PYRAZINE-2,3,5,6-TETRACARBOXYLATE AND WATER LIGANDS W. Starosta, J. Leciejewicz 94 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXIV. THE CRYSTAL AND MOLECULAR STRUCTURE OF A ZINC(II) COMPLEX WITH PYRAZOLE-4-CARBOXYLATE AND WATER LIGANDS M. Gryz, W. Starosta, J. Leciejewicz 96

RADIOBIOLOGY 97

IRON CHELATORS INHIBIT DNIC FORMATION TO THE SAME EXTENT, INDEPENDENTLY OF PERMEABILITY K. Brzóska, H. Lewandowska, S. Męczyńska, B. Sochanowicz, J. Sadło, M. Kruszewski 99 GHRELIN, A LIGAND FOR THE GROWTH HORMONE SECRETAGOGUE RECEPTOR, INCREASES DNA BREAKAGE IN X-IRRADIATED PIGLET BLOOD MONONUCLEAR CELLS M. Kruszewski, T. Iwaneńko, J. Woliński, M. Wojewódzka 100 GHRELIN INCREASES HYDROGEN PEROXIDE-INDUCED DNA BREAKAGE IN PIGLET BLOOD MONONUCLEAR CELLS T. Bartłomiejczyk, T. Iwaneńko, M. Wojewódzka, J. Woliński, R. Zabielski, M. Kruszewski 101 THE EFFECT OF LEPTIN ON DNA BREAKAGE INDUCED BY GENOTOXIC AGENTS IN HUMAN PERIPHERAL BLOOD MONONUCLEAR CELLS M. Kruszewski, T. Iwaneńko, M. Wojewódzka, J. Woliński, R. Zabielski 102 CABAS – A FREELY AVAILABLE PC PROGRAM FOR FITTING CALIBRATION CURVES IN CHROMOSOME ABERRATION DOSIMETRY J. Deperas, M. Szłuińska, M. Deperas-Kaminska, A. Edwards, D. Lloyd, C. Lindholm, H. Romm, L. Roy, R. Moss, J. Morand, A. Wójcik 103 THE TEMPERATURE EFFECT ON THE FREQUENCY OF RADIATION-INDUCED MICRONUCLEI IN HUMAN PERIPHERAL BLOOD LYMPHOCYTES IS ABOLISHED BY DMSO K. Brzozowska, A. Wójcik 104 VARIABLE RADIOSENSITIVITY OF CHROMOSOMES 2, 8 AND 14 IN HUMAN PERIPHERAL BLOOD LYMPHOCYTES EXPOSED TO 480 MeV/n 12C-IONS M. Deperas-Kaminska, G.N. Timoshenko, E.A. Krasavin, A. Wójcik 105 EFFICIENT DOUBLE STRAND BREAK REJONING AND SURVIVAL IN X-IRRADIATED HUMAN GLIOMA M059 CELLS ARE DEPENDENT ON EGF RECEPTOR KINASE ACTIVITY I. Grądzka, B. Sochanowicz, I. Szumiel 106 DECREASED PERSISTANCE OF γH2AX FOCI IN X-IRRADIATED xrs6 CELLS TREATED WITH SIRTUIN INHIBITOR M. Wojewódzka, M. Kruszewski, I. Szumiel 107 TWO p53 BINDING PROTEINS ARE PRESENT IN LY-R (REPAIR COMPETENT) AND LY-S (REPAIR DEFICIENT) CELLS IN DIFFERENT PROPORTIONS B. Sochanowicz, I. Szumiel 108 PREMATURE CHROMOSOME CONDENSATION IN BIOLOGICAL DOSIMETRY AFTER HIGH DOSE GAMMA IRRADIATION S. Sommer, I. Buraczewska, A. Wójcik 109

NUCLEAR TECHNOLOGIES AND METHODS 111

PROCESS ENGINEERING 113 METHOD FOR COLLECTION OF NITRATE FROM WATER SAMPLES AND DETERMINATION OF NITROGEN AND OXYGEN ISOTOPE COMPOSITION M. Derda, S.M. Cuna, R. Wierzchnicki 113 THE KINETICS OF TRANS-DICHLOROETHYLENE DECOMPOSITION IN AIR UNDER ELECTRON-BEAM IRRADIATION Y. Sun, A.G. Chmielewski, S. Bułka, Z. Zimek, H. Nichipor 114 ELECTRON BEAM OF VOCs TREATMENT EMITTED FROM OIL COMBUSTION PROCESS A. Ostapczuk, J. Licki, A.G. Chmielewski 115 ELECTRON BEAM TREATMENT OF FLUE GAS FROM FUEL OIL COMBUSTION A.G. Chmielewski, A. Pawelec, B. Tymiński, Z. Zimek, J. Licki, A.A. Basfar 117 DOSIMETRY FOR COMBUSTION FLUE GAS TREATMENT WITH ELECTRON BEAM K. Mehta, S. Bułka 118 CATALYTIC CRACKING OF POLYOLEFINE WASTES IN A LARGE LABORATORY INSTALLATION B. Tymiński, K. Zwoliński, R. Jurczyk 119 ECONOMICAL COMPARISON OF ABSORPTION AND MEMBRANE METHODS APPLIED FOR THE ENRICHMENT OF METHANE IN BIOGAS M. Harasimowicz, G. Zakrzewska-Trznadel, W. Ziółkowska, A.G. Chmielewski 120 STUDY OF BOUNDARY-LAYER PHENOMENA IN MEMBRANE PROCESSES G. Zakrzewska-Trznadel, A. Miśkiewicz, M. Harasimowicz, E. Dłuska, S. Wroński, A. Jaworska, C. Cojocaru 121 A STUDY OF STABLE ISOTOPE COMPOSITION IN MILK R. Wierzchnicki, M. Derda 123 INTERLABORATORY TESTS OF 3H MEASUREMENTS IN WATER SAMPLES W. Sołtyk, J. Walendziak, J. Palige 124 MODELLING FOR GROUNDWATER FLOW IN THE OPENCAST BEŁCHATÓW AREA R. Zimnicki 124 TRACER AND CFD INVESTIGATIONS OF SEDIMENTATION PROCESSES IN RECTANGULAR SETTLER J. Palige, A. Dobrowolski, S. Ptaszek, A.G. Chmielewski 125 NATIVE AND TRANSPLANTED Pleurozium schreberi (Brid.) Mitt. AS BIOINDICATOR OF NITROGEN DEPOSITION IN A HEAVY INDUSTRY AREA OF UPPER SILESIA G. Kosior, A. Samecka-Cymerman, A.G. Chmielewski, R. Wierzchnicki, M. Derda, A.J. Kempers 126

MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS 128 IDENTIFICATION OF LEAD WHITE OF THE 15th CENTURY GDAŃSK PANEL PAINTINGS BY MEANS OF INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS E. Pańczyk, J. Olszewska-Świetlik, L. Waliś 128 ELEMENTAL COMPOSITION AND PARTICLES MORPHOLOGY OF LEAD WHITE PIGMENTS B. Sartowska, E. Pańczyk, L. Waliś 130 ULTRAVIOLET BLUE FLUORESCENCE OF CENTRAL EUROPEAN BAROQUE GLASS (FURTHER RESULTS) J. Kunicki-Goldfinger, J. Kierzek, P. Dzierżanowski 134 LATE 17th CENTURY GLASS VESSELS FROM EILAND – TECHNOLOGICAL APPROACH J. Kunicki-Goldfinger, M. Mádl, P. Dzierżanowski 136 WATER SOLUBLE SILICA BIOCIDES CONTAINING QUATERNARY AMMONIUM SALTS A. Łukasiewicz, D.K. Chmielewska, L. Waliś 141 THE ROLE OF CARBON, CHROMIUM AND NITROGEN IN AUSTENITIZATION OF UNALLOYED AND ALLOYED STEELS BY INTENSE PLASMA PULSES J. Piekoszewski, L. Dąbrowski, B. Sartowska, L. Waliś, M. Kopcewicz, J. Kalinowska, M. Barlak, J. Stanisławski, Z. Werner, A. Barcz 141 THERMAL STABILITY OF THE PHASES FORMED IN THE NEAR SURFACE LAYERS OF CARBON STEEL BY NITROGEN PULSED PLASMA TREATMENT B. Sartowska, J. Piekoszewski, L. Waliś, J. Stanisławski, L. Nowicki, R. Ratajczak, M. Kopcewicz 142 ELECTRON-BEAM IRRADIATION OF PVDF MEMBRANES AS A METHOD FOR OBTAINING BRITTLE FRACTURES FOR SEM OBSERVATIONS B. Sartowska, O. Orelovitch, A. Nowicki 144 SELECTED PROPERTIES OF POLYPYRROLE NANOSTRUCTURES DEPOSITED IN TRACK-ETCHED MEMBRANE TEMPLATES M. Buczkowski, W. Starosta, B. Sartowska, D. Wawszczak 145 SOL-GEL-DERIVED HYDROXYAPATITE AND ITS APPLICATION TO SORPTION OF HEAVY METALS A. Deptuła, J. Chwastowska, W. Łada, T. Olczak, D. Wawszczak, E. Sterlińska, B. Sartowska, M. Brykała, K.C. Goretta 147

PHYSICAL AND CHEMICAL PROPERTIES OF YTTERBIUM DOPED KY(WO4)2 NANOCRYSTALS A. Deptuła, M.T. Borowiec, V.P. Dyakonov, W. Łada, T. Olczak, D. Wawszczak, P. Aleshkevych, W. Domuchowski, T. Zayarnyuk, M. Barański, H. Szymczak, M. Brykała 151 SAXS STUDY OF XERO- AND AERO-GELS FORMED FROM MONOSACCHARIDE GELATORS H. Grigoriew, D.K. Chmielewska 153

NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS 156 MEASUREMENT OF 222Rn AND 220Rn WITH SINGLE SCINTILLATION CELL B. Machaj, P. Urbański, J. Bartak 156 DOSIMETRIC GATE DSP-15 E. Świstowski, J. Mirowicz, P. Urbański, J. Pieńkos 158 GAMMA THIN LAYER CHROMATOGRAPHY ANALYZER SC-05 E. Świstowski, B. Machaj, E. Kowalska, J. Pieńkos, E. Gniazdowska 159 INVESTIGATION OF DUST POLLUTION IN ASSEMBLING HALL OF TV SETS J. Pieńkos, P. Urbański 160 COMMERCIAL APPLICATION OF ELECTRON BEAM ACCELERATORS AT R&D AND SERVICE CENTER A.G. Chmielewski, W. Migdał, Z. Zimek, I. Kałuska, S. Bułka 161 ELECTRON GUN FOR 10 MeV, 10 kW ELECTRON ACCELERATOR Z. Dźwigalski, Z. Zimek 163

THE INCT PUBLICATIONS IN 2006 165

ARTICLES 165 BOOKS 173 CHAPTERS IN BOOKS 173 THE INCT REPORTS 174 CONFERENCE PROCEEDINGS 175 CONFERENCE ABSTRACTS 176 SUPPLEMENT LIST OF THE INCT PUBLICATIONS IN 2005 185

NUKLEONIKA 186

INTERVIEWS IN 2006 191

THE INCT PATENTS AND PATENT APPLICATIONS IN 2006 192 PATENTS 192 PATENT APPLICATIONS 192

CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2006 193

Ph.D./D.Sc. THESES IN 2006 198

Ph.D. THESES 198 D.Sc. THESES 198

EDUCATION 199

Ph.D. PROGRAMME IN CHEMISTRY 199 TRAINING OF STUDENTS 199

RESEARCH PROJECTS AND CONTRACTS 201

RESEARCH PROJECTS GRANTED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN 2006 AND IN CONTINUATION 201 RESEARCH PROJECTS ORDERED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN 2006 202 IAEA RESEARCH CONTRACTS IN 2006 202 IAEA TECHNICAL CONTRACTS IN 2006 202 EUROPEAN COMMISSION RESEARCH PROJECTS IN 2006 202 OTHER FOREIGN CONTRACTS IN 2006 203

LIST OF VISITORS TO THE INCT IN 2006 204

THE INCT SEMINARS IN 2006 206

LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2006 207

LECTURES 207 SEMINARS 209

AWARDS IN 2006 211

INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS 212

INDEX OF THE AUTHORS 224 GENERAL INFORMATION 9

GENERAL INFORMATION

The Institute of Nuclear Chemistry and Technology (INCT) is one of the successors of the Institute of Nuclear Research (INR) which was established in 1955. The latter Institute, once the biggest Institute in Poland, has exerted a great influence on the scientific and intelectual life in this country. The INCT came into being as one of the independent units established after the dissolution of the INR in 1983. At present, the Institute research activity is focused on: • radiation chemistry and technology, • radiochemistry and coordination chemistry, • radiobiology, • application of nuclear methods in material and process engineering, • design of instruments based on nuclear techniques, • trace analysis and radioanalytical techniques, • environmental research. In the above fields we offer research programmes for Ph.D. students. At this moment, with its nine electron accelerators in operation and with the staff experienced in the field of electron beam (EB) applications, the Institute is one of the most advanced centres of radiation research and EB processing. The accelerators are installed in the following Institute units: • pilot plant for radiation sterilization of medical devices and transplants, • pilot plant for radiation modification of polymers, • experimental pilot plant for food irradiation,

• pilot plant for removal of SO2 and NOx from flue gases, • pulse radiolysis laboratory, in which the nanosecond set-up was put into operation in 2001. A new 10 MeV accelerator was constructed in the INCT for this purpose. Based on the technology elaborated in our Institute, an industrial installation for electron beam flue gas treatment has been implemented at the EPS “Pomorzany” (Dolna

Odra PS Group). This is the second full scale industrial EB installation for SO2 and NOx removal all over the world. *** In 2006, the INCT scientists published 81 papers in scientific journals registered in the Philadelphia list, among them 49 papers in journals with an impact factor (IF) higher than 1.0. The INCT research workers are also the authors of one book and 7 chapters in scientific books published in 2006. In 2006, the Ministry of Science and Higher Education (MSHE) granted 5 research projects. Altogether the INCT is carrying out 23 MSHE research projects including 3 ordered projects and 1 implementation project, and 6 research projects supported finan- cially by the European Commission. Annual rewards of the INCT Director-General for the best publications in 2006 were granted to the following research teams: • First degree group award to Leon Pszonicki, Jadwiga Chwastowska, Witold Skwara and Elżbieta Sterlińska for two publications in “Talanta” presenting methods for the determination of platinum, palladium and chromium in trace quantities in environmental samples and speciation analysis of Cr(VI) in the presence of Cr(III). 10 GENERAL INFORMATION • Second degree group award to Marcin Kruszewski, Hanna Lewandowska, Teresa Bartłomiejczyk, Teresa Iwaneńko and Barbara Sochanowicz for publications in the journals “Biochemical and Biophysical Research Communications”, “Journal of Biological Chemistry” and “Acta Biochimica Polonica” devoted to studies of relations between the metabolism of iron on a cell level and DNA oxidative damage. • Third degree group award to Sławomir Siekierski and Kinga Frąckiewicz for the essential contribution to the work on basic studies of secondary periodicity of elements of the block p (group 13) published in “European Journal of Inorganic Chem- istry”. In 2006, the INCT scientific community was especially active in organizing scientific conferences. In total, in 2006, five international meetings have been organized: • Regional Training Course “Application of Monte Carlo modeling methods for dosimetry calculation in radiation processing” in the frame of the IAEA Technical Cooperation Project RER/8/010 “Quality control methods and procedures for radiation technology” (3-7 April 2006, Warszawa); • The Workshop “Dosimetry for radiation application in technologies for environmental pollution control” in the frame of the Marie Curie Host Fellowships for the EU Transfer of Knowledge “Advanced methods for environment research and control (AMERAC)” (5 April 2006, Warszawa); • The Workshop “Methods of enviromental research” in the frame of the Marie Curie Host Fellowships for the EU Transfer of Knowledge “Advanced methods for environment research and control (AMERAC)” (10 August 2006, Warszawa); • Symposium on Chemistry and Radiation Techniques: Challenge and Possibilities – Jubilee of the 80th Anniversary of Prof. Zbigniew P. Zagórski, Ph.D., D.Sc. (17 October 2006, Warszawa); • IV Conference on Problems of Waste Disposal (27 November 2006, Warszawa). The international journal for nuclear research – NUKLEONIKA, published by the INCT, was mentioned in the SCI Journal Citation List. MANAGEMENT OF THE INSTITUTE 11

MANAGEMENT OF THE INSTITUTE

MANAGING STAFF OF THE INSTITUTE

Director Assoc. Prof. Lech Waliś, Ph.D.

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

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

Accountant General Małgorzata Otmianowska-Filus, M.Sc.

HEADS OF THE INCT DEPARTMENTS

• Department of Nuclear Methods of Materials • Department of Analytical Chemistry Engineering Prof. Rajmund Dybczyński, Ph.D., D.Sc. Wojciech Starosta, Ph.D. • Department of Radiobiology and Health • Department of Radioisotope Instruments Protection and Methods Prof. Irena Szumiel, Ph.D., D.Sc. Prof. Piotr Urbański, Ph.D., D.Sc. • Experimental Plant for Food Irradiation • Department of Radiochemistry Assoc. Prof. Wojciech Migdał, Ph.D., D.Sc. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc. • Laboratory for Detection of Irradiated Food • Department of Nuclear Methods of Process Wacław Stachowicz, Ph.D. Engineering • Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. Laboratory for Measurements of Technological Doses • Department of Radiation Chemistry Zofia Stuglik, Ph.D. and Technology Zbigniew Zimek, Ph.D.

SCIENTIFIC COUNCIL (2003-2007)

1. Prof. Grzegorz Bartosz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology University of Łódź • radiation chemistry, photochemistry, biophysics • biochemistry 4. Sylwester Bułka, M.Sc. 2. Assoc. Prof. Aleksander Bilewicz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology • electronics • radiochemistry, inorganic chemistry 5. Prof. Witold Charewicz, Ph.D., D.Sc. 3. Prof. Krzysztof Bobrowski, Ph.D., D.Sc. Wrocław University of Technology (Chairman) • inorganic chemistry, hydrometallurgy 12 MANAGEMENT OF THE INSTITUTE

6. Prof. Stanisław Chibowski, Ph.D., D.Sc. 21. Prof. Józef Mayer, Ph.D., D.Sc. Maria Curie-Skłodowska University Technical University of Łódź • radiochemistry, physical chemistry • physical and radiation chemistry

7. Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. 22. Prof. Jacek Michalik, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology • chemical and process engineering, nuclear che- • radiation chemistry, surface chemistry, radical mical engineering, isotope chemistry chemistry

8. Prof. Jadwiga Chwastowska, Ph.D., D.Sc. 23. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology • analytical chemistry • radiochemistry, coordination chemistry

9. Prof. Rajmund Dybczyński, Ph.D., D.Sc. 24. Jan Paweł Pieńkos, Eng. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology • analytical chemistry • electronics

10. Prof. Zbigniew Florjańczyk, Ph.D., D.Sc. 25. Prof. Leon Pszonicki, Ph.D., D.Sc. (Vice-chairman) Institute of Nuclear Chemistry and Technology Warsaw University of Technology • analytical chemistry • chemical technology 26. Prof. Sławomir Siekierski, Ph.D. 11. Prof. Leon Gradoń, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Warsaw University of Technology • physical chemistry, inorganic chemistry • chemical and process engineering 27. Prof. Sławomir Sterliński, Ph.D., D.Sc. 12. Assoc. Prof. Edward Iller, Ph.D., D.Sc. Central Laboratory for Radiological Protection Radioisotope Centre POLATOM • physics, nuclear technical physics • chemical and process engineering, physical 28. Prof. Irena Szumiel, Ph.D., D.Sc. chemistry Institute of Nuclear Chemistry and Technology 13. Assoc. Prof. Marek Janiak, Ph.D., D.Sc. • cellular radiobiology Military Institute of Hygiene and Epidemiology 29. Prof. Jerzy Szydłowski, Ph.D., D.Sc. • radiobiology Warsaw University 14. Iwona Kałuska, M.Sc. • physical chemistry, radiochemistry Institute of Nuclear Chemistry and Technology 30. Prof. Jan Tacikowski, Ph.D. • radiation chemistry Institute of Precision Mechanics 15. Assoc. Prof. Marcin Kruszewski, Ph.D., D.Sc. • physical metallurgy and heat treatment of me- Institute of Nuclear Chemistry and Technology tals • radiobiology 31. Prof. Marek Trojanowicz, Ph.D., D.Sc. 16. Prof. Marek Lankosz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology AGH University of Science and Technology • analytical chemistry • physics, radioanalytical methods 32. Prof. Piotr Urbański, Ph.D., D.Sc. 17. Prof. Janusz Lipkowski, Ph.D., D.Sc. (Vice-chairman) Institute of Physical Chemistry, Polish Academy Institute of Nuclear Chemistry and Technology of Sciences • radiometric methods, industrial measurement • physicochemical methods of analysis equipment, metrology 18. Zygmunt Łuczyński, Ph.D. 33. Assoc. Prof. Lech Waliś, Ph.D. Institute of Electronic Materials Technology Institute of Nuclear Chemistry and Technology • chemistry • material science, material engineering 19. Prof. Andrzej Łukasiewicz, Ph.D., D.Sc. 34. Prof. Andrzej Wójcik, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology (Vice-chairman) • material science Institute of Nuclear Chemistry and Technology • cytogentics 20. Prof. Bronisław Marciniak, Ph.D., D.Sc. Adam Mickiewicz University 35. Prof. Zbigniew Zagórski, Ph.D., D.Sc. • physical chemistry Institute of Nuclear Chemistry and Technology MANAGEMENT OF THE INSTITUTE 13 • physical chemistry, radiation chemistry, elec- • electronics, accelerator techniques, radiation trochemistry processing

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

HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (2003-2007)

1. Prof. Antoni Dancewicz, Ph.D., D.Sc. • biochemistry, radiobiology 14 SCIENTIFIC STAFF

SCIENTIFIC STAFF

PROFESSORS

1. Bobrowski Krzysztof 9. Piekoszewski Jerzy radiation chemistry, photochemistry, biophysics solid state physics

2. Chmielewski Andrzej G. 10. Pszonicki Leon chemical and process engineering, nuclear chem- analytical chemistry ical engineering, isotope chemistry 11. Siekierski Sławomir 3. Chwastowska Jadwiga physical chemistry, inorganic chemistry analytical chemistry 12. Szumiel Irena 4. Dybczyński Rajmund cellular radiobiology analytical chemistry 13. Trojanowicz Marek 5. Leciejewicz Janusz analytical chemistry crystallography, solid state physics, material science 14. Urbański Piotr 6. Łukasiewicz Andrzej radiometric methods, industrial measurement material science equipment, metrology

7. Michalik Jacek 15. Wójcik Andrzej radiation chemistry, surface chemistry, radical che- cytogenetics mistry 16. Zagórski Zbigniew 8. Ostyk-Narbutt Jerzy physical chemistry, radiation chemistry, electro- radiochemistry, coordination chemistry chemistry

ASSOCIATE PROFESSORS

1. Bilewicz Aleksander 6. Pogocki Dariusz radiochemistry, inorganic chemistry radiation chemistry, pulse radiolysis

2. Grigoriew Helena 7. Przybytniak Grażyna solid state physics, diffraction research of non- radiation chemistry -crystalline matter 8. Waliś Lech 3. Grodkowski Jan material science, material engineering radiation chemistry

4. Kruszewski Marcin 9. Zakrzewska-Trznadel Grażyna radiobiology process and chemical engineering

5. Migdał Wojciech 10. Żółtowski Tadeusz chemistry, science of commodies nuclear physics

SENIOR SCIENTISTS (Ph.D.)

1. Bartłomiejczyk Teresa 3. Buczkowski Marek biology physics

2. Borkowski Marian 4. Cieśla Krystyna chemistry physical chemistry SCIENTIFIC STAFF 15

5. Danilczuk Marek 27. Owczarczyk Andrzej chemistry chemistry 6. Danko Bożena 28. Palige Jacek analytical chemistry metallurgy 7. Dembiński Wojciech 29. Panta Przemysław chemistry nuclear chemistry 8. Deptuła Andrzej 30. Pawelec Andrzej chemistry chemical engineering 9. Derda Małgorzata 31. Pawlukojć Andrzej chemistry physics 10. Dobrowolski Andrzej 32. Polkowska-Motrenko Halina chemistry analytical chemistry 11. Dudek Jakub 33. Rafalski Andrzej chemistry radiation chemistry

12. Dźwigalski Zygmunt 34. Sadło Jarosław high voltage electronics, electron injectors, gas chemistry lasers 35. Samczyński Zbigniew 13. Frąckiewicz Kinga analytical chemistry chemistry 36. Skwara Witold 14. Fuks Leon analytical chemistry chemistry 37. Sochanowicz Barbara 15. Gniazdowska Ewa biology chemistry 16. Grądzka Iwona 38. Sommer Sylwester biology radiobiology, cytogenetics 17. Harasimowicz Marian 39. Stachowicz Wacław technical nuclear physics, theory of elementary radiation chemistry, EPR spectroscopy particles 40. Starosta Wojciech 18. Kierzek Joachim chemistry physics 41. Strzelczak Grażyna 19. Kornacka Ewa radiation chemistry chemistry 42. Stuglik Zofia 20. Krejzler Jadwiga radiation chemistry chemistry 43. Sun Yongxia 21. Kunicki-Goldfinger Jerzy chemistry conservator/restorer of art 44. Szpilowski Stanisław 22. Lewandowska-Siwkiewicz Hanna chemistry chemistry

23. Machaj Bronisław 45. Szreder Tomasz radiometry chemistry 24. Mikołajczuk Agnieszka 46. Tymiński Bogdan chemistry chemistry

25. Mirkowski Jacek 47. Warchoł Stanisław nuclear and medical electronics solid state physics 26. Nowicki Andrzej 48. Wąsowicz Tomasz organic chemistry and technology, high-tempera- radiation chemistry, surface chemistry, radical che- ture technology mistry 16 SCIENTIFIC STAFF

49. Wierzchnicki Ryszard 52. Zielińska Barbara chemical engineering chemistry

50. Wiśniowski Paweł 53. Zimek Zbigniew radiation chemistry, photochemistry, biophysics electronics, accelerator techniques, radiation processing 51. Wojewódzka Maria radiobiology RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 19 REACTIONS OF SUPEROXIDE RADICAL ANION WITH METHIONINE-ENKEPHALIN AND ITS TERT-BUTOXYCARBONYL DERIVATIVE. PULSE AND GAMMA RADIOLYSIS STUDIES Olivier Mozziconacci, Jacek Mirkowski, Krzysztof Bobrowski, Chantal Houée-Levin1/ 1/ Université Paris-Sud, Orsay, France

The pentapeptide methionine-enkephalin (Met-enk) (Chart 1) is a natural opiate that inhibits signals of pain. Many studies have demonstrated the connection between the interactions of the opiate and reactive oxygen species (ROS) with cell injuries [1]. The aromatic amino acid residues are especially good targets for oxidation by ROS during oxidative stress. In particular tyrosine can be converted into a dimer or into dihydroxyphenylalanine (DOPA) in enkephalins [2,3]. This interesting free-radical chemistry occurs widely in biological systems but it is still a largely unexplored area of research. The – addition of superoxide radical anion (O·2 ) to a tyro- syl radical (TyrO·) leads to a hydroperoxide, which gets cyclized by the Michael addition of the amine onto the ring [4]. The stability of the hydroperoxide depends on the neighboring function [5]. How- ever, the occurrence of this mechanism on peptides Fig.1. Absorption spectra obtained after oxidation of or proteins has never been directly demonstrated. Met-enk (c) and t-Boc-Met-enk (z) by N·3 radicals In this report we report evidence for this mecha- in N2O-saturated aqueous solutions containing 0.1 – μ nism on a natural peptide, Met-enk. Moreover, we mM of peptides and 50 mM of N3 taken 55 s after show that, when the amine function is blocked by the pulse. the tert-butoxycarbonyl group – t-Boc-Met-enk – → + – (Chart 1), tyrosine is restored by O·2 . TyrOH + N·3 TyrO· + H + N3 The transient absorption spectrum of Met-enk Similar transient absorption spectrum with the μ recorded 55 s after the pulse in N2O-saturated two absorption bands at 390 and 405 nm and again solution containing azide ions, revealed two ab- assigned to TyrO· radicals was observed in the same sorption bands with maxima in the visible region conditions in solution containing t-Boc-Met-enk at 390 and 405 nm (Fig.1, curve a). This absorp- (Fig.1, curve b). tion is assigned to TyrO· radicals which were form- Like in N2O-saturated solutions, the transient ed upon oxidation of the tyrosine residue (TyrOH) absorption spectra recorded 55 μs after the pulse in Met-enk by N·3 radicals: observed in O2-saturated solutions containing Met-enk and t-Boc-Met-enk were assigned to TyrO· radicals.

However, in O2-saturated solutions containing Met-enk and t-Boc-Met-enk a new absorption band at 360-380 nm appeared at the millisecond time scale (Fig.2). This band was attributed to the – product of the reaction of O·2 with TyrO·. How- ever, the kinetic traces leading to this spectrum were different (Fig.2, insets). In solution containing t-Boc-Met-enk, the decay at 405 nm reached a pseudo-plateau around 1 ms after the pulse. Two peaks were observed in HPLC chromato-

grams after gamma-irradiation in N2O-saturated solutions containing Met-enk. The first peak corresponds to the native Met-enk. The second peak increased with the dose (Fig.3A). It was the most intense peak when fluorescence detection (exc. 284 nm, em. 425 nm) was applied. Additionally, a third peak appeared which also increased with the dose and was fluorescent with the same characteristics (Fig.3B). Both peaks were attributed to dimers of Met-enk linked by bityrosine, the most intense as the 3,3’-bityrosine. UV-VIS spectrum of the irradiated Chart 1. Met-enk solution was characteristic of bityrosine. 20 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES On the other hand, HPLC chromatograms after

irradiation of O2-saturated solution containing t-Boc-Met-enk showed only one peak (Fig.4B) which had the same retention time as the native peptide (Fig.4A) and its density remained very close to that in non-irradiated solution. This indicates that irradiation of Boc-Met-enk in aerobic conditions does not lead to oxidation products since the amount of non-modified peptide was unchanged. All observations described above showed that blocking the amine function by the tert-butoxycarbonyl group does not affect the reaction pathway of TyrO· radicals in anaerobic conditions.

Fig.2. Absorption spectrum obtained after oxidation of t-Boc-Met-enk (z) by N3· radicals in O2-saturated aqueous solutions containing 0.1 mM of the peptide – and 5 mM of N3 taken 1 ms after the pulse. Insets: λ The time profiles recorded at =405 nm in O2-satu- – rated aqueous solutions containing 5 mM of N3 and 0.1 mM of Met-enk (left) or t-Boc-Met-enk (right).

In O2-saturated solution containing Met-enk, the peak that corresponds to 3,3’-bityrosine was visible only by its very weak fluorescence. This indicates a small yield of 3,3’-bityrosine formation in Met-enk dimer. On the other hand, another new peak with elution time shorter than the native

Met-enk was observed. Compared to N2O-saturated solution, the shape of the UV-VIS spectrum was different. The bands at 290 and 315 nm were much weaker, with two intense absorption bands located at 275 and 285 nm. This indicates a lower amount of Met-enk dimers with bityrosine and formation Fig.4. HPLC chromatograms recorded in (A) non-irradi- of a new stable product. ated, (B) irradiated with 84 Gy O2-saturated aque- In N2O-saturated solution containing t-Boc- ous solutions containing 0.25 mM of t-Boc-Met-enk – -Met-enk, the stable product pattern was similar and 50 mM of N3. Detection by UV-Vis absorption to that observed in N2O-saturated solution contain- at 274 nm. ing Met-enk (vide supra). In spite of the fact that the first step of oxidation of Met-enk and t-Boc-Met-enk by N3· in aerobic conditions is the same, there are different mechanisms for the secondary reactions occurring in Met-enk and t-Boc-Met-enk in the presence of oxygen compared to its absence. These differences can be rationalized in the fol- – lowing way. In both peptides the addition of O·2 to the aromatic ring of TyrO· occurs resulting in their respective peroxide anion enones which further protonate forming the hydroperoxide enones. In Met-enk the hydroperoxide enone undergoes the Michael-addition-type reaction leading to the cyclized compound which further hydrolyses forming stable compound. Its formation might be indicated by a new peak observed in the HPLC chromatogram

of irradiated O2-saturated solutions of Met-enk, but not in t-Boc-Met-enk ones. Since the amine Fig.3. HPLC chromatograms recorded in irradiated with functionality is not available in t-Boc-Met-enk, the respective hydroperoxide enone cannot undergo 84 Gy N2O-saturated aqueous solution containing 0.25 – Michael-addition-type reaction. Moreover, it was mM of Met-enk and 50 mM of N3. Detection by: (A) UV-VIS absorption at 274 nm and (B) fluorescence observed [5] that efficient conversion to the respec- (exc. 284 nm, em. 425 nm). tive hydroperoxides occurs only in peptides contain- RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 21 ing a free amino group in tyrosine itself. Therefore, References in t-Boc-Met-enk one has to consider reaction pathway involving hydroperoxide anion, which might [1]. Fontana M., Mosca L., Rosei M.A.: Biochem. undergo oxygen elimination with simultaneous Pharmacol., 61, 1253-1257 (2001). formation of phenoxide-type anions followed by [2]. Rosei M.A., Mosca L., De Marco C.: Biochim. their instantaneous protonation (regeneration of Biophys. Acta, 1243, 71-77 (1995). t-Boc-Met-enk). Blocking the terminal amine had [3]. Rosei M., Blarzino C., Coccia R., Foppoli C., Mosca L., Cini C.: Int. J. Biochem. Cell Biol., 30, 457-463 thus a key role in the protection of tyrosine. This (1998). finding might be exploited in the search for new [4]. Jin F., Leitich J., Sonntag von C.: J. Chem. Soc., Perkin pain inhibitors. Trans., 1583-1588 (1993). Work was supported by the EC Marie Curie [5]. Winterbourn C.C., Parsons-Mair H.N., Gebicki S., Research Training Network SULFRAD under con- Gebicki J.M., Davies M.J.: Biochem. J., 381, 241-248 tract No. HPRN-CT-2002-000184. (2004).

REACTIONS OF HYDROGEN ATOM WITH METHIONINE-ENKEPHALIN AND RELATED PEPTIDES. PULSE RADIOLYSIS STUDY Olivier Mozziconacci, Krzysztof Bobrowski, Carla Ferreri1/, Chryssostomos Chatgilialoglu1/ 1/ Institute for Organic Synthesis and Photoreactivity (ISOF), National Research Council (CNR), Bologna, Italy The role of hydrogen atoms (H·) in biology has not yet been completely assessed. It has been suggested that their involvement is not only based on the effect of ionizing radiation in water systems since H· can be generated efficiently by the reaction of electrons with dihydrogen phosphate an- – ion (H2PO4) present in the biological environment [1]. Therefore, a peptide and/or protein damage due to the H· attack has to be considered in great detail in order to establish its contribution to the context of radical stress to biomolecules [2]. The selectivity shown by the involvement of methionine (Met) residues could be conveniently evaluated in short amino acid sequences, which also allow gathering further data on the H· reactivity. As a model peptide, we considered Met-enkephalin, a neuropeptide composed by five amino acid residues (Tyr-Gly-Gly-Phe-Met; Tyr – tyrosine, Gly – Fig.1. Resolution of the spectral components in the tran- glycine, Phe – phenylalanine), its leucine analogue sient absorption spectrum following the H· atom re- (Leu instead of Met), and few selected peptides action with Met-enkephalin (0.1 mM) in argon-satu- containing Met. The presence of aromatic residues rated aqueous solutions containing t-BuOH (0.5 M) (Tyr and Phe) and a sulfur-containing amino acid at pH 1.5 taken 10 μs after the pulse. (Met), together with the possibility of comparing analogous sequences without Met, represents an in order to obtain spectra of isolated radicals de- ideal case to study any selectivity of reducing species rived from Tyr, Phe, and Met. Experiments were towards the sulfur-containing amino acid and/or performed with a tripeptide Tyr-Gly-Gly, and two the participation of other reactive sites in the ovearll dipeptides, Phe-Leu and Gly-Met under identical molecular reactivity. Here, we report pulse radi- conditions as for enkephalins. These peptides were olysis study of Met- and Leu-enkephalins applying selected in order to mimic an appropriate fragment reaction conditions where the H· are the relevant of either Leu-enkephalin or Met-enkephalin and reactive species, which affect the Met residues. also the position with respect to the N- and/or The optical absorption spectra obtained from C-terminal functions of the most vulnerable amino the pulse irradiation of argon-purged aqueous sol- acids (Tyr, Phe and Met) towards the H· attack. utions of Met- or Leu-enkphalin (0.1 mM) and The transient spectra obtained from these peptides tert-butanol – t-BuOH (0.5 M) at pH 1.5 are shown were then used as possible components in the resol- in Figs.1 and 2, respectively. Under these condi- ution of the transient spectra following reaction tions, the hydroxyl radicals (·OH) are scavenged of H· with Leu- and Met-enkephalins. After resol- – by t-BuOH and eaq are efficiently converted to H·. ution of the spectrum for Met-enkephalin (Fig.1), In order to evaluate the relative reactivity of the the G×ε values for Tyr-Gly-Gly and Phe-Leu are two enkephalins towards H· and the site of the at- 1.8×10–4 and 1.5×10–4 dm3J–1cm–1, respectively. tack, pulse radiolysis experiments were performed Analogously, after resolution of the Leu-enkepha- 22 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES reduced the amount of H· by 55% from further reaction with the Tyr and Phe residues. Moreover, the pulse radiolysis experiments indicated that about 50% of H· attack the thioether moiety of Met moiety presumably via a sulfuranyl radical (>S·-OH) [3,4] with formation of CH3SH and/or CH3S· radicals. By using a peptide-liposome model, the cis-trans isomerization of phospholipids has been detected highlighting the role of trans lipid as marker of this radical damage [5]. Work was supported by the EC Marie Curie Research Training Network SULFRAD under contract No. HPRN-CT-2002-000184. References [1]. Ferreri C., Manco I., Faraone-Minella M.R., Torre- giani A., Tamba M., Manara S., Chatgilialoglu C.: ChemBioChem., 7, 1738-1744 (2006). Fig.2. Resolution of the spectral components in the tran- [2]. Lipinski B.: Br. J. Nutr., 87, 93-94 (2002). sient absorption spectrum following the H· atom re- [3]. Ferreri C., Manco I., Faraone-Minella M.R., Torre- action with Leu-enkephalin (0.1 mM) in argon-satu- giani A., Tamba M., Manara S., Chatgilialoglu C.: rated aqueous solutions containing t-BuOH (0.5 M) ChemBioChem., 5, 1710-1712 (2004). μ at pH 1.5 taken 10 s after the pulse. [4]. Wiśniowski P., Bobrowski K., Carmichael I., Hug G.L.: J. Am. Chem. Soc., 126, 14468-14474 (2004). lin spectrum (Fig.2), the G×ε values for Tyr-Gly-Gly [5]. Mozziconacci O., Bobrowski K., Ferreri C., Chatgilia- and Phe-Leu are 4.0×10–4 and 2.5×10–4 dm3J–1cm–1, loglu C.: Chem. Eur. J., (2007), in press (available on respectively. Therefore, substitution of Leu by Met the website).

PULSE RADIOLYSIS GENERATION OF THE RADICAL ANION DERIVED FROM 2,3-DIHYDRO-OXOISOAPORPHINE IN ORGANIC SOLVENTS Krzysztof Bobrowski, Gabriel Kciuk, Eduardo Sobarzo-Sanchez1/, Julio R. De la Fuente2/ 1/ University of Santiago de Compostela (USC), Spain 2/ Universidad de Chile, Santiago de Chile, Chile Oxoisoaporphines are a family of oxoisoquino- control over the nature of the radical ionic species line-derived alkaloids that have been isolated from formed in secondary reactions in irradiated sol- Menispermaceae as the sole known natural source utions, and thus generate both radical anions and [1]. Formation of radical anions (A·–) and neutral cations or preferentially one of them. We have ini- hydrogenated radicals (A-NH·) from the triplet tiated this study in order to obtain a knowledge manifold (3A) was postulated during photoreduc- about the spectral properties of radical ions de- tion of 2,3-dihydro-oxoisoaporphine dye (A) by rived from oxoisoaporphines. The present work is amines [2]. Quantum mechanical semi-empirical of interest in shedding some light on spectral prop- PM3 and ZINDO/S calculations reproduce ad- erties of the radical anion derived from 2,3-di- equately experimentally observed absorption spec- hydro-oxoisoaporphine. Both acetonitrile and tra of the excited triplet (3A) and of neutral hydro- acetone are known for pulse radiolytic generation genated radicals (A-NH·) with maxima located at of cation as well anion radicals precursors. In these 450 and 390 nm, respectively [2]. However, the two solvents, both radical ions and only the radi- λ calculated absorption maximum ( max~600 nm) of cal cation are formed under N2 and O2 saturation, the isolated 2,3-dihydro-oxoisoaporphine radical respectively [3,4]. anion (A·–) did not match the experimentally ob- The optical absorption spectra obtained from served transient absorption spectrum with maxi- the pulse irradiation of argon-purged acetonitrile λ mum located at max~490 nm. Therefore, the latter solutions of 2,3-dihydro-oxoisoaporphine (0.1 spectrum was assigned to the radical ion-pair be- mM) are shown in Fig.1. tween the radical anion of 2,3-dihydro-oxoisoapor- The transient spectrum recorded 0.2 μs after phine and the radical cation of the respective amine. electron pulse show two maxima at 450 and 605 This assignment was further confirmed by Molecu- nm, respectively (Fig.1, curve a). They become sup- lar Mechanics and ZINDO/S calculations [2]. pressed upon O2 saturation (Fig.1, curve c), suggest- Many previous studies have revealed that radi- ing that they might be associated with the 2,3-di- cal ions can be easily generated by pulse radiolysis hydro-oxoisoaporphine radical anion (A·–). The in a number of non-polar, polar-nonprotic, and location of the maximum at longer wavelength is polar-polar protic solvents. Therefore, one may, by in excellent agreement with that calculated for iso- choice of solvent and saturating gas, excercise some lated 2,3-dihydro-oxoisoaporphine radical anion RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 23 (A·–). Therefore, the 605-nm band was unequivo- cally assigned to the radical anion (A·–). While, the radical anion (A·–) decays over a microsecond μ time scale (t1/2~5 s) (Fig.1, right inset), a new transient spectrum appears which is characterized by two absorption maxima located at 420 and 500 nm, respectively (Fig.1, curve b). Since these two absorption bands are also suppressed in oxygenated solutions they might be assigned to the secondary product(s) derived from the radical anion (A·–). This new absorption could be attributed to the neutral N-hydrogen radical of 2,3-dihydro-oxoisoaporphine (A-NH·) formed through protonation of the radical anion (A·–). The decay of neutral N-hydrogen radical (A-NH·) occurs on the hundred of microseconds time range (Fig.1, left inset). Fig.2. Transient absorption spectra recorded (a) 1 μs and μ μ (b) 40 s in argon-saturated and (c) 0.2 s in O2-saturated acetone solutions containing 2,3-dihydro-oxoisoaporphine (0.1 mM) after electron pulse. Inset: Absorption changes at λ=610 nm vs. time following pulse irradiation of 2,3-dihydro-oxoisoaporphine (0.1 mM) in argon-saturated acetone solutions.

tion bands become suppressed upon O2 saturation (Fig.2, curve c). Again, they can be assigned to the radical anion (A·–). However, at shorter wavelength we cannot rule out the contribution of the excited triplet state of 2,3-dihydro-oxoisoaporphine (3A) [2]. The decay of radical anion (A·–) in τ μ acetone is slightly slower ( 1/2~10 s) in comparison to acetonitrile (Fig.2, inset). It is evident that the spectral changes observed on a longer time Fig.1. Transient absorption spectra recorded (a) 0.2 μs and scale (Fig.2, curve b) after decay of the radical an- (b) 50 μs in argon-saturated and (c) 0.2 μs in O -satu- – 2 ion (A· ) are similar to those observed in acetoni- rated acetonitrile solutions containing 2,3-dihydro-oxo- trile. Therefore, the absorption could be attributed isoaporphine (0.1 mM) after electron pulse. Insets: λ λ again to the neutral N-hydrogen radical of 2,3-di- Absorption changes at =420 nm (left) and =605 hydro-oxoisoaporphine (A-NH ). nm (right) vs. time following pulse irradiation of · 2,3-dihydro-oxoisoaporphine (0.1 mM) in argon-saturated acetonitrile solutions. References Acetone is known to give both solute cations and [1]. Sugimoto Y., Babiker H.A.A., Inanaga S., Kato M., anions, as well excited states. The optical absorp- Isogay A.: Phytochemistry, 52, 1431-1435 (1999). [2]. De la Fuente J.R., Neira V., Saitz C., Jullian C., tion spectra obtained from the pulse irradiation of Sobarzo-Sanchez E.: J. Phys. Chem. A, 109, 5897-5904 argon-purged acetone solutions of 2,3-dihydro-oxo- (2005). isoaporphine (0.1 mM) are shown in Fig.2. The tran- [3]. Bobrowski K., Das P.K.: J. Phys. Chem., 90, 927-931 sient spectrum recorded 1 μs after electron pulse (1986). show two maxima at 430 and 610 nm, respectively [4]. Bobrowski K., Das P.K.: J. Phys. Chem., 89, 5733-5738 (Fig.2, curve a). As in acetonitrile, both absorp- (1985).

PULSE RADIOLYSIS STUDY OF THE INTERMEDIATES FORMED IN IONIC LIQUIDS. NATURE OF INTERMEDIATES IN PULSE IRRADIATED p-TERPHENYL SOLUTION IN THE IONIC LIQUID METHYLTRIBUTYLAMMONIUM BIS[(TRIFLUOROMETHYL)SULFONYL]IMIDE Jan Grodkowski, Rafał Kocia, Jacek Mirkowski Room temperature ionic liquids (IL) [1-5] are con- nuclear industry brought the question of radiation sidered non-volatile and non-flammable and serve chemistry in these media. Up to now, only a limited as good solvents for various reactions and have been number of experiments were directly focused on proposed as solvents for green processing and very radiation stability of IL, the rate constants of several effective media for numerous reactions [3-5]. Prom- elementary reactions in IL have been studied by ising experiments concerning application of IL in the the pulse radiolysis technique instead [6-12]. 24 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES In this study, the formation of intermediates derived from p-terphenyl (TP) in the ionic liquid methyltributylammonium bis[(trifluoromethyl)sulfonyl]imide (R4NNTf2) solutions has been studied by pulse radiolysis. TP was chosen because resulting anionic, cationic and excited intermediates have absorption spectra in UV/VIS range (Table) [13].

The pulse radiolysis of TP solution in R4NNTf2 gives subsequently some insight into the nature of primary products of R4NNTf2 radiolysis. The relations between TP* (excited singlet and triplet states) and TP·– have been already described. TP photocata- lytic activity was the other reason to chose this compound for experiments in IL and select the best conditions for TP·– formation. In photochemical – Fig. Spectrum at 400 ns after subtraction of the initial spec- process TP· (often used in CO2 reduction [14,15 and references therein]) is formed mainly from sin- trum (corrected for spectrum of solvated electron), Ar-saturated 14 mM TP solutions in R NNTf with glet excited states 1TP* by reaction with electron 4 2 3% TEA added, dose – 15 Gy. donor triethylamine (TEA) and in radiolysis directly in reaction with solvated electrons [14,15]. even under the best conditions for radiolytic TP·– TP* in IL solution can also be formed by energy formation (Ar and TEA presence) TP·– is always transfer from excited radiolysis products of IL and accompanied by other intermediates, mostly 3TP*. in direct TP excitation by Èerenkov light. TEA enhances the yield of TP·– due to scavenging 1 λ of cation radicals and TP*, however it reacts more Table. Position of max of absorption spectra of intermedi- 3 ates derived from TP [13]. slowly with TP* [15]. The presence of solvated electron scavengers cuts the initial spectrum in the region 400-500 nm to about half value. This indicates that under Ar most of the TP·– is formed in the reaction of TP with solvated electrons and their precursors, dry electrons. Some of TP·– (less than 50%) are produced in the presence of TEA from 1TP*. Kinetics of the total absorption decay (in the range 400-500 nm) is quite complicated and the

The pulse radiolysis of TP solution in R4NNTf2 best fitting to the experimental results can be has been carried out under Ar, CO2, O2 and N2O achieved using exponential decay equation with at in the presence or absence of TEA. Fast kinetic least three different constants. Addition of O2 to measurements have been carried out using 10 ns, the TP solution, besides elimination of solvated 10 MeV electron pulses from a LAE 10 linear elec- electrons and consequently decreasing the inten- tron accelerator [16] delivering a dose up to 20 Gy sity of the spectra, drastically increases the rate of per pulse. The details of the computer controlled absorption decay. – – measuring system were described before [11,17]. The reduction potentials of TP· and CO·2 in Resulted under Ar intermediate spectra are IL are close to each other and the reactions be- formed in two steps, one very fast already completed tween TP and CO2 and their radical anions in any during the pulse, and the second lasting hundreds directions cannot be seen in pulse radiolysis ex- of nanoseconds depending on TP concentrations. periments. The second step is eliminated in the presence of Concluding, the primary radiolysis products of electron acceptors. The initial spectra are related R4NNTf2 solvent constitute of dry and solvated elec- to the species listed above and also to solvated electrons, cation radicals and excited species. Reduc- trons, except 1TP* which is too short lived to be tion potential of cationic species it is not high observed in nanosecond time scale. enough to oxidize Br– or SCN– but allows forma- In Figure, there is presented an absorption spec- tion of cation radicals of TP. TP·– is produced trum corresponding to the second step only. It is mainly in the reaction with dry and solvated elec- set up from the difference between the spectrum at trons and its lifetime is in order of tens of micro- 400 ns after the electron pulse (end of the second seconds in the pulse radiolysis experiments. step) and the initial spectrum (corrected for spectrum of solvated electron) obtained in pulse radi- References olysis of Ar-saturated 14 mM TP solutions in [1]. Welton T.: Chem. Rev., 99, 8, 2071-2083 (1999). R4NNTf2 with 3% TEA added. Very similar spectrum is calculated from the results without added [2]. Wasserscheid P., Keim W.: Angew. Chem. Int. Ed., – 39, 21, 3772-3789 (2000). TEA. The spectra can be ascribed to the TP· be- [3]. Ionic liquids: Industrial application to green chemistry. cause of the similarity to the reported before re- Eds. R.D. Rogers, K.R. Seddon. ACS Symp. Ser., 818 sults in frozen systems [13]. Comparison of the (2002). – calculated TP· spectrum with the shape of direct [4]. Chiappe C., Pierracini D.: J. Phys. Org. Chem. 18, experimental spectra leads to the conclusion that 275-297 (2005). RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 25

[5]. Jain N., Kumar A., Chauchan S., Chauhan S.M.S.: [13]. Shida T.: Electronic absorption spectra of radical Tetrahedron, 61, 1015-1060 (2005). ions. Elsevier, Amsterdam 1988, p. 446. [6]. Grodkowski J., Neta P.: J. Phys. Chem. A, 106, 22, [14]. Grodkowski J.: Radiacyjna i fotochemiczna redukcja 5468-5473 (2002). dwutlenku węgla w roztworach katalizowana przez [7]. Grodkowski J., Neta P.: J. Phys. Chem. A, 106, 39, kompleksy metali przejściowych z wybranymi układa- 9030-9035 (2002). mi makrocyklicznymi. Instytut Chemii i Techniki [8]. Grodkowski J., Neta P.: J. Phys. Chem. A, 106, 46, Jądrowej, Warszawa 2004, 56 p. Raporty IChTJ. Seria 11130-11134 (2002). A nr 1/2004 (in Polish). [9]. Wishart J.F., Neta P.: J. Phys. Chem. B, 107, 30, [15]. Fujiwara H., Kitamura T., Wada Y., Yanagida S., 7261-7267 (2003). Kamat P.V.: J. Phys. Chem. A, 103, 4874-4878 (1999). [10]. Grodkowski J., Neta P., Wishart J.F.: J. Phys. Chem. [16]. Zimek Z., Dźwigalski Z.: Postępy Techniki Jądrowej, A, 107, 46, 9794-9799 (2003). 42, 9-17 (1999), in Polish. [11]. Grodkowski J., Płusa M., Mirkowski J.: Nukleonika, [17]. Grodkowski J., Mirkowski J., Płusa M., Getoff N., 50, Suppl.2, s35-s38 (2005). Popov P.: Radiat. Phys. Chem., 69, 379-386 (2004). [12]. Wishart J.F., Funston A.M., Szreder T.: Radiation chemistry of ionic liquids. In: Molten saltz. The Electrochemical Society, Pennigton, NJ, USA, 2006.

STEREOELECTRONIC CONTROL OVER THE MECHANISM OF SINGLET OXYGEN-INDUCED DECARBOXYLATION IN ALKYLTHIOCARBOXYLIC ACIDS Monika Celuch, Mirela Enache1/, Dariusz Pogocki 1/ Institute of Physical Chemistry “I.G. Murgulescu”, Romanian Academy, Bucharest, Romania

Our recent investigations have been devoted to philic dissociation [4,5,7]. The observed influence understanding the irreversible pathways of singlet of β-carboxylic groups on the efficiency of decar- 1 β oxygen-induced ( O2-induced) oxidation of carboxylation suggest that -carboxylate may catalyze 1 α boxyl-substituted thioethers. The reaction of O2 decarboxylation of -carboxylate in the intramol- with thioether sulphur initially leads to the forma- ecular process: tion of peroxysulphoxide [1,2]: 1 → (+) (–) O2 + >S >S O-O (1) being in the equilibrium with superoxide radical – anion (O·2 ) and respective sulphur-centered radi- (5) cal cation: (+) (–) + – >S O-O = >S· + O·2 (2) The major, enzymatically reversible [3], pathway of persulphoxide decay is the bimolecular reaction with the second molecule of thioether that leads The differences in the decarboxylation yield be- to the formation of respective sulphoxide [1,2]: tween the acids (Table) can be rationalized in terms >S(+)O-O(–) + >S → 2 >S=O (3) of the stereoelectronically controlled Wagner-Meer- Our previous experimental observation [4,5] for wein rearrangement [8,9] previously observed for the following model thioethers: 2,2’-thiodiethanoic carbocations: acid (TDEA), 3,3’-thiodipropionic acid (TDPA), 2-(methylthio)ethanoic acid (MTEA), 3-(carboxy- methylthio)propionic acid (CMTPA), 2-(carboxy- (6) methylthio)succinic acid (CMTSA), have shown the presence of the competitive, irreversible process of decarboxylation that can be schematically represented by below reaction: The upper branch of this mechanism shows the frag- + – → R- S· -CH2-CO2 R-S-CH2· + CO2 (4) mentation pathway that could be easily adopted for That process could be quite effective for the sul- decarboxylation of sulphur-centered radical cations phur-centered radical cations of α-carboxyl-sub- in alkylthiocarboxylic acids. stituted thioethers. Moreover, the nucleophilic catalysis of reaction (2) seems to be crucial for the (7) competitiveness of the irreversible reaction pathway. In such catalytic process, the weak nucleo- In this mechanism, the electron from the σ bond – – ≈ phile O·2 (pKA(HO2·/O·2 ) 4.8 [6]) is replaced by a (between Cα and carboxylate) is donated to the radi- stronger nucleophile like OH– or Cl– anions. The cal-cation center. The weakening of the bond results DFT calculations have predicted the formation of in a subsequent release of carbon dioxide. There- tetravalent transient – product of OH– (or halogenic fore, the quite objective measure of the radical-cat- anions) addition to persulphoxide, pointing at the ion propensity to undergo such fragmentation could σ occurrence of two-step (AN+DN)-type mechanism be distortion of the donor bond toward the elec- of subsequent nucleophilic addition and nucleo- tron acceptor site at oxidized thioether sulphur. 26 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES

Table. Alkylthiocarboxylic acids, structures and relative 1 yields of O2-induced decarboxylation.

1 Fig.2. Relative yield of O2-induced decarboxylation in alkylthiocarboxylic acids vs. the ξ angle. In the DFT quantum chemical calculations [10] we obtained geometries and electronic structures of leaning of σ bond towards the radical-cation centre sulphur-centered radical cations derived from each that seems to confirm the assumed mechanism. of the investigated transient species. (The represen- This work described herein was supported by tative example for CMTSA is presented in Fig.1.) the Polish Ministry of Education and Science For CMTPA and CMTSA, the sulphur-centered (grant No. 3 T09A 066 26). The computations were performed employing the computer resources of the Interdisciplinary Centre for Mathematical and Computational Modelling, Warsaw University (ICM G24-13).

References [1]. Clennan E.L.: Acc. Chem. Res., 34, 875-884 (2001). [2]. Jensen F., Greer A., Clennan E.L.: J. Am. Chem. Soc., 120, 4439-4449 (1998). [3]. Sharov V.S., Ferrington D.A., Squier T.C., Schöneich C.: FEBS Lett., 455, 247-250 (1999). [4]. Celuch M., Enache M., Pogocki D.: Singlet oxygen- -induced oxidation of alkylthiocarboxylic acids. In: INCT Annual Report 2005. Institute of Nuclear Chem- istry and Technology, Warszawa 2006, pp. 26-28. Fig.1. The DFT (B3LYP/6-31G(d)) calculated structure of [5]. Celuch M., Pogocki D.: Singlet oxygen-induced decar- sulfur-centered radical cation in CMTSA. The angle boxylation of carboxyl substituted thioethers. In: INCT ξ has been chosen as a measure of distortion of the Annual Report 2004. Institute of Nuclear Chemistry σ and Technology, Warszawa 2005, pp. 27-29. donor bond (Cα-CO2) toward the electron acceptor radical cation. [6]. Bartosz,G.: Druga twarz tlenu. Wolne rodniki w przy- rodzie. Wydawnictwo Naukowe PWN, Warszawa radical cations being precursor of α-carboxylate de- 2003, pp. 1-447 (in Polish). carboxylation could be stabilized by the formation [7]. Williams A.: Concerted organic and bio-organic of three-electron-bonded species with the oxygen mechanisms. CRC Press, Boca Raton 2000, pp. 1-286. atom of adjacent β-carboxylate group. (The geo- [8]. Rauk A.: Orbital interaction theory of organic chem- metries and electronic structures of such species istry. John Wiley & Sons, Inc., New York 2001, pp. we have extensively investigated previously [11,12].) 1-343. In order to analyze the structures of sulfur-cen- [9]. Chanon M., Rajzman M., Chanon F.: Tetrahedron, 46, 6193-6299 (1990). tered radical cations in terms of the Wagner-Meer- [10]. Frisch M.J. et al.: Gaussian 03. (Rev. B.03). Gaussian wein rearrangement mechanism we chose the angle ξ σ Inc., Pittsburgh PA 2003. (Fig.1) as a measure of distortion of the bond [11]. Pogocki D., Schöneich C.: J. Org. Chem., 67, 1526-1535 toward the radical-cation centre. Indeed, the com- (2002). putational results show a quasi-linear dependence [12]. Pogocki D., Serdiuk K., Schöneich C.: J. Phys. Chem. of relative yield of decarboxylation on ξ (Fig.2). A, 107, 7032-7042 (2003). The decarboxylation yield increases with growing RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 27 OXIDATION OF THIOETERS BY ORGANIC COMPLEXES OF COPPER Monika Celuch, Katarzyna Serdiuk1/, Jarosław Sadło, Mirela Enache2/, Dariusz Pogocki 1/ Jan Długosz University of Częstochowa, Poland 2/ Institute of Physical Chemistry “I.G. Murgulescu”, Romanian Academy, Bucharest, Romania

The presence of cupric ions is essential for proper metabolism of many organisms. The best recognized and appreciated function of cupric ions is their participation in the active centers of numerous enzymes [1]. On the other hand, the faults in copper homeo- stasis in humans are frequently related to disorders with neurological symptoms [2,3]. For example, copper is bind by β-amyloid peptide (βA), the most abundant constituent of senile plaques observed in Alzheimer’s disease (AD) brains [2,3]. The βA-bound copper can be involved in the cycle of Fenton like reactions, in which free radicals and other reactive oxygen species (ROS) presented in pathology of AD may be formed [4]. In this work, we continue investigation of the mechanisms that may explain the ability of βA to reduce copper in reaction: Fig.1. The ESR signal changes vs. incubation time in ar- β II ↔ β I + gon-saturated (solid symbols) and oxygen-saturated MetS + A(Cu ) A(Cu ) + MetS· (1) (open symbols) solutions containing: 1.5×10–3 M Such process seems thermodynamically unfavor- × –3 × –3 CuCl2, 7.5 10 M Im and 0.75 10 M (square) or able [5], since in normal conditions the difference 3.0×10–3 M (triangle) of MTAA. between the reduction potentials of βA(CuI/CuII) + 2+ (0.5-0.55 V vs. Ag/AgCl) [6] and MetS· /Met The reduction of Cu(Im)4 by thioethers was (1.26-1.5 V vs. Ag/AgCl) [7-10], is about ca. 0.7-1.0 investigated in oxygen- or argon-saturated aque- × –3 × –3 V, thus equilibrium (1) should be shifted to the far ous solution containing 1.5 10 M CuCl2, 7.5 10 left-hand side [5]. M Im, and (0.75; 1.5 or 3.0)×10–3 M of thioethers However, reaction (1) may occur if coupled with at neutral pH, incubated at 50oC. The progress of the other exergonic reaction. One of possible scen- reaction was monitored using three independent ario is the removing of MetS·+ from the equilibrium methods: high performance ion chromatography by the formation of α-(alkylthio)alkyl radicals exclusion (HPICE) [15] was applied for quantitative (αS·) in exergonic, general base catalyzed reaction: determination of products and substrates. Decay of MetS·+ + B → Met(αS)· + BH+ (2) CuII was monitored by electron spin resonance Therefore, in this work we studied, on the model (ESR) spectroscopy (in the redox pair CuII/CuI only systems, reactions that may spontaneously lead to CuII cations are paramagnetic). The formation of the formation α-(alkylthio)alkyl radicals, potentially CuI was followed using UV-VIS absorption spec- influencing equilibrium (1) and accelerating oxidation of the methionine (Met) residue in peptides. We examined a molecular system, in which II the complex of Cu with imidazole mimics cupric site of βA. The fifth fold excess of imidazole (Im) over Cu2+ guarantee that at least 95% of copper 2+ is in the form of Cu(Im)4 -type complex of known λ ≈ ε –1 –1 properties: max 590 nm ( =53 ±2 M cm ) [11] and E0(CuII/CuI)≤0.2 V and E0(CuI/Cu0)≤0.6 V vs. SCE [12]. The methionine residue was mimicked by organic α-substituted thioethers: 2,2’-thiodi- acetic acid (TDEA, HO2C-CH2-S-CH2-CO2H), and 2-(methylthio)acetic acid amide (MTAA,

CH3-S-CH2-CO2-NH2). In both cases the reduction 2+ of Cu(Im)4 -complexes should be accompanied by a simultaneous formation of the resonance stabilized α-(alkylthio)alkyl radicals. For TDEA, en- 3– Fig.2. The concentration of Cu(BCA)2 complexes vs. in- tropy driven decarboxylation is the main source of cubation time for argon-saturated solutions contain- α-(alkylthio)alkyl radicals, whereas for MTAA the ing: 3.0×10–3 M of thioether (MTAA – squares, TDEA × –3 × –3 facilitated deprotonation, due to the captodative – triangles), 1.5 10 M CuCl2 and 7.5 10 M Im. effect stabilizing α-(alkylthio)alkyl radicals, will dominate [13]. Contrary to fast decarboxylation of troscopy of 2,2’-bicinchoninic acid (BCA) complex + 3– λ ≈ ε≈ TDEA, deprotonation in MTAA should be sus- with Cu cations (Cu(BCA)2 : max 562 nm, 7700 ceptible to the presence of proton acceptors [14]. M–1cm–1) [16]. 28 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES show faster changes for TDEA, which reduces CuII with more than two times higher efficiency than MTAA. On the other hand, we obtained the evidence that the process of CuII-complexes reduction, induced by deprotonating thioether such as MTAA, could be accelerated in general acid-base catalysis by phosphate ions (Fig.3). The mechanism shown in Scheme is a preliminarily attempt to rationalize current observation for MTAA. It requires, however, additional consideration especially on the mechanistic details of the conversion of peroxyl radicals regenerating the mother compounds. This work described herein was supported by the Polish Ministry of Education and Science (grant No. 3 T09A 066 26).

– 2– Fig.3. The influence of phosphate ions (H2PO4/HPO4 ) on the kinetics of CuII reduction by MTAA in argon-satu- References × –3 rated solutions containing: 0.75 10 M thioether, [1]. Holm R.H., Kennepohl P., Solomon E.I.: Chem. × –3 × –3 1.5 10 M CuCl2, 7.5 10 M Im and (solid symbols) Rev., 96, 2239-2314 (1996). × –3 0.15 10 M phosphate buffer, (open symbols) phos- [2]. Strausak D., Mercer J.F., Dieter H.H., Stremmel W., phate free solution. Multhaup G.: Brain Res. Bull., 55, 175-185 (2001). [3]. Gaggelli E., Kozłowski H., Valensin D., Valensin G.: For the all samples containing TDEA, and for Chem. Rev., 106, 1995-2044 (2006). argon-saturated samples containing MTAA we ob- [4]. Halliwell B., Gutteridge J.M.: Free radicals in biology served the decay of ESR signal. Whereas for oxy- and medicine. Oxford University Press, Oxford 1999, gen-saturated samples of MTAA the intensity of pp. 1-936. ESR signal remained on the same level for more [5]. Schöneich C.: Arch. Biochem. Biophys., 397, 370-376 than 300 h of incubation (see example in Fig.1). (2002). [6]. Huang X. et al.: J. Biol. Chem., 274, 37111-37116 Also, the HPICE measured changes of MTAA (1999). concentration during incubation in oxygen-satu- [7]. Merényi G., Lind J., Engman L.: J. Phys. Chem., 100, rated solutions were insignificant. Similarly, the 8875-8881 (1996). 3– formation of Cu(BCA)2 complexes was observed [8]. Engman L., Lind J., Merényi G.: J. Phys. Chem., 98, in the presence of both thioethers in argon-satu- 3174-3182 (1994). rated samples (Fig.2). Generally, the significant [9]. Huie R.E., Clifton C.L., Neta P.: Radiat. Phys. Chem., differences in kinetics between thioethers were ob- 92, 477 (1991). served. For the same concentrations of TDEA and [10]. Sanaullah, Wilson S., Glass R.S.: J. Inorg. Biochem., MTAA, both the ESR and the UV-VIS experiments 55, 87-99 (1994). [11]. Edsall J.T., Falsenfeld G., Goodman D.S., Guard F.R.N.: J. Am. Chem. Soc., 76, 3054-3061 (1954). [12]. Li N.C., White J.M., Dood E.: J. Am. Chem. Soc., 76, 6219-6223 (1954). [13]. Wiśniowski P.: Wpływ grup funkcyjnych na inicjowane radiacyjnie procesy rodnikowe w tioeterach (The influence of functional groups on the radiation initiated radical processes in thioethers). Ph.D. thesis. Instytut Chemii i Techniki Jadrowej, Warszawa 2001 (in Polish). [14]. Mönig J., Goslich R., Asmus K.-D.: Ber. Bunsen-Ges. Phys. Chem., 90, 115-121 (1986). [15]. Weiss J.: Ion chromatography. VCH, Weinheim 1995, pp. 1-465. [16]. Boyd-Kimball D., Mohmmad A.H., Reed T., Sultana R., Butterfield D.A.: Chem. Res. Toxicol., 17, 1743-1749 Scheme. (2004).

ORGANOSILVER RADICALS IN ZEOLITES Jerzy Turek, Jarosław Sadło, Jacek Michalik During radiolysis of solutions containing silver (EPR) measurements reveal a doublet with silver salts, Ag+ cations are reduced to Ag0 atoms which hyperfine splitting in the range 60-70 mT represent- initiate silver agglomeration process. The solvent ing Ag0 atoms [1]. During thermal annealing, a 0 radicals formed radiolytically compete with Ag to doublet with much smaller splitting Aiso(Ag)=13.6 react with Ag+ cations. Just after irradiation at 77 mT appears together with a less intense triplet with K in frozen solution of methanol containing silver A(Ag)=30.0 mT. Based on the electron spin echo perchlorate the electron paramagnetic resonance envelope modulation (ESEEM) result, the doublet RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 29 was assigned to an adduct of Ag+ cation and hy- Ag·C radical structure, we performed density func- + droxymethyl radical (·CH2OH) with a one-electron tional theory (DFT) calculations for a system of Ag bond between silver and carbon. cation interacting with hydroxymethyl radical. Those In gamma-irradiated silver zeolites exposed to calculations confirmed that the one-electron bond methanol vapour the doublet of silver hydroxy- between silver and carbon is able to stabilize the + methyl radical is also observed, but hyperfine split- [Ag·CH2OH] adduct. The formation of the adduct ting values vary very much for different zeolite struc- causes a substantial shift of spin density from carbon tures [2]. The goal of our studies was to define the to silver. An EPR doublet cannot originate from nature of bonding between Ag+ cation and small the Ag·O one-electron bond because such configu- carbon radicals and to determine the factors that ration gives a very low spin density on silver. affect the value of A(Ag) hyperfine splitting for The results of DFT calculations show that the + organosilver radicals. A(Ag) of [Ag·CH2OH] radical depends strongly After dehydration at 200oC, the zeolite samples on the interaction of Ag+ with the surroundings have been oxidized with O2 under pressure of 300 especially with electronegative atoms. Theoretical Torr for one hour. Next, oxygen was pumped out value of hyperfine splitting of the free silver hydroxy- and the methanol was adsorbed at room tempera- methyl radical is equal to 16.4 mT. If one takes into ture. The samples were gamma-irradiated at 77 K consideration the interaction of one methanol 60 + in a Co source. The EPR spectra were measured molecule with the metallic centre of [Ag·CH2OH] using a Bruker ESP-300 spectrometer equipped radical, the A(Ag) value calculated by the DFT with a cryostat operating in the temperature range method decreases to 14.2 mT which is very close 100-350 K. to the experimental value observed in gamma-irradiated frozen solutions of silver perchloride in methanol. But when the radical forms a hydrogen bond A(Ag) this value increases to 216 G. Comparing DFT results with the data of EPR experiments, it was proved that in zeolites with big cation capacity the silver hydroxymethyl radical interacts with a silicaallumina network by the metallic centre of the radical. The decrease of cation capacity modifies the radical surroundings changing electronic density distribution. In zeolites with small cation capacity, the formation of hydrogen Fig. The EPR spectra at 160 K of (a) Ag-ferrierite and (b) bonds with zeolite network is postulated as a domi- Ag-NaA zeolites exposed to methanol vapour and gamma-irradiated at 77 K. Ag·C dublets represent nating interaction of silver hydroxymethyl radical. silver hydroxymethyl radicals. The theoretical calculations showed also a substantial influence of the functional group on the Ag + Typical EPR doublets of [Ag·CH2OH] adduct hyperfine splitting for different adducts with the labelled as Ag·C are shown in Fig. for Ag-NaA and Ag·C one-electron bond (Table 2). It depends on Ag-ferrierite zeolites exposed to methanol. The the ability of the functional group to attract or re- hyperfine splitting values for various zeolite struc- pulse electrons. Electron donor functional groups tures are presented in Table 1. They differ from 12.0 mT for 4A zeolite to 19.5 mT for ferrierite. Table 2. Theoretical values of A(Ag) for different organosilver radicals. The dependence of Aiso(Ag) constant on the Si/Al ratio is strong in big cation capacity zeolites and probably is linear. However, the cation capacity + affects A(Ag) value of [Ag·CH2OH] only to a mi- nor degree as was proved by the experiments with Ag-ZSM-5 zeolites with Si/Al ratio in the range 30 to 200 and MCM-41 zeolites with Si/Al ratio from 10 to 30. To verify our experimental conclusions concerning the zeolite lattice influence on the

Table 1. Experimental values of A(Ag) hyperfine splitting + for [Ag·CH2OH] in different zeolites.

increase spin density on the Ag nucleus which results with large values of hyperfine splitting ranging from 13 to 20 mT. In contrast, A(Ag) for Ag·C organosilver radicals with electron acceptor groups are in the range 5-8.5 mT because they decrease the spin density on silver. 30 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES It is worthy of stressing that the functional References groups which decrease or increase A(Ag) splitting [1]. Symons M.C.R., Janes R., Stevens A.D.: Chem. Phys. are similar to those which, in a similar way, affect Lett., 160, 386 (1989). electron density on π orbitals of benzene ring. Thus, [2]. Michalik J., Sadlo J., van der Pol A., Reijerse E.: Acta we can speculate that resonance structures similar Chem. Scand., 51, 330 (1997). to the structures in the chemistry of aromatic hydrocarbons are responsible for the observed effect.

EPR STUDY ON RADIATION-INDUCED RADICAL DISTRIBUTION IN MASSIVE BONE GRAFTS Jarosław Sadło, Jacek Michalik, Grażyna Strzelczak, Anna Dziedzic-Gocławska 1/ , Artur Kamiński1/ 1/ Central Tissue Bank, Medical University of Warsaw, Poland

The bone transplantation method, a useful tool of radiated massive bones renders the percentage of orthopedic surgery, requires advanced and fully hydroxyapatite through bone cross-section. The controlled methods of sterilization, mainly using radical concentration is higher in bone pieces con- ionizing radiation sources. Radiation can fast pro- taining more hydroxyapatite. vide sufficient energy to sterilize a whole volume of bone pieces. Small volume grafts – like bone powder fillers or pieces of compact bone like plates or poles, have been sterilized in the Institute of Nu- clear Chemistry and Technology (INCT) by accelerators for many years. Recently, tissue banks offer also massive grafts – the whole fragments of bone. In that case, because of complicated shape and composition of compact and spongy bone types, it is necessary to control the dose distribution as well as the distribution of radiation-induced radicals. It should be stressed that dose distribution must not be identical with radical distribution because of inhomogeneity of bone structure. For experiments, the human tibia bones were used. A massive fragment was cut into thin slices assembled back into the anatomical shape. Next, it was one-sided irradiated by a 10 MeV electron beam (Elektronika, INCT) with a dose of 30 kGy. A similar fragment was two-sided irradiated with a dose of 2x20 kGy. The fragment of the same con- Fig.1. EPR spectrum of CO– radical induced in irradiated 60 2 figuration was irradiated by Co gamma rays bone. (Issledovatel, INCT, 30 kGy). Next, all the slices were cut into about 100 small pieces and then For one-sided irradiation, the distribution of crushed into powder to avoid anisotropic effects. radicals is similar to dose depth dependence: maxi- Electron paramagnetic resonance (EPR) measure- mum concentration is at the depth of one centi- ments were carried out using an X-band Bruker meter. Concentration difference between the upper ESP 300 spectrometer. The measured EPR signal, and lower part is about 60% indicating that the ap- an anisotropic singlet with g⊥=2.003 and gll=1.997 plied dose does not guarantee sterility of the bone (Fig.1), origins from mineral part of the bone was (Fig.2A). In case of two-sided irradiation, the dis- – assigned earlier to CO2 radical. The signal is stable tribution of radical concentration is much more flat and its intensity increases linearly with absorbed and the difference between the highest and lowest dose. values is about 30% (Fig.2B). The highest difference in the concentration of The dose distribution during electron beam irra- – CO2 radicals in small pieces of the bone irradiated diation was estimated using a PVC foil dosimeter in a 60Co source does not exceed 18%. That type of (spectrophotometric method) as well as a powder radiation can easily penetrate the bone fragments alanine dosimeter (EPR dosimetry). In both cases in the whole volume because of high penetrability the dosimeters were placed between two bigger of gamma rays. Thus, the radicals concentration bone parts and then one-sided irradiated. The ala- should be similar in the whole cross-section of the nine powder was placed in small flat bags. The ala- bone. However, the experimental results are differ- nine from each bag was measured separately. The ent because of inhomogeneity of bone structure and, results confirmed that the profile of distribution in practice, the radical concentration in gamma-ir- is rather complex because of the complicated shape RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 31

Fig.2. Dose distribution in one-sided (A) and two-sided (B) massive bone grafts. of irradiated object and the presence of bone chan- It is concluded that for massive bone fragments nels. For both dosimeters, the maximum dose was one-sided irradiation does not guarantee steriliza- equal to about 120% of the initial value, and the tion of the whole fragments, therefore two-sided dose distribution was very similar to radical con- irradiation should be applied as a routine in that centration distribution. case.

RADIATION CHEMISTS VIEW ON PANSPERMIA HYPOTHESIS Zbigniew P. Zagórski The year 2006 was the last full year of my partici- The doses which decide about very low prob- pation as the member of Managing Committee in ability of panspermia are similar to doses applied the European action in chemistry COST D27 (Pre- in technology of radiation sterilization, widely used biotic chemistry and early evolution), as the only for killing all microorganisms in medical devices and radiation and radiochemist in the Committee. The medicaments [5]. The radiation should not damage field is closely connected to the so-called astro- the sterilized material, which survives the irradia- biology, which deals with life and prebiotic chemi- tion with a minimal loss of active compound or re- cal compounds present anywhere in the universe. mains with negligible degradation of material, usu- Problems involve transportation of that material ally a polymer. The same applies to celestial bodies: in any directions, what can be involved in the ori- if the sojourn in space is comparatively short, the gin of life on earth. only change, however important, is the killing of life, The very old [1] concept of panspermia hypoth- e.g. of spores which otherwise would be the seeds esis may be traced to Greek philosophers. Even now, of life transported to earth. As one can see from the idea that the transportation of spores from the the Clark table, the time of travelling in space with universe is responsible for the origin of life on resulting sterilization only, is astronomically speak- earth, is always widely accepted as long as it is not ing short. However, the real sojourn in radiation confronted with conditions in the universe. These fields lasts very much longer and the absorbed, ad- are characterized mainly by the existence of invis- ditive doses grow [6]. ible, but chemically and biologically active ionizing Clark’s table (in modified version see [4]) shows radiations. Their intensity is sufficient to kill highly more than when and in what object the spores will organized life and also primitive life, if the time of be inactivated. What happens during longer stays, interaction is long enough. We have presented the especially to objects of small size like cosmic dust, quantitative relationships on practically all work- easily penetrated not only by electromagnetic ion- shops organized during COST D27 meetings and izing radiations like gammas, but also by particles other conferences, e.g. on ISSOL 05 [2], stressing like protons and by heavier ions, present in galac- the chemical mechanism of the irreversible radia- tic cosmic rays? These objects are absorbing mam- tion damage to dry spores. The best description of moth doses of radiation energy, which causes many possibilities of spores to survive the transportation chemical reactions. The next to sterilization dose in the universe is the table published by Benton is the dose not very much higher, causing abstrac- Clark [3], then slightly modified [4]. Clarks paper tion of parts of biopolymers or parts of organic is seldom quoted; it is simply non-existent among compounds. There are many examples of such re- enthusiasts of panspermia. actions, the most general is the fact common in 32 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES radiation chemistry, i.e. the abstraction of a group dramatically lower in comparison to those at am- which leaves in the molecule a site with unpaired bient temperatures. electron. The common reaction of abstraction of hydro- Another example is the destruction of chirality. gen, not limited to spores but of general occurrence Abstraction of a group, e.g. of ammonia from the [8], corroborates well with characteristic feature α-carbon in an amino acid, turns off the asymmetry of organic compounds, identified spectroscopically of the remaining radical. The free radical can attach in interstellar spaces of the universe. They are as a group, and the new compound will be chiral, if poor in hydrogen as possible, e.g. methyltriacetylene the group is different from the remaining three. (C7H4), methylcyanodiacetylene (C6NH3), cyano- Therefore, if the original amino acid was a pure allene (C4NH4), ketenimine (C2NH3), cyclopro- enantiomer, any products of the subsequent reac- penone (C6OH2) and many polyaromatics. The tion will keep chirality, but will be racemic, 1:1 D remaining hydrogen atoms are difficult to detach to L. Hypothetical homochirality of a compound during absorption of ionizing radiation, because achieved (perhaps) far from the Earth will be lost they usually belong to structures, mainly polyun- during the travel. saturated and aromatic which possess the ability Moving to higher doses resulting from even to dissipate the absorbed ionization energy with- longer stays in the universe, we are turning into out ionization. the zone of complete degradation, and sometimes The question remains why the life on earth is even to disappearance of an organic compound. not destroyed after sufficiently long action of ion- The Scheme shows possible degradation reactions. izing radiation. The ionizing radiation which im- pregnates the universe is reaching the surface of earth in much reduced intensity, due to the shield of the atmosphere, equivalent to 3 meters of con- crete. Even the most penetrating galactic cosmic rays, which reach the earth in cascades of secondary ionizing radiations are responsible for only small contributions to mutations forming in living organisms. Other ionizing radiations coming from outer space, like gamma bursts, proton beams from events in the Sun and other stars, are almost fully absorbed. Therefore, the contribution of space radiation to the radiation background on earth is Scheme. only similar to the present level supplied by radioactive material on earth. The deciding fact causing The final result can depend on the surrounding, not the inactivation of life on earth but, vice versa, whether oxidative presence of oxygen, or reducing, even some positive effects, is the interaction of or vacuum. In both two last named cases, the final radiation with living matter. Whereas the DNA in product can be nano-sized carbon dust, and such the living species, i.e. in aqueous suspensions, when reaction is called radiation-induced carbonization. damaged slightly by ionizing radiation can be re- Large objects staying for a long time in space paired, the DNA in dry spores is effectively, irre- obtain highest doses of ionizing radiation at the versibly damaged by the very first doses of radia- surface, gradually diminishing towards the inside. tion. The effect is additive, and even low doses are The depth dose can be estimated from the Clark damaging, after accumulation of elementary acts, table. The surface of the object is the most irradi- mainly of hydrogen abstraction, over ages. Repaired ated part and the best known object is the planet of damages to living populations do not accumulate. Mars [7]. Its regolith is not only completely steril- The by-product of low level radiation damage are ized but also relieved from organics. Perhaps part possible mutations, like many other factors in the of organics has been degraded to elementary car- environment. They occur only due to the action on bon, present, if so, as black dust moved with the living organisms, they do not occur when spores

Martian thin CO2-wind. Anyway, chances for de- are irradiated, when irreversible changes take place. tection of organics on the surface of Mars are poor. The soon coming fifth anniversary of the COST Similar conclusions have been drawn by photo- action D27 asks for formulation of conclusions. In- chemists, assuming devastating chemical influence tensive, also experimental investigation of the frag- of deep UV reaching the surface of Mars. Their ar- ment of the action connected with panspermia and gument is poor, because supposed the Martian or- more, i.e. the action of ionizing radiation in the ganics show usually no absorption in UV, but even universe on objects travelling in space, demands in the presence of chromophoric groups the effect revision of some well established opinions. Theoreti- is of low importance, because the depth of penetra- cal considerations as well as experimental simulation is shallow. Therefore, the deciding influence of tions show that these objects are not only sterilized, ionizing radiation is more important. what demands comparatively low doses, but also The low temperature of space on the route of deprived of its homochirality, if any, and eventually moving objects is not a protecting factor, because even freed from organic compounds. Therefore, here radiation-induced reactions proceed with low ac- are examples of defined conclusions: tivation energy and presented chemical effects The very thoroughly investigated Murchison observed at liquid nitrogen temperatures are not meteorite, supposed to originate ca. 4 Giga years RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 33 ago and bringing to the earth samples of organic years it was radiolysed down to inorganic remains. compounds, including amino acids from the begin- Therefore, there should be no hope to find organic ning of the solar system, could not be so old as matter whatsoever on Mars. And really, no traces claimed. Such a long sojourn in space is connected of organics have been found yet. Actual efforts to with the deamination of amino acids and related refine methods of investigation for organic matter loss of homochirality. The ancient origin of pres- look like waste of money. ence of any organic compounds is highly doubtful. The work was supported by the Polish Ministry The lifetime of Murchinson meteorite should be es- of Scientific Research and Information Technol- timated in millions and not milliards (US – billions) ogy and by the European Project COST D27 (Pre- of years. The identity of organic matter found in biotic chemistry and early evolution). hundreds of published papers indicates that this object has been ejected from earth later than 200 References million years ago, that means not earlier than deposites of coal have been formed on earth. Es- [1]. Luisi P.L.: The emergence of life, from chemical origins to synthetic biology. Cambridge University Press, pecially polyaromatics and lignine related com- Cambridge 2006. pounds indicate the origin in large coal deposits, [2]. Zagórski Z.P.: Origins Life Evol. Biosphere, 36, 244-246 covering a lot of earth surface. Specialists in con- (2006). siderations of ejection of meteorites from Mars, [3]. Clark B.C.: Origins Life Evol. Biosphere, 31, 185-197 which have reached Earth agree that ejections from (2001). Earth to Earth are a little bit less probable, but not [4]. Zagórski Z.P.: Postępy Techniki Jądrowej, 46, 42-52 impossible [9]. The matching of location and time (2003), in Polish. of oblique strike of an asteroid on Earth demands [5]. Zagórski Z.P.: Sterylizacja radiacyjna (Radiation ster- more analysis and studies. ilization). 2nd ed. Instytut Chemii i Techniki Jądrowej, The second, but not last conclusion refers to Warszawa 2007 (in Polish). [6]. Zagórski Z.P.: Radiat. Phys. Chem., 66, 329-334 (2003). Mars, an object lasting under the ionizing radiation [7]. Zagórski Z.P.: Nukleonika, 50, Suppl.2, S59-S63 for Giga years. Assuming that 4 Giga years or so (2005). ago, Mars had oceans of water, the organic soup [8]. Zagórski Z.P.: Indian J. Rad. Res., 3, 89-93 (2006). was formed, not concluding into creation of life. If [9]. Artemieva N. (Institute for Dynamics of Geospheres, water has evaporated and disappeared, the organic RAS, Moscow, Russia): private communication matter should remain, but in the next millions of (21.11.2006).

MODIFIED BENTONITE FILLERS IN POLYMER COMPOSITES Zbigniew Zimek, Grażyna Przybytniak, Andrzej Nowicki, Krzysztof Mirkowski

In our previous work, maleic anhydride (MA) was samples of montmorillonite were obtained from grafted on the inorganic surface of bentonites con- Wrocław University of Technology. taining montmorillonite (MMT) [1]. The main con- Maleic anhydride was absorbed on bentonites clusion driven from the studies was that maleic an- from 10% w/w solution in acetone for half an hour. hydride reacts via the anhydride group with active The solids were washed with acetone (to remove ionic sites of bentonite forming a salt-like compound. excess of anhydride) and dried for 6 h under low Irradiation with electron beam leads to the break- pressure at 30oC. The samples of MMT/MA were age of double bond in maleic anhydride and to the irradiated with 10 MeV electron beam. The overall production of new organic phases. The range of ion- doses were 26, 52, 78 or 104 kGy. All the samples, izing radiation doses was found to optimize filler before testing and mixing with a polymer, were production [2,3]. ground and sieved in order to select fraction of par- In the recent work, we have used the obtained ticles below 70 μm, used for further processing. fillers to prepare composites with polypropylene (PP) The composites of polypropylene and modified and compare properties of the pure polymer and bentonites were prepared in a Brabender mixer in polypropylene composites with bentonite modified the temperature range of 185-210oC. After mixing, ammonium salts. the samples were pressed in the form of foils of a Isotactic polypropylene (iPP) Malen P J601 was thickness of about 0.35 mm. purchased from Basell Orlen Polyolefines. Unmodi- For scanning electron microscopy (SEM), the fied bentonite Tixogel VP (TVP) containing >90% foils were frozen in liquid N2 and broken. SEM montmorillonite in the form of sodium salt was photos at different magnifications were obtained obtained from Riedel-deHaen. Two kinds of un- using a Zeiss SEM microscope after gold deposi- modified Polish bentonites were received from tion. Mine “Zebiec”, Starachowice: “Special”, containing Structure of modified montmorillonite was more than 70% of pure montmorillonite and type studied by the WAXD (wide-angle X-ray diffrac- “SW”, containing ca. 50% of pure montmorillonite. tion) method using a URD-6 X-ray diffractometer Samples of Polish bentonites “Special” modified with graphite monochromatized Cu-Kα radiation. with ammonium salts (benzyldodecyldimethyl and SEM photos were obtained with a Jena DSM 942 didecyldimethyl bromides) were obtained from (Germany) scanning electron microscope with dif- Rzeszów University of Technology and extra pure ferent magnification. 34 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES The mechanical properties: tensile strength, a periodic distance. Diffractogram (b) of modified yield stress and elongation at break were tested montmorillonite reveals a new peak at the position using a universal testing machine Instron 5565. All 2θ=21o what has to be assigned to the changes in the measurements were performed at ambient tem- the structure in (002) plane and might suggest that perature according to PN/ISO-527 standard. maleic anhydride is attached to the surface of mont- Infrared (IR) measurements were conducted on morillonite layers. a Bruker FTIR spectrometer in single reflection IR spectra recorded for montmorillonite, ma- mode (ATR), using a Si prism. leic andydride modified montmorillonite before and WAXD diffractograms of pristine and modified after irradiation with a dose of 75 kGy, do not show with maleic anhydride bentonite “Special” are shown details of bond type between montmorillonite and in Fig.1. The results clearly confirm the presence maleic anhydride forming before and after irradia- of montmorillonite in bentonites which is charac- tion with electron beam (Fig.2). This is probably terized by specific reflection to the planes (001) and due to low concentration of organic compounds in the modified montmorillonite. Only the presence of maleic anhydride is visible in the spectra of modi-

Fig.1. WAXD diffractograms of: (a) bentonite “Special”, as purchased, (b) bentonite “Special” after absorption of maleic anhydride and irradiation with a dose of 26 kGy.

(002). The basal spacing of the montmorillonite is Fig.2. FTIR (Fourier-transform infrared) spectra of: (a) un- 1.55 nm calculated from the peak on diffractogram modified bentonite “Special”, (b) bentonite “Special” o a (position 2θ=5.7 ). Upon modification with ma- modified with maleic anhydride, (c) bentonite “Spe- leic anhydride, a diffraction peak of bentonite is cial” modified with maleic anhydride and irradiated almost at the same place (2θ=5.6o, d=1.58 nm) with a dose of 78 kGy. (Fig.1, diffractogram b) proving that the spacing between layers is not changed significantly and that fied montmorillonite as a band in 1600 cm–1 region the anhydride is not intercalated between intergallery (C=O band of carbonyl compound). layers of montmorillonite. However, intensity of the SEM photos at different scale levels of polypro- lines becomes lower what must result from greater pylene foils containing 2.9 wt% of “Special” mont- disorder of the layered silicates, while maintaining morillonite modified with maleic anhydride and

Fig.3. SEM images of polypropylene filled with bentonite “Special” modified by didecyldimethylammonium bromide (cross-section of thin foil) at different magnifications. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 35

Fig.4. SEM images of polypropylene filled with bentonite “Special” modified by maleic anhydride and irradiated with a dose of 26 kGy (cross-section of thin foil) at different magnifications. irradiated with a dose of 50 kGy (Fig.3) were com- excellent homogeneity of the obtained samples. No pared with similar photos of foil obtained from mineral parts of dimensions above 500 nm are vis- polypropylene containing 2.9 wt% of “Special” mont- ible. Magnification is too low to confirm exfolia- morillonite modified with didecyldimethylammo- tion of montmorillonite, but on the basis of visible nium bromide (Fig.4). Photos of the selected com- structure of the polymeric mixture it is very prob- posite confirm homogeneity of material obtained able. Presented photos confirm that the laboratory from polypropylene and montmorillonite modified method used by us for the preparation of compos- by maleic anhydride, and subsequently irradiated. ite samples was correct. At the micrometer level, images indicate that ag- Mechanical properties of the original polypro- gregates of a few micrometers are statistically dis- pylene and composites of montmorillonite based persed in the matrix. On the basis of the consistuents on polypropylene are collected in Table. Presented corresponding to 5 μm one can conclude that there data are the average values calculated from three are particles strongly interacting with the matrix. independent measurements. Since the addition to Their structure is indistinct, borders between com- polymeric matrix more than 5% w/w of the filler ponents are blur, it seems that fragments of fillers causes a significant growth of viscosity in melted are separated by a polymer. Such a picture indicates state, the experiments were performed at a concen- on apparent compatibility between fillers and the tration of ca. 2.9% w/w of dispersed phase. Samples matrix. Some tactoids that contain montmorillonite of polypropylene mixed with unmodified bentonite, layers are not parallel thus, disorder of clay signifi- except for one composite from a very fine, labora- cantly increases during mixing of the polymer with tory purified sample of montmorillonite, showed fillers. SEM photos of polypropylene mixed with insufficient mechanical properties: they were very ammonium salt modified montmorillonite show fragile and cracked at low elongation. One of the

Table. Mechanical properties of polypropylenes filled with modified bentonites. 36 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES representative examples of these results is shown irradiation with electron beam shows that particles in Table. obtained in this process are good fillers for the pro- In all the composites the yield stress is unaffected duction of composites on the basis of polypropy- or slightly increased in comparison with the pristine lene. Some properties of final materials are better polymer, while the tensile strength decreases for than those of initial polypropylene, especially for all the studied components. The elongation at break composites obtained from modified and irradiated drops for Tixogel VP and “SW” composites from montmorillonite with low impurity level. 790 to 686% and 549%, respectively, and increases Ionizing radiation facilitates compatibilization to 808% when clay loading is bentonite “Special”. of MMT/MA fillers with the matrix due to intro- Generally speaking, the presence of the montmo- duction of organophilic bridges between dispersed rillonite, even upon modification, does not have a minerals and polypropylene. However, anhydrides large effect on the mechanical properties of the are not able to intercalate significantly into inter- composites, but the role of purity of montmorillo- layer galleries increasing d-spacing. The proposed nite is visible. Unexpectedly, poor results are ob- processing might reduce the contribution of maleic tained for composites of polypropylene and mont- anhydride and inhibit the degradation associated morillonite “Special” modified with two types of with the presence of larger amount of anhydride. ammonium salt, although the samples observed in This work was supported by the State Com- SEM have shown excellent dispersion of the fillers mittee for Scientific Research (KBN) – grant in the polymer matrix. PBZ-KBN-095/T08/2003. The best mechanical properties exhibit polypropylene filled with extra fine, laboratory prepared References montmorillonite modified with maleic anhydride and irradiated; quality of composites containing (in [1]. Zimek Z., Przybytniak G., Nowicki A., Mirkowski K.: Modification of montmorillonite fillers by ionizing order) “Special”, Tixogel VP, and “SW” bentonites radiation. In: INCT Annual Report 2005. Institute of are lower. The melt transition of polypropylene is o Nuclear Chemistry and Technology, Warszawa 2006, 162 C and increases upon dispersion of montmo- pp. 34-35. rillonite in the matrix. [2]. Polish Patent Application P. 379779 (2006). Modification of the different types of bento- [3]. Filho F.G.R., Jeferson T., Melo A., Rabello M.S., Silva nite by absorption of maleic anhydride, followed by M.L.: Polym. Degrad. Stabil., 89, 383-392 (2005).

POLY(SILOXANEURETHANE) UREAS BASED ON ALIPHATIC AND AROMATIC DIISOCYANATES MODIFIED BY IONIZING RADIATION Ewa M. Kornacka, Grażyna Przybytniak, Janusz Kozakiewicz1/, Jarosław Przybylski1/ 1/ Industrial Chemistry Research Institute, Warszawa, Poland Ionizing radiation is often used to sterilize medical seems that during irradiation urethane-based prod- devices made from polymeric materials. However, ucts can undergo chain scission at urethane hard except lowering the level of bioburden, irradiation regions as well as at siloxane segments. The charac- affects physicochemical and mechanical properties ter of isocyanates used for polymerization, propor- of polymers leading usually to degradation or/and tions between NCO and OH groups and the length crosslinking. A proportion between both processes of siloxane chains determine resistance of materials determines final effect. Among products that are towards ionizing radiation. Data obtained from the supposed to be sterilized are polyurethanes used as recent investigations show that radical processes in scaffolds for culturing of biological (e.g. human) aliphatic poly(siloxaneurethane) ureas (PSURURs) cells for tissue engineering purposes. Recently, seg- proceed predominantly in siloxane segments [2]. mented polyurethanes have been studied exten- Nevertheless participation of urethane domains also sively due to their biocompatibility and excellent must have an influence on direction and yield of mechanical properties [1]. One of the interesting radiation-induced reactions. Their contribution is examples of such a material is polyurethane con- determined by NCO/OH ratio as the excess of NCO taining siloxane soft segments that provide hydro- groups is converted to urea bonds in a moisture-cur- lytic stability, elasticity and chemical inertness. It ing processes. The length of isocyanate sequences

Scheme. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 37 in hard segments increases with concentration of free isocyanate units in a prepolymer [3]. Hard and soft segments create two distinct microphases (or in some cases even macrophases). On the other hand, it is generally accepted that urethane or urea groups form extensive hydrogen bonding systems. Yilgör et al. found that the strength of hydrogen bonds between urethanes is much weaker than between urea links due to highly polar character of the later group [4]. Thus NCO/OH ratio changes properties of urethane based polymers and is supposed to modify their radiation resistance. On the other hand, quantum mechanical calculations indicated the absence of interaction between silicones and urea groups [5]. The polyurethane based materials were prepared from methylene di(p-phenyl isocyanate) or isophorone diisocyanate, oligosiloxanediol and water used as a chain-extending agent (Scheme). The synthesis was performed with the prepolymer method [1]. Samples of structures shown in Table were investigated by electron paramagnetic resonance (EPR) after exposure to a dose of 6 kGy in a 60Co gamma source (Issledovatel) under cryogenic conditions, i.e. at 77 K, since free radicals appeared to be unstable at ambient temperature. EPR measurements were performed on an X-band Bruker ESP 300 spectrometer. Spectra Fig.1. EPR spectra of listed in Table PSURURs irradiated were recorded directly upon irradiation of the to a dose of 6 kGy at 77 K. samples and after their annealing to indicated temperatures. associated with the occurrence of methylene radical, ≡ Samples of PSURURs investigated by gas chro- SiCH2· that was identified also in oligosiloxanediols matography were irradiated with a 10 MeV elec- applied as substrates in PSURUR synthesis [2]. tron beam generated in a linear electron accelera- One representative EPR spectrum recorded for tor Elektronika 10/10 to indicated doses. The total oligosiloxanediol of n=10 is shown in Fig.2(a). The doses were obtained by multipass exposure (30 kGy proportion 1:2:1 among lines characteristic of in- per one pass). teraction of two equivalent protons is perturbed The yield of hydrogen in the gas phase vola- due to sharp singlet situated in the middle of the tilize from irradiated at room temperature poly- spectrum that has been attributed to the silicon mers was determined with a gas chromatograph radical ≡Si·. Thus, the methylene radical is pro- Shimadzu-14B. The thermoconductivity method duced by hydrogen abstraction whereas the sili- was used for detection. cone one by losing the methyl group. An evidence for Si-C bond scission might be also found in some Table. Composition of PSURUR. spectra detected upon irradiation. Enlargement of the scale leads to the disclosure of quartet characteristic of the methyl radical, A(3H)=2.3 mT. The gaseous product decays just at 77 K, therefore only traces of CH3· were detected in some samples (Fig.2(c)). The efficiency of methylene radical production in siloxane segments was determined on the basis of analysis high field peak indicated in Fig.1 with an arrow in all experimental spectra. This external line does not represent superposition of signals but exclusively a side peak of the triplet. Depending on the structure of PSURURs, either The EPR spectra recorded under cryogenic spectrum shown in Fig.2(a) or a signal of its ana- conditions for PSURURs of structures presented logue for n=30 were used for quantitative analysis. in Table are shown in Fig.1. Relative concentration of methylene radicals de-

A triplet of hyperfine splitting near 2.2 mT is pends on –[Si(CH3)2O]n– size; for n=30 the contri- the dominant component of all experimental sig- bution is significantly higher than for n=10, both in nals. A centerfield absorption varies and depends aromatic and aliphatic urethanes (Fig.3). Introduc- predominantly on the proportions between NCO tion of aromatic rings determines also relative con- and OH groups and a length of –[Si(CH3)2O]n– centration of siloxane radicals. Aliphatic PSURURs units. Previous studies revealed that the triplet is show a smaller relative contribution of paramagnetic 38 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES

≡ Fig.3. Relative concentrations of methylene radical SiCH·2 determined on the basis of analysis of EPR signals (see text). quence 1>3>4, for NCO/OH=2, 2.5, 3, respectively. When the ratio NCO/OH increases, unpaired spins more frequently are localized at urethane and urea bonds. Character of the intermediates is unknown as the EPR spectra that could be assigned to such radicals take the shape of unresolved singlet (Fig.2(b)). The signal represents radicals of unpaired spin localized at heteroatoms. Lost of hydrogen atoms is expected in both segments, hard and soft. Yields of the product measured by the gas chromatography method are shown in Fig.2. EPR spectrum of (a) oligosiloxanediol, n=10, irra- Fig.4. Emission of H in aliphatic PSURURs, 2 and diated at 77 K; (b) signal obtained by subtraction of 2 spectrum (5) from (3) presented in Fig.1 assigned to 6, significantly prevails over that found for aromatic radicals that unpaired spins are localized at hetero- polyurethanes. The results directly indicate that atoms; (c) experimental evidence for production of deposited radiation energy initiates radical pro- CH·3 . cesses more effectively if polymeric chains comprise isophorone ring instead of phenyl groups. species in siloxane units than aromatic ones since The yield of hydrogen abstraction for aromatic energy deposited in soft domains and aliphatic re- PSURURs is above three times smaller than for gions of hard segments rather induces radicals than their aliphatic analogues as can be concluded is transformed into heat, as it takes place in aromatic from the comparison of G(1) and G(2), as well as hard segments. Thus, comparison of the results ob- G(5) and G(6) values. Dissipation of radiation en- tained for samples 1-2 and 5-6 (Fig.3) leads to the ergy by aromatic rings involves protection against conclusion that the ability to dissipation of ioniz- radical processes not only in urethane segments but ing radiation energy by phenyl groups diminishes also in siloxane domains. The G values of aromatic the population of radicals. PSURUR are comprised in the narrow range from Distribution of radical centers varies depending 0.20 to 0.36/100 eV. It seems that the influence of on NCO/OH proportions; the amount of methylene NCO/OH ratio plays an insignificant role in hydro- radicals for n=10 decreases in the following se- gen release.

Fig.4. Radiation yield of hydrogen determined by gas chromatography (A) and consumption of oxygen resulting from radical processes (B). RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 39

Simultaneously, with radiation yield of H2, the polyurethanes prepared from isophorene cyanate. consumption of oxygen from the space above the To some extent the protection effect spreads over sample inserted in the vial was estimated (Fig.4(b)). the whole polymeric material. Proportion between Considerable scattering of results makes detailed urethane and urea groups do not influence hy- analysis impossible. However, all G(O2) values for drogen abstraction processes that proceed only in aliphatic PSURURs are in a similar range as G(H2) hydrocarbon regions or in methyl groups of siloxane data found for aromatic analogues. Thus, unex- units. It seems that aliphatic PSURURs have a ten- pectedly, O2 consumption in aliphatic PSURURs dency to efficient crosslinking. is much lower than the hydrogen yield. Such a dis- proportion between results might be tentatively References interpreted as a result of very efficient recombi- [1]. Kozakiewicz J.: Advances in moisture-curable siloxane- nation between carbon centered radicals leading -urethane polymers. In: Advances in urethane science to crosslinking. It seems that in aliphatic PSURURs and technology. Eds. K.C. Frisch, D. Klempner. Lan- the yield of oxidation processes is very limited, caster-Basel: Technomic Publ. Co. Inc., 2000, vol. 14, however this suggestion needs further investiga- pp. 97-149. tions. [2]. Kornacka E.M., Kozakiewicz J., Legocka I., Przybylski In aromatic PSURURs, the concentration of J., Przybytniak G., Sadło J.: Polym. Degrad. Stabil., 91, 82 (2006). radicals situated at hard segments is lower than in [3]. Kwiatkowski R., Włochowicz A., Kozakiewicz J., Przy- aliphatic ones due to efficient dissipation of ioniz- bylski J.: Fibres Text. East. Eur., 11, 5, 107 (2003). ing radiation energy. Therefore, the relative con- [4]. Yilgör E., Yilgör I.: Polymer, 42, 7953 (2001). centration of methylene radicals is higher and the [5]. Yilgör E., Burgaz E., Yurtsever E., Yilgör I.: Polymer, yield of dehydrogenation is much smaller than in 41, 849 (2000).

RADIATION EFFECTS IN POLYPROPYLENE/POLYSTYRENE BLENDS Wojciech Głuszewski, Zbigniew P. Zagórski

Several applications of polymers demand resistance cation of radiolysis extent, but in the chosen sys- towards ionizing radiation, e.g. for disposable tem of polypropylene/polystyrene, also formations medical devices sterilized by radiation, for appli- of methane and carbon monoxide (after oxidative cations in nuclear industry and in nuclear reactors, experiments) in the function of dose and compo- also for outer space localizations etc. Depending sition were studied, as well as kinetics of oxygen on the nature and extent of radiation damage, sol- consumption in the presence of air. Further stages ution of the problem consists in application of ad- of oxidative degradation of polypropylene were ditives, produced for general application of poly- studied by diffuse reflection spectrophotometry mers. They work often very well also as a protection (DRS) [4,5]. from radiation damage, especially when they con- Introduction of small molecule additives into tain aromatic groups which act as energy sink via polymer composition is simple, but preparation of energy transfer mechanism. Some additives are not aliphatic/aromatic polymer blends is more com- acceptable, especially in medical applications and plicated and demanded new procedures. The case one of the aims of this investigation was to answer of polypropylene/polystyrene, i.e. of a semicrystal- a question if an aromatic polymer as an additive line, nonpolar thermoplastic polymer with a polar, can limit the extent of radiation damage. However, amorphous polymer is known to be immiscible. the main topic of the project is basic research on Mechanical mixing proved formation of unsatis- classic aliphatic/aromatic energy transfer, this time factory blend from the point of view of energy extended from small molecules to polymers. transfer, but other approaches resulted in a proper Freeman [1] first has found that in irradiated mixture. simple system of cyclohexane/benzene, radiolytic Sample “A” was prepared by mixing commercial hydrogen was not formed in proportion to the com- polymers: polypropylene Malen P J-400Z*1632/01 position, i.e. benzene was reducing the hydrogen from Basell-Orlen and polystyrene from Owispol- yield to a higher degree than was expected. The -Dwory. The proportions were: 0, 10, 25, 50, 75, effect was investigated later in several laboratories 100% of polystyrene. In spite of the most thorough and was called “deviation from the mixture law”. blending injection and pressing in a mechanical It was investigated also in frozen systems, gaining way, the surface area of contact between both poly- interesting facts connected with the solid crystal- mers was assumed not to be as most favourable line state. Deviation from the mixture law was never for energy transfer and, therefore, two other pro- investigated systematically in the field of radiation cedures of sample preparation have been developed. chemistry of polymers. Albano et al. investigated Sample “B” was prepared from virgin polypropy- the polypropylene/polystyrene (PP/PS) 20/80% lene (F 401) in the shape of powder, collected from blends, at low doses [2] and high doses [3] (70-400 the Orlen-Olefins production line, without addi- kGy) with resulting full protection of polypropylene, tives, next impregnated with polystyrene dissolved to be expected. in a styrene monomer (fresh distilled, free from As in the case of cyclohexane/benzene system, stabilizers) in proportion of polypropylene/poly- the hydrogen production was used as a basic indi- styrene as above. Afterward, the styrene was removed 40 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES by evaporation during gentle heating. Sample “C” was prepared by soaking polypropylene powder with stabilizer – free styrene and polymerization/grafting in the gamma field from cobalt-60 at a dose rate of 1.5 kGy/h. All added styrene has polymerized totally, but the adjusted percentage was checked gravimetrically as in sample ”B”. Polymerization grafting of styrene proceeds in a chain mechanism in the presence of polypropylene, with high radiation yield (12 000 effects/100 eV), due to the gen- erous supply of free radicals by irradiated polypropylene. Styrene alone (the same batch), gamma- or electron beam irradiated, polymerizes very slowly and the progress of reaction can be followed by the increase of viscosity only. All proportions of both polymers were checked by weighing the final prepa- Fig.2. Radiation yield of methane in the function of polypropylene/polystyrene composition. A curve does not rations. All irradiations, except gamma exposure start at the same point as curves B and C, because a mentioned above, were done with electron linacs, commercial polypropylene containing already addi- “Elektronika” 10/10 (10 MeV, 9 kW) or “LAE 13/9” tives was in this case used. Curves B and C start from (up to 13 MeV, 9 kW straight beam, or 6 kW bent virgin polypropylene. Dose – 25-100 kGy. beam of improved monoenergetic spectrum) [6]. Determination of hydrogen, methane, and second- tion against radiolysis of polypropylene by poly- ary product carbon monoxide as well as of oxygen styrene (Figs.1 and 2). Mechanical methods can- consumption were done by gas chromatography not secure sufficiently large interphase for energy using a Shimadzu GC 2040 and GC 2010, molecu- transfer. Classical case of previously investigated, lar sieves 5A, in carrier gas argon. protection phenomena, i.e. benzene/cyclohexane The applied methods of analysis and investiga- was effective only in liquid state or frozen from the tion, i.e. gas chromatography together with diffuse gas phase. Application of grafting of styrene on reflection spectrophotometry have shown to be polypropylene, by two slightly different procedures effective in recognition of protection effects in ali- resulted in a proper response to expected protec- phatic/aromatic blends of polymers. Key interme- tion effect. It extended, according to a vague esti- diates and final products of radiolysis have been mate to be a distance of 9-12 mers of polypropy- determined, i.e. hydrogen, methane and carbon lene. Thus, the classical case of radiation protection monoxide. effect in the benzene/cyclohexane system has been extended into the field of polymers. The solid state system benzene/cyclohexane shows energy transfer only if it is crystallized from the gas phase to secure close contact of constituents. In the case of polymeric system of polypropylene/polystyrene, the mechanical mixing is not sufficient and the effect of energy transfer occurs only in the case of impregnated and grafted samples. Chains of both polymers, aliphatic and aromatic must have sufficient area of contact- ing, or exhibit low distance sites for energy transfer to the aromatic structure, which is the sink of energy. This investigation was supported by a grant No. 0989/T08/2005/28 from the Polish Ministry of Edu- cation and Science.

Fig.1. Radiation yield of hydrogen in the function of References polypropylene/polystyrene composition. A curve does not start at the same point as curves B and C, [1]. Freeman G.R.: J. Chem. Phys., 33, 71 (1960). because a commercial polypropylene containing al- [2]. Albano C., Reyes J., Ichazo M., Gonzáles J., Hernán- ready additives was in this case used. Curves B and dez M., Rodrígues M.: Polym. Degrad. Stabil., 80, 251 C start from virgin polypropylene. Dose – 25-100 (2003). kGy. [3]. Albano C., Reyes J., Ichazo M.N., González J., Rodrí- guez M.: Nucl. Instrum. Meth. Phys. Res. B, 208, 485 For the preparation of blends and mixtures of (2003). aliphatic/aromatic polymers three methods have [4]. Zagórski Z.P.: Int. J. Polimer. Mater., 52, 323 (2003). been proposed. Conventional blending of polypro- [5]. Zagórski Z.P.: Rafalski A.: Radiat. Phys. Chem., 48, pylene and polystyrene in Brabender and/or by 595 (1996). injection does not give desired results of protec- [6]. Zagórski Z.P.: Radiat. Phys. Chem., 22, 409 (1983). RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 41 APPLICATION OF GAS CHROMATOGRAPHY TO STUDY POSTIRRADIATION PROCESSES OF POLYMER OXIDATION Wojciech Głuszewski, Zbigniew P. Zagórski

Oxidation of polymers in the atmospheric envi- inhomogeneity (in comparison to scanned beam) ronment is responsible for the degradation of prop- of the radiation field is neutralized by a special ala- erties. These processes are initiated by increased nine – powder dosimetry, with the diffuse reflec- temperature and/or by UV light. Conventional pre- tion spectrophotometry (DRS) measuring method vention of these undesired phenomena in appli- [3]. The method is using the fact that the free radi- cation of commercial polymers is the addition of cal derived from alanine shows an optical absorp- photostabilizers and antioxidants. Radiation pro- tion spectrum. The use of straight electron beam is cessing, e.g. radiation sterilization by electron beam similar to its use in the first versions of our pulse or gamma radiation causes additional oxidation of radiolysis system. Application of higher, kilogray polymers already during irradiation (polyethylene doses proved to be more convenient by conven- – PE, polypropylene – PP and many others), as well tional, technological irradiation on a conveyor, by as oxidation by oxygen after irradiation, by a chain mechanism, in particular in the case of polypropylene. The last mentioned reaction prevents the application of common polypropylene for production of medical objects to be sterilized by ionizing radiation. Conventional additives mentioned above do not help in full extent, therefore additional components are looked for, in particular among specific aromatic compounds. Observation of dynamics of oxidation processes in polymers is comfortable by the gas chromatographic method [1]. One record secures determination of abstracted hydrogen, carbon monoxide and methane (Fig.1). The present report shows also the advantages of oxygen determination, in particular the loss of oxygen, consumed in oxidation of a

Fig.2. Radiation yields of H2, O2 and CO in the function of postirradiation time (polypropylene).

the bent beam of electrons. The septa are covered with a thick hood made of lead in this case. Experi- ment with an empty vial did not show the presence of hydrogen, what has demonstrated no significant irradiation of septa made from rubber. This technique was applied for high doses only; application of this mode for low doses of radiation yields erratic doses, because of the structure of the beam. That limitation has been recognized already before the construction of the machine and cannot Fig.1. Chromatographic retention (column packed with be avoided due to the pulsing regime of the accel- molecular sieves 5A): H , O , N , CO and CH . 2 2 2 4 erator action and scanning frequency of 5 Hz. Lower polymer. Therefore, the determination of oxidation doses were applied in a 60Co gamma source, with rate is easily measured, as well as the formation of due analysis of differences of radiation quality in one of the oxidation products (Fig.2). comparison to the electron beam, if any. The integration of irradiation and gas chroma- A gas chromatograph Shimadzu GC 2014 has tography determination, for the case of solids in- been installed in an air conditioned and thermo- volved a special approach to the specific technique statted (23.5oC) room. The column was 1 m long of electron beam irradiation of cells closed with packed with molecular sieves 5A, the detector was septa, and consideration of different solubility of thermo-conductivity (TCD-2014) element by Shi- hydrogen in a variety of polymers, resulted in new madzu. The carrier gas was argon (99.99%). Op- procedures. Three milliliter glass vials, closed by erations were done with syringes (volume – 10, 25 septa, are filled only in one third with a sample and 500 μL). The system was working at 220oC, on and only this part is irradiated with a straight beam the column kept at 40oC and the detector at 120oC. of electrons from the linear electron accelerator The rate of flow of carrier gas was 10 mL/min. LAE 13/9, leaving the rubber septa intact. This Parameters of separations are as follows: technique allows the application of small doses of -H2: retention time – tR(H2)=1.48 min, coefficient radiation energy, by triggering single pulses [2]. of oxygen – R(H2-O2)=2.7, coefficient of peak The use of straight beam of electrons has cre- symmetry – As(H2)=1.1, number of theoretical ≈ ated some problems with dosimetry. The increased shelves – N(H2) 86; 42 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES

-O2: retention time – tR(O2)=2.77 min, coefficient of hydrogen – R(O2-H2)=2.5, coefficient of nitrogen – R(O2-N2)=3.7, coefficient of peak symmetry – As(O2)=1.2, number of theoretical shelves ≈ – N(O2) 488.

Fig.5. Relation between polystyrene concentration in polypropylene/polystyrene blends and radiation yield of postirradiation oxidation processes (postirradiation time: 24-108 h).

Fig.3. Relation between naphtalene concentration in The gas chromatographic method has been polypropylene and radiation yield of oxygen. applied also in the study of postirradiation oxidation processes of ageing polymers (Fig.5). The loss The described method has proved its efficiency of oxygen helped to trace the oxidation process, and in the description of protective action of naphtha- the parallel production of hydrogen has helped to lene towards degradation of polypropylene [4] estimate the participation of aromatic compounds (Fig.3). That method helped also to show that the in the process of blocking peroxide groups and rate of radiation-induced oxidation of polypropy- crosslinking with the polypropylene chain. These lene at low temperature (under liquid nitrogen) is processes interrupt the cycle of polymer degrada- higher than at ambient temperature (Fig.4). That tion and can help in branching of chains, thus im- is the first exception of the rule of rather lowered proving properties of the material. Analysis of the radiation yields of radiation-induced reactions at influence of polystyrene (PS) content on the oxi- cryogenic temperatures. Further investigations in dation process shows that the protection effect is higher in the case of samples undergoing a longer ageing process. One can explain that by the improved contact of aromatics with the polypropylene matrix. These few examples have shown that a simple and sensitive at the same time analytical method helps to investigate not only radiation oxidation phenomena but also photo- and thermooxidation. The investigation was supported by a grant No. 0989/T08/2005/28 from the Polish Ministry of Edu- cation and Science. References [1]. Zagórski Z.P., Głuszewski W.: Application of gas chromatography to the investigations on polypropylene radiolysis. In: INCT Annual Report 2005. Institute of Nuclear Chemistry and Technology, Warszawa 2006, Fig.4. Relation between polystyrene concentration in p. 42 polypropylene/polystyrene blends and radiation yield [2]. Głuszewski W, Zagórski Z.P.: Tworzywa Sztuczne i Che- of oxygen in temperature: -196oC, z +22oC. mia, 3 (Suppl.), 28 (2006), in Polish. [3]. Zagórski, Z.P.: Int. J. Polym. Mater., 52, 323 (2003). this fragment of radiation chemistry will show to [4]. Głuszewski W., Zagórski Z.P.: Radiation effects on what extent physical conditions in the system are PP/PS blends as model of aromatic protection effects. responsible for that exceptional behaviour. Nucl. Instrum. Meth. Phys. Res. B, submitted.

CHEMICAL-RADIATION DEGRADATION OF NATURAL POLYSACCHARIDES (CHITOSAN) Andrzej G. Chmielewski, Wojciech Migdał, Urszula Gryczka, Wojciech Starosta

Naturally occurring polysaccharides have a wide Chitin is second, next to cellulose, most abundant range of applications in agriculture, medicine and polysaccharide on the earth. It is present in crusta- cosmetics, food industry and water waste treatment. cean shells, insect exoskeletons and fungal cell walls. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 43 Chitosan, (1-4)-2-amino-2-deoxy-β-D-glucan, is deacetylated derivative of chitin. Commercially available chitosan possesses high molecular weight and low solubility in most solvents what limits its applications. The solubility of chitosan can be improved by decreasing its molecular weight [1]. Water soluble chitosan can be prepared through oxidative degradation with hydrogen peroxide in concentration higher than 1 M [2]. Low molecular weight chitosan can be prepared by chemical, radiation or enzymatic degradation of a high molecular weight polymer. Radiation is one of the most popular tools for modification of polysaccharides. For decreasing of the polymerization degree, com- Fig.2. Radiation and chemical-radiation degradation of bined chemical-radiation methods can also be used. chitosan. Chitosan oligomers were obtained through irradia- η a tion of chitosan dissolved in acetic acid [3]. Another [ ] = K·Mw η popular method is also chemical degradation with where: [ ] – intrinsic viscosity; Mw – average hydrogen peroxide which even in small quantity molecular weight; K and a – constants for chitosan reduces gradually molecular weight of chitosan [2]. independent of molecular weights, K=1,81·10–3 Treating plants with oligochitosan increase their cm3/g and a=0.93 determined in 0.1 M acetic acid disease resistance and also plant growth is stimu- and 0.2 M sodium chloride solution at a tempera- lated. Degraded polysaccharides such as alginate, ture of 25oC [9]. Results of vicometric measure- chitosan or carrageenan can increase tea, carrot or ment of chitosan modified with ionizing radiation cabbage productivity by 15 to 40% [4]. Chitosan ir- are shown in Fig.1. radiated with 70-150 kGy strongly affect the growth Results shown in Fig.2 indicate that irradiation of wheat and rice plant and reduces damages caused of a dry powder of chitosan lead to the reduction by vanadium. [5]. Alginate degraded with radiation of molecular weight. The Mw decreased remark- at concentration 20-50 ppm promotes the growth ably with increasing dose up to 200 kGy. For higher of rice seedlings, at a concentration of 100 ppm it doses, there was no significant change in molecu- causes an increase of peanut shoots by about 60% lar weight. Hydrogen peroxide caused breaking of compared to control [6]. Foliar application of 1,4-β-D-glucoside bonds, used at small concentra- chitosan on pepper plants reduces their transpira- tion caused a rapid decrease of molecular weight. tion and water use and the biomass-to-water ratio Increasing concentration or reaction time did not is significantly better in the treated plants compared affect the further decrease of polymerization de- to the control plants [7]. Chitosan can also be used gree. Chitosan degraded with the chemical-radia- in plant protection from diseases because it is a tion method attained 95% mass reduction. Using strong antimicrobial agent [8]. hydrogen peroxide at the first stage of degradation The goal of this work was to use radiation for the required doses of radiation can be decreased polysaccharide structure modification. Depolymer- what is much more appropriate from the economi- ization of chitosan can be carried out by radiation cal point of view. or oxidative degradation with hydrogen peroxide Figure 3 shows the X-ray diffraction patterns of initial chitosan and modified chitosan. Initial chitosan and after radiation exhibited two characteristic peaks at 2θ=8.9o and 2θ=20.2o. There is no change in intensity of the peaks. Radiation degradation did not destroy crystal structure of chitosan.

Fig.1. Results of vicometric measurement of chitosan modified with ionizing radiation. combined with irradiation with electron beam. Efficiency of degradation methods was verified by Fig.3. X-ray diffraction patterns of (a) initial chitosan, (b) viscometric measurements using an Ubbelohde chitosan after radiation degradation with a dose of capillary viscometer k=0.01073. Average molecu- 250 kGy and (c) chitosan after chemical-radiation lar weights were calculated from the equation: degradation. 44 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES

For chitosan after chemical-radiation degradation, [4]. Kume T., Nagasawa N., Yoshii F.: Radiat. Phys. Chem., the first peak is not observed and the peak at 63, 625-627 (2002). 2θ=20.2o is much less intensive. The results show [5]. Tham L.X., Nagasawa N., Matsuhashi S., Ishioka N.S., that chemical-radiation degradation of chitosan Ito T., Kume T.: Radiat. Phys. Chem., 61, 171-175 caused destruction of the crystal structure. (2001). [6]. Hien Q.N., Nagasawa N., Tham L.X., Yoshii F., Dang References V.H., Mitomo H., Makuuchi K., Kume T.: Radiat. Phys. Chem., 59, 97-101 (2000). [1]. Mao S., Shuai X., Unger F., Simon M., Bi D., Kissel T.: [7]. Bittelli M., Flury M., Cambell G.S., Nichols E.J.: Agric. Int. J. Pharm., 281, 45-54 (2004). For. Meteorol., 107, 167-175 (2001). [2]. Tian F., Liu Y., Hu K., Zaho B.: Carbohydr. Polym., [8]. Zheng L.Y., Zhu J.F.: Carbohydr. Polym., 54, 527-530 57, 31-37 (2004). (2003). [3]. Choi W.S., Ahn K.J., Lee D.W., Byun M.W., Park H.J.: [9]. Roberts G.A.F., Domszy J.G.: Int. J. Biol. Macromol., Polym. Degrad. Stabil., 78, 533-538 (2002). 4, 374-377 (1982).

DSC STUDIES OF GAMMA IRRADIATION EFFECT ON INTERACTION OF POTATO STARCH WITH THE SELECTED FATTY ACIDS AND THEIR SODIUM SALTS Krystyna Cieśla, Hubert Rahier1/ 1/ Department of Physical Chemistry and Polymer Science, Vrije Universiteit Brussel, Belgium

Differential scanning calorimetry (DSC) appeared or sodium palmitate per 1 g of starch and 0.274 to be the appropriate method for detection of and 0.68 mmol of palmitic acid per 1 g of starch. gamma irradiation influence on starch interaction Melting of dry solid lauric and palmitic acids with lipids [1-3]. Structural modification of macro- are accompanied by endothermal effects with molecules and possible changes in the lipid sur- peaks at 45.2 and 65.5oC. Melting of both sodium rounding induced by gamma irradiation, as well salts occurs at a considerably higher temperature as possible modification of the lipid molecules, and is accompanied by double thermal effects with were found to affect the properties of the inclusion peaks at ca. 122 and 135oC. No influence of water amylose-lipid complexes formed with naturally presence was noticed on the temperature range of occurring lipids on heating wheat starch and flour melting of both fatty acids, while melting of both (A-type) [1,2]. Our preliminary DSC studies have sodium salts occur under such conditions at a con- also shown differences between the complexes siderably lower temperature. During the first heat- formed by irradiated and the non-irradiated potato ing, melting of lauric acid and sodium laurate in starch (B-type) and admixed 1-mono-lauroyl glyc- water takes place in a temperature range lower erol [3]. Currently, the effect of potato starch irradiation with 60Co gamma rays using a 30 kGy dose was studied on its interactions with two fatty acids (lauric and palmitic) and their sodium salts. Irradiations with 60Co gamma radiation were carried out in a gamma cell “Issledovatel” in the Department of Radiation Chemistry and Technol- ogy, Institute of Nuclear Chemistry and Technology. DSC studies were carried out using a DSC calorimeter of TA Instruments instaled in Vrije Univer- siteit Brussel (Belgium). DSC studies were carried out during several heating-cooling-heating cycles with a heating and cooling rate of 10oCmin–1. The Universal Thermal Analysis Package was applied for data analysis. The suspensions placed in hermetically closed pans were characterized by the surfactant : polysaccharide : water ratio of 1:10:10. This corresponds to 0.498 mmol of lauric acid, 0.390 mmol of palmitic acid, 0.458 mmol of sodium laurate and 0.359 mmol of sodium palmitate per 1 g of starch. DSC studies were carried out during several heating-cooling-heating cycles with a heat- o –1 ing and cooling rate of 10 Cmin . Additionally, Fig.1. Thermal effects attributted to the melting of amy- some complementary studies were continued with lose-lipid complexes recorded during the first and a heating and cooling rate of 5oCmin–1 applying third heating of the system containing lauric acid the smaller lipid to starch ratios. These values cor- admixed to the non-irradiated and irradiated starch respond to 0.274 and 0.137 mmol of sodium laurate (at weight ratio equal to 1:10). RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 45 than gelatinization (the example in Fig.1; thermal separate enthalpies of both processes was, how- effect recorded at a temperature below 60oC). ever, less evident. Melting of sodium palmitate starts also at a lower During the subsequent cooling and heating temperature but continues during gelatinization cycles, the processes of crystallization and melting while sodium palmitate melts in the same tempera- of the amylose-lipid complexes and of free lipid, present in excess in the system, took place. The differences were noticed between thermal effects recorded for the non-irradiated and irradiated starch during the first cooling and during the subsequent heating and cooling routes. However, only on addition of lauric acid the results correspond well to those obtained previously for the complexes formed in wheat starch with naturally occurred lipids, or in the complexes formed by potato starch with mono-lauroyl-glycerol [1-3]. Transformations of starch lipid complexes occur then at lower temperature in the irradiated than in non-irradiated samples containing lauric acid as well on heating and on cooling (Figs.1 and 2) and are accompanied by a smaller enthalpy. Melting and crystallization processes taking place during the course of thermal analysis induces in both cases ordering in the complex structure (proved by an increase in the enthalpy and temperature of the complex transi- Fig.2. Thermal effects attributted to the crystallization tions). However, that effect is considerably larger amylose-lipid complex recorded during the first and third cooling of the system containing lauric acid in the case of non-irradiated starch than in the case admixed to the non-irradiated and irradiated starch of irradiated starch. (at weight ratio equal to 1:10). ture range as starch gelatinizes. Formation of the inclusion complex (exothermal) occcurs during gelatinization of starch (endothermal). Accord- ingly, the lower total enthalpy was determined on the basis of the second thermal effect than that expected for gelatinization of pure starch present in the system containing simultaneously lauric acid, sodium laurate or sodium palmitate. Transition of the resulting amylose-lipid complex occurs in the range of higher temperatures. In the case of palmitic acid addition, decrease of joint enthalpy of gelatinization and melting of lipid, in relation to the

Fig.4. Thermal effects recorded during the first, second and third cooling of the system containing sodium palmitate admixed to the non-irradiated and irradiated starch (at weight ratio equal to 1:10). The enthalpies determined for the first, second and third crystallization of the free-lipid phase in the non-irradiated system are equal to -6.0, -4, 8, -3,7 and the irradiated Fig.3, Thermal effects recorded during the third heating and system -3.8, -7.0, -8.6. The enthalpy determined for the third cooling of the system containing sodium melting of this phase during heating was equal to 9.4 palmitate admixed to the non-irradiated and irradi- and 9.2 both on the third and second heating of these ated starch (at weight ratio equal to 1:10). systems. 46 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES uted to the differences in the structure of the intermediate phase containing lipid and the non-irradiated and those containing lipid and the irradiated starch. Furthermore, after thermal treatment an increase in the enthalpy of crystallization is observed in the system containing the irradiated starch, while a decrease in enthalpy of crystallization occurs in that containing the non-irradiated starch (Fig.4). This points out the weaker interaction between free lipids and non-irradiated starch as compared to the irradiated starch with additional weakening caused by thermal treatment of the irradiated system, in contrary to the strengthening induced in the non- -irradiated starch. Simultaneously, no differences were noticed between enthalpies determined for the second and the third melting of this phase in both systems (Fig.4, the caption). Similar results as in the system containing sodium palmitate were obtained in heating the system con- Fig.5. Thermal effects attributed to the melting of amy- taining sodium laurate with that difference that lose-lipid inclusion complexes recorded during the exothermal process accompanies melting of the second and third heating of the system containing complex formed in the mixtures containing the ir- sodium laurate admixed to the non-irradiated and radiated starch (Fig.5). This process probably con- irradiated starch (at weight ratio equal to 1:10).

In contrary to the previously examined systems, thermal effect that can be attributed to melting of the amylose-lipid complex occurs at higher temperature during heating of the system containing sodium palmitate and the irradiated starch as compared to that containing the non-irradiated one (Fig.3). However, similarly as in the previous cases, crystallization of the complex was observed at considerably lower temperature in the case of irradiated starch as compared to the non-irradiated one and was accompanied additionally by the endothermal process occurring in a low temperature range (Fig.3). Moreover, the differences were noticed between the route of melting and crystallization of free lipid phase (examples in Fig.4). Therefore, melting occurs at lower temperature in the case of non-irradiated than irradiated starch. This can be attrib-

Fig.7. Thermal effects recorded during the first, second and third cooling of the system containing palmitic acid admixed to the non-irradiated and irradiated starch (at weight ratio equal to 1:10). The enthalpies determined for the first, second and third crystallization of the free-lipid phase in the non-irradiated system Fig.6. Thermal effects attributed to the melting of amy- are equal to -6.0, -4, 8, -3,7 and in the irradiated sys- lose-lipid inclusion complexes recorded during the tem -3.8, -7.0, -8.6. The enthalpy determined for melt- second and third heating of the system containing ing of this phase during heating was equal to 9.4 and palmitic acid admixed to the non-irradiated and ir- 9.2 both on the third and second heating of these radiated starch (at weight ratio equal to 1:10). systems. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 47 sist in crystallization of the complex phase during tions were considerably smaller in the irradiated melting (resulting probably in the increased peak starch as compared to the non-irradiated starch. temperature) and was not detected in non-irradi- Although the differences were noticed between ated starch. The other difference is that crystalliza- structural properties of the connections formed tion taking place at the first, second and third cool- between the irradiated and non-irradiated starch ing of the complexes formed in both irradiated and with all the examined ligands, the effect of irradia- non-irradiated starch was always accompanied by tion differs depending on the ligand. Moreover, the single exothermal effects with a peak at 89-90oC. differences were detected between the influence of A similar conclusion concerning the irradiation thermal treatment on these properties. effect on weakening the starch interaction with the The work was sponsored in the frame of Ministry free lipid phase can be, however, derived as in the of Scientific Research and Information Technology system containing sodium palmitate. research grant No. 2P06T 026 27. Formation of the inclusion complex occurs with low efficiency in palmitic acid addition and during References the third heating small effects of the complex melt- [1]. Cieśla K., Eliasson A.-C.: Radiat. Phys. Chem., 68, ing were detected only in the non-irradiated starch 933-940 (2003). (Fig.6). However, a strong interaction were noticed [2]. Cieśla K., Eliasson A.-C.: J. Therm. Anal. Calorim., between the starch and free-lipid phase (Fig.7). This 79, 19-27 (2005). concerns probably formation of the so-called sur- [3]. Cieśla K., Eliasson A.-C.: DSC studies of gamma face complex. In fact, the homogeneous residues radiation effect on the amylose-lipid complex formed were obtained after thermal analyses performed in wheat and potato starches. Acta Aliment., in press. with a small palmitic acid content. These interac-

SURFACE TENSION STUDIES OF BINDING CETYLTRIMETHYLAMMONIUM BROMIDE TO GAMMA IRRADIATED AND NON-IRRADIATED POTATO AMYLOPECTIN Krystyna Cieśla, Henrik Lundqvist1/, Ann-Charlotte Eliasson1/ 1/ Department of Food Technology Engineering and Nutrition, University of Lund, Sweden Decrease in molecular weight and the order in and was kindly supplied by Lyckeby Stärkelsen starch granules affects gelatinization processes in (Sweden). The native dry amylopectin was irradi- both A and B types of starch [1-4]. Accordingly, ated with 60Co gamma rays with a 30 kGy dose in a the influence of gamma irradiation was discovered gamma cell “Issledovatel” installed in the Depart- on the interaction of A-type starches with naturally ment of Radiation Chemistry and Technology, occurring lipids [2,3]. In regard to the structural Institute of Nuclear Chemistry and Technology. modification of macromolecules and the formation Moreover, commercial potato starch was used for of short molecular products, differences were also the complementary experiments using a Brookfield found between the possibilities for binding at am- voscometer. Native dry potato starch or 1% starch bient temperature of iodine by the irradiated and gels were irradiated with doses of 10, 20 and 30 kGy. non-irradiated starch and the structure of the result- Axisymmetric drop shape analysis (ADSA) with ing products [4]. Accordingly, gamma radiation is a Tracker instrument (IT Concept, Longessan, also expected to modify interaction of B-type starches France) installed at the University of Lund (Sweden) with admixed surfactants: binding of the ligands and was applied for surface tension studies. A syringe the product properties. with a u-shaped needle was lowered into the sample Surface tension measurements have appeared cell and an air bubble was produced from the syringe. useful in studying the interaction of iodine and sur- The dynamic surface tension was measured by film- factants with starch polysaccharides [5,6]. This is ing the rinsing buble and analysing the contour of because that surface tension can be considered as the bubble. The experiments were performed at a measure of the monomer surfactant in solution. 27oC (above the Kraft temperature of CTAB). CTAB Therefore, the more the monomer of surfactant in was gradually introduced to 0.25% polysaccharide solution, the more the surface tension will decrease gel solutions and the effect of addition each por- before micelles of surfactant start to form. At pres- tion of surfactant was studied on their surface ten- ent, our preliminary results are shown dealing with sion. The dynamic surface tension was monitored the effect of irradiation on binding of cetyltrimethyl- for one hour in each measurement and the equi- ammonium bromide (CTAB) on starch polysaccha- librium surface tension was determined as the rides. The method was applied for examination of value when a stable level was reached. The curves the process taking place at only slightly elevated tem- representing dependence of equilibrium surface perature enabling to obtain homogeneous CTAB tension on CTAB concentration were then con- solution. structed accordingly to the method described by Waxy potato starch (a pure potato amylopectin) Lundquist et al. [6]. Appearance of the free CTAB was obtained due to genetic engineering methods induces a decrease in surface tension, while stabi- 48 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES lization of surface tension indicates the formation taining less branched molecules or even straight of micelles. The amount of CTAB bound to the amylose chains as a result of radiation-induced solution is thus shown by the difference between scission of the strongly branched polysaccharide the total amount of CTAB added and the amount chains. of free CTAB. Micelles start to form at such CTAB Complementary studies were conducted using concentration when the free energy of the surfac- a Brookfield viscometer for the gels prepared on tant in the micelles is less than in the surfactant – the way of prolonged heating at 90oC of commer- polysaccharide aggregates or as free monomer in cial potato starch (non-irradiated and irradiated solution. The critical association concentration of using various doses) with CTAB (at starch : CTAB CTAB is very low and in the present experiment mass ratio equal to 1:0.08). Irradiation with a dose binding of CTAB to polysaccharides starts at the of 30 kGy of dry native starch induces ca. a 45-fold moment when the first portion of CTAB is added decrease in viscosity of its gel formed with CTAB [6]. It was also discovered [6] that the same amount addition (from 47.5 to 1.1 cP determined in the of CTAB can be bound to starch polysaccharides, case of 1.2% solutions) and ca. an 11-fold decrease independently on its structure (34 mmol CTAB per after irradiation with a dose of 10 kGy (to 4.27 cP). mol glucose units). Four sets of experiments were This correspond to 12-fold decrease discovered performed for each irradiated and non-irradiated after irradiation with the same dose of 10 kGy in starch. gels formed using starch alone (from 105 to 8.8 cP Differences were observed between the route of determined for 2% solutions). The differences surface tension changes taking place due to CTAB between viscosities of both types of gels prepared addition to the non-irradiated and irradiated amy- using the irradiated and control starch result due lopectin solutions (Fig.). Binding of CTAB to the to decrease in swelling power (by 2.5 times) and irradiated starch appeared more “co-operative” than the essential increase in the amount of the soluble binding of CTAB to the reference non-irradiated polysaccharide (at least 4 times) induced by irra- starch. The “more co-operative type of binding is diation [4]. Therefore, no particular conclusion shown by the more sigmoidal shape of the curve concerning the irradiation effect on capability of starch for CTAB binding can be drawn on the basis of the experiment performed for potato starch at high temperature, similarly as on the basis of the surface tension studies carried out at low temperature for potato amylopectin. However, the capability for further binding of CTAB was significantly reduced when gel solution was submitted to irradiation before addition of CTAB. This was shown by the presence of the crystallites of CTAB in the products obtained after addition of CTAB to the irradiated gels, while no free CTAB can be detected in the case of those obtained under the same conditions but using the non-irradiated gels. Irradiation of the gels result in the more evident decrease in the viscosity of the starch-CTAB system. A 50-fold decrease in the viscosity was found already after irradiation with a 10 kGy dose (to 1.1 cP), with no Fig. Equilibrium surface tension of CTAB – 0.25% potato particular influence on further dose increase to 20 amylopectin solution non-irradiated and irradiated and 30 kGy. using a 30 kGy dose. The work was done in the frame of the Polish Ministry of Scientific Research and Information representing the dependence of surface tension on Technology research grant No. 2P06T 026 27. CTAB concentration (Fig.). This occurs despite the fact that binding of CTAB to potato amylopec- References tin was proved to be, in general, of Langmuir type [1]. Cieśla K., Eliasson A.-C.: Radiat. Phys. Chem., 64, (apart from the first stage of process when elec- 137-148 (2002). trostatic interaction of CTAB with starch phos- [2]. Cieśla K., Eliasson A.-C.: Radiat. Phys. Chem., 68, phate groups takes place) [6]. This means that 933-940 (2003). binding occurs to a number of the equivalent sites [3]. Cieśla K., Eliasson A.-C.: J. Therm. Anal. Calorim., on polysaccharides and the process is not influ- 79, 19-27 (2005). enced by the fraction of bound ligands. In oppo- [4]. Cieśla K., Eliasson A.-C.: DSC studies of gamma radiation effect on the amylose-lipid complex formed in wheat site, binding of CTAB to amylose was found to be and potato starches. Acta Aliment., in press. a cooperative process. This means that the forma- [5]. Svensson E., Gudmundson M., Eliasson A.-C.: Colloid. tion of the individual complexes is coupled to each Surfaces B: Biointerfaces, 6, 227-233 (1996). other. The increase in co-operative type of binding [6]. Lundqvist H., Eliasson A.-C., Olofsson G.: Carbohydr. after irradiation might be thus explained in terms Polym., 49, 43-55 (2002). of appearance of the polysaccharide fraction con- RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 49 GAMMA IRRADIATION INFLUENCE ON STRUCTURE OF POTATO STARCH GELS STUDIED BY SEM Krystyna Cieśla, Bożena Sartowska, Edward Królak1/, Wojciech Głuszewski 1/ Analytical Centre, Warsaw Agricultural University, Poland Decrease in molecular weight and ordering in diation Chemistry and Technology, Institute of starch granules induced by gamma irradiation in- Nuclear Chemistry and Technology (INCT). The fluences its gelling properties. An essential decrease doses of 5, 10, 20 and 30 kGy were used. Swelling in swelling power occurs after irradiation of starch power of these samples were examined using the and flour [1,2] and the resulting gels reveal signifi- modified procedure of Eliasson et al. described in cantly decreased viscosities as compared to those details in [3]. Moreover, viscosity of the gels (2 wt%) of the reference non-irradiated gels. This suggests were determined using a Brookfield viscometer. that irradiation modifies structural properties of the Gels containing 10 wt% dry matter were pre- gels. Accordingly, at present the studies dealing with pared on the way of heating starch suspensions for the influence of gamma irradiation on the structure 45 min in glass tubes placed in a heating chamber of starch gels were initiated applying scanning elec- stabilized at 100oC. These gels were submitted to tron microscopy (SEM). Several procedures of gels four experimental procedures. The first series of gels preparation were tested in purpose to select proper was rapidly frozen in liquid nitrogen and examined conditions that could enable to observe differences directly at depressed temperature. The second se- between the SEM images obtained for the non-ir- ries was also rapidly frozen in liquid nitrogen but radiated gels and those irradiated applying various afterwards lyophilized. The third series was obtained doses. The influence of each procedure on the re- on the way of rapid freezing, further storage at -18oC sulting images was analysed. The differences be- for two weeks followed by chemical staining and tween the photos taken for the particular gels were critical point drying. The fourth series was prepared related to the differences between their physical on the way of chemical staining and critical point properties. drying of the gels obtained after slow cooling and Solid potato starch (laboratory extracted) was storage at 4oC for 2 days. Chemical staining was irradiated with 60Co gamma rays in a gamma cell performed accordingly to the modified procedure “Issledovatel” installed in the Department of Ra- of Kaczyńska et al. [4].

0 kGy 20 kGy

0 kGy 30 kGy

Fig.1. Images recorded (at magnification x600) at depressed temperature for the gels frozen in liquid nitrogen: upper row – fractures, non-irradiated and irradiated; lower row – surfaces, non-irradiated and irradiated. 50 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 0 kGy 0 kGy

5 kGy 5 kGy

10 kGy 10 kGy

20 kGy 20 kGy

30 kGy 30 kGy

Fig.2. Typical areas of the gels recorded after rapid cooling at liquid nitrogen and further lyophilization: upper row – fractures, lower row – surfaces. Magnification of all images is x1000. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 51 0 kGy 0 kGy

5 kGy 5 kGy

10 kGy 10 kGy

20 kGy 20 kGy

30 kGy 30 kGy

Fig.3. Typical images obtained for the gels recorded after chemical staining followed by the critical point drying: upper row – fractures of the gels obtained on the way of rapid freezing (all at magnification x1000), lower row – gels slowly cooled and stored at 4oC (at magnification x500). 52 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES SEM studies were conducted using a DSM 942 the fractures of the rapidly frozen and chemically Scanning Electron Microscope (Zeiss-Leo produc- stained gels (with orientation starting from a 10 tion) for measurements carried out at ambient kGy dose radiation) (Fig.3) as in the case of these temperature of dried samples covered with a thin lyophilized after freezing. Smoothness of the sur- gold layer. The instrument is installed in the INCT. faces and a lamella size increased with irradiation The rapidly frozen gels were examined at depressed dose alike in the case of lyophilized gels, while sur- temperature (-15oC) at low vacuum using a Quanta face porosity of secondary type was avoided in con- 200 Microscope (FEI) installed at the Analytical trary to these gels owing to the chemical staining. Centre, Warsaw Agricultural University. The frac- Fragile, brittle gels were obtained after storage tures and surfaces of gels were examined. at 4oC followed by chemical staining (Fig.2). Images of all the non-irradiated gels indicate a Smoothing of the gels can be stated after irradia- honey-comb structure, independently of the way of tion with 5 kGy, while the lamellar structure results further treatment, with that difference that lyophiliza- at higher doses (10 kGy) with further rupture of tion induces thinning of the comb walls, as com- the lamellas (20 and 30 kGy). The radiation effect pared to the samples examined directly after freez- was, however, less evident than in the other cases. ing or those submitted to the chemical staining. This occurs probably because of the influence of Smooth areas, but with oriented fractures, have staining procedure on the final structure of these appeared after irradiation of the rapidly frozen gels soft gels. examined at depressed temperature both at the Our results show that SEM enable to observe the fractures and at the surfaces (Fig.1). Smoothing differences between the structure of the non-irra- shows a higher homogeneity of the irradiated gels. diated potato starch gels and those irradiated apply- Orientation results probably due to the preparation ing various doses. The appropriate preparation pro- procedure and is caused by the weak internal forces cedures were selected enabling to detect structural of the soft irradiated gels as compared to the gravi- modification of gels. Moreover, the relationship tation force or to the applied mechanical stress. was found between modification of gel structure Both homogeneity of the gels and the weakening and the applied dose. Similar irradiation influence of their internal forces was proved by a decrease in on gel surfaces and fractures can be stated on the viscosity. Therefore, a 12-fold decrease in viscosity basis of SEM images obtained after rapid freezing was found already after irradiation with a dose of of gels independently of their further treatment. 10 kGy (from 105 cP determined for the non-irra- The radiation effect on the images of the gels slowly diated 2% gel to 8.8 cP). Swelling power decreases cooled and stored at 4oC was, however, less evident. linearly with irradiation dose applied. The amount The differences in structural properties of gels of gel formed after irradiation with a 30 kGy dose shown by SEM result due to the radiation-induced is equal to ca. 0.35% of that formed before irra- weakening of the internal forces in gels and in- diation [1]. crease in their homogeneity. Similarly, irradiation induces the appearance The work was sponsored in the frame of the of flat and smooth structural elements in the case Polish Ministry of Scientific Research and Informa- of rapidly frozen but lyophilized gels (Fig.2). This tion Technology research grant No. 2P06T 026 27. was observed already after irradiation performed using a dose of 5 kGy. Moreover, further cracking References of these smooth surfaces led to the appearance of lamellar structure. Further increase in the size of [1]. Cieśla K., Eliasson A.-C.: DSC studies of gamma radiation effect on the amylose-lipid complex formed in lamellas, and, consequently, the formation of large wheat and potato starches. Acta Aliment., in press. blocks (observed in the gels fractures) as well as [2]. Cieśla K.: J. Therm. Anal. Calorim., 74, 1271-1286 the secondary porosity detected on their surfaces (2003). result with increasing irradiation dose. [3]. Eliasson A.-C.: Starch/Stärke, 37, 411-415 (1985). Similar observation concerning orientation and [4]. Kaczyńska B., Autio K., Fornal J.: Food Struct., 12, the lamellar structure formation can be done for 217-224 (1993).

RADIOLYTIC DEGRADATION OF FUNGICIDE CARBENDAZIM BY GAMMA RADIATION FOR ENVIRONMENTAL PROTECTION Anna Bojanowska-Czajka, Przemysław Drzewicz, Zbigniew Zimek, Bogdan Szostek1/, Henrietta Nichipor2/, Marek Trojanowicz 1/ DuPont Haskell Laboratory for Health and Environmental Sciences, Newark, USA 2/ Institute of Radiation Physical-Chemical Problems, National Academy of Sciences of Belarus, Minsk, Belarus Intensive growth of various industrial branches and contemporary agriculture, their toxicity and in many the use of chemicals in agriculture results in increas- cases slow degradation in natural environment. ing flux of anthropogenic toxic pollutants to natu- Pesticide residues are detected both in the environ- ral environment. A significant group of these pol- ment (waters, soil), and also in vegetables and fruits, lutants are pesticides, because of the wide use in as well as in processed food. Hence, constant need RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 53 The aim of this study was to develop a high pressure liquid chromatography (HPLC) method for simultaneous determination of carbendazim and its decomposition products, identification of products of gamma radiolysis of carbendazim and examination of different factors affecting the efficiency of radiolytic degradation of carbendazim, Fig.1. Structure of carbendazim. including dose rate, initial concentration and pH of irradiated solutions. for improvement and simplification of analytical For monitoring the effectiveness of radiolytic de- methods for the determination of pesticides in vari- composition of carbendazim and studies of mech- ous samples is obvious, as well as development of anism of this process, investigation on the develop- technologies for their effective removal from in- ment of HPLC method enabling simultaneous dustrial wastes and environmental media. determination of carbendazim and products of its

Fig.2. The effect of initial concentration of carbendazim in gamma-irradiated aqueous solutions on (A) yield of decomposition at different irradiation doses and (B) the magnitude of the dose required for 90% decomposition of pesticide. Fungicides and chemicals used for the destruc- degradation observed in similar processes has been tion of unwanted fungi in various applications, are carried out. These products include benzimidazole, employed on a large scale since the 1960s, and since 2-aminobenzimidazole, aniline, o-phenylenedi- then their use constantly increases. Species of most amine and 2-hydroksybenzimidazole. It was found common use for this purpose are thiabendazole, that pH of the eluent affects significantly reten- fuberidazole, benomyl, methyl thiophanate and tion time of the determined compounds and shape carbendazim (MBC – methyl-2-benzimidazole car- of chromatograms. The pH 8.0 and wavelength 277 bamate) [1]. Carbendazim is also a product of hy- nm were selected as optimum for separation in fur- drolysis of benomyl and methyl thiophanate. The ther measurements. structure of carbendazim is shown in Fig.1. It is used Effect of the initial concentration and pH for protection of crops, fruits and vegetables It was found that the radiation dose needed for against fungal diseases, and also for protection of 90% degradation of carbendazim increases almost harvested products during their storage and trans- linearly with the value of initial concentration of portation. Its toxicity is well documented [2], hence fungicide in the examined concentration range its residues are considered as environmental pol- 20-100 μmol L–1 (Fig.2). The reported measure- lutants. ments have been carried out in aqueous solution at Methods of decomposition of carbendazim, de- pH 7. scribed so far in the literature are based on photo- In preliminary experiments with carbendazim lysis by UV irradiation in various chemical condi- the effect of pH on the yield of decomposition of tions [3-7]. The main subject of those works was carbendazim was examined in solutions non-ir- the determination of yield of carbendazim pho- radiated and gamma-irradiated. It is reported in tolysis at different pH of irradiated solutions and the literature and confirmed experimentally in various concentrations of dissolved oxygen. The this work that aqueous solutions of carbendazim efficiency of carbendazim decomposition is facili- in acidic and neutral media are stable for at least tated by alkaline pH, where the non-dissociated 3-4 months, while slow hydrolytic decomposition form of the substrate is present (protonation con- occurs at highly alkaline solutions (Fig.3), where stant for carbendazim pKa=4.2), and in the pres- 2-aminobenzimidazole has been detected by ence of oxygen in irradiated solution [6]. HPLC. 54 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES

Fig.3. Protonation equlibrium and hydrolysis of carbendazim [6]. In gamma-irradiated aerated solutions of car- Radiolytic decomposition in oxidating bendazim 100 μmol L–1 in the pH range from 3 to and reducing conditions 10 practically complete decomposition has been ob- Irradiation of aqueous solutions of carbendazim served at small doses up to 0.6 kGy (Fig.4). In alka- has been carried out in different conditions, where solutions were saturated with air, argon or nitrogen monoxide, and without or with added tert-butanol, hence the different products of water radiolysis predominate in further reactions with the target compound (see Table in Fig.5). In solutions saturated with nitrogen monoxide, efficient scavenging of solvated electrons and hydrogen radicals takes place [8]: → 6 –1 –1 H· + N2O N2 + ·OH k = 2.1 x 10 mol L s → – 9 –1 –1 eaq + N2O N2 +OH· k = 9.1 x 10 mol L s and as result of that, the largest yield of hydroxyl radicals is obtained. The addition of tert-butanol to irradiated solutions is used to scavenge hydroxyl radicals according to the reaction [9]: → OH·+ (CH3)3COH H2O + ·CH2C(CH3)2OH k = 6 x 108 mol–1L s–1 So, in such case reducing conditions exist and radical reactions with solvated electron or hydrogen radicals predominate. In solution containing tert-butanol in acidic media additionally solvated electron is Fig.4. The effect of pH of irradiated solutions of carben- scavenged, hence the reaction with hydrogen radi- dazim on yield of decomposition at initial concen- cals predominates. In solutions saturated with argon tration 100 μM. in neutral media all three main oxygen containing radicals can react with the target pesticide. line solutions it occurs slightly faster and this can be In experiments carried out at different irradia- attributed to simultaneous hydrolysis. It is oppo- tion doses it was found that in conditions where site to observations reported for photochemical de- hydroxyl radical predominates the yield of carben- composition, which was strongly affected by pH of dazim decomposition is the largest, that means the the initial solution of carbendazim [6]. irradiation does need for more complete decom-

μ Fig.5. Radiolytic decomposition of aqueous 100 M solutions of carbendazim in different conditions: N2O-saturated solution at pH 7.0 (z), saturated solution at pH 7 (), argon-saturated solution at pH 1.5 with added 106 μM tert-butanol (c) and argon-saturated solution at pH 7.0 with added 106 μM tert-butanol (T). RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 55

Fig.6. Chromatograms obtained for 100 μM aqueous solutions of carbendazim at pH 7.0 gamma-irradiated with 0.2 kGy dose: (A) before irradiation, (B) irradiated in the presence of 106 μM tert-butanol saturated with argon, and (C) saturated with nitrogen monoxide. Eluent – 10 mM amonium acetate pH 8.0 with acetonitrile-gradient program. Column – Phenomenex C18(2) Luna 5 μM (250×4.6 mm). Flow rate – 1 mL/min. Detection at 277 nm. Peak assignment: (1) benzimidazole, (2) product of reaction with tert-butanol, (3) carbendazim, (4) product of reaction with tert-butanol, (5) 5-hydroxycarbendazim, (6) hydroxybenzimidazole, (7) 6-hydroxycarbendazim. position of fungicide is the smallest (Fig.5). Much anism of occurring processes. In photochemical less efficient is the decomposition in reducing con- processes as the main product of decomposition of ditions, where both reactions with solvated elec- carbendazim, 2-aminobenzimidazol has been iden- tron or hydrogen radical predominate. At a 0.6 kGy tified [7], while when the process was carried out in dose, only 50% yield of carbendazim decomposi- the presence of hydrogen peroxide hydroxy deriva- tion is observed, while in oxidizing conditions de- tives of carbendazim were postulated [3]. In our ex- composition occurs with 100% yield. In aerated periments carried out in different conditions, with solutions at a dose of 0.6 kGy also satisfactory 90% HPLC measurements using mass spectrometry de- yield of decomposition is observed, which is im- tection different products of decomposition were portant from eventual practical applications, where found in different conditions (Fig.6). When oxida- saturation with nitrogen monoxide would be too tion with hydroxyl radicals predominate as the prod- difficult and expensive. ucts of radiolysis hydroxybenzimidazol and two iso- The identification of products formed in radiolytic mers of hydroxycarbendazim were identified, while decomposition of carbendazim, in various condi- in reducing conditions the main product in the ap- tions is important for the determination of mech- plied conditions benzimidazole was found.

Fig.7. Comparison of experimental results with kinetic modelling for radiolytic decomposition in different conditions: (A) μ effect of initial concentration, (B) irradiation of aqueous 100 M solutions of carbendazim: N2O-saturated solution at pH 7.0 (z), saturated solution at pH 7 (), argon-saturated solution at pH 1.5 with added 106 μM tert-butanol (c) and argon-saturated solution at pH 7.0 with added 106 μM tert-butanol (T). Full points – experimental results, open points – calculated data. 56 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES

Further research will be focused on compari- [2]. Tomlin C.: The pesticide manual. 10th ed. British Crop son of experimental data for irradiation in differ- Protection Council, Bracknell, London 1994. ent conditions with modelling based on available [3]. Mazellier P., Leroy E., De Laat J., Legube B.: Environ. reaction rate constants for radical reactions, and also Chem. Lett., 1, 68-72 (2003). a study of similar processes in natural matrices of [4]. Mazellier P., Leroy E., De Laat J., Legube B.: New J. Chem., 26, 1784-1790 (2002). industrial wastes. Some preliminary results on com- [5]. Fleeker J.R., Lacy H.M.: J. Agric. Food Chem., 25, parison of kinetic modelling with experimental 51-55 (1977). data for the effect of initial concentration and ir- [6]. Pandés R., Ibarz A., Esplugas S.: Water Res., 34, radiation of carbendazim solutions in different con- 2951-2954 (2000). ditions are shown in Fig.7. The observed correla- [7]. Boudina A. Emonelin C., Baaliouamer A., Grenier-Lou- tion is especially satisfactory for irradiation in dif- stalat M.F., Chovelon J.M.: Chemosphere, 50, 649-655 ferent conditions with different doses. (2003). [8]. Buxton G.V., Greenstock C.L., Helman W.P., Ross A.B.: References J. Phys. Chem. Ref. Data, 17, 513-531 (1988). [9]. Wojnárovits L., Takács E., Dajka K., Emmi S.S., Russo [1]. Modern selective fungicides. Ed. C.J. Delp. Wiley, M., D’Angelantoniano M.: Radiat. Phys. Chem., 69, London 1987, pp. 233-244. 217-219 (2004).

COMPARISON OF PPSL AND TL METHODS FOR THE DETECTION OF IRRADIATED FOOD AND FOOD COMPONENTS Grzegorz P. Guzik, Wacław Stachowicz

At present, the main food products being suspected minerals only, while PPSL IR stimulated lumines- as treated with the use of ionizing radiation are cence the light released from all mineral and/or spices. Thermoluminescence (TL) examination of crystalline components of the sample [3]. minerals isolated from spices is the best, most sen- The detailed analytical procedure of sample sitive method for the detection of irradiation in preparation for TL measurements are based on these substances. However, mineral separation is PN-EN 1788:2001 [4]; the sample treatment to pro- time-consuming and needs special care. Therefore, ceed PPSL measurements, in turn, are described in the accomplishment of one TL analysis lasts usually PN-EN 13751:2003 (U) [5]. a few days. The second analytical method adapted TL examination is achieved with the use of PC for the detection of radiation treatment in spices is operated TL reader, type TL/OSL, model TL-DA-15 pulsed photostimulated luminescence (PPSL). In (Risø National Laboratory, Denmark) under the contrast to the latter, the method is simple and fast following measuring conditions: initial tempera- but has some limitations. In general, it is less sen- ture – 50oC, final temperature – 500oC, heating rate sitive than the TL method and is not capable of – 6oC/s. measuring the luminescence in all kinds of spices. Routinely, the normalizing irradiation with 1 kGy Having both methods in the Laboratory of of gamma rays from a 60Co gamma source is de- Detection of Irradiated Food, Institute of Nuclear scribed in [4]. Chemistry and Technology (INCT), we performed The routine preparation of samples [6] compiles a series of parallel experiments to prove the appli- grinding, washing, density separation of a debris of cability of the PPSL method to detect irradiation minerals contained in investigated products. This in the variety of spices, herbs, composites with spices procedures is time-consuming and takes normally and herbs admixed, and some other food products. a full workday. Current research programme covers the PPSL In TL, two criteria for the confirmation of radia- analysis of archival samples examined earlier by the tion treatment are in force: glow ratio (glow 1/glow TL method followed by the evaluation and com- 2) and the shape and maximum of radiation in- parison of the results obtained with both methods. ducing TL within the temperature range 150-250oC. Mineral debris of silicates and bioinorganic The details can been found elsewhere [4,5]. composites (calcite and hydroxyapatite) are the In contrast to TL, the preparation method of natural contaminants of spices, herbs and season- samples for PPSL examination is simple: the prod- ings. Mineral in food is composed mainly of quartz uct is dispersed in Petri dishes used for the PPSL and feldspar, as proved earlier [1]. These debris are measurement. Some samples require earlier treat- capable of storing steadily the energy of ionizing ments like cutting or grating. radiation in charge carriers trapped at structural, PPSL measurement for customers is being done interstitial or impurity sites. Charge carriers stable by the calibrated measurement, equivalent to the at ambient temperatures, are freed from mineral TL normalizing procedure (re-irradiation with debris by increasing the temperature (TL method) gamma rays). Such treatment delivers more ad- and/or under IR (infrared) illumination (PPSL equate results, while luminescence measurements method) [2]. Both methods enable to record the are accomplished before and after exposing the released energy, but methodological difference sample to a defined dose of ionizing radiation. The between them lies in the state of samples examined: recommended calibrating dose as adapted in the TL measures isolated mineral fraction, i.e. silicate Laboratory is from 1 to 4 kGy [5,7]. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 57 There are three types of divergences of the PPSL method with TL results (Table 1). Nineteen samples (52.7% of the total number, i.e. above 1/2) could not be classified by means of PPSL. Three samples (8.3% of 36 samples in question) were qualified as non-irradiated (resultant screening measurement is intermediate, while calibration measurement is positive) or should not be investigated by means of the PPSL method. For 14 samples (38.8% of 36 samples in question i.e. above 1/3), the divergences were caused by too low sensitivity of the PPSL Fig. Comparison of the results obtained by means of the method. However, for a vast majority of the samples PPSL and TL methods. (almost 2/3), the results obtained by both PPSL and TL methods were found consistent. Typically, irradiated samples indicate only a small Each type of the three divergences discussed increase of the PPSL signal, whereas in the non-irra- above compiles the variety of products that are clas- diated ones the increase is markedly higher. sified in Table 2.

A lower threshold (T1=700 counts/60 s) and an For example, the type “samples nonmeasurable by upper threshold (T2=5000 counts/60 s) are used means of PPSL; TL only” is represented by several to classify the sample as non-irradiated (below 700 products classified as: seasonings and spices, plant counts/60 s) or irradiated (above 5000 counts/60 extracts, pharmaceuticals, processed food products s) [7-9]. and food colouring dyes, respectively.

Table 1. Qualification of samples as measured by the PPSL method.

Signal levels between the two thresholds are clas- The type ”samples non-irradiated and/or needing sified as intermediate, and, if appear, the sample to be approved by TL” gathers the products classi- needs further investigations by means of the TL fied as pharmaceuticals and processed food prod- method [5,10]. ucts only. The total number of samples examined was 100. And finally, the type ”too low sensitivity of PPSL Consistent results were obtained with 64 samples method; TL approval recommended” is represented (about 2/3), while non-consistent with 36 samples by the products classified as: seasonings and spices, (about 1/3) of the total number of samples (Fig.). row seasoning herbs, plant extracts, pharmaceuti-

Table 2. The products investigated in the Laboratory. 58 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES cals, fresh fruits and vegetables, dried vegetables [4]. PN-EN 1788:2001: Foodstuffs – Thermoluminescence and mushrooms, respectively. detection of irradiated food from which silicate min- As seen, despite the fact that some differences erals can be isolated. between the types do appear, it is not possible to [5]. PN-EN 13751:2003 (U): Artykuły żywnościowe – Wy- say in advances that a given product will delivered krywanie napromieniowania żywności za pomocą fotoluminescencji. a given response in PPSL. In other words, each prod- [6]. Research procedures PB-SLINŻ 03: Research pro- ucts needs individual treatment. cedures and analysis of the results of the examination In conclusion it can be said that PPSL is a very of irradiated food by TL method (Wykonanie badań useful method for the qualification of food samples i analiza wyników badania napromieniowania żyw- suspected to be irradiated, but from the practical ności metodą termoluminescencji). No. 3/2006 (in point of view it seems reasonable to construct the Polish). list of food products which can be easily examined [7]. Research procedures PB-SLINŻ 04: Research pro- by PPSL and those which should be rather subjected cedures and analysis of the results of the examination in advance to TL examination. of irradiated food by PPSL method (Wykonanie The results of TL examination of investigated badań i analiza wyników badania napromieniowania żywności metodą luminescencji stymulowanej świat- samples, as used for present comparison, were de- łem). No. 2/2006 (in Polish). livered by M. Laubsztejn, M.Sc. and Mrs G. Liśkie- [8]. Guzik G.P., Stachowicz W.: Pomiar luminescencji sty- wicz. mulowanej światłem, szybka metoda identyfikacji References napromieniowania żywności. Instytut Chemii i Tech- niki Jądrowej, Warszawa 2005. Raporty IChTJ. Seria [1]. Sanderson D.C.W., Slater C., Cairns K.J.: Radiat. B nr 3/2005 (in Polish). Phys. Chem., 34, 915-924 (1989). [9]. Sanderson D.C.W, Carmichael L., Fisk S.: Food Sci. [2]. The SURRC Pulsed Photostimulated Luminescence Technol. Today, 12(2), 97-102 (1998). (PPSL) Irradiated Food Screening System. Users [10]. Sanderson D.C.W., Carmichael L.A., Naylor J.D.: manual. Royal Society of Chemistry, Cambridge 2004, Food Sci. Technol. Today, 9(3), 150-154 (1995). 17 p. [3]. Soika Ch., Delincée H.: Lebensm.-Wiss. Technol., 33, 440-443 (2000), in German.

DEVELOPMENT AND ACCREDITATION OF EPR METHOD FOR DETECTION OF IRRADIATED FOOD CONTAINING SUGAR Katarzyna Lehner, Wacław Stachowicz

The method for the detection of irradiated food- subsequently normalized having actually the status stuffs containing crystalline sugar by the electron of European standard PN-EN 13708 [5]. In the paramagnetic resonance spectrometry (EPR) is validation procedure the Laboratory for Detection based on the detection in the investigated product of Irradiated Food, Institute of Nuclear Chemistry of stable free radicals evoked by radiation treatment. and Technology (INCT), participated, too [6]. The majority of radicals produced by radiation in The aim of the present study was to prove the food is short lining and decays within a few seconds effectiveness of the detection of irradiation in the or minutes. However, if irradiated product contains variety of sugar-containing food by the procedure crystalline sugar as one of the composites, the pres- given in PN-EN 13708 with the use of an EPR spec- ence of relatively stable radicals in the product is trometer – EPR-10 MINI installed in the Labora- quite probable. The same concerns other food prod- tory. This is the only acceptable way to adapt the ucts containing cellulose or bone, both character- method for routine control of food in the INCT. ized by the presence of micro-crystalline structure. The investigated products were dried pineapple, The crystalline domains in food, as proved in nu- banana, date, fig, papaya, and raisin. Each product merous experiments, are very effective in stabiliza- was divided into four samples irradiated with 0.5, tion of radiation induced radicals that can survive 1 and 3 kGy with 60Co gamma rays from an “Issle- for months or years. dovatel” irradiator. The fourth sample was a con- Due to the fact that in sugar-containing foods, trol. the variety of mono- and disaccharides appear and The EPR measurements have been done in that in various products different proportion be- X-band with the use of the EPR-10 MINI mentioned tween them occur, the EPR spectra recorded may above and were conducted during 12 months. differ, too. On the other hand, they differ from the The measuring conditions were as recommended EPR signals of single mono- and/or disaccharides. in PN-EN 13708. The intensity of signals, in turn, depends on the Both the irradiated and non-irradiated samples content of crystalline sugar in the product. So, the were measured together with Mn2+ and DPPH stan- EPR detection of irradiation in sweet foods depends dards to evaluated the g factor in the centre of spec- on the sufficient content of sugar crystals in the food tra and spectral width. [1-4]. The selection of the resultant spectra recorded The method of the detection of irradiation in food through the study is given in enclosed Figs.1-3. containing crystalline sugar has been validated and Figure 1 presents the spectra of dehydrated pine- RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 59

Fig.2. EPR spectra non-irradiated fruits: a) pineapple, b) fig, c) banana.

change, while its intensity decreased by about 35% (different attenuation of both spectra). Neverthe- less, the identification of irradiation is still simple after 1 year of storage, too. The detection level of irradiation in dehydrated foodstuffs was as follows: after exposure of samples to 0.5 kGy of gamma rays, the radiation treatment was reliably detected with pineapple, fig, papaya and raisin. In banana and date the dose of 0.5 kGy is not detectable within experimental error. The exposure to 1 kGy is detectable satisfactory. The stability of the EPR signals after 12 months of storage was, in general, satisfactory, too. In addition to banana and date (see above), the dose of 0.5 kGy could be detected at the lowest level of detection with raisin only. A reasonable reproducibility of the spectra was achieved with the incidentally selected samples of fig, papaya and raisin. No influence of the orientation of samples inside the resonant cavity was observed.

Fig.1. EPR spectra irradiated 3 kGy of dehydrated fruits: a) pineapple, b) banana, c) date, d) fig, e) papaya, f) raisin. apple, banana, date, papaya and raisin. The difference in the shape of the spectra reflects the various proportion and composition of sugars in the products. However, gc factor is in all spectra similar, about 2.0035, while the spectral width varied from 7.4 to 9.2 mT. Figure 2 shows the EPR spectra of non-irradiated pineapple, fig and banana. The spectra are recorded at a high gain (see high noise level) and differ entirely from those of irradiated stuffs. The signal, if present, is a narrow singlet with g about 2.0040. Distinction between irradiated and non-irradiated samples is very simple. Figure 3 shows the EPR spectra of the same sample of papaya recorded 1 month and 1 year after radia- Fig.3. EPR spectra of papaya 1 month (a) and 1 year (b) tion treatment. The shape of the signal did not after radiation treatment. Dose – 0.5 kGy. 60 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES

The study was a basis for further validation of tection of foods treated with ionising radiation. In: De- the method followed by its accreditation by the tection methods for irradiated foods, current status. Eds. Polish Centre of Accreditation. C.H. McMurray et al. The Royal Society of Chemistry, Information Service, 1996. Special Publication No. 171, References pp. 23-32. [5]. PN-EN 13708: Artykuły żywnościowe – Wykrywanie na- [1]. Raffi J., Angel J.-P.: Radiat. Phys. Chem., 34, 6, 891-894 promieniowania żywności zawierającej cukry krysta- (1989). liczne metodą spektroskopii ESR. Polski Komitet Nor- [2]. Raffi J., Angel J.-P., Ahmend S.H.: Food Technol., malizacyjny, Warszawa 2003 (in Polish). 3/4, 26-30 (1991). [6]. Raffi J., Stachowicz W., Migdał W., Barabassy S., Kal- [3]. Stachowicz W., Burlińska G., Michalik J., Dziedzic-Goc- man B., Yordanov N., Andrade E., Prost M., Callens ławska A., Ostrowski K.: Radiat. Phys. Chem., 46, 4-6, F.: Establishment of an eastern network of laboratories 771-777 (1995). for identification of irradiated foodstuffs. Final report [4]. Stachowicz W., Burlińska G., Michalik J., Dziedzic-Goc- of Copernicus Concerted Action CIPA-CT94-0134. ławska A., Ostrowski K.: EPR spectroscopy for the de- CCE, 1998.

DETECTION OF IRRADIATION IN HERBAL PHARMACEUTICALS WITH THE USE OF THERMOLUMINESCENCE AND ELECTRON PARAMAGNETIC RESONANCE SPECTROMETRY Magdalena Laubsztejn, Kazimiera Malec-Czechowska, Grażyna Strzelczak, Wacław Stachowicz In view of the two European Union (EU) directives pills (4 samples) and capsules (one sample). A part on food irradiation (1999/2/EC [1] and 1999/3/EC of the samples was irradiated with a dose of 5 kGy [2]) the labelling of radiation treated food is obliga- of gamma rays in November 2003, while the other tory. This regulation concerns food ingredients too, remained non-irradiated. It is supposed that the independently of their content in the product. For investigated samples contained garlic powder and that reason, more and more frequently such prod- vegetal dry extracts, talc, magnesium stearate, mono- ucts as dried vegetal extracts and pharmaceuticals and polysaccharides, colloidal silica and dyes like containing vegetal ingredients are delivered to the titanium dioxide. Laboratory for Detection of Irradiated Food, Insti- Irradiated and non-irradiated samples were regis- tute of Nuclear Chemistry and Technology (INCT), tered as model samples and labelled in a way adapted for examination. The standardized methods for the in the Laboratory (Table 1). detection of irradiation of foods were typically vali- Samples for thermoluminescence (TL) exami- dated with the use of selected products or groups nation were subjected to analytical procedure ac- of products as spices, herbs, crystalline cellulose and cording to PN-EN 1788:2002 in order to attain ef- sugars contained in food, etc. fective isolation of mineral fraction from the remain- So, the reliability of these methods is related to these ing vegetal slurry. Subsequently, the mineral frac- selected products only. tion was submitted to TL measurements with the The aim of research activity of the Laboratory dur- use of a computer operated TL reader under the ing the year 2006 was to prove the ability of the use following conditions: initial temperature – 50oC, of both thermoluminescence – TL (PN-EN 1788:2002) final temperature – 500oC, heating rate – 6oC/s. Tem- [3] and electron paramagnetic resonance spectros- perature dependent glow curves were doubly mea- copy – EPR (PN-EN 13708:2003) [4] methods for sured: once at the beginning and the second time the detection of irradiation in pharmaceuticals which after normalized irradiation with a dose of 1 kGy contain vegetal components and typically mono- with gamma rays. The intensity of TL integrated and polysaccharides as cohering agent. over the temperature range 150-250oC and the TL The experiments have been done with the samples glow ratio for irradiated and non-irradiated samples of 5 pharmaceuticals containing all these ingredi- are shown in Table 2. ents. They are available in drugstores and resemble The criterion of the classification of irradiated the samples delivered for examination to the Labo- foodstuff is based, according to PN-EN 1788:2002, ratory. The product appears in the form of coated on the evaluation of the TL glow ratio (glow 1/glow Table 1. Composition of investigated samples – main constituents.

* Sample irradiated with a dose of 5 kGy of gamma rays. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 61

Table 2. Thermoluminescence intensity of mineral fraction isolated from irradiated and non-irradiated pharmaceuticals integrated over the temperature range 150-250oC with the corresponding TL glow ratios.

2) and on the analysis of the shape of the glow curve shows quite often a relatively strong TL at higher recorded within the temperature range 150-250oC temperature with a maximum or maxima above from the mineral fraction isolated from food. TL 300oC. This luminescence is presumably released glow ratio of irradiated food sample are typically from deep structural traps in a mineral and origi- greater than 0.1. However, in addition to the de- nates from natural radionuclides (i.e. potassium, termination of glow ratio it is advised – in the Labo- thorium, actinium) which appear in rocks and soil. ratory obligatory – to analyse the shape of the glow For example, the glow 1 curves recorded for curves (TL vs. temperature relationship) recorded samples: SL/T3/A/06 (irradiated) and SL/T4/A/06 for both preliminarily isolated mineral fractions, (non-irradiated) are shown in Fig.1. The shape and and the same mineral fraction exposed to normal- the temperature of the maxima (about 240oC), as presented for selected sample, is typical of irradiated products. In comparison, the presented curve with a low intensity and maximum defined near to 350oC is typical of non-irradiated samples [3,5]. The glow ratios calculated for all, irradiated and non-irradiated samples are compared in the graph (Fig.2). The TL glow ratios for irradiated samples are higher than 0.1, whereas the ratios for non-irradiated samples are in all cases lower than 0.1. The results obtained in the above described test examination of pharmaceuticals with TL method indicate conclusively that it is possible to proceed the classification of this products whether irradiated or non-irradiated with the use of the criteria applicable to other food products, i.e. consistent with PN-EN 1788:2002. Fig.1. Comparison of glow 1 thermoluminescence curves of Samples for electron paramagnetic resonance mineral fraction isolated from irradiated (SL/T3/A/06) (EPR) examination were prepared as follows: pills and non-irradiated (SL/T4/A/06) pharmaceutical. and a capsule were mechanically crushed and then the samples weighing about 200 mg each were poured ized irradiation. Generally, the glow 1 curve for into thin wall sample tubes for EPR measurement, irradiated foodstuff has its maximum near to 200oC 4 mm in diameter. For each sample three parallel (±50oC). The mineral fraction isolated from foods aliquots were prepared. 62 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES ago and then every month during half a year. No evident decrease of intensity and/or change of shape of the signals were observed. The EPR examination of non-irradiated pharmaceuticals results in the recording of a weak single, symmetric line with g=2.0035 ±0.0035. Similar single lines are observed in non-irradiated foodstuffs containing crystalline sugars. The results of the presented experiments are a goal recommendation for the application of the relatively simple and fast EPR method for preliminary examination of pharmaceuticals to prove their ir- Fig.2. Thermoluminescence glow ratios of investigated radiation prior to the obligatory TL examination. pharmaceuticals calculated within the temperature Thermoluminescence examination of mineral range 150-250oC. fraction isolated from various pills and capsules of herbal pharmaceuticals can be useful for the The samples were measured in the EPR spectro- evaluation whether these products were irradiated meter Bruker ESP 300 under measuring conditions or not. The essential condition to proceed correctly recommended in PN-EN 13708:2003 for examina- the TL examination of herbal pharmaceuticals in tion of foodstuffs containing crystalline sugar. the form of pills and capsules is a very careful analy- The EPR spectra of the investigated samples are sis of results and looking deeper in the shape of the shown in Fig.3. resultant glow curves than in the case of typical food- The recorded spectra of irradiated pharmaceu- stuffs. ticals superpose on several complex spectra that, The EPR examination, in turn, enables the detection of radiation treatment of pharmaceuticals in pills, if they contain as a binding-flavouring agent crystalline mono- and/or poly-sugars. The experiments show conclusively that the next to TL method used for the evaluation of radiation treatment of this product, if contains sugars, is the EPR method. Present results prove the reliability of both methods for the detection of irradiation in herbal pharmaceuticals and are an important step of their validation, opening perspective of their future application in practice. The examination of other products of this type, containing vegetal components and sugars, is worthwhile of future including this combined detection method as one of those accredited in the Laboratory today.

References [1]. Directive 1999/2/EC of the European Parliament and of the Council of 22 February 1999 on the approximation of the Member States concerning foods and food ingredients treated with ionising radiation. Off. J. European Communities L 66/16-23 (1999). [2]. Directive 1999/3/EC of the European Parliament and of the Council of 22 February 1999 on the establishment Fig.3. EPR spectra (first derivative) of non-irradiated and of a Community list of food and food ingredients irradiated pharmaceuticals. treated with ionising radiation. Off. J. European in the majority, can be assigned to sugar born radi- Communities L 66/24-25 (1999). cals. The width of the spectra was 7.2-7.6 ±0.2 mT, [3]. Standard PN-EN 1788:2002: Foodstuffs – Thermolu- minescence detection of irradiated food from which while the g factor in the centre of the spectra was silicate minerals can be isolated. 2.0028 ±0.0002. The shape of the spectra is simi- [4]. Standard PN-EN 13708:2003: Foodstuffs – Detection lar, although a slight difference appears in the reso- of irradiated food containing crystalline sugar by ESR lution and intensities of some spectra components. spectroscopy. The signals resemble that of pure crystalline sugar. [5]. Malec-Czechowska K., Stachowicz W.: Nukleonika, The observed EPR signals are stable. This was proved 48, 3, 127-132 (2003). by the examination of all five samples two years RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 63 ACTIVITY OF THE LABORATORY FOR DETECTION OF IRRADIATED FOOD IN 2006 Wacław Stachowicz, Kazimiera Malec-Czechowska, Katarzyna Lehner, Grzegorz P. Guzik, Magdalena Laubsztejn

In 2006, the activity of the Laboratory for Detec- of Accreditation Nr AB 262 and concerns the de- tion of Irradiated Food, Institute of Nuclear Chem- tection of radiation treatment in: istry and Technology (INCT) was focused on the - food containing bone, e.g. meat, poultry, fish and following topics: egg shell (PN-EN 1786:2000) [5]; - development of the methods for detection of - food containing crystalline cellulose, e.g. shelled irradiated food implemented and accredited nuts, selected spices and some fresh fruits, as earlier in the Laboratory; strawberries (PN-EN 1787:2001) [6]; - implementation and accreditation of two stan- - food from which silicate minerals can be iso- dardized detection methods to be included to lated, i.e. in the variety of spices, herbs, heir the group of methods adapted for routine ana- blends, dried and fresh vegetables, fresh shrimps lytical service for customers; (PN-EN 1788:2002) [7]; - analytical service to fulfil the growing require- - food containing crystalline sugar, e.g. dried fruits ments of the customers representing firms and like dates, figs, raisins etc. (PN-EN 13708:2003) organizations in the country and from abroad. [8]; The task is to classify the variety of more or less - food giving rise to photostimulated luminescence complex food products delivered for examina- (PPSL), e.g. herbs, spices and their composities tion whether treated with ionizing radiation or (PN-EN 13751:2003) [9]. not. Article 7 (3) of the Directive 1999/2/EC says: “the The development of detection methods accred- EU Member States shell forward to the Commis- ited in the Laboratory considers, generally speak- sion every year the results of checks carried out at ing, the enlargement of the ability of the methods the product marketing stage and the methods used to identify radiation treatment in food products of to detect irradiated foods”. a more and more complex composition as delivered Poland, the EU Member State, is obliged to fol- very often by the customers for examination. The low the above regulation since 2004. Thus, the Table. The total number of samples in the Laboratory for Detection of Irradiated Food from 2004 to 2006 under Chief Sanitary Inspector of Poland programme.

reason of the growing interest of food trade in the country wide control and monitoring system of examination of complex products containing typi- food to prevent illegal trade of irradiated prod- cally only a small admixture of irradiated ingredi- ucts has been established by the Chief Sanitary ent (e.g. spices) has its source in the regulation that Inspector of Poland. The samples of food prod- are in force in all EU Member Countries now. ucts available in the market are delivered to the These are stated in the Directive 1999/2/EC of the Laboratory from the 16 provincial (voivodeship) European Parliament and of the Council [1]. The sanitary-epidemiological inspections every year. document says that if a foodstuff contains irradi- In Table, the number of both thermolumines- ated ingredient constituting even less than 2.5% cence (TL) and electron paramagnetic resonance of the product, it is treated in the same way as a (EPR) examinations accomplished in the Labora- foodstuff that was irradiated in whole, in 100%. tory within this programme from 2004 to 2006 in- Taking into consideration the requirements of the cluding foodstuff examined and classification of Laboratory customers, we proceed research works samples whether irradiated or not are compiled. leading to the extension of the applicability of our The results of 2004 monitoring is included in detection methods to more complex foodstuffs, too. the Report from the Commission on food irradia- The survey of this works can be found in [2-4]. tion for the year 2004 (3.20. Poland) [10]. Now-a-day five detection methods implanted In 2006, except for the above 39 samples, 339 earlier in the Laboratory received PCA (Polish examinations of foodstuffs delivered by the Labo- Centre for Accreditation) Accreditation Certifi- ratory customers from abroad (Germany, Italy, cate of Testing Laboratory Nr AB 262 issued on United Kingdom, Denmark, Switzerland, France, 25.10.2006 and valid until 24.10.2010. Thailand – 315 samples) and from domestic firms The list of detection methods, all addressed to (24 samples) have been done. The total number of specific groups of foodstuffs is included in the Scope samples examined for the customers in 2006 was 64 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES - shrimps (18.6%); - herbal pharmaceuticals, herbal extracts (21.7%); - poultry and fish (3.6%); - nuts in shell (7.3%); - fresh fruits – strawberries (1.5%); - others, i.e. instant soups, red fermented rice, all purpose savoury seasoning (1.7%).

References [1]. Directive 1999/2/EC of the European Parliament and of the Council of 22 February 1999 on the approximation of the Member States concerning foods and Fig.1. Classification of food samples taken for examina- food ingredients treated with ionising radiation. Off. tion in 2006. J. European Communities L 66/16-23 (13.3.1999). [2]. Guzik G.P., Stachowicz W.: Comparison of PPSL and 478. 87.9% of the total number of samples were TL methods for the detection of irradiated food and examined by the TL method (PN-EN 1788:2002) food components. In: INCT Annual Report 2006. In- while 12.1% by the EPR methods (PN-EN 1786:2000 stitute of Nuclear Chemistry and Technology, War- and PN-EN 1787:2001). szawa 2007, pp. 56-58. [3]. Laubsztejn M., Malec-Czechowska K., Strzelczak G., Among all food samples examined in 2006, Stachowicz W.: Detection of irradiation in herbal 93.7% were found not to be irradiated, while 6.3% pharmaceuticals with the use of thermoluminescence samples were irradiated (Fig.1). and electron paramagnetic resonance spectrometry. In: INCT Annual Report 2006. Institute of Nuclear Chemistry and Technology, Warszawa 2007, pp. 60-62. [4]. Lehner K., Stachowicz W.: Development and accreditation of EPR method for detection of irradiated food containing sugar. In: INCT Annual Report 2006. Institute of Nuclear Chemistry and Technology, War- szawa 2007, pp. 58-60. [5]. PN-EN 1786:2000: Foodstuffs – Detection of irradiated food containing bone. Method by ESR spectroscopy. [6]. PN-EN 1787:2001: Foodstuffs – Detection of irradiated foods containing cellulose Method by ESR spectroscopy [7]. PN-EN 1788:2002: Foodstuffs – Thermoluminescence detection of irradiated food from which silicate minerals can be isolated. Fig.2. Assortment of foodstuffs examined in 2006. [8]. PN-EN 13708:2003: Foodstuffs – Detection of irradi- The assortment of foodstuffs that were examined ated food containing crystalline sugar by ESR spectroscopy. in 2006 (Fig.2) compiles: [9]. PN-EN 13751:2003: Foodstuffs – Detection of irradi- - spices, herbs and their blends that may contain ated food using photostimulated luminescence. small admixture of irradiated spices as a flavour [10]. Report from the Commission on food irradiation for ingredient (40.2%); the year 2004. Off. J. European Communities EN C - seasonings, fresh and dried vegetables (5.4%); 230/28 (23.09.2006), 3.20. Poland. RADIOCHEMISTRY STABLE ISOTOPES NUCLEAR ANALYTICAL METHODS GENERAL CHEMISTRY RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 67 103Ru/103mRh GENERATOR Barbara Bartoś, Ewa Kowalska, Aleksander Bilewicz, Gunnar Skarnemark1/ 1/ Department of Chemical and Biological Engineering, Chalmers University of Technology, Göteborg, Sweden

The possibility of using electron emitters to cure generating Cl2 molecules: 1 M HCl+KIO4. The Cl2 cancer metastasis depends on the energy of the molecules, formed in this solution are distributed emitted electrons. Electrons with high energy give among the two liquid phases keeping RuO4 in the a high absorbed dose to large tumors, but the dose organic phase. Milking of 103Rh was performed by absorbed by small tumors or single tumor cells is shaking the organic phase with 0.01 M solution of –1 low, because the range of the electrons is too long. H2SO4 containing 0.2 mg ml of KIO4. In this pro- The fraction of energy absorbed within the tumor cess 103mRh is totally transferred to the aqueous decreases with increasing electron energy and de- phase together with small amounts of 103Ru. The creasing tumor size. For tumors smaller than 1 g, 103 the tumor-to-normal-tissue mean absorbed dose-rate Table. Distribution coefficient for extractions of Ru and 103mRh. ratio (TND) will be low, e.g. for 131I and 90Y, because of the high energy of the emitted electrons. For radiotherapy of small tumors, radionuclides emitting charged particles with short ranges (a few micrometers) are required. The short path length of particles also may limit toxicity to neighboring normal tissue. Using various selection criteria like electron energy, suitable half-life, low photon/electron ratio and availability, Bernhardt and co-workers found aqueous phase was purified from tracers of 103Ru 103m that the Auger emitter Rh meets these criteria by three times extraction with CCl4, and finally by [1]. 103mRh has a short half-life (56 min) and is pro- passing through an anion exchange resin. The reduced via β– decay of 103Ru or EC decay of 103Pd. sults of stepwise extractions are presented in Table.

These mother nuclides have half-lives of 39 and 17 If the ruthenium remained as RuO4 there would days, respectively, and can be used as generators for be no problem; it would be easy to wash the rhodium 103mRh. So far, however, only 103Ru has been tested fraction a few times with a pure organic solvent to as the generator, mainly because it is easy to pro- remove the contamination. Unfortunately, a small duce in large amounts, either by fission of uranium fraction of the ruthenium in the aqueous phase is – or by neutron activation of ruthenium. For thera- reduced to RuO4 or RuO2, which are difficult to 103m peutic applications, the Rh would be attached remove. The RuO4 was removed by few washings 103 to, e.g. a peptides or monoclonal antibodies to find with CCl4. The residue of Ru in the aqueous phase – the cancer cells. was absorbed as RuO4 on the anion exchange resin. The goal of the present work is the elaboration The separation process involving three solvent 103 103m of a Ru/ Rh generator for milking therapeutic extractions with CCl4 and adsorption on an anion quantities of 103mRh. 103Ru. The mother nuclide of exchange resin gave separation factors between 103mRh, was obtained by neutron irradiation of a 103mRh and 103Ru of more than 5x103. natural ruthenium target at a neutron of flux 3x1014 The work was carried out in the frame of Marie n cm–2 s–1 in the nuclear reactor MARIA at Świerk. Curie Action for the Transfer of Knowledge – con- After 36 h irradiation of a 9.6 mg target, 130 MBq tract No. MTKD-CT-2004-509224 with the Euro- of 103Ru was obtained. The target was then dissolved pean Commission. in a mixture of NaOH and KIO4. After complete dissolution of the target, the solution was acidified, References and RuO4 formed was extracted to an organic [1]. Bernhardt P., Forssell-Aronsson E., Jacobson L., (CCl4) phase. To avoid reduction of RuO4 to RuO2, Skarnemark G.: Acta Oncol., 40, 602-608 (2001). the organic phase was contacted with a solution

ZOLEDRONIC ACID LABELED WITH 47Sc AND 177Lu FOR BONE PAIN THERAPY Maria Neves1/, Ines Antunes1/, Agnieszka Majkowska, Aleksander Bilewicz 1/ Nuclear and Technological Institute, Sacavém, Portugal

Bisphosphonates (BPs) have a strong affinity for been the chosen molecules for bone scanning im- calcium phosphates and for hydroxyapatite. Be- aging. Some bisphosphonate compounds exhibit cause of their chemical structure and the charac- short side chains, such as clodronate andetidronate; teristic P-C-P- bond, which is non-biodegradable others have aliphatic chains of different lengths bear- and non-hydrolysed in vivo, bisphosphonates have ing terminal amino groups (pamidronate, alendro- RADIOCHEMISTRY, STABLE ISOTOPES, 68 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY nate, and neridronate) or substituted amino groups (olpadronate and ibandronate). Among the last generation of bisphosphonates with cyclic side chains, zoledronate with a nitrogen atom in the imidazole ring, is the most potent bisphosphonate described so far to inhibit bone resorption. Bis- phosphonates labeled with technetium-99mTc are main radiopharmaceuticals used for bone scanning imaging. Bisphosphonates are also able to coordi- nate β-emitter as 153Sm and 186Re, and found application in clinical nuclear medicine for bone metastasis therapy (Re-186-HEDP-Metastron and Sm-153-EDTMP-Quadramet). Until now, bisphosphonates were labeled with β-emitters of rela- 153 188 166 Fig.1. Dependence of labeling efficiency of zoledronate on tively high energy like Sm, Re and Ho. Due the ligand-to-metal mole ratio. to a long distance interaction of hard β-particles, the degradation of bone marrow is observed. To stronger complexes with zoledronate than 177Lu avoid this harmful effect we plan to apply bisphos- does. This results from much smaller ionic radius phonates labeled with soft β-emitters, e.g. 47Sc and of Sc3+ than Lu3+. 177Lu instead of hard β-emitters. The distance of The zoleodronates labeled with 46Sc and 177Lu in particles emitted by soft β-emitters in bone is much molar ratio 100:1 was used for studies of adsorp- shorter, less than 1 mm, therefore bone marrow tion of labeled bisphosphonates on hydroxyapa- would not be affected. tite. Adsorption of bisphosphonates on hydroxy- The sample of sodium salt of zoledronic acid apatite is commonly used as model for adsorption (1-hydroxy-2-imidazol-1-yl-phosphonoethyl) was a of bisphosphonate radiopharmaceuticals on min- gift from Novartis Pharma AG. Due to the short eral components of the bones. The dependence of half-life of 47Sc, the labeling of bisphosphonates adsorption percent on the mass of hydroxyapatite γ 46 was studied using the -emitting Sc (t1/2=83.8 d) samples are shown in Fig.2. radiotracer. 46Sc and 177Lu radiotracers were obtained by neutron irradiation of Sc2O3 and Lu2O3 targets at a neutron flux of 3x1014 n cm–2s–1 for 6 h. The specific activities of the radionuclides obtained were 100 MBq/mg for 46Sc and 700 MBq/mg for 177Lu. The targets were dissolved in 0.1 M HCl solution. The radiolabeling efficiency and stability evaluation of the radiocomplexes were accomplished by ascend- ing instant thin layer chromatography (ITLC) using ITLC-SG (Polygram, Macherey-Nagel) strips developed with the mobile phase: H2O/NH3 (25:1). The hydroxyapatite-binding assay was performed according to the procedure described previously after a slight modification [1]. In brief, to vials con- Fig.2. Percent of 46Sc and 177Lu adsorption on hydroxyapa- taining 1.0, 2.0, 5.0, 10.0 and 20.0 mg of hydroxy- tite as a function of hydroxyapatite mass sample. apatite, were added 2 ml of saline solution at pH 7.4 and the mixtures were shaken for 1 h. Then, 50 The maximum adsorption, higher than 98%, μl of each radioactive preparation was added and was achieved by 177Lu-zoledronate using more than the mixtures was shaken for 24 h at room tem- 5 mg of hydroxyapatite, and by 46Sc-zoledronate perature. All suspensions were centrifuged and the for more than 20 mg of hydroxyapatite. radioactivity of the supernatant was measured with The obtained results showed that 46Sc forms well γ-scintillation counter. Control experiments more stable complexes than 177Lu zoledronate com- were performed using a similar procedure in the plexes, while the adsorption of 177Lu complexes on absence of hydroxyapatite beads. The percentage hydroxyapatite is higher than that of 46Sc-zoleodro- binding of 46Sc and 177Lu to hydroxyapatite (HAP) nate. was calculated according to HA=(1 – A/B)*100, The work was carried out in the frame of Marie where A is the final and B – the initial activity of Curie Action for the Transfer of Knowledge – con- solution. tract No. MTKD-CT-2004-509224 with the Euro- In ITLC studies, 46Sc and 177Lu zoledronate com- pean Commission. plexes migrate (Rf 0.8-1.0), while the ionic and colloidal radioactive forms of 46Sc and 177Lu remain at References the origin. The labeling efficiency of zoledronate with [1]. Neves M., Gano L., Pereira N., Costa M.C., Costa M.R., 177Lu and 46Sc, obtained from the ITLC studies, is Chandia M., Rosado M., Fausto R.: Nucl. Med. Biol., presented in Fig.1. As shown in Fig.1, 46Sc forms 29, 329 (2002). RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 69 Rh[16aneS4]211At AND Ir[16aneS4]211At COMPLEXES AS PRECURSORS FOR ASTATINE RADIOPHARMACEUTICALS Marek Pruszyński, Aleksander Bilewicz, Michael R. Zalutsky1/ 1/ Department of Radiology, Duke University Medical Center, Durham, USA Alpha-targeted therapy is a significant method for that thioether ligand was absent. First optimiza- treatment of small solid tumors and hematologic tion of reaction conditions was performed with malignancies (e.g. leukemias and lymphomas). Re- 125I/131I isotopes and later repeated for 211At. For- cently, these diseases are treated with convention- mation and the radiochemical yield of the com- ally 131I or 90Y radiolabelled immunoconjugates, but plexes were estimated by paper electrophoresis, ion without great success. These radionuclides emit beta- exchange and high performance liquid chromato- -particles with ranges much larger than the diameter graphy (HPLC) methods. Electrophoresis was per- of a cancer cell. The maximum beta-energies vary formed using Whatman #1 paper strips. Reversed from 0.5 to 2 MeV and the corresponding ranges phase HPLC was carried out using a Beckman are from 1-10 mm. This results in undesirable irradiation of normal cells such as stem cells in the marrow, even if the cancer cell is successfully targeted. The alpha-particles are more suited for tiny clusters of cancer cells and micrometastases, because of their high energy (enable to make double strand breaks in DNA) and short range, contributing to their high linear energy transfer (LET) and radio- biologic effectiveness (RBE). 211At is one of the most promising alpha-emitters that has, so far, been studied for cancer therapy. This isotope is artificially produced in a cyclotron 209 211 via the Bi(α,2n) At reaction and has a 7.2 h Fig.1. HPLC chromatogram of Rh[16aneS4]211At complex half-life that allows sufficient time for its produc- recorded directly after formation: 1 – free unbounded tion, synthetic chemistry, quality control, transpor- astatide, 2 – peak of Rh[16aneS4]211At complex. tation and medical application. It decays by double branch pathway with a mean alpha-energy of 6.7 Coulter device and a Waters Xterra RP18 column MeV. As a consequence of its electron capture coupled to a beta-detector for radiometric analy- branching to its daughter 211Po, X-rays of 71 to 92 sis. The gradient elution system utilized mobile keV are emitted, enabling external imaging (includ- phase A (deionized H2O) and mobile phase B ing SPECT) and gamma counting of blood samples (100% acetonitrile) and flow rate of 1 ml/min, as an additional advantage. started with 95%A/5%B for 5 min at which time The current study was focused on finding a stable the linear gradient was initiated over 30 min inter- labelled prosthetic group for the use in labelling val to 100%B. Both mobile phases contained 0.1% of biomolecules with 211At. Our idea was to attach trifluoroacetic acid (TFA). An example of HPLC the astatide anion using its halogen properties to radiochromatogram is shown in Fig.1. RP HPLC soft metal cations, which are complexed by a bi- and the Waters Sep-Pak (C18) columns were also functional ligand. We decided to use rhodium and used to isolate the complexes from synthesis sol- iridium, because they are moderately soft metal ution for further stability studies. The in vitro sta- cations, which should form very strong bond with bility of complexes was determined in phosphate- the soft astatide. The high kinetic inertness of the -buffered saline (PBS) at 37oC with the 131I isotope low-spin d6 Rh(III) and Ir(III) complexes is also a as an analogue of astatine. very important advantage for the formation of stable conjugate. Macrocyclic sulphur ligand 1,5,9,13-tetrathia- cyclohexadecane-3,11-diol (16aneS4) was chosen for model studies because it forms stable complex with Rh(III) and can be modified to a bifunctional chelate ligand [1]. Complexes between 211At, Rh(III) or Ir(III) and thioether ligand were synthesized in an aqueous ethanolic solution. The formation of complexes was studied by heating the solution at different time periods (15-120 min) and over a wide range of temperature (30-90oC). The pH was varied from 2 to 7.5 by addition of HNO3 or NaOH. The quantity of Rh(III)/Ir(III) and 16aneS4 was changed in the range of 0.125-125 nmol and 2.5-250 nmol, respectively. All control experiments were carried Fig.2. Dependence of the complex formation on the Rh(III) out under identical conditions with the exception and Ir(III) concentration. RADIOCHEMISTRY, STABLE ISOTOPES, 70 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY Dependence of the Rh3+ and Ir3+ mixed ligand complex formation on the metal cations and sulphur ligand concentration are shown in Figs.2 and 3. In

Fig.4. Yield of the complexes vs. pH of reaction.

cated the expected cationic character of the com- 131 Fig.3. Dependence of the complex formation on the plexes. Both Rh(III) and Ir(III) complexes with I 16aneS4 concentration. showed a good stability at pH 7.4 PBS after 51 h of incubation. The stability studies in human serum Figure 4, the influence of pH of the solution on and biodistribution of complexes in normal mice the reaction yield is presented. Maximum complex are in progress. formation yields 75 and 80% for Rh[16aneS4]211At Part of the work was carried out in the frame of and Ir[16aneS4]211At, respectively, were obtained Marie Curie Action for the Transfer of Knowledge at pH 3-5 after heating for 1-1.5 h at 75-80oC. The – contract No. MTKD-CT-2004-509224 with the optimal concentration of Rh(III)/Ir(III) was 62.5 European Commission. and 250 nmol for sulphur ligand. The yield of the reaction with 211At was high, but less than with its References analogue 131I. Paper electrophoresis analysis indi- [1]. Venkatesh M. et al.: Nucl. Med. Biol., 23, 33 (1996).

FORMATION KINETICS AND STABILITY OF SOME TRI- AND TETRAAZA DERIVATIVE COMPLEXES OF SCANDIUM Agnieszka Majkowska, Aleksander Bilewicz

Radionuclides with medium energy beta-emission lanthanides, therefore ligands developed for these and a several day half-life are attractive candidates cations should be suitable for chelating 47Sc. In for radioimmunotherapy. Among the most promis- order to find the best chelators for attaching 47Sc to ing in this category is 47Sc [1]. It has desirable nuclear biomolecules the formation of Sc3+ complexes with properties since it is a beta-emitter (Eβ1=600 keV, 1,4,7,10-tetraazacyclododecane-1,7-bis acetic acid Eβ2(max)=439 keV) with a 3.35 d half-life. In ad- (DO2A), 1,4,7,10-tetraazacyclododecane-1,4,7,10-te- dition, 47Sc has a primary gamma ray at 159 keV traacetic acid (DOTA) and 1,4,7-triazacyclono- that is suitable for imaging. The methods for pro- nane-1,4,7 triaacetic acid (NOTA), were studied duction high activities of 47Sc was described by by capillary and paper electrophoresis and thin 47 Kolsky et al. [2]. Enriched TiO2 target was irradi- layer chromatography (TLC). The formulae of the ated with high energy neutrons (En>1 MeV) to ligands are presented in Fig.1. produce 47Sc via the 47Ti(n,p)47Sc reaction. These The DOTA and DO2A ligands were purchased authors also developed a new separation scheme from Macrocyclics. The NOTA ligand was synthe- based on cation exchange on a Dowex AG 50W sized by reaction of 1,4,7-triazacyclononane with resin with elution of 47Sc using HCl/HF solution. bromoacetic acid. Chemical purity of the product Sc3+ of ionic radius 74.5 pm (CN=6) is chemi- was checked by mass spectrometry (MS) and nu- cally similar to Ga3+, In3+, Y3+ and to the heaviest clear magnetic resonance (NMR) methods. Stabil-

Fig.1. Ligands selected for complexation of Sc3+ cations. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 71 ity constants of scandium macrocyclic complexes Table. Stability constansts of Sc3+ and Lu3+ complexes with were determined using capillary electrophoresis. DOTA, DO2A and NOTA ligands. The Sc3+ complexes were synthesized by mixing of 1.5 mM aqueous solution of a given ligand with 1.5 mM aqueous solution of Sc3+, at pH=3 for DOTA and NOTA, and at pH=5 for DO2A. When the complexation process reached equilibrium (8 days), small aliquots of the solution were injected into the capillary to determine the concentrations The electrophoresis and ion exchange studies of the complex, free Sc3+ and ligand, respectively. indicate that Sc3+ forms complexes with different A typical electrophorogram is presented in Fig.2. charge: anionic with DOTA, neutral with NOTA and cationic with DO2A. Therefore, we can conclude that in DOTA complexes, Sc3+ has a coordination number of 8, while in NOTA and DO2A exhibit a coordination number of 6. The kinetics of Sc3+ DOTA complex formation was measured at pH=2, 3 and 4. The formation of the complex under this condition is quite rapid. The half-time of the equilibrium was reached in 300 s at pH=2.04, in 236 s at pH=3 and in 106 s at pH=4. The high thermodynamic stability and inertness of the studied scandium chelates indicate that 47Sc Fig.2. Electrophorogram of ScCl2 and DOTA mixture at 90 buffer pH 3, applied voltage – 10 kV, capillary – 50 labeled biomolecules could be an alternative to Y 177 μm, length – 25 cm, detection wave length – 222 nm. and Lu radiopharmaceuticals.

Initial concentration ScCl2 and DOTA – 1.5 mM. Part of the work was carried out in the frame of Marie Curie Action for the Transfer of Knowledge The conditional stability constants were calcu- – contract No. MTKD-CT-2004-509224 with the lated based on the determined equilibrium con- European Commission. centration of the free ligand using the procedure described by Zhu and Lever [3]. Taking into ac- References count the stepwise k , k , k and k protonation 1 2 3 4 [1]. Mausner L.F., Kolsky K.L., Joshi V., Srivastava S.C.: constants of DOTA, the stability constants were Appl. Radiat. Isot., 49, 285-294 (1998). calculated. The results are presented in Table. As [2]. Kolsky K.L., Joshi V, Mausner L.F., Srivastava S.C.: 3+ shown in Table, Sc forms most stable complexes Appl. Radiat. Isot., 49, 1541-1549 (1998). with the DOTA ligand similarly to the lanthanides [3]. Zhu X, Lever S.Z.: Electrophoresis, 23, 1348-1356 and Y3+. (2002).

IN VITRO STABILITY OF TRICARBONYLTECHNETIUM(I) COMPLEXES WITH N-METHYL-2-PYRIDINECARBOAMIDE AND N-METHYL-2-PYRIDINECARBOTHIOAMIDE – HISTIDINE CHALLENGE Monika Łyczko, Jerzy Narbutt

The strategy to design new 99mTc radiopharma- Under conditions of the challenge experiments ceuticals involves incorporation of the radionuclide (0.07 M Cl–), two forms of the complexes were dis- 99m + into biologically active molecules, which requires tinguished, [ Tc(CO)3LNX(H2O)] and/or 99m 99m chelating Tc at an appropriate oxidation state [ Tc(CO)3LNXCl] (X=O or S), the equilibrium and linking the obtained chelate to the biomolecule. between these two forms being dependent on the

The chelates should be stable, kinetically inert, ligand, LNX. The formation of each complex was small in size and moderately lipophilic. As a part of confirmed by high performance liquid chromato- our systematic studies [1-3] on tricarbonyltechnet- graphy (HPLC) analysis. Molecular structure of the ium(I) chelates with the derivatives of picolinic and complexes was confirmed by infrared (IR) studies thiopicolinic acids: N-methyl-2-pyridinecarbo- on the analogous 99Tc and rhenium complexes fol- amide (LNO) and N-methyl-2-pyridinecarbothio- lowed by X-ray diffraction studies on the latter amide (LNS); we studied the stability of these com- [1,6,7], and also by advanced quantum chemistry plexes using histidine challenge method. Histidine calculations [2]. and cysteine challenge tests are often used to deter- Histidine challenge experiments were performed mine in vitro stability of technetium complexes [4,5]. by adding 0.5 mL of aqueous phosphate buffer 99m 99m –3 The Tc-LNO and Tc-LNS complexes were solution (pH 7.4) containing 2·10 M histidine, to obtained from their tricarbonyl precursor, fac- 0.5 mL of the 99mTc complex solution containing 99m + –3 -[ Tc(CO)3(H2O)3] , as described elsewhere [1]. excess (2·10 M) of LNO or LNS. The samples were RADIOCHEMISTRY, STABLE ISOTOPES, 72 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY complexes with bidentate ligands undergo significant substitution by tridentate histidine [8,9]. In 99m view of the above information, the Tc-LNO complex studied may be considered fairly stable, while 99m the Tc-LNS complex is extremely stable. This difference in the stability of both tricarbonyltechnetium(I) complexes well corresponds to that in their yields [1]. On the other hand, the more negative 99m formation energy of the Tc-LNO complex calculated for the gas state [2] can result from the different configurations of the substrates and products in the gas state and the aqueous solution, as

well as from different hydration energies of the LNO and LNS ligands in the solution [2]. Part of the work was carried out in frame of Marie Curie Action for the Transfer of Knowledge – contract No. MTKD-CT-2004-509224 with the Fig.1. HPLC chromatogram of the [99mTc(CO) L ] com- 3 NO European Commission. plex after incubating (0.5 h, 37oC) with histidine sol-

ution (the concentrations of histidine and LNO are –3 99m + References equal to 1·10 M). Peaks: 1 – [ Tc(CO)3(H2O)3] – (at 4.5 min) practically absent, 2 – TcO4, 3a – [1]. Łyczko M., Narbutt J.: Tricarbonyltechnetium(I) com- 99m + 99m [ Tc(CO)3LNO(H2O)] , 3b – [ Tc(CO)3LNOCl], 4 plexes with neutral bidentate ligands: N-methyl-2-pyri- 99m – [ Tc(CO)3histidine]. dinecarboamide and N-methyl-2-pyridinecarbothioamide. In: INCT Annual Report 2005. Institute of o incubated at 37 C and analyzed by means of HPLC Nuclear Chemistry and Technology, Warszawa 2006, 99m after 0.5, 2 and 24 h. After incubating the Tc-LNO pp. 71-74. complex for 0.5 h, a new peak of a moderate height [2]. Narbutt J., Czerwiński M., Zasępa M.: Tricarbonyl- appeared in the chromatogram at 12.4 min (Fig.1), technetium(I) complexes with N,O- and N,S-donating which corresponds well to the position of the ligands – theoretical and radiochemical studies. In: 99m Proceedings of the DAE-BRNS Symposium on Nuclear [ Tc(CO)3histidine] complex. This means that histidine partly replaces the L ligand in the com- and Radiochemistry NUCAR 2005, Amritsar, India, NO 15-18.03.2005. Eds. K. Chander, R. Acharya, B.S. Tomar plex. The relative magnitude of this 12.4 min peak 99m and V. Venugopal. BARC, Trombay, Mumbai 2005, after incubating the Tc-LNO complex for 2 h is pp. 64-67. only slightly greater than that after 0.5 h. On the [3]. Narbutt J., Zasępa-Łyczko M., Czerwiński M., Schibli 99m other hand, in the chromatogram of the Tc-LNS R.: Tricarbonyltechnetium(I) complexes with neutral complex practically no peak of the histidine com- bidentate ligands: N-methyl-2-pyridinecarboamide plex was observed even after incubation as long as and N-methyl-2-pyridinecarbothio-amide. Experi- 24 h (Fig.2). Generally, tricarbonyltechnetium(I) mental and theoretical studies. In: International Symposium on Trends in Radiopharmaceuticals (ISTR-2005), Vienna, Austria, 14-18.11.2005. Book of extended synopses. IAEA, Vienna 2005, pp. 61-62. [4]. La Bella R., Garcia-Garayoa E., Bahler M., Blauen- stein P., Schibli R., Conrath P., Tourwe D., Schubiger P.A.: Bioconjugate Chem., 13, 599-604 (2002). [5]. Alves S., Paulo A., Correia J.D.G., Gano L., Smith C.J., Hoffman T.J., Santos I.: Bioconjugate Chem., 16, 438-449 (2005). [6]. Fuks L., Gniazdowska E., Mieczkowski J., Narbutt J., Starosta W., Zasępa M.: J. Organomet. Chem., 89, 4751-4756 (2004). [7]. Gniazdowska E., Fuks L., Mieczkowski J., Narbutt J.: Tricarbonylrhenium(I) complex with a neutral bidentate N-methyl-2-pyridinecarboamide ligand, as a precursor of therapeutic radiopharmaceuticals. In: International Symposium on Trends in Radiopharmaceuticals (ISTR-2005), Vienna, Austria, 14-18.11.2005. Book of extended synopses. IAEA, Vienna 2005, pp. 190-191. 99m Fig.2. HPLC chromatogram of the [ Tc(CO)3LNS] complex [8]. Schibli R., La Bella R., Alberto R., Garcia-Garayoa after incubating (24 h, 37oC) with histidine solution E., Ortner K., Abram U., Schubiger P.A.: Bioconjugate

(the concentrations of histidine and LNO are equal Chem., 11, 345-351 (2000). –3 99m + to 1·10 M). Peaks: 3a – [ Tc(CO)3LNS(H2O)] [9]. Bayly S.R., Fisher C.L., Storr T., Adam M.J., Orvig 99m practically absent, 3b – [ Tc(CO)3LNSCl]. C.: Bioconjugate Chem., 15, 923-926 (2004). RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 73 ION EXCHANGE STUDIES 99m + ON THE ORGANOMETALLIC AQUA-ION fac-[ Tc(CO)3(H2O)3] IN ACIDIC AQUEOUS SOLUTIONS Zbigniew Samczyński, Monika Łyczko, Rajmund Dybczyński, Jerzy Narbutt

99m The “semi aqua-ion” fac-triaquatricarbonyltech- graphy (HPLC). Another impurity, TcO2 (3) re- 99m + netium(I) (fac-[ Tc(CO3)(H2O)3] ), 1, is a well moved on a guard C-18 HPLC column, could not known precursor of potential diagnostic radiophar- be detected this way. To study the hydrolysis of 1 in maceuticals labelled with 99mTc [1,2]. The carbonyl water at higher pH and to confirm the sign of the ligands are very strongly attached to the central electric charge on 1 we used paper electrophoresis metal ion due to dπ→pπ back-bonding. Substitu- with radiometric detection of 99mTc. The pH of the tion of bi- or tridentate chelating ligands for the initial alkaline solution of 1 (soon after synthesis) labile water molecules leads to the formation of was adjusted to a required value in the range of numerous complexes, both thermodynamically 1.0÷10.7, by adding some HClO4 or NaOH, and stable and moderately kinetically inert. This inert- then 10 μL of the solution was brought on the centre ness can be explained by the d6 electron configu- of a paper stripe (1×15 cm) soaked with an electro- ration of the central metal ion in the octahedral lyte of the same pH. The electrophoresis was carried environment [1]. Both 1 and its Re(I) analog (1a) out at 100 V out for 20 min. A large broad peak are much more acidic than the aqua-ions of other was observed on the electrophorograms, either mi- monovalent metals. Titration experiments with grating to the cathode in the pH range of 1.0÷8.65, macroamounts (10–3 M solutions of Re or 99Tc) re- or remaining in the origin at pH≥9.2 (Fig.1). The ≈ sulted in: for 1a pKa 7.5 [3], and for 1 pKa>8 [1] positively charged species was undoubtedly 1, while ≈ or pKa 8.7 [4]. Oligomerization of the hydrolyzed that remaining in the origin would be the neutral 99m species in macroamounts was also observed [1-4]. [ Tc(CO)3(H2O)2OH] complex (4) – the prod- In aqueous halide solutions the water molecules in uct of deprotonation of 1 at higher pH. Basing on

1 are partly substituted by halide ions with the for- this, we estimate the pKa of 1 to be in the range of mation of rather weak neutral and anionic halide 8.8÷9.0, which is consistent with the data for the complexes [4,5]. The aim of the present work was macroamounts [1,4]. In the acidic and neutral sol- to study speciation of 1 at n.c.a. level in acidic aque- utions small amounts of impurities, probably 2 and ous solutions, and in particular the ion exchange 3, were also detected, either remaining in the origin behaviour of the various Tc(I) species. or slowly migrating to the anode. At pH>9 these The complex 1 was obtained following Alberto’s small peaks were overlapped by the large, broad peak method [1]. The yield exceeded 95%, the main im- of 4. 99m – purity being the non-reacted TcO4 anion (2) as The ion exchange studies were carried out with detected by high performance liquid chromato- acidic (HNO3 and HCl) solutions, pH<2, at room temperature. Two different ion exchange resins were used: - an amphoteric resin with aminophosphonic groups, Purolite S-950, 35-65 μm; - a strongly basic anion exchanger, Dowex 1X4, 200-400 mesh. Strongly acidic cation exchanger of the gel type, Dowex 50WX4, appeared inconvenient for this study because of rather low affinity for 1 and significant peak tailing. In order to separate 99mTc(I) species from the impurities 2 and 3, the amount of which increased with ageing the solution, the dynamic (chromatographic) method of study was applied. Glass columns (0.071 cm2 × 8 cm) were filled with the given

resin, and then washed with either 0.05÷2 M HNO3 (Purolite S-950), or 0.1÷12 M HCl (Dowex 1X4). 99m μ Tc samples (50 L each) in HNO3 or HCl solutions of the same concentration were introduced on the top of the resin bed, and then the 99mTc species were eluted from the column at the average flow rate of 0.64 mL/min. Three 99mTc species were

found in the HNO3 effluent from the column filled Fig.1. Electrophorograms of slightly alkaline aqueous sol- with the amphoteric resin: a small peak of 3 in the utions of 1: (A) pH 8.65 – the peak moved to the free volume, the main peak of 1, and a peak of 2 99m + of varying magnitude (Fig.2). cathode – [ Tc(CO)3(H2O)3] (1); (B) pH 9.20 – the peak remained at the origin (75 mm from the The distribution ratio, Di, of the given species i 99m cathode) – the neutral [ Tc(CO)3(H2O)2OH] com- was determined from the position of its peak on plex (4). the chromatogram: RADIOCHEMISTRY, STABLE ISOTOPES, 74 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY

whole range of HNO3 concentrations studied, so DIV=0. On the contrary to the HNO3 systems, only one large peak was observed in the HCl effluents from the anion exchanger columns. In this peak various chemical forms of Tc(I) were eluted altogether: the precursor 1 and three chloride complexes – – [Tc(CO)3(H2O)2Cl] (5), [Tc(CO)3(H2O)Cl2] (6) 2– and [Tc(CO)3Cl3] (7), in dynamic equilibrium [4,5]. Although the equilibrium between 1, 5, 6 and 7 establishes slowly in the NMR time-scale [5], it is very fast in the time-scale of the ion exchange experiment (minutes). The latter results in the elution of all these Tc(I) species in the common single

broad peak. In some experiments at DI>10, a small 99m Fig.2. Tc species eluted with 0.3 M HNO3 from ampho- peak of 3 could be distinguished in the HCl efflu- teric ion exchange resin, Purolite S-950, loaded with ent, at the free volume (DIV=0). On the contrary aged solution of [99mTc(CO) (H O) ]+. The numbers 3 2 3 to the Purolite S-950/HNO3 system, the peak of 2 denote the Tc(I) species defined in the text. was never observed in the HCl effluent. That was due to a very high affinity of the pertechnetate ion, –1 Di = (Vmax,i – V0)·mr (1) 2, to the Dowex 1X4 resin in the chloride form. where Vmax,i – effluent volume at the peak maximum The expected DVII values for the Dowex 1X4/HCl of the species i [mL]; V0 – sum of the dead volume systems were too large to be experimentally deter- of the column and the free volume of the resin bed mined.

[mL]; mr – mass of the dry resin [g]. The use of the dynamic method at the slow kinetics of redox reactions of 99mTc (see above) allowed us to determine the distribution ratios, Dm, of the 99mTc compounds at each valence state of technetium,

Tc(m). In the experiments with the HNO3 solutions we dealt with only one chemical form of 99mTc(I),

1. The slope of linear function logDI vs. log[HNO3], equal to -0.96 ±0.04 (Fig.3), combined with the results of the electrophoretic studies, confirms the +1 charge of 1. The cation 1 is not very hydro- –1 philic: in 1 M HNO3 we have DI=12 mL g . The slope of linear function logDVII vs. log[HNO3],

99m + Fig.4. Distribution ratio of the [ Tc(CO)3] species, DI, in the system anion exchange resin Dowex 1X4/HCl, as a function of HCl concentration.

Figure 4 shows the dependence of DI (determined from equation 1) on the molar concentration of HCl in the Dowex 1X4/HCl system. Let 1–i us denote the [Tc(CO)3(H2O)3–iCli] formula as 1–i MCli and assume that the two anionic species formed, 6 and 7 adsorb on the Dowex 1X4 resin (R-Cl) according to the anion exchange equation: 1–i ⎯⎯Ki → – (i – 1)RCl + MCli ←⎯⎯ Ri–1MCli + (i – 1)Cl (2) Fig.3. The dependence of the distributions ratios, DI and D , of two ionic 99mTc species on the HNO concen- where Ki denotes the equilibrium constant of the VII 3 anion exchange reactions. K may be expressed by tration in the system Purolite S-950/HNO3 solutions. i the mass action law using thermodynamic activities equal to -1.00 ±0.05 (Fig.3), corresponds to the –1 of the participating species, provided the activity charge of 2. The anion 2 is rather strongly adsorbed of water (solvant) does not change within the whole on the amphoteric resin studied. On the other hand, range of concentrations studied (constant ionic 99m TcO2 is not adsorbed on the resin within the strength). This asumption, however, can hardly be RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 75 satisfied in ion exchange experiments at a broad best-fit polynomial (4)) we evaluated for the three 99m 1–n range of the electrolyte (HCl) concentrations. As- chloride complexes fac-[ Tc(CO)3(H2O)3–nCln] β β β 3 –1 suming that also the neutral form, 5, is adsorbed on the values: 1=0.45, 2=0.085, 3=0.0046 (dm mol the Dowex-1 resin according to (2), we may express units). The values obtained are less (by the factor the distribution ratio of Tc(I) as follows: of 2.4÷3) than the literature values of the respec- 33−1 tive concentrational stability constants, determined ⎧⎫⎧⎫1i− (3) 99 D[RMCl][MCl]Ii1iiaq=×⎨⎬⎨⎬− by Tc-NMR for the macroamounts of Tc at a con- ∑∑ o ⎩⎭⎩⎭i1== i0 stant ionic strength (I=4) at 22 C [5]. Taking into where square brackets denote the molar concen- account that the ion exchange experiments were trations of the given species in the aqueous phase carried out at varying ionic strength of the HCl (index aq) and those in the resin phase (no index). solutions (I=0.1÷12) we consider our values for o Assuming Ki to be constant values, and including n.c.a. amounts of Tc at 25 C to be unexpectedly i-1 the constant value [RCl] into the Ki, we arrive at: good approximations for the literature stability − constants. A[Cl ]aq DI = −−−23(4) 1+β1aq2aq3aq [Cl ] +β [Cl ] +β [Cl ] References β β β where 1, 2 and 3 are the concentrational stabil- [1]. Alberto R., Schibli R. , Waibel R., Abram U., Schubiger ity constants of the chloride complexes 5, 6 and 7 A.P.: Coord. Chem. Rev., 190-192, 901-919 (1999). in aqueous solution: [2]. Alberto R.: Top. Curr. Chem., 252, 1-44 (2005). [3]. Egli A. et al.: Organometallics, 16, 1833-1840 (1997). 1i−+−−− 1 i β=[MCl ] × [M ] × [Cl ] (5) [4]. Suglobov D.N. et al.: In: Technetium, rhenium and other i i aq aq aq β β β metals in chemistry and nuclear medicine. 6. Eds. M. and A=K1 1+K2 2+K3 3. Considering A to be a Nicolini, U. Mazzi. SGEditoriali, Padova 2002, pp. constant (which is a very rough assumption), and 123-126. basing on the experimental dependence of logDI [5]. Gorshkov N.I., Lumpov A.A., Miroslavov A.E., (determined from equation 1) on log[HCl] in the Mikhalev V.A., Suglobov D.N.: Czech. J. Phys., 53, Dowex 1x4/HCl system (Fig.4; the solid line is the A745-A749 (2003).

SYNERGISTIC EFFECT OF NEUTRAL BIDENTATE N-HETEROCYCLIC LIGANDS ON THE SEPARATION OF Am(III) FROM Eu(III) BY SOLVENT EXTRACTION WITH TETRADENTATE 6,6’-BIS-(DIETHYL-1,2,4-TRIAZIN-3-YL)-2,2’-BIPYRIDINE Jerzy Narbutt, Jadwiga Krejzler The research in the partitioning of long-lived radio- tractants for the SANEX process, very selectively nuclides of minor actinides (An) from nuclear wastes, extracting actinides(III) over lanthanides from HNO3 directed on their further transmutation, is an im- solutions [4,5]. Solvent extraction of Am(III) and portant programme in Europe and in several nu- Eu from 1 M HNO3 by 6,6’-bis-(diethyl-1,2,4-tri- clear countries in the world. In particular, it is the azin-3-yl)-2,2’-bipyridine (C2-BTBP, scheme 1), subject of an integrated project EUROPART real- with high SFAm/Eu, has been reported [5].Very slow ized in the 6th Framework Programme of EU within kinetics of extraction with these lipophilic N-tetra- EURATOM [1]. One of the numerous extraction dentate ligands, not acceptable in technology, can systems proposed for the selective separation of be improved by the use of “phase transfer reagents”, minor actinides from lanthanide (Ln) fission prod- but at the cost of somewhat lowered the An/Ln sepa- ucts (the SANEX process) was the subject of our ration factor, SFAn/Ln [4]. recent studies [2,3]. N-tetradentate heterocyclic ligands, the derivatives of 6,6’-bis-(1,2,4-triazin-3-yl)-2,2’-bipyridine (BTBP), have been selected as most promising ex-

Scheme 2. 5,6-dimethyl-3-pyridin-2-yl-1,2,4-triazine (PT). In the present work, we investigated the effect of bidentate N-heterocyclic ligands, 5,6-dimethyl- -3-pyridin-2-yl-1,2,4-triazine (PT, scheme 2) [6], and 5,5',6,6'-tetraethyl-3,3'-bi-1,2,4-triazine (TT, scheme 3) [6], on the efficiency of the Am(III)/Eu(III) separation by solvent extraction with C2-BTBP. Prelimi- nary liquid-liquid distribution studies have shown Scheme 1. 6,6’-bis-(5,6-diethyl-1,2,4-triazin-3-yl)-2,2’-bi- that both C2-BTBP and TT are very lipophilic and pyridine (C2-BTBP). exhibit very low basicity (pKa<<1), while PT is RADIOCHEMISTRY, STABLE ISOTOPES, 76 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY moderately lipophilic and moderate weakly basic ≈ (pKa 2.7). Dilute 1,1,2,2-tetrachloroethane solutions of C2-BTBP (and its mixtures with PT or TT) were used to extract carrier-free 152Eu and 241Am from 1 M HNO3. The test tubes with the two liquid phases were mildly (60 times per min) mechanically

Scheme 3. 5,5',6,6'-tetraethyl-3,3'-bi-1,2,4-triazine (TT). shaken at a temperature of 25oC for various time intervals (from 10 to 180 min). Other experimental Fig.2. The increase in the Am(III)/Eu(III) separation factor details are described elsewhere [3]. with the time of solvent extraction of Am(III) and Figure 1 presents the dependence of the distri- Eu(III) in the systems: 0.05 M C2-BTBP (squares), 0.05 M C2-BTBP+0.5 M PT (circles) and 0.05 M bution ratios of the metal ions, DAm and DEu, on C2-BTBP+0.5 M TT (triangles) in 1,1,2,2-tetrachloro- the extraction time in all the systems studied. In o ethane/1 M HNO3 at 25 C. no system studied the extraction equilibrium was attained even after 180 min of the slow shaking. In The enhancement of the extraction exerted by the system with 0.05 M C2-BTBP alone all the ex- the TT ligand is somewhat greater than that from traction parameters: DAm, DEu and SFAm/Eu are much PT. All the experimental quantities, DAm, DEu and SFAm/Eu, observed after 180 min mild shaking in the mixed-ligand systems seem to approach the equi-

librium values. The fact that the DAm and DEu values are by 2÷4 times lower than the respective equilibrium values reported for the system with C2-BTBP alone [5] may be interpreted as due to the higher C2-BTBP concentration in that reference system (0.068 M). Surprisingly, however, the highest sepa-

ration factors, SFAm/Eu, in the C2-BTBP+PT and C2-BTBP+TT systems, 230 and 340, respectively, are significantly greater than the reported reference

value, 160 ±16 [5]. On the other hand, all the DAm, DEu and SFAm/Eu values observed in our system with C2-BTBP alone are clearly non-equilibrium quantities, even after 180 min mild shaking. Fig.1. Kinetics of solvent extraction of Am(III) (full symbols) If further studies confirm this preliminary ob- and Eu(III) (open symbols) in the systems: 0.05 M servation that 180 min mild shaking makes it pos- C2-BTBP (squares), 0.05 M C2-BTBP+0.5 M PT (circles) and 0.05 M C2-BTBP+0.5 M TT (triangles) sible to reach equilibrium in the mixed-ligand ex- in 1,1,2,2-tetrachloroethane/1 M HNO at 25oC. traction systems studied, while not in the system 3 with C2-BTBP alone, we will be able to conclude lower than the respective values reported for the that the synergism observed is of kinetic origin. In same system, but under vigorous 60 min shaking, that case the bidentate ligands studied will be con- e.g. SFAm/Eu=160 [5]. Moreover, the rate of Am ex- sidered the phase transfer regents which do not traction appears somewhat less than that of Eu. decrease the SFAm/Eu value observed in the system Therefore, the SFAm/Eu value also increases with the with C2-BTBP alone, surely because of the selec- time of extraction (Fig.2). tivity of the ligands for Am(III) over Eu(III) ions. The 1,1,2,2-tetrachloroethane solutions of PT The other option, i.e. the thermodynamic syner- and TT alone, 0.2÷1.5 M, do not noticeably extract gism due to preferential formation of mixed-ligand –4 Am(III) ions from 1 M HNO3 (DAm<10 ), which is Am(III) complexes, is less probable because both consistent with the data by Hudson et al. [6]. Figure tetradentate and bidentate ligands studied are neu- 1 shows that the bidentate ligands, PT and TT, tral molecules of the same chemical character, which either improve the kinetics of solvent extraction of can hardly exert synergistic effects in solvent ex- Am(III) and Eu(III) ions with C2-BTBP or cause traction of metal ions. a thermodynamic synergistic effect in extraction of The work was carried out within the European both metal ions, much stronger for Am than for Eu. Commission project EUROPART (contract No.

A great increase in the DAm values is observed when FI6W-CT-2003-508854) and was co-financed by the comparing to the system with C2-BTBP alone, while Polish Ministry of Education and Science (decision the respective increase in the DEu values is relatively No. 619/E-76/SPB/6). We thank our EUROPART less. This difference leads to a sygnificant increase partner, Dr. M.R.St.J. Foreman, for supplying us also in the SFAm/Eu values which grow with the time with the extractants studied. We also thank Prof. of extraction more and faster than that in the sys- S. Siekierski for discussion and Mrs. W. Dalecka tem with C2-BTBP alone (Fig.2). for technical assistance. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 77

References [3]. Krejzler J., Narbutt J., Foreman M.R.St.J., Hudson M.J., Casensky B., Madic C.: Czech. J. Phys., 56, D459-D467 [1]. Madic C., Lecomte M., Dozol J.-F., Boussier H.: Ad- (2006). vanced chemical separation of minor actinides from high [4]. Geist A., Hill C., Modolo G., Foreman M.R.St.J., level nuclear wastes. In: Proceedings of the Conference Weigl M., Gompper K., Hudson M.J.: Solvent Extr. Ion EURADWASTE’04, Luxembourg, 29.03.-01.04.2004. Exch., 24, 463-483 (2006). EUR 21027. [5]. Drew M.G.B., Foreman M.R.St.J., Hill C., Hudson M.J., [2]. Narbutt J., Krejzler J.: Separation of Am(III) from Madic C.: Inorg. Chem. Commun., 8, 239-241 (2005). Eu(III) by mixtures of triazynylbipyridine and bis(dicar- [6]. Hudson M.J., Foreman M.R.St.J., Hill C., Huet N., bollide) extractants. The composition of the metal com- Madic C.: Solvent Extr. Ion Exch., 21, 637-652 (2003). plexes extracted. In: INCT Annual Report 2005. Insti- tute of Nuclear Chemistry and Technology, Warszawa 2006, pp. 74-76.

ESTIMATION OF CYTOSTATIC AND ANTIMICROBIAL ACTIVITY OF PLATINUM(II) COMPLEXES WITH THIOUREA DERIVATIVES Elżbieta Anuszewska1/, Bożena Gruber1/, Hanna Kruszewska1/, Leon Fuks, Nina Sadlej-Sosnowska1/ 1/ National Medicines Institute, Warszawa, Poland cis-Platin (cis-diamminedichloroplatinum(II), CDDP) is used in clinical practice as one of the most effective anticancer drugs. Unfortunately, its use- fulness is limited due to the growing resistance of tumor cells, and significant side effects of the drug. It has been found that direct structural analogues Scheme. N-tetrahydrofurfurylthiourea (1) and N-2-methyl- of cis-platin, e.g. diaminocyclohexane (DACH) tetrahydrothiophenethiourea (2). platinum(II) complexes, do not show the expected improvement of the clinical efficacy in compari- synthesis as well as the physicochemical and cyto- son with the parent drug. Thus, since a few years toxic characterization of the compounds with the after the discovery of CDDP a continuing effort is non-acridine thiourea derivatives. The main ob- being made to develop other platinum complexes in jective of the presented study was to determine bio- order to overcome the above shortcomings [1,2]. logical, i.e. cytotoxic and antimicrobial activity of In the last two decades, the interest in plati- platinum(II) complexes with N-2-tetrahydrofurfuryl- num(II) complexes with chelating ligands contain- thiourea (1) and N-2-methyltetrahydrothiophene- ing both nitrogen and sulfur donor atoms has in- thiourea (2), see Scheme. MTT assay (test for mea- creased, because these complexes seem to exhibit suring cell growth with colorimetric assay using either higher anticancer activity or reduced toxicity yellow colorimetric indicator: MTT – 3-(4,5-dime- in relation to known metal containing drugs [3]. thylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) As a result of these studies, a number of novel plati- was performed as described by Gruber and Anu- num(II) complexes sufficiently interesting for clini- szewska [9]. cal trials have been synthesized. However, only a In addition to the cytotoxic properties, biologi- few of them have overcome the parent drug in their cal activity of the platinum complexes against dif- efficacy [4]. On the other hand, several combined ferent microorganisms was tested. The antimicro- chemotherapeutic procedures consisting in the bial activity was expressed by minimal inhibitory application of various platinum(II) complexes to- concentration (MIC). Results of the MIC measure- gether with compounds containing S-donor groups ments are presented in Table 1. (in this case called chemoprotectants) have been The results are displayed on the bar char, where tested with the aim of reducing the platinum-based L(O) and L(S) stand for the platinum(II) complex side effects. with 1 and 2, respectively (Fig.1). As a result of our previous studies [5,6], a ques- It can be seen that both complexes are especially tion arises whether complexes containing the efficient against Staphylococcus epiderminis: plati- II Pt (R1R2tu) fragment, where (R1R2tu) denotes a num(II)-1 complex inhibited growth of the strain differently substituted thiourea (tu) molecule, at a concentration of 5 mM, whereas platinum(II)-2 might exhibit the desired biological activity. Lit- was active against Staphylococcs epidermidis at 2.5 erature data suggest, that platinum(II) complexes mM. The latter was also active against Bacillus with certain thiourea derivatives (in particular con- pumilus at a concentration of 5 mM. All other taining the acridine fragment, called ACRAMTUs bacterial strains were inhibited by platinum(II)-1 [7,8]) can really be potential pharmaceuticals. The complex at a concentration of 10 mM, and by mode of their therapeutic action differs, however, platinum(II)-2 at a concentration of 20 mM. On from that established for the cis-platin. Our search- the other hand, the fungal strains were resistant ing for the platinum(II) complexes with ligands to both compounds even at the highest concentra- containing the thiourea derivatives focused on the tion, i.e. of 20 mM. RADIOCHEMISTRY, STABLE ISOTOPES, 78 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY

Table 1. MIC values of the investigated platinum(II) com- Table 2. The IC50 values of the investigated platinum(II) plexes. complexes.

The obtained data indicate that mammalian cells are about 10 times more sensitive than bacterial cells with reference to the platinum complexes studied. Stability of both complexes, with 1 and 2, in the standard aqueous physiological solution was checked by recording their UV-Vis spectra (200-800 nm,

nmax=235 nm) vs. time. No changes in the spectra have been detected within one week. The HPLC chromatograms of samples withdrawn occasionally from the saline solutions of the complexes during

one week (isocratic elution using a CH3CN-H2O mixture, vol:vol=20:80; 230 nm) did not exhibit noticeable changes either. As a result of the presented work, we can conclude that the biological activity of both platinum(II)-1 and platinum(II)-2 complexes, deter-

mined as their cytostatic IC50 and antimicrobial Cytotoxic activity of the complexes was deter- MIC values, is not very high. The same concerns mined with the use of MTT test. As shown in Table the results obtained already for the standard L1210 2 and Fig.2, all kinds of cells examined exhibit com- murine leukemia cell line [10]. However, the found parable sensitivity to both platinum(II)-1 and plati- cytotoxicity is significantly improved as compared num(II)-2 complexes. The less sensitive to the to that of platinum(II) complexes with the unsubsti- platinum(II) complexes appeared HeLa cells (an tuted thiourea molecules [5]. These results moti-

Fig.1. Activity of the investigated platinum(II) complexes against the bacterial strains. immortal cell line derived from cervical cancer cells taken from Henrietta Lacks, who died from her cancer in 1951), while the most sensitive were WS1 Fig.2. Activity of the investigated platinum(II) complexes cells – normal human fibroblasts. against the tumor cells. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 79 vate us to continue the investigations, in particular [6]. Fuks L.: Pt(II) chloride complexed by tetrahydrofur- on platinum(II) complexes with other thiourea de- furyl- or tetrahydrotiophenylthiourea: structural and rivatives, possibly useful in the chemotherapy. biological features. 3rd Cental European Conference Chemistry towards Biology, Kraków-Przegorzały, References Poland, 08-12.09.2006. [7]. Hess S.M., Anderson J.G., Bierbach U.: Bioorg. Med. [1]. Cvitkovic E., Spaulding J., Bethune V., Martin J., Chem. Lett., 15, 443 (2005). Whitmore W.F.: Cancer, 39, 1357 (1977). [8]. Choudhury J.R., Bierbach U.: Nucleic Acids Res., [2]. Burchenal J.H., Kalaher K., Dew K., Lokys L.: Cancer 33, 5626 (2005). Treat. Rep., 63, 1493 (1979). [9]. Gruber B.M., Anuszewska E.L.: Toxicol. In Vitro, [3]. Faraglia G., Fregona D., Sitran S., Giovagnini L., 16, 663 (2002). Marzano C., Baccichetti F., Cesellato U., Graziani R.: [10]. Fuks L., Kruszewski M., Sadlej-Sosnowska N.: Struc- J. Inorg. Biochem., 83, 31 (2001). tural studies and cytotoxicity assays of platinum(II) [4]. Canetta R., Rozencweig M., Wittes R.E., Shacter L.P.: chloride complexed by (tetrahydrothiophene)thio- In: Proceedings of the Fifth Nagaya International urea. In: INCT Annual Report 2005. Institute of Nuc- Symposium on Cancer Treatment. Excerpta Medica, lear Chemistry and Technology, Warszawa 2006, pp. Tokyo 1990, pp. 318-323. 68-70. [5]. Fuks L., Sadlej-Sosnowska N., Samochocka K., Sta- rosta W.: J. Mol. Struct., 740, 229 (2005).

TRANSITION METAL SORPTION BY ALGINATE BIOSORBENT Dorota Filipiuk1/, Leon Fuks, Marek Majdan2/ 1/ Białystok Technical University, Poland 2/ Maria Curie-Skłodowska University, Lublin, Poland

Contamination of aquatic environment by various sorbate species, the latter is bound by different pollutants (synthetics, organic, heavy metals, etc.) mechanisms. causes imbalance in natural functioning of the eco- The biosorption equilibrium of heavy metals was system. Heavy metals cause particularly severe modelled using adsorption-type isotherms. The damage to the living systems at various levels. Main Langmuir [5] and Freundlich [6] models are used sources of heavy metal contamination are: (i) urban as the most popular ones. The form of the Langmuir industrial aerosols created by combustion of fuels, model is metal ore refining and other industrial process; (ii) (b)(qme )(C ) liquid and solid wastes generated from animals and qe = (1) humans; (iii) mining activities; and (iv) industrial 1(b)(C)+ e and agricultural chemicals. The most important where: qe – the sorption capacity at equilibrium –1 –1 feature that distinguishes heavy metal ions from [mol g ], qm – maximum sorption capacity [mol g ], –1 other toxic pollutants is their non-biodegradability. Ce – equilibrium concentration of metal ion [mol L ], The toxicity due to metal ion is owing to their ability b – the Langmuir model constant [L/mol]. to bind with protein molecules and prevent repli- The form of the Freundlich model is 1/n cation of DNA and subsequent cell division [1]. qe = K(Ce) (2) To avoid health hazard, it is essential to remove where K and n – the Freundlich model constants these toxic heavy metals from water before their (dimensionless). intake by living organisms. Seaweeds are accounted among the most popu- Search for new technologies involving the re- lar biosorbents because their macroscopic structures moval of toxic metals from wastewaters has directed offer a convenient basis for production of sorbent attention towards biosorption, i.e. metal binding particles suitable for sorption process. Brown mar- by various biological materials. Biosorption can be ine algae tend particularly to sequester heavy metals defined as the ability of biological materials to ac- [7,8], in particular cell wall material obtained from cumulate heavy metals from aqueous solutions Sargassum biomass [9]. As a result, ion exchange through metabolically mediated or physicochemi- properties of certain natural polysaccharides have cal pathways of uptake [2]. Algae, bacteria and fungi been studied in detail, and it was found that bivalent and yeasts have proved to be potential biosorbents metal cations exchange with counter ions coming of metal ions [3]. The major advantages of biosorp- from the polysaccharides, e.g. alginic acid (Scheme) tion over conventional treatment methods include: according to the following reaction [3]: (i) low cost, (ii) high efficiency, (iii) minimization of chemical and/or biological sludge, (iv) no additional nutrient requirement; (v) easy regeneration of biosorbent, and (vi) possibility of metal recovery [4]. Biosorption process involves a solid phase (sorbent or biosorbent; biological material) and a liquid phase (solvent, normally water) containing a dissolved species to be sorbed (sorbate, metal ions). Due to higher affinity of the sorbent for the Scheme. Alginic acid carbohydrate chain. RADIOCHEMISTRY, STABLE ISOTOPES, 80 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY

Table. Isotherm model constants and correlation coefficients for biosorption of the selected divalent transition metal cations (concentrations expressed in mol L–1).

) * Co=0.0005 mol/L. 2+ ↔ + 2NaAlg + Me Me(Alg)2 + 2Na (3) thetic aqueous solutions containing a given metal In the presented paper, sorption data for the ion of known concentration. Then, the equilibrium selected divalent transition metal cations are re- metal content was determined spectrophotometri- ported, obtained from a batch equilibrium sorption cally using 4-(2-pyridylazo)resorcinol (PAR) as an procedure using calcium alginate pellets. The sor- indicator. The amounts of metal sorbed by the algi-

Fig.1. Langmuir adsorption isotherms for Mn(II) and Ni(II) ions. bent studied is comparable at low price to the orig- nate were calculated as the difference between the inal alginic acid, however its mechanical, chemi- initial and equilibrium concentrations in the aque- cal and thermal resistance significantly exceeds ous phase. The best fit parameters of equations (1) those of the acid. and (2) were obtained by regression analysis using Experiments were performed by shaking (6 h) the software package Microcal Origin for Windows the weighed amount of calcium alginate with syn- (release 6.0). Table shows the model constants and

Fig.2. Freundlich adsorption isotherms for Cu(II) and Cd(II) ions. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 81 correlation coefficients for the isotherms, determined served for the majority of the metal ions, indicate for the divalent transition metal cations studied. that a monolayer coverage on the surface of the Figures 1 and 2 present the Langmuir and Freundlich calcium alginate is formed in the process. This isotherms determined for some of the metal ions means that the sorption proceeds on the functional studied. groups/binding sites of the sorbent. The process The essential characteristics of the Langmuir should be regarded as monolayer adsorption. isotherms can be expressed in terms of a dimensionless constant, called the separation factor or equi- References librium parameter (R ) defined as: L [1]. Kar R.N., Sahoo B.N., Sukla L.B.: Pollut. Res., 11, RL = 1/(1+bCo) (4) where: b – the Langmuir constant mentioned above, 1-13 (1992). [2]. Fourest E., Roux J.-C.: Appl. Microbiol. Biotechnol., Co – initial concentration of the metal cation. Ac- 37, 399-403 (1992). cording to McKay [10] the RL value indicates the [3]. Volesky B.: Biosorption of heavy metals. CRC Press, type of isotherm as follows: RL>1 – unfavourable, Boca Raton, Florida 1990, 396 p. RL=1 – linear, 0

GALLIUM AND INDIUM ISOTOPE EFFECTS IN THE DOWEX 1-X8/HCl SYSTEM Irena Herdzik, Wojciech Dembiński , Witold Skwara, Ewa Bulska1/, Agnieszka Wysocka1/ 1/ Faculty of Chemistry, Warsaw University, Poland

In recent studies on the fractionation of gallium with aqueous Rhodamine B, respectively [3], and and indium by chemical methods we have discov- then quantitatively determined in selected samples ered the gallium and indium isotope effects in the by atomic absorption analysis with flame atomiza- system: strongly acidic cation exchanger (Dowex tion. 50W-X8)/HCl [1,2]. The ratio (R) of the isotope concentrations, The aim of the present work was to seek similar [113In]/[115In] and [69Ga]/[71Ga], in the selected chemical isotope effects of the same elements in the fractions of the effluent was determined using an analogous system: strongly basic anion exchanger inductively coupled plasma mass spectrometer Dowex 1-X8/HCl solution. The experimental (ICP-MS) Perkin Elmer Elan 6100. The relative method was the same as that used in the earlier studies. A long glass chromatographic column, 0.5 cm in inner diameter, was filled with the Dowex 1-X8 resin, 200-400 mesh up to the bed height of 95 cm. The “merry-go-round” elution method was used with the flow rate of the effluent (HCl at a given concentration) of 0.11 ml/min. The concentrations of the HCl were selected in such a way as to obtain moderate values of the distribution coefficient of the metal ions, required for chromatographic experiment. At the HCl concentration 3+ 3+ equal to 2.5 M for Ga and 1.0 M for In , the Kd values were close to 4 (Fig.1). Two cycles of the elution were done for gallium and 5 cycles for indium. During the last cycle the 1 ml fractions of the effluent were collected. The contents of indium and gallium in the consecutive fractions were evaluated Fig.1. Kd of indium and gallium vs. HCl concentration in by spot tests with alcoholic solution of alizarin and the Dowex 1-X8/HCl system. RADIOCHEMISTRY, STABLE ISOTOPES, 82 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY standard deviation of these measurements was usually 0.05÷0.07%. Prior to the analysis, chlorides were removed from the samples by evaporating with 4 M HNO3 to dryness and dissolving the residue in 0.1 M HNO3. The local separation factors, defined as qi =Ri/Rfeed, or the local separation gains, ε defined as i=ln(qi), were calculated from these data.

Fig.3. Isotope separation gain of indium and gallium vs. eluted fraction. X-asis in Z units.

mation, under the assumption that the shape of the eluted band resembles the normal distribution [5,6]. According to this theory, ε is equal to S/N0.5, ε where S is the slope of linear function of i vs. the eluted fraction (Δn/n) at the X-axis scaled in standardized differences (Z) of normal distribution Fig.2. Isotope separation gain of indium (in 1.0 M HCl) (Fig.3), and N is the number of theoretical plates and gallium (in 2.5 M HCl) vs. eluted fraction of the metal. passed by the band. This work was supported by the State Commit- Figure 2 shows the results of the separation tee for Scientific Research (KBN), under grant No. experiments, performed with 1.0 M HCl for indium, 4 T09A 057 25. and in 2.5 M HCl for gallium. The opposite slopes of the S-shape curves demonstrate opposite sign References of the indium and gallium isotope effects. The resin [1]. Dembiński W., Herdzik I., Skwara W., Bulska E., Wysoc- phase was enriched with the light isotope of gal- ka A.: Indium isotope effect in the Dowex 50-X8/HCl lium and the solution with the heavy isotope. The system – comparison with the isotope effect of gallium. light isotope of indium was accumulated in the sol- In: INCT Annual Report 2005. Institute of Nuclear ution whereas the heavy isotope – in the resin Chemistry and Technology, Warszawa 2006, pp. 77-78. phase. The value of the unit separation factor for [2]. Dembiński W., Herdzik I., Skwara W., Bulska E., Wysoc- gallium was found to be ε=+5.9x10–4, and for in- ka A.: Nukleonika, 51, 217-220 (2006). dium ε=-1.5x10–4. The opposite signs (using the [3]. Feigl F., Anger V.: Spot tests in inorganic analysis. 6th same convention) of the isotope effects in the sys- ed. Elsevier, Amsterdam-London-New York 1972, pp. 233-247. tems with the cation and anion exchanger reflect [4]. Smith M.R., Martell A.E.: Critical stability constants. the difference in the stability constants of the chlo- Vol. 4. Inorganic complexes. Plenum Press, New York 3+ ride complexes of the metals, for Ga – log and London 1976, pp. 109-110. β 3+ β β 1=0.01; while for In – log 1=2.32, log 2=3.62 [5]. Glueckauf E.: Trans. Faraday Soc., 51, 34-44 (1955). β and log 3=4.0 [4]. The unit separation factor was [6]. Glueckauf E.: Trans. Faraday Soc., 54, 1203-1208 calculated on the basis of the Glueckauf approxi- (1958).

PROFICIENCY TESTING SCHEME PLANTS 6 – DETERMINATION OF As, Cd, Cu, Hg, Pb, Se AND Zn IN DRY MUSHROOM POWDER (Suillus bovinus) Halina Polkowska-Motrenko, Ewelina Chajduk, Jakub Dudek, Monika Sadowska-Bratek, Michał Sypuła

Proficiency testing (PT) schemes are one of the ISO/IEC 17025:2005 [1] and can be used by ac- elements of quality assurance and quality control creditation bodies in accreditation decisions. The system in chemical measurements. PTs are one of Institute of Nuclear Chemistry and Technology the instruments of independent assessing the qual- (INCT) has been involved in providing PT since ity of routine measurements. Participation in PT 2003. PT scheme PLANTS has been designed for enables laboratories to demonstrate the reliability the purposes of laboratories from Poland and of the data they are producing. It is also one of Central and Eastern Europe determining trace el- the requirements of the international standard ements in food of plant origin. PT PLANTS 6 – RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 83 Determination of As, Cd, Cu, Hg, Pb, Se and Zn ing to a procedure commonly used by food con- in dry mushroom powder (Suillus bovinus) has centrate producers (mainly 25oC, from time to time been conducted in 2006. The adopted strategy of 60oC). Dried mushrooms were milled in a centrifu- the PT scheme complies with the ISO/IEC Guide gal mill made of stainless steel and sieved by stain- 43-1:1997 [2], ISO 13528:2005 [3] and IUPAC har- less steel sieves. The fraction of particles with di- monized protocol [4]. ameter ≤1 mm was collected. This fraction (ca. 5 Test material kg) was then homogenized by mixing and bottling Preparation of test material of 20 g test samples. Care was taken to avoid con- Wild mushrooms (ca. 60 kg) were collected in tamination. In order to ensure the long-term sta- the forest in north-west Poland, cleaned from dust, bility of the test samples radiation sterilization was soil and attached mosses. The end part of stalks were carried out. All bottles with the test material were removed. Mushrooms (caps and stalks) were then irradiated with electron beam (energy 10 MeV, 9 cut into small pieces and air dried in a dryer accord- kW) from a linear accelerator LAE-13/9 (Depart-

Table 1. Results of As, Cd, Cu, Hg, Pb, Se and Zn determination provided by the reference laboratories. RADIOCHEMISTRY, STABLE ISOTOPES, 84 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY ment of Radiation Chemistry and Technology, ratories. The obtained results are summarized in INCT). The sterilization dose was 30 kGy. Table 1. The assigned values and their uncertain- Moisture determination ties (Table 2) were calculated as the robust aver- The procedure of moisture determination was established on the basis of water desorption curves Table 2. Assigned values and their uncertainties. determined at different temperatures. The reference point has been chosen on a plateau that ensures satisfactory reproducibility of the results. It has been recommended to dry subsamples of the material for 24 h at 50oC. In this case, the uncertainty associated with moisture content determination was evaluated to be ≤1%. Homogeneity testing Homogeneity testing was carried out according to the ISO 13528:2005 standard [3]. Contents of the elements in question in 10 randomly selected bottles were determined by the atomic absorption spectrometry (AAS) method. Two samples of 250 mg were taken from each bottle and analyzed. Mean * Expanded standard uncertainty (k=2). value (Xmean), standard deviation of mean value (Sx), repeatability standard deviation (Sr) and be- age of the results reported according to the proce- tween samples standard deviation (Ss) were cal- dure recommended by the ISO 13528:2005 stan- culated using the following equations: dard [3].

Xmean = ΣXaverage/g Calculation of performance statistics Xaverage = (xt,1 + xt,2)/2 For the purpose of performance evaluation, the z-score and E -test score have been employed. Sx=− (X X )2 /(g − 1) n mean average En-test was used only when a participating labora- 2 tory reported its own estimation of uncertainty. Sr=− (xt,1 x t,2 ) /(2g) The value of the z-score was calculated using the equation: Ss=− Sx22 (Sr / 2) x – x where: X – average result for t bottle, t – bottle z = lab ref average σ^ number (t=1, 2, 3,…, g).

The material is considered to be homogeneous where: xlab – result reported by participating labora- ^σ if: tory, xref – assigned value, – standard deviation Ss < 0.3^σ for proficiency assessment calculated from Horwitz’s where ^σ is standard deviation for proficiency as- formula [5]: sessment. ^σ = 0.02 c0.8495 On the basis of obtained results, it has been where c is concentration of the element in g g–1. found that the material could be considered as ho- The ^σ values are equal to 0.065 mg kg–1 for As, mogenous for the sample masses ≥250 mg for all 0.053 mg kg–1 for Cd, 1.05 mg kg–1 for Cu, 0.036 the determined elements. mg kg–1 for Hg, 0.085 mg kg–1 for Pb, 0.209 mg kg–1 Assigning property values for Se and 5.25 mg kg–1 for Zn. Some of the test samples were selected ran- The value |z|<3 has been set as an acceptance domly and analyzed by a group of reference labo- level for this PT.

Table 3. Number of PT participating laboratories determining individual elements, number of applied methods and number of accepted results. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 85

Fig.1. Results of laboratories participating in PT (z-score) Fig.3. Results of laboratories participating in PT (z-score) for As determination. for Hg determination.

Fig.2. Results of laboratories participating in PT (z-score) Fig.4. Results of laboratories participating in PT (z-score) for Cd determination. for Zn determination.

The value of the En-test score are calculated from cepted on the basis of z-score value. Some examples the following equation [11]: of summary results are shown in Figs.1-4. xx− E = lab ref References n 22 UUref+ lab [1]. ISO/IEC 17025:2005 – General requirements for the where U is expanded standard uncertainty (k=2). competence of testing and calibration laboratories. ≤ The value |En| 1 has been set as an acceptance ISO, Geneva 2005. level for this PT. [2]. ISO/IEC Guide 43-1:1997 – Proficiency testing by inter- Eighteen Polish laboratories participated in the laboratory comparisons. Part 1: Development and PT. Seventeen laboratories provided the results. operation of proficiency testing schemes. ISO, Geneva Number of PT participating laboratories determin- 1997. [3]. ISO 13528:2005 – Statistical methods for use in profi- ing individual elements, number of applied methods ciency testing by interlaboratory comparisons. ISO, and number of accepted results are summarized Geneva 2005. in Table 3. [4]. Thompson M., Ellison S.L.R., Wood R.: Pure Appl. As can be seen, the performance of the partici- Chem., 78, 1, 145-196 (2006). pating laboratories can be recognized as satisfac- [5]. Thompson M.: Analyst, 125, 385-386 (2000). tory. Only 5 from 89 provided results are not ac-

NEW POLISH CERTIFIED REFERENCE MATERIALS FOR INORGANIC TRACE ANALYSIS: CORN FLOUR (INCT-CF-3) AND SOYA BEAN FLOUR (INCT-SBF-4) Halina Polkowska-Motrenko, Rajmund Dybczyński, Ewelina Chajduk, Bożena Danko, Krzysztof Kulisa, Zbigniew Samczyński, Michał Sypuła, Zygmunt Szopa

Certified reference materials (CRMs) are an im- mand for suitable CRMs in very big. The produc- portant element of the metrological system. In tion and use of CRMs should meet requirements chemical measurements, CRMs are used as an in- of international guidelines [4-8]. The Institute of ternal tool of quality assurance for checking accu- Nuclear Chemistry and Technology (INCT) has racy of results and for validation of measurement issued two new materials of biological origin lately, methods [1-3]. As CRMs should be as similar to namely: Corn Flour (INCT-CF-3) and Soya Bean the analyzed material as possible, the potential de- Flour (INCT-SBF-4). The general strategy of prepa- RADIOCHEMISTRY, STABLE ISOTOPES, 86 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY ration and certification of CRMs developed in the erence Materials and Measurements – IRMM (Gell, INCT [3] has been employed. The concentration Belgium) laboratory using the Karl-Fischer titration level of trace elements in these matrices are much method. It amounted to 11.09 g/100 g with relative lower than in the biological type CRMs issued pre- expanded uncertainty of 11.3% in INCT-CF-3 and viously by the INCT and differ strongly in fat con- 7.33 g/100 g with relative expanded uncertainty of tent what is important for the way of decomposition 10.9% in INCT-SBF-4. of the sample. So, INCT-CF-3 and INCT-SBF-4 Radiation sterilization supplement the issued CRMs and should fulfill spe- All containers with the candidate CRMs were cific laboratory needs. sterilized by irradiation with electron beam (en- Origin, preparation and testing ergy 10 MeV, 9 kW) from a linear accelerator of the materials LAE-13/9 (Department of Radiation Chemistry Collection, grinding and sieving and Technology, INCT). The sterilization dose was Both raw materials were chosen from among 28 kGy. the materials present on the Polish market. Corn Stability testing flour was prepared from corn grown in Poland and Long-term stability was checked by comparing soya bean flour from soya grown in India. Corn flour the results obtained for one bottle (randomly was produced by ViVi-Tak s.c. (Poland) accord- chosen) stored under controlled conditions: in an ing to Polish standard PN-A-74205:1997, then air-conditioned room at 20oC (normal storage). sieved through the 250 μm nylon sieves and stored Samples of the CRM (ca. 100 mg) were taken from in a polyethylene (PE) bag. Soya bean was milled, the bottle after 0, 20 and 32 months of storage and sieved through the 150 μm nylon sieves and stored concentration of six selected elements (Co, Fe, K, in a PE bag. Approximately 50 kg of sieved corn Rb, Sc and Zn) was determined by the INAA flour and soya bean flour were collected. method. Short-term stability was examined by the Homogenization and preliminary homogeneity determination of concentrations of the above men- testing tioned elements in the bottle stored in the CO2 In order to homogenize, the whole lot of each of incubator (ASAB) at 37oC, 100% humidity and 5% 3 flours (ca. 50 kg) was transferred to a 110 dm PE CO2. Statistical evaluation of the obtained results drum, placed in a homogenizer and the material using t-Student’s test [9] indicates that there are was mixed by the rotation for 20 hours. After this no significant differences between the results ob- time, a preliminary homogeneity testing was per- tained in both experimental conditions examined formed determining selected elements in the samples and that no significant trends can be observed. Con- randomly selected from the drum by the X-ray fluo- sequently, it can be stated that the material is stable rescence (XRF) method. It was found that the in time. The test is being continued and stability materials did not show any significant inhomoge- of INCT-CF-3 and INCT-SBF-4 will be monitored neity. The materials were then distributed in 50 g during all storage. portions (future CRM) into 150 cm3 polypropylene Determination of dry mass (PP) bottles with a screw-on cap and 10 g portions In order to refer the results of analysis to the (intercomparison sample) into 60 cm3 poly(ethylene same dry state of the material, a methods of water tetraphtalate) (PET) bottles, respectively. determination on the basis of water desorption Determination of particle size curves determined at few temperatures were estab- Examination by optical microscopy revealed that lished. The reference points have been chosen on Martin’s diameter (arithmetic mean of the maximum a plateau that ensures satisfactory reproducibility distance between opposite sides of a particle and of the results. It has been recommended to dry a distance in perpendicular direction) of over 98% the subsample of the materials for 24 h at 80oC. of particles of INCT-CF-3 was below 25 μm and The standard uncertainty due to moisture content over 90% of particles of INCT-SBF-4 was below determination was established on the basis of rep- 50 μm. licate measurement to be 0.51 and 0.45% for Final homogeneity testing INCT-CF-3 and INCT-SBF-4, respectively. Homogeneity have been studied by the deter- Characterization of the materials mination of selected element contents in 100 mg The assignment of the certified values for ele- samples using instrumental neutron activation ment concentrations has been based on the results analysis (INAA). For INCT-CF-3, these were Br, of the interlaboratory comparison organized in the Co, Fe, K, Mn, Na, Rb and Sc and Co, Fe, K, Sc years 2004-2005. Ninety two laboratories from 19 and Zn for INCT-SBF-4. The results (variances and countries participated in the intercomparison. The means) for six samples randomly taken from dif- laboratories were asked to analyze two candidate ferent containers and for six samples from a single CRMs and a CRM of their own choice for a qual- container (also randomly chosen) were compared ity assurance (QA) reason. Moreover, the partici- by means of Fisher’s test (F-test) and t-Student’s pating laboratories were asked to analyze the CRM test (t-test). No significant differences in variances sent together with the intercomparison samples, and means were found. Hence, the materials can be the identity of which was known only to the orga- considered as homogeneous for the sample masses nizer. The results of the analysis of that CRM were ≥100 mg. then applied in the process of the certification. Two Determination of total water content data sets were created and evaluated: the first – Total water content in the candidate reference “original” – consisted of all results reported by the materials was determined in the Institute for Ref- laboratories and the second – “alternative” – con- RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 87

Fig.1. Comparison of central values and their confidence limits for Co in INCT-SBF-4 obtained by various Fig.2. Comparison of the certified values and their confi- approaches to the background of original range of dence limits and the result obtained by the definitive results submitted by participants. method for Mo in INCT-CF-3 on the background of original range of results submitted by the partici- sisted of the results provided by the laboratories pants. for elements certified in the CRMs when the confidence limits of the laboratory results overlapped level of 0.05, followed by calculation of the overall with the confidence limits of the CRM, i.e. when means of results remaining after outlier rejection, there is fulfilled the condition: standard deviations, standard errors, confidence x−≤ xku ⋅ +⋅ ku intervals. The results of the evaluation of both data CRM lab CRM CRM lab lab (1) sets, i.e. original and alternative one were very simi- – where: xCRM – certified value, xlab – laboratory mean, lar in the most cases. u – combined standard uncertainties, k – coverage For some elements, the results obtained by the factors at a level of confidence of 95%. radiochemical neutron activation analysis (RNAA) A method of data evaluation leading to assignment definitive method [11-18] were also employed in of certified values was the same as that used previ- the process of certification, as it is illustrated in ously in our Laboratory [10]. This approach is be- Figs.1 and 2 and as it was done previously with the ing based on outlier’s rejection procedure which respect to the former CRMs issued by the INCT. uses concurrently four statistical tests (Dixon, The certified values for Al, Ba, Br, Ca, Co, Cs, Cu, Grubbs, skewness and kurtosis) at the significance K, La, Mg, Mn, Ni, P, Rb, S, Sr, Th and Zn were

Table 1. Certified values for Corn Flour (INCT-CF-3). RADIOCHEMISTRY, STABLE ISOTOPES, 88 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY

Table 2. Certified values for Soya Bean Flour (INCT-SBF-4).

determined using the alternative database. In such the result of the interlaboratory comparison uinterlab, a way, these data are traceable to the existing CRM. the long-time stability ulstab, the short-time stability On the other hand, the use of the CRM confirms usstab and the moisture determination usm (expressed the validity of the applied method of data evaluation as standard uncertainties): [17]. The values for other elements were derived from 2222 the original database. The combined standard un- uu=+++interlab u lstab u sstab u sm (2) certainty of certified values uc consists of four un- uinterlab is estimated as a relative standard deviation certainty contributions, which are associated with of the overall mean, ulstab – the standard uncertainty estimated from the long-term stability studies, usstab – the standard uncertainty estimated from the

short-term stability studies, and usm – the standard uncertainty estimated from the moisture determination study. The expanded uncertainty (U) is obtained by multi-

plying uc by a coverage factor k=2 (corresponds to a level of confidence of approximately 95%). Certified values and their uncertainties (X ±U) established in the course of the present work for several elements in INCT-CF-3 and INCT-SBF-4 are presented in Tables 1 and 2. Information values are listed in Table 3. Fig.3. Frequency of the use of analytical technique in the The relative frequency of using various analyti- certification campaign. cal techniques in this intercomparison is illustrated RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 89

Table 3. Information values for Corn Flour (INCT-CF-3) good cooperation. This work was in part supported and Soya Bean Flour (INCT-SBF-4). by the State Committee for Scientific Research (KBN) grant No. 032290/C.PO6-6/2003.

References [1]. Stoeppler M., Wolf W.R., Jenks P.J.: Reference materials for chemical analysis. Certification, availability and proper usage. Wiley-VCH, Weinheim 2001. [2]. Reference materials in analytical chemistry. A guide for selection and use. Ed. A. Zschunke. Springer, Berlin 2000. [3]. Dybczyński R.: Food Addit. Contam., 19, 928 (2002). [4]. ISO/IEC Guide 35: Certification of reference materials – general and statistical principles. ISO, Geneva 2006. [5]. ISO Guide 30: Terms and definitions used in connection with reference materials. ISO, Geneva 1992. [6]. ISO/IEC Guide 34: Quality system guidelines for the production of reference materials. ISO, Geneva 2000. [7]. ISO/IEC Guide 33: Uses of certified reference materials. ISO, Geneva 2000. [8]. ISO Guide 31: Contents of certificates of reference materials. ISO, Geneva 2000. [9]. Linsinger T.P.J., Pauwels J. Lamberty A., Schimmel H.G., van der Veen A.H.M., Siekmann L.: Fresenius J. Anal. Chem., 370, 183 (2001). [10]. Dybczyński R., Danko B., Kulisa K., Chajduk-Male- szewska E., Polkowska-Motrenko H., Samczyński Z., Szopa Z.: Chem. Anal. (Warsaw), 49, 143 (2004). [11]. Dybczyński R., Danko B, Polkowska-Motrenko H.: Fresenius J. Anal. Chem., 370, 130 (2001). [12]. Samczyński Z., Dybczyński R.: Chem. Anal. (Warsaw), 41, 873 (1996). [13]. Polkowska-Motrenko H., Danko B., Dybczyński R., Becker D.A.: J. Radioanal. Nucl. Chem., 207, 401 in Fig.3. As can be seen, atomic absorption spectro- (1996). metry (AAS), neutron activation analysis (NAA), [14]. Danko B., Dybczyński R.: J. Radioanal. Nucl. Chem., emission spectroscopy (OES) and mass spectro- 216 (1), 51 (1997). metry (MS) were the methods most frequently [15]. Polkowska-Motrenko H., Danko B., Dybczyński R.: Anal. Bioanal. Chem., 379, 221 (2004). used. The very significant share of results by NAA, [16]. Polkowska-Motrenko H., Danko B., Dybczyński R.: much greater than could have been expected on Chem. Anal. (Warsaw), 50, 155 (2005). the basis of global contribution of this method to [17]. Polkowska-Motrenko H., Dybczyński R.: J. Radioanal. routine analyses worldwide, is worth emphasizing. Nucl. Chem, 269, 339 (2006). The authors express their thanks to all labora- [18]. Dybczyński R., Danko B., Polkowska-Motrenko H., tories participating in this intercomparison for Samczyński Z.: Talanta, 71, 529 (2007).

DETERMINATION OF CADMIUM, LEAD AND COPPER IN FOOD PRODUCTS AND ENVIRONMENTAL SAMPLES BY ATOMIC ABSORPTION SPECTROMETRY AFTER SEPARATION BY SOLID PHASE EXTRACTION Jadwiga Chwastowska, Witold Skwara, Elżbieta Sterlińska, Jakub Dudek, Leon Pszonicki

The growing contamination of environment causes to interferences caused by the matrices of such that many toxic elements are able to form various samples and by low concentration of the elements organo-metallic compounds. In this form they can to be determined. The mentioned difficulties may be solubilized and enter soils, sediments, waters be eliminated by the preliminary separation and and plants, and, in consequence, they can enter the preconcentration of the contaminating elements. food chain. This fact causes the necessity to check From among the methods usually used for this pur- the contamination level of environment by heavy pose, the solid-phase extraction is applied more and metals and what their physiological effect is. There- more frequently because of its simplicity and many fore, the determination of these metals in soil, advantages in comparison with other methods waters, plants and also in food products at very low [1-5]. concentration levels as μg g–1 and ng g–1 is required. Previously, we elaborated a dithizone sorbent and However, the direct application of suitable analyti- applied it for the determination of noble metals in cal instrumental methods is often restricted owing environmental samples [5], speciation of selenium RADIOCHEMISTRY, STABLE ISOTOPES, 90 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY [6] and the determination of some heavy metals in ditions, on the other hand, the toxic elements can highly mineralized waters [7]. In the presented work, form easy volatile organo-metallic compounds that we demonstrate that this sorbent has a versatile may be easy lost. In the proposed method the samples

Table 1. Conditions for sample mineralization and dilution (sample – 0.2-0.5 g, maximum volume of solution – 8 mL).

character and may be applied for the separation and were dried, ground and mineralized in a micro- determination by graphite furnace atomic absorp- wave mineralizer. The mineralization conditions tion spectrometry of most toxic elements in various are presented in Table 1. The obtained solutions environmental materials and food products. This were evaporated to wet residues, dissolved in 0.2 M

Table 2. Results of analysis of certified materials.

* a – certified values. ** b – determined values (mean values of 5 determinations). fact enables the unification of analytical methods hydrochloric acid, neutralized by sodium hydrox- and, thereby simplification of the work in the labo- ide to pH 4 and put into a column with the dithizon ratories analyzing materials of various types. sorbent. The adsorbed elements were eluted by 2 M The preliminary preparation of samples, their nitric acid and determined by graphite tube atomic mineralization and transformation into solution is absorption spectrometry. a very important step of any analytical procedure. The accuracy of the method was checked by the In the case of environmental and food samples con- determination of cadmium, lead and copper in three taining mostly organic matter these operations various certified reference materials. The obtained

Table 3. Results of copper, cadmium and lead determination in selected food products and environmental materials (mean values for n=5).

create often serious problems. On the one hand, results are established in Table 2. All of them are some organic compounds are resistant to mineral- inside the confidence intervals what proves that the ization and require application of very strong con- tested method is accurate. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 91

The presented method was applied for the analy- [3]. Pramanik S., Dhara S., Bhattacharyya S.S., Chatto- sis of some environmental materials (soil, street dust padhyay P.: Anal. Chim. Acta, 556, 430 (2006). and grass) and various food products. The obtained [4]. Burham N., Abel-Azeem S.M., El-Shahat M.F.: Anal. results and their precision expressed as relative Chim. Acta, 579, 193 ( 2006). standard deviations (RSD) are demonstrated in [5]. Chwastowska J., Skwara W., Sterlińska E., Pszonicki L.: Talanta, 64, 224 (2004). Table 3. The relative standard deviations vary in the [6]. Chwastowska J., Skwara W., Sterlińska E., Dudek J., range from 0.5 to 3% due to the type of sample and Pszonicki L.: Speciation analysis of selenium in mineral the determined element and indicate that the pre- waters by graphite furnace atomic absorption spectro- cision of the applied methods is satisfactory. metry after separation on dithizone sorbent. Chem. Anal. (Warsaw), in press. References [7]. Chwastowska J., Skwara W., Sterlińska E., Dudek J., [1]. Goswami A., Singh A.K.: Anal. Chim. Acta., 454, 229 Pszonicki L.: Determination of cadmium, lead, copper (2002). and bismuth in highly mineralized waters by solid phase [2]. Osman M.M., Kholeif S.A., Aboul Al.-Mauty N.A.: extraction and atomic absorption spectrometry. Chem. Microchim. Acta, 143, 25 (2003). Anal. (Warsaw), in press.

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LIX. THE CRYSTAL AND MOLECULAR STRUCTURE OF A ZINC(II) COMPLEX WITH PYRIDAZINE-3,6-DICARBOXYLATE AND WATER LIGANDS Michal Gryz1/, Wojciech Starosta, Janusz Leciejewicz 1/ Office for Registration of Medicinal Products, Medical Devices and Biocides, Warszawa, Poland The structure of bis(μ-pyridazine-3,6-dicar- the rms deviation of 0.0408(10) Å. Carboxylate boxylato-κ4N,O:N’,O’)-bis[diaquazinc(II)], groups deviate from the mean ring plane by 5.4(5)o o Zn2(C6H2N2O4)2(H2O)4, is composed of isolated (C7O1O2) and 5.0(5) (C8O3O4). Hydrogen bonds centrosymmetric dinuclear units built up of two Zn(II) ions bridged by two fully deprotonated pyridazine-3,4-dicarboxylate ligand molecules. The Zn1 ion is cheleted by two N,O bonding groups each donated by a different ligand molecule: Zn1-O1 2.033(2) Å, Zn1-O3 2.045(2) Å, Zn1-N1 2.160(2) Å, Zn1-N2 2.172(2)Å and two water oxygen atoms in axial positions (Zn1-O5 2.145(2)Å, Zn1-O6 2.121(2) Å) forming an octahedral enviroment. Figure 1 shows the molecule of the dimer with atom labelling scheme, Fig.2 – the packing of dimers in the unit cell. The inversion centres of the complex molecules coicide with the

Fig.1. The asymmetric unit of the title compound with atom labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. inversion centres generated in the unit cell by the symmetry elements of the space group Pbca. Zn(II) Fig.2. The alignment of dimeric molecules in the unit cell. ions and the pyridazine rings are coplanar with For clarity, only a half of the dimers is shown. RADIOCHEMISTRY, STABLE ISOTOPES, 92 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY with lengths in the range from 2.743(3) to 2.816(3) [2]. Part LVI. Gryz M., Starosta W., Leciejewicz J.: trans-Di- Å operate between the coordinated water mol- aquabis(pyridazine-3-carboxylato-κ2O,N)-magnes- ecules, and carboxylate oxygen atoms belonging to ium(II) dihydrate. Acta Crystallogr., E62, m123-m124 adjacent dimers. They are responsible for the co- (2006). hesion of the structure. [3]. Part LVII. Starosta W., Leciejewicz J., Premkumar T., Govindarajan S.: Crystal structures of two Ca(II) com- X-ray diffraction data collection was carried out plexes with imidazole-4,5-dicarboxylate and water on a KUMA KM4 four circle diffractometer at the ligands. J. Coord. Chem., 59, 557-564 (2006). Institute of Nuclear Chemistry and Technology. [4]. Part LVIII. Starosta W., Leciejewicz J.: catena-Po- Structure solution and refinement was performed ly[[aquacalcium(II)]bis(μ-1H-imidazole-4-carboxy- using SHELXL-97 program package. lato)κ4N,O:O,O’; κ3O,O’:O’]. Acta Crystallogr., E62, m2648-m2650 (2006). References [5]. Part LIX. Gryz M., Starosta W., Leciejewicz J.: Bis(μ-pyridazine-3,6-dicarboxylato-κ4N,O:N’,O’)-bis[di- [1]. Part LV. Premkumar T., Govindarajan S., Starosta W., aquazinc(II)]. Acta Crystallogr., E62, m3470-m3472 Leciejewicz J.: Diaquatetrakis(pyrazine-2-carboxy- (2006). lato-κ2O,N)-thorium(IV) trihydrate. Acta Crystallogr., E62, m98-m100 (2006).

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LX. THE CRYSTAL AND MOLECULAR STRUCTURES OF MAGNESIUM(II) AND ZINC(II) COMPLEXES WITH IMIDAZOLE-4-CARBOXYLATE AND WATER LIGANDS Michal Gryz1/, Wojciech Starosta, Janusz Leciejewicz 1/ Office for Registration of Medicinal Products, Medical Devices and Biocides, Warszawa, Poland

Magnesium imidazolate: trans-diaquabis(imidazole-4-carboxylato-κ2N,O)-magnesium(II),

Mg(C4H3N2O2)2(H2O)2, crystallizes in the monoclinic system (space group P21/c). The structure is composed of monomeric molecules, each containing a Mg(II) ion located at the inversion centre and chelated by two imidazole-4-carboxylate ligand molecules via their N,O bonding moieties (Mg-N 2.193(2) Å, Mg-O 2.070(2) Å) and two water oxygen atoms (Mg-O 2.063(2) Å). A fairly regular octahedron with water oxygen atoms at the apical

Fig.2. Packing diagram of Mg(C4H3N2O2)2(H2O)2.

one, the Zn(II) ion is octahedrally coordinated by two, oriented in trans mode ligand molecules, each via its N,O bonding moiety and two water oxygen atoms. In the other, the Zn(II) ion is pentacoordinated by N,O bonding moieties of two ligand molecules and one water oxygen atom (Fig.3). Six

Fig.1. Mg(C4H3N2O2)2(H2O)2 molecule with atom labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. positions is formed (Fig.1). The imidazole rings are coplanar. The monomers are kept together by hydrogen bonds in which the water molecules and protonated nitrogen atoms act as donors (Fig.2). Triclinic unit cell (space group P1) of zinc imidazolate: [trans-diaquabis(imidazole-4-carboxylato-κ2N,O)-zinc(II)][monoaquabis(imi- Fig.3. The molecules of [Zn(C4H 3N2O2) 2(H2O)2] dazole-4-carboxylato-N,O)-zinc(II)] trihydrate, [Zn(C4H3N2O2)2(H2O)]·3H2O with atom labeling [Zn(C4H3N2O2)2(H2O)2][Zn(C4H3N2O2)2(H2O)]·3H2O, scheme. Displacement ellipsoids are drawn at the contains two monomeric complex molecules. In 50% probability level. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 93 solvation water molecules in three symmetry independent sites complete the content of the unit cell. The octahedron around the Zn(II) ion is

slightly distorted with Zn-O, Zn-N and Zn-OH2 bond distances of 2.152(2) Å, 2.041(3) Å and 2.179(3) Å, respectively. The mean bond distances in the pentacoordinated Zn(II) polyhedron are: 2.101(2) Å (Zn-O), 2.040(2) Å (Zn-N) and 2.002(3)

Å (Zn-OH2). An extended network of hydrogen bonds in which solvation water molecules, coordinated water molecules and protonated ring-nitrogen atoms act as donors is responsible for the cohesion of the structure. Hydrogen bond lengths range from 2.705(2) to 2.950(2) Å (Fig.4). X-ray diffraction data collection was carried out on a KUMA KM4 four circle diffractometer at the Institute of Nuclear Chemistry and Technology. Structure solution and refinement was performed using SHELXL-97 program package.

Fig.4. Packing diagram of [Zn(C4H 3N2O2) 2(H2O)2] [Zn(C4H3N2O2)2(H2O)]·3H2O.

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXI. THE CRYSTAL AND MOLECULAR STRUCTURE OF A MANGANESE(II) COMPLEX WITH PYRAZOLE-3,5-DICARBOXYLATE AND WATER LIGANDS Thatan Premkumar1/, Subbian Govindarajan1/, Wojciech Starosta, Janusz Leciejewicz 1/ Department of Chemistry, Bharathiar University, Coimbatore, Tamilnadu, India

The structure of trans-diaquabis(1H-pyrazole-3,5- labelling scheme, Fig.2 – the packing diagram of the -dicarboxylate-N,O)-manganese(II) dihydrate, structure. The protonated carboxylic oxygen atoms,

Mn(C5H3N2O4)2·2H2O, is composed of monomeric the coordinated water molecules, the solvation molecules in which Mn(II) ions situated at the water molecules and the protonated pyrazole ring inversion centres are chelated, each by two singly nitrogen atoms participate in a network of hydro- deprotonated pyrazole-3,5-dicarboxylate ligand molecules and two water oxygen atoms in trans arrangement. The coordination around the Mn(II) ion is slightly distorted octahedral. The chelation of the pyrazole-3,5-dicarboxylate ligand proceeds via its N,O bonding moiety consisting of the hetero- -ring nitrogen atom N2 and the oxygen atom O1 of the nearest carboxylate group: Mn1-O1 2.183(2) Å, Mn1-N2 2.215(1) Å, Mn1-O5 2.156(2) Å. The other carboxylate group remains protonated and participates only in a network of hydrogen bonds. The pyrazole ring is planar: rms 0.0005 Å. The protonated carboxylic group C7O3O4 deviates from it only by 1.9(1)o, the carboxylic group C6O1O2 – by 10.3(1)o. Figure 1 shows the molecule with atom

Fig.2. The unit cell of Mn(C5H3N2O4)2·2H2O. Dashed lines indicate hydrogen bonds.

Fig.1. The molecule of Mn(C5H3N2O4)2·2H2O with atom gen bonds responsible for the stability of the struc- labeling scheme. Displacement ellipsoids are drawn ture. Their lengths are in the range from 2.509(2) at the 50% probability level. to 2.916(2) Å. RADIOCHEMISTRY, STABLE ISOTOPES, 94 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY X-ray diffraction data collection was carried out Structure solution and refinement was performed on a KUMA KM4 four circle diffractometer at the using SHELXL-97 program package Institute of Nuclear Chemistry and Technology.

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXII. THE CRYSTAL STRUCTURE AND MOLECULAR DYNAMICS OF 2-AMINOPYRIDINE-3-CARBOXYLIC ACID Andrzej Pawlukojć, Wojciech Starosta, Janusz Leciejewicz, Ireneusz Natkaniec1,2/, Dorota Nowak1,3/ 1/ Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, Dubna, Russia 2/ The Henryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, Poland 3/ Faculty of Physics, Adam Mickiewicz University, Poznań, Poland

An interesting feature of the 2-aminopyridine-3-car- gen bonds are in the range from 2.6472(14) to boxylic acid molecule is its zwitterionic structure in 2.7951(14) Å. Figure 2 shows the alignment of hy- which the carboxylic proton is transferred not to the drogen bridged almost flat molecular ribbons. The amino group but to the hetero-ring nitrogen atom. pyridine ring of the title molecule is almost planar Figure 1 shows the molecule with atom labelling (rms 0.0129(1) Å). The dihedral angles between

Fig.2. The unit cell of 2-aminopyridine-3-carboxylic acid. Dashed lines indicate hydrogen bonds. the hetero-ring plane and the carboxylate and amino group planes are 5.6(1)o and 2.3(1)o, respectively. X-ray diffraction data collection was carried out Fig.1. The molecule of 2-aminopyridine-3-carboxylic acid on a KUMA KM4 four circle diffractometer using with atom labeling scheme. Displacement ellipsoids an Oxford Cryogenic Cooler to maintain the tem- are drawn at the 50% probability level. perature of the sample at 100 K. Structure solution and refinement was performed using SHELXL-97 scheme. This configuration produces intermolecu- program package. An analysis of inelastic neutron lar hydrogen bonds in which the amino group and scattering spectra recorded at the Pulsed Reactor hetero-ring nitrogen atoms act as donors and the IBR-2 at Dubna (Russia) using a NERA-PR spec- carboxylate oxygen atoms in adjacent acid mol- trometer shows a good agreement with those cal- ecules act as acceptors. The lengths of these hydro- culated for a crystal.

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXIII. THE CRYSTAL AND MOLECULAR STRUCTURE OF A CALCIUM(II) COMPLEX WITH PYRAZINE-2,3,5,6-TETRACARBOXYLATE AND WATER LIGANDS Wojciech Starosta, Janusz Leciejewicz Centrosymmetric, triclinic unit cell of Ca(II) contains carboxylate (2,3,5,6-PZTC) ligand molecules with four (in two symmetry independent sites) Ca(II) their geometrical centres in the inversion centres ions, two fully deprotonated pyrazine-2,3,5,6-tetra- at 0,1/2,1/2 (molecule 1) and 0,1/2,0 (molecule 2) RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 95 and two water molecules coordinated to the metal centre at 0,0,0. The N,O bonding moieties com- ions. All potential chelating sites of both ligand posed of N21, O21 and N21IX, O21IX atoms coor- molecules are engagged in bridging the metal ions dinate the Ca2 and Ca2IX ions, respectively, while giving rise to a three-dimensional molecular net- the second carboxylate oxygen atoms O22 and work. O22IX acting as bidentate are linked to Ca2IV, Ca1IV and Ca2VI, Ca1VI ions, respectively. Oxygen atoms of the carboxylate groups which do not form the N,O bonding moieties act also as bidentate: O23 chelates Ca2IV and Ca2II ions, while the O23IX atom – the Ca2VI and Ca2XIV ions. The O24 and O24IX atoms are bonded to Ca1IV and Ca1XIV ions, respectively. In this way, the ligand molecule 2 bridges six Ca2 and four Ca1 ions.

Fig.1. The bridging mode of ligand molecule 1.

N,O and NXIII, OXIII bonding moieties of the ligand molecule 1 chelate the Ca1 and Ca1XIII ions, while the second oxygen atoms O12 and O12XIII are coordinated to Ca1VII and Ca1VI ions, respectively. Belonging to the remaining carboxylate groups oxygen atoms O13 and O13XIII are bonded to Ca2I and Ca2IX ions respectively and the O14 and O14XII oxygen atoms, each acting as bidentate are bonded to the Ca1VI and Ca1VIII ions (O14) and Ca1II and Ca1VII ions (O14XIII). Thus, the ligand molecule 1 bridges six Ca1 ions and two Ca2 ions. This bridging pathway with the atom labelling in respect to Fig.3. The packing of molecules in the unit cell of the inversion centre at 0,0,0 is shown in Fig.1. Ca2(2,3,5,6-PZTC)(H2O)2. The bridging pathways via ligand molecules 1 and 2 are interconnected by carboxylate oxygen atoms O13 and O13IX donated by the ligand molecule 1 to the coordination (Fig.3). In the third bridging pathway, the coordinated water oxygen atom O10 joins two adjacent Ca1 and Ca2 ions. Since the Ca1-O10-Ca2 angle is 94.81(8)o, a catenated zig-zag motif is observed. The water molecule O10 acting as a donor provides also an additional pathway via very weak hydrogen bonds to carboxylate O14VIII and O12VII atoms. X-ray diffraction data collection was carried out on a KUMA KM4 four circle diffractometer at the Institute of Nuclear Chemistry and Technology. Structure solution and refinement was performed using SHELXL-97 program package. Symmetry code in respect to the inversion cen- I II III Fig.2. The bridging mode of ligand molecule 2. tre at 0,0,0: x, y, z-1; x, y-1, z; -x+1, -y+2, -z+1; IV -x+1, -y+1, -z+2; V -x+1, -y+2, -z+2; VI x-1, y, z; Having its geometrical centre at the inversion VII -x+1, -y+1, -z+1; VIII -x, -y+2, -z+1; IX -x, -y+2, centre at 0,1/2,0, the ligand molecule 2 chelates -z+1; X x+1, y, z; XI x, y, z+1; XII x, y+1, z; XIII -x, ten Ca ions. Figure 2 illustrates the bridging path- -y+1, -z+1; XIV -x, -y+2, -z+2. way with atom labelling in respect to the inversion RADIOCHEMISTRY, STABLE ISOTOPES, 96 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART LXIV. THE CRYSTAL AND MOLECULAR STRUCTURE OF A ZINC(II) COMPLEX WITH PYRAZOLE-4-CARBOXYLATE AND WATER LIGANDS Michal Gryz1/, Wojciech Starosta, Janusz Leciejewicz 1/ Office for Registration of Medicinal Products, Medical Devices and Biocides, Warszawa, Poland

The monoclinic structure (space group C2/c) of trans-tetraquabis(pyrazole-4-carboxylato-N)-zinc(II) trihydrate, Zn(C4H3N2O2)2·3H2O, contains monomeric molecules in which the central metal ion located at the inversion centre is chelated by two pyrazole-4-carboxylate ligands via their hetero-ring nitrogen atoms and by four water oxygen atoms. The coordination around the Zn(II) ion is octahedral with Zn-N bond distance of 2.078(2) Å and mean Zn-O bond length of 2.125(3) Å (Fig.1). Deprotonated carboxylate groups of the ligand

Fig.2. The unit cell of Zn(C4H3N2O2)2·3H2O. Dashed lines indicate hydrogen bonds. Fig.1. The molecule of Zn(C4H3N2O2)2·3H2O with atom labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. X-ray diffraction data collection was carried out on a KUMA KM4 four circle diffractometer at the molecules are not active in coordination but par- Institute of Nuclear Chemistry and Technology. ticipate in a network of hydrogen bonds responsible Structure solution and refinement was performed for the cohesion of the crystal (Fig.2). using SHELXL-97 program package. RADIOBIOLOGY RADIOBIOLOGY 99 IRON CHELATORS INHIBIT DNIC FORMATION TO THE SAME EXTENT, INDEPENDENTLY OF PERMEABILITY Kamil Brzóska, Hanna Lewandowska, Sylwia Męczyńska, Barbara Sochanowicz, Jarosław Sadło, Marcin Kruszewski

Dinitrosyl iron complexes (DNIC) are a group of physiologically important transducers of nitric oxide (NO) [1,2]. The low molecular-weight DNIC have been shown to modulate redox properties of the cellular interior through the inhibition of glu- tathione-dependent enzymes. Previously, we have shown [3] that depletion of lysosomal LIP (labile iron pool) by either chelation with deferoxamine (DFO) or lysis inhibition (by treatment with 10 mM

NH4Cl) in K562, human myelogenous leukemia cells leads to a considerable decrease (down to 50%, depending on the incubation time) of DNIC forming in the cells treated with 70 μM nitric oxide do- nor (DEANO). We further investigated the nature of the cellular LIP involved in formation of DNIC in K562 Fig.2. Inhibition of EPR signal induction in K562 cells incu- cells. The cells were treated with a nitric oxide do- bated with 100 μM SIH for 0, 1, 3 and 6 h, and then nor in the presence of a permeable (salicylaldehyde treated with 100 μM NO for 15 min at 37oC. Solid isonicotinoyl hydrazone – SIH) or a nonpermeable bars – mean ±SD, n=3. Asterix denotes statistically (DFO) iron chelator. SIH is a highly lipophilic mol- significant difference vs. samples treated with 100 μM ecule that readily enters cells and firmly chelates NO alone (a positive control), p<0.05. Open bars – the intracellular pool of redox active iron. Thus, it per cent of initial value (cells treated with 100 μM was plausible to suppose that it would chelate both NO alone). cytosolic and compartmented LIP, including lyso- GHz, modulation amplitude – 3.027 G and time somal LIP. The nonpermeable iron chelator, DFO, constant – 41 ms. In order to estimate the values of is a hydrophilic molecule that is taken up predomi- g coefficients computer simulation was performed on SimFonia 1.25 software (Bruker Analytische Messtechnik, DE). The results presented in Figs.1-3 show that DFO inhibits DNIC formation to the similar extent as

Fig.1. Dose dependent induction of DNIC specific EPR signal in K562 cells incubated for 6 h with different concentrations of SIH or DFO then treated with 100 μM NO for 15 min at 37oC. Solid bars – mean ±SD, n=3. Asterix denotes statistically significant difference vs. Fig.3. Inhibition of EPR signal induction in K562 cells incu- μ samples treated with 100 M NO alone (a positive bated with 1000 μM DFO for 1, 3 and 6 h, and then control), p<0.05. Open bars – per cent of initial value treated with 100 μM NO for 15 min at 37oC. Solid μ (cells treated with 100 M NO alone). bars – mean ±SD, n=3. Asterix denotes statistically μ nantly via endocytosis and localizes almost exclu- significant difference vs. samples treated with 100 M sively within the lysosomal compartment, where it NO alone (a positive control), p<0.05. Open bars – per cent of initial value (cells treated with 100 μM seems to remain. Hence, we expected that the ef- NO alone). fect exerted by DFO would depend on the control of reactivity of the intralysosomal iron pool. SIH, indicating that both chelators affect similar DNIC formation was recorded using EPR (elec- pool of labile iron. Taken together, our present and tron paramagnetic resonance). The EPR spectra previous results support the view that lysosomal were recorded on Bruker ESP 300 at 77 K, micro- iron considerably contributes to the total LIP in wave power – 1 mW, microwave frequency – 9.31 the cell. 100 RADIOBIOLOGY

The work was supported by the Polish Ministry J.L. Zweier. Kluwer Academic Publishing, Boston 1999, of Education and Science statutory grant for the pp. 49-82. INCT. [2]. Ueno T., Yoshimura T.: Jpn. J. Pharmacol., 82, 95-101 (2000). References [3]. Męczyńska S., Lewandowska H., Kruszewski M.: Acta Biochim. Polon., 55, Suppl. 1, 192 (2006). [1]. Vanin A., Kleschyov A.: In: Nitric oxide in transplant rejection and anti-tumor defence. Eds. S. Lukiewicz,

GHRELIN, A LIGAND FOR THE GROWTH HORMONE SECRETAGOGUE RECEPTOR, INCREASES DNA BREAKAGE IN X-IRRADIATED PIGLET BLOOD MONONUCLEAR CELLS Marcin Kruszewski, Teresa Iwaneńko, Jarosław Woliński1/, Maria Wojewódzka 1/ The Kielanowski Institute of Animal Physiology and Nutrition, Polish Academy of Sciences, Jabłonna, Poland

Ghrelin, a recently described endogenous ligand of DNA damage was evaluated by the alkaline comet for the growth hormone secretagogue receptor assay [2]. To investigate the influence of ghrelin on (GHS-R), is a 28 amino acid peptide encoded by cells’ ability to repair DNA damage, BMNC were GHRL gene and is derived from a 117 amino acid irradiated with 2 Gy of X-radiation and disappear- precursor peptide. It is produced by stomach cells ance of DNA breaks was monitored 0.5, 1 and 2 h and is a potent regulator of food intake, energy ex- after irradiation. penditure, adiposity, and growth hormone secre- We found that ghrelin had a marked effect on tion (reviewed in [1]). Ghrelin reduces peripheral the level of X-ray induced DNA damage: there was energy expenditure and enhances appetite by ac- a significant increase in the initial level of DNA tivating neurons that express Agouti-related pep- strand breaks in cells from ghrelin treated animals tide and neuropeptide Y. GHS-R and ghrelin are as compared with untreated controls (Fig.1). How- expressed in human T lymphocytes and monocytes, ever, no effect of ghrelin was observed on the cel- where ghrelin inhibits the expression of proinflam- lular capacity to rejoin DNA strand breaks (Fig.2). matory cytokines. Other functional roles of ghrelin at the cellular level remain poorly defined. We investigated the effect of ghrelin addition to food on the susceptibility of peripheral blood mononuclear cells (BMNC) to DNA damage generated by X-irradiation. Ghrelin was applied intragastrically to newborn piglets for 7 days at a dose of 15 μg/kg body mass. After treatment, blood was collected by heart puncture and BMNC were isolated by density gradient centrifugation on Histopaque 1137, resuspended in RPMI1640 medium supplemented with 20% of foetal calf serum. Isolated cells were exposed to X-radiation (dose range – 0-3 Gy, 200 kV, 5 mA, dose rate – 1.2 Gy/min). The extent Fig.2. Lack of effect of ghrelin treatment on the capacity of piglet BMNC to repair DNA damage induced by 2 Gy of X-radiation. This is the first observation of the participation of ghrelin in the cellular response to X-irradiation. It points to the role of ghrelin in enhancing the genotoxicity of oxidative stress-inducing factors generated during inflammation. The work was supported by the Polish Minis- try of Education and Science, project number PBZ-KBN-093/P06/2003.

References [1]. Gil-Campos M., Aguilera C.M., Canete R., Gil A.: Br. Fig.1. The effect of ghrelin treatment on the initial X-ray-in- J. Nutr., 96, 201-226 (2006). duced DNA breaks in piglet BMNC evaluated by the [2]. Wojewodzka M., Kruszewski M., Iwanenko T., Collins alkaline comet assay. A.R., Szumiel I.: Mutat. Res., 416, 21-35 (1998). RADIOBIOLOGY 101 GHRELIN INCREASES HYDROGEN PEROXIDE-INDUCED DNA BREAKAGE IN PIGLET BLOOD MONONUCLEAR CELLS Teresa Bartłomiejczyk, Teresa Iwaneńko, Maria Wojewódzka, Jarosław Woliński1/, Roman Zabielski2/, Marcin Kruszewski 1/ The Kielanowski Institute of Animal Physiology and Nutrition, Polish Academy of Sciences, Jabłonna, Poland 2/ Warsaw Agricultural University, Poland

The recently described endogenous ligand for the growth hormone secretagogue receptor, ghrelin, was found to inhibit hydrogen peroxide-induced cytokine release in human umbilical vein endothe- lial cells [1]. This suggested that the peptide blocks redox-mediated cellular signalling. Moreover, ghrelin inhibited basal and TNF-alpha-induced activation of nuclear factor-kappaB [1], a process initiated by DNA damage [2]. However, the effect of ghrelin on DNA damage induction has not been studied until now. We investigated the effect of ghrelin addition to food on the susceptibility of piglet peripheral blood mononuclear cells (BMNC) to DNA damage generated by hydrogen peroxide. Ghrelin was applied intragastrically to newborn piglets for 7 days Fig.2. Lack of effect of ghrelin dose on the initial hydro- at two doses (7.5 and 15 μg/kg body mass). After gen peroxide-induced DNA breaks in piglet BMNC treatment, blood was collected by heart puncture evaluated by the alkaline comet assay. and BMNC were isolated by density gradient centrifugation on Histopaque 1137, resuspended in trols (Fig.1). This effect did not depend on ghrelin RPMI1640 medium supplemented with 20% of dose (Fig.2), supporting the relation of the observed foetal calf serum. Isolated cells were exposed to hy- enhancement of DNA damage to cellular signal- drogen peroxide (0-250 μM) in phosphate buffered ling. saline for 15 min at 4oC. The extent of DNA dam- Together with the preceding report on the ef- age was evaluated by the alkaline comet assay [3]. fect of ghrelin on the initial DNA breaks in X-irradiated cells, this observation points to the role of ghrelin in enhancing the genotoxicity of oxidative stress-inducing factors generated during inflammation. Overproduction of ghrelin may lead to excessive DNA damage and consequent cytotoxicity, especially under inflammatory conditions, where DNA damaging agents, such as reactive oxygen or nitrogen species, are produced. Thus, the discovered effect of ghrelin may have some relevance to the pathophysiology of obesity-linked diseases. The work was supported by the Polish Minis- try of Education and Science, project number PBZ-KBN-093/P06/2003. Fig.1. The effect of ghrelin treatment on the initial hydrogen peroxide-induced DNA breaks in piglet BMNC References evaluated by the alkaline comet assay. [1]. Li W.G., Gavrila D., Liu X., Wang L., Gunnlaugsson S., Stoll L.L., McCormick M.L., Sigmund C.D., Tang C., We found that ghrelin had a marked effect on Weintraub N.L.: Circulation, 109, 2221-2226 (2004). the level of hydrogen peroxide-induced DNA dam- [2]. Wu Z.H., Shi Y., Tibbetts R.S., Miyamoto S.: Science, age: there was a significant increase in the initial 311, 1141-1146 (2006). level of DNA strand breaks in cells from ghrelin [3]. Wojewódzka M., Kruszewski M., Iwaneńko T., Collins treated animals as compared with untreated con- A.R., Szumiel I.: Mutat. Res., 416, 21-35 (1998). 102 RADIOBIOLOGY THE EFFECT OF LEPTIN ON DNA BREAKAGE INDUCED BY GENOTOXIC AGENTS IN HUMAN PERIPHERAL BLOOD MONONUCLEAR CELLS Marcin Kruszewski, Teresa Iwaneńko, Maria Wojewódzka, Jarosław Woliński1/, Roman Zabielski2/ 1/ The Kielanowski Institute of Animal Physiology and Nutrition, Polish Academy of Sciences, Jabłonna, Poland 2/ Warsaw Agricultural University, Poland

Leptin, an adipose tissue cytokine is known to reduce food intake and to increase energy expenditure. Previous studies in rats indicated that gastric leptin is involved in cytoprotection in the rat pan- creas and gastric mucosa. This protection depends upon vagal activity and sensory nerves and involves hyperemia probably mediated by nitric oxide and mimicking the gastroprotective effect of cholecys- tokinin (CCK) [1]. On the other hand, long form of leptin receptor (Ob-Rb) is expressed on the peripheral blood mononuclear cells (BMNC) and the existence of a reciprocal regulatory network is an- ticipated, by which leptin may control immune cell activation and inflammation (reviewed in [2,3]). Fig.2. The effect of leptin treatment on the initial hydro- Leptin up-regulates growth hormone secretagogue gen peroxide-induced DNA breaks in human BMNC receptor (GHS-R) expression on human T lym- evaluated by the alkaline comet assay. phocytes, modulates the activation of peripheral BMNC and it is known to have a proinflammatory (20 μg/ml) for 20 h. After pretreatment, cells were action. X-irradiated (dose range – 0-8 Gy) in an ANDREX We examined the influence of leptin on the sus- X-ray machine (Holger Andreasen, Denmark; 200 ceptibility of human cells to ionizing radiation or kV, 5 mA, dose rate – 1.2 Gy/min) or exposed to μ hydrogen peroxide. Human peripheral BMNC H2O2 (0-250 M) in phosphate buffered saline for were isolated from whole blood by density gradi- 15 min at 4oC. The extent of DNA damage was evaluated by the alkaline comet assay [3]. Leptin had no effect on BMNC proliferation after PHA stimulation. Pretreatment with leptin had

no effect on the level of X-radiation- and H2O2-induced DNA breakage (Figs.1 and 2). The results described here and in the preceding two reports indicate that leptin has different effects on cellular susceptibility to DNA damaging agents in vivo and in vitro. The work was supported by the Polish Minis- try of Education and Science, project number PBZ-KBN-093/P06/2003.

References Fig.1. Lack of effect of leptin treatment on the initial X-ray- [1]. Brzozowski T., Konturek P.C., Pajdo R., Kwiecien S., -induced DNA breaks in human BMNC evaluated Ptak A., Sliwowski Z., Drozdowicz D., Pawlik M., by the alkaline comet assay. Konturek S.J., Hahn E.G.: J. Physiol. Pharmacol., 52, 583-602 (2001). ent centrifugation on Histopaque 1137, resus- [2]. Popovic V., Duntas L.H.: Horm. Metab. Res., 37, pended in RPMI1640 medium supplemented with 533-537 (2005). 20% of foetal calf serum, stimulated with phyto- [3]. Broberger C.: J. Intern. Med., 258, 301-327 (2005). hemagglutinin (PHA) and pretreated with leptin RADIOBIOLOGY 103 CABAS – A FREELY AVAILABLE PC PROGRAM FOR FITTING CALIBRATION CURVES IN CHROMOSOME ABERRATION DOSIMETRY Joanna Deperas1/, Marta Szłuińska2/, Marta Deperas-Kaminska3,4/, Alan Edwards2/, David Lloyd2/, Carita Lindholm5/, Horst Romm6/, Laurence Roy7/, Raymond Moss8/, Josselin Morand8/, Andrzej Wójcik1,4,8/ 1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland 2/ Health Protection Agency, Centre for Radiation, Chemical and Environmental Hazards, Chilton, Didcot, United Kingdom 3/ Joint Institute for Nuclear Research, Dubna, Russia 4/ Świętokrzyska Academy, Kielce, Poland 5/ Radiation and Nuclear Safety Authority (STUK), Helsinki, Finland 6/ Bundesamt für Strahlenschutz, Neuherberg, Germany 7/ Institut de Radioprotection et de Sûreté Nucléaire, Fontenay-aux-Roses Cedex, France 8/ Institute for Energy – JRC European Commission, Petten, the Netherlands

The aim of biological dosimetry is the calculation frequently used, sometimes combined with centric of the dose and the range of uncertainty to which rings, and the cytokinesis blocked micronucleus an accident victim was exposed. This process re- (CBMN) assay has also been developed. Numerous quires the use of the maximum likelihood method studies, performed both on animals and humans, for the proper fitting of an in vitro calibration curve, have demonstrated a close correspondence between a procedure which is not implemented in popular, aberrations or micronuclei induced in peripheral commercially available statistical computer pro- blood lymphocytes under in vitro and in vivo condi- grams. tions. This allows one to estimate a radiation dose The most specific and sensitive technique of bio- absorbed during an accident by reference to an in logical dosimetry relies on estimating the frequency vitro calibration curve. This curve is generated by of unstable chromosomal damage in peripheral irradiating blood samples, collected from control blood lymphocytes of the exposed person [1,2]. The donors, with several doses of radiation. Following dicentric chromosome aberration assay is the most culturing of lymphocytes, microscopic slides are

Fig. A screenshot of the main menu of the program. 104 RADIOBIOLOGY prepared and the frequencies of dicentrics and tion, and (iv) a module for calculating the dose in rings are estimated in first division metaphases or the case of a fractionated or protracted exposure micronuclei in binucleate cells. The points of the (Fig.). dose-response relationship are fitted to an equa- The program can be downloaded as freeware tion which is linear-quadratic for low LET (linear from http://www.pu.kielce.pl/ibiol/cabas or obtained energy transfer) radiation and linear for high LET from any of the present authors. The use of the pro- radiation. gram is straightforward and it can be expected that The correct fitting procedure is not trivial be- its use will improve the precision of dose estimates cause it requires an appropriate weighting of data by biological dosimetry in cases of radiation acci- points. Several laboratories have produced their dents. Furthermore, it should facilitate setting up own curve fitting programs for internal use but these inter-laboratory dose effect curves. are frequently not user-friendly and not available The work was supported by the Polish Ministry to outside users. Therefore, a PC-based freely avail- of Education and Science statutory grant for the able program called CABAS, for fitting dose-re- INCT. sponse curves to chromosomal aberration or micronucleus data and for calculating the dose and con- References fidence limit (CL) has been developed and tested. [1]. Cytogenetic analysis for radiation dose assessment. A The program consists of (i) the main curve-fitting manual. IAEA, Vienna 2001. and dose estimating module, (ii) a module for cal- [2]. Voisin P., Barquinero J.F., Blakely B., Lindholm C., culating the dose in cases of partial body exposure, Lloyd D., Luccioni C., Miller S., Palitti F., Prasanna (iii) a module for estimating the minimum number P.G., Stephan G., Thierens H., Turai I., Wilkinson D., of cells necessary to detect a given dose of radia- Wojcik A.: Cell. Mol. Biol., 48, 501-504 (2002).

THE TEMPERATURE EFFECT ON THE FREQUENCY OF RADIATION-INDUCED MICRONUCLEI IN HUMAN PERIPHERAL BLOOD LYMPHOCYTES IS ABOLISHED BY DMSO Kinga Brzozowska, Andrzej Wójcik

The impact of temperature on the frequency of Whereas temperature of pre-irradiation incu- radiation-induced chromosome aberrations in the bation as well as that during exposure exerted a human lymphocytes was first described by Bajerska distinct effect on the frequency of radiation-induced and Liniecki [1]. We have previously described [2] micronuclei in human peripheral blood lympho- experiments carried out to analyze the impact of cytes, the presence of DMSO completely abolished blood temperature at irradiation in vitro on the this effect: the dose-effect curves for all three tem- level of radiation-induced micronuclei. We found peratures were identical. that temperature of pre-irradiation incubation as In the interaction of ionizing radiation with well as that during exposure exerted an effect on DNA one discerns direct and indirect effect, the the frequency of radiation-induced micronuclei in latter produced in the water layer surrounding the human peripheral blood lymphocytes. The highest DNA molecule. Since DMSO is a scavenger of the frequency of micronuclei was observed for blood OH• radical which is produced in the process of samples incubated at 37oC before and during irra- water radiolysis, the presented results indicate diation in vitro with doses of 2 and 2.7 Gy, inter- that temperature conditions affect the indirectly mediate – at 20oC and the lowest one – at 0oC. induced damage. At this stage of our research, Blood samples were drawn from two healthy we cannot explain which mechanisms are respon- male donors aged 24 and 45 years and irradiated sible for the effect of temperature on the level of at 0, 20 and 37oC with X-rays 200 kVp, 5 mA, 3 mm radiation-induced cytogenetic damage, although Cu filter. The doses were: 0, 1 and 2 Gy for the we presume that chromatin conformation may first donor, and 0, 1.35 and 2.7 Gy for the second play a role. It is plausible to assume that acces- donor. For 20 min before irradiation as well as dur- sibility of DNA to the radical attack depends on ing irradiation, the blood samples were incubated the steric relations of the chromatin components at 0, 20 or 37oC. dimethylsulphoxide (DMSO) was and specifically, on the extent of protection by added 5 min before irradiation at the concentra- proteins. Temperature dependent structural tran- tion of 0.5 mol/dm3. After irradiation, the samples sitions in the protein-DNA complex (e.g. [4]), as were centrifuged in order to discard supernatants well as temperature dependence of binding of containing DMSO; cells were then transferred into specific nuclear proteins to DNA (e.g. [5,6]) have 4.5 ml RPMI 1640 medium supplemented with 25% been described but not systematically explored calf serum, 2.5% phytohaemagglutinin (PHA), from the point of view of chromatin radiosensi- antibiotic solution and incubated for 72 h at 37oC tivity. and 5% CO2. Lymphocyte preparations for micro- The work was supported by the Polish Ministry nuclei analysis were prepared according to the of Education and Science statutory grant for the standard method of Fenech [3]. INCT. RADIOBIOLOGY 105

References [3]. Fenech M.: Mutat. Res., 285, 35-44 (1993). [4]. Peters W.B., Edmondson S.P., Shriver J.W.: J. Mol. [1]. Bajerska A., Liniecki J.: Int. J. Radiat. Biol., 16, 483-493 Biol., 343, 339-360 (2004). (1969). [5]. Santilli G., Schwab R., Watson R., Ebert C., Aronow [2]. Brzozowska K., Wójcik A.: The effect of temperature B.J., Sala A.: J. Biol. Chem., 280, 15628-15634 (2005). on the frequency of radiation-induced micronuclei in [6]. Ferreira M.E., Hermann S., Prochasson P., Workman human peripheral blood lymphocytes. In: INCT Annual J.L., Berndt K.D., Wright A.P.: J. Biol. Chem., 280, Report 2005. Institute of Nuclear Chemistry and Tech- 21779-21784 (2005). nology, Warszawa 2006, pp.102-103.

VARIABLE RADIOSENSITIVITY OF CHROMOSOMES 2, 8 AND 14 IN HUMAN PERIPHERAL BLOOD LYMPHOCYTES EXPOSED TO 480 MeV/n 12C-IONS Marta Deperas-Kaminska1,2/, Gennady N. Timoshenko1/, Eugene A. Krasavin1/, Andrzej Wójcik2,3/ 1/ Joint Institute for Nuclear Research, Dubna, Russia 2/ Świetokrzyska Academy, Kielce, Poland 3/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland

For a wide variety of biological effects, radiations tions including the complex ones were transformed of high linear energy transfer (LET) have been into primary breaks. The break frequencies were known to have greater biological effectiveness per scaled to the whole genomic frequencies. The re- unit dose than those of low LET [1]. Little is known sults are presented in Fig.1. For all donors, the low- about the extent of individual variability in the est frequency of breaks was observed in chromo- radiosensitivity of human cells to high LET radia- some 2 and the highest in chromosome 14 in lym- tion. In all published studies dealing with individual phocytes of donor 3, chromosome 8 of donor 2, radiosensitivity, the studied cells (lymphocytes or and at the same level in chromosomes 8 and 14 of fibroblasts) were only exposed to low LET radia- donor 1 (Fig.1A). The found break frequency is tion. The purpose of this study was to investigate below the expected values for chromosome 2 and by FISH the distribution of radiation-induced above the expected values for chromosomes 8 and chromosomal aberrations in chromosomes 2, 8 and 14. Only for chromosome 14 of donor 2 the ratio 14 in lymphocytes of 3 donors. is close to unity (Fig.1B). Irradiation of blood from 3 healthy donors was The lowest frequencies of exchanges were performed at the Nuclotron accelerator at the Joint scored in chromosome 2 and the inter-donor vari-

Fig.1. Primary breaks observed in the painted chromosomes of 3 donors. Breaks calculated from aberrations observed after exposed to 3.5 Gy of 480 MeV/n 12C-ions were summed up and scaled to the whole genomic frequency. The absolute numbers are shown in Fig.1A and the ratios of found to expected are shown in Fig.1B. Error bars represent standard deviations from the mean; also, values are shown for the three painted chromosomes of all donors.

Institute for Nuclear Research (Dubna, Russia). ability was low. Chromosomes 8 and 14 were in- Whole blood samples were irradiated with 1.1, 2.3 volved in exchanges more frequently than expected and 3.5 Gy of 12C-ions. At the position of the sample on the basis of DNA content. In contrast, the in- the beam energy was 480 MeV/n and LET=10.6 volvement of chromosome 2 was less frequent than keV/μm. Chromosomes 2, 8 and 14 were painted expected. in different colors and aberrations scored with the This is the first study investigating the individual help of an image-analysis system, as described in [2]. radiosensitivity of chromosomes of human periph- In order to assess the overall radiosensitivity of eral blood lymphocytes to heavy ions. Generally, the painted chromosomes, chromosomal aberra- the sensitivity of chromosome 2 was lower, and that 106 RADIOBIOLOGY of chromosomes 8 and 14 – higher than expected. References These data suggest that the sensitivity of human [1]. Goodhead D.T.: J. Radiat. Res., 40 (Suppl.), 1-13 chromosome to heavy ions is individually variable. (1999). The results are in line with those of a recent study [2]. Sommer S., Buraczewska I., Wojewodzka M., Bouzyk on the sensitivity of chromosomes 2, 8 and 14 to E., Szumiel I., Wojcik A.: Int. J. Radiat. Biol., 81, gamma rays [2]. 741-749 (2005).

EFFICIENT DOUBLE STRAND BREAK REJOINING AND SURVIVAL IN X-IRRADIATED HUMAN GLIOMA M059 CELLS ARE DEPENDENT ON EGF RECEPTOR KINASE ACTIVITY Iwona Grądzka, Barbara Sochanowicz, Irena Szumiel

The epidermal growth factor (EGF) receptor down the DSB rejoining in M059 K and has no (EGFR) is a mediator of both proliferative and sur- effect in M059 J cells. This suggested a direct link vival signals in mammalian cells (reviewed in [1]). between EGFR kinase activity and DNA-PK-de- Nuclear translocation of EGFR was observed after pendent DSB rejoining and was consistent with ob- X-irradiation and was found to be important for servation of other authors [3]. Now, we have examin- regulation of DNA repair processes [2,3]. We inves- ed survival of both cell lines after X-irradiation tigated the effect of EGFR inhibition on various combined with tyrphostin treatment. The dose aspects of the cellular response to X-irradiation range for each cell line was chosen so that the sur- in two related human glioma cell lines M059 K and vival level was comparable (between 90 and 1%). M059 J, the latter highly sensitive to X-radiation The survival data were expressed as the ratio of due to the lack of a catalytic subunit (DNA-PKcs) survival after combined treatment to that after of DNA-dependent protein kinase (DNA-PK) [4]. X-irradiation alone. Ratio equal to unity means a Tyrphostin AG 1478 was used as a specific inhibi- strictly additive effect, that is, independent effect tor to block EGFR tyrosine kinase activity. of each of the agents tested. A less than additive We have previously found that double strand effect (protection) or more than additive effect (sen- break (DSB) rejoining after X-irradiation is faster sitisation) indicate an interaction of both agents. in M059 K than in M059 J cells [5] because of a de- As shown in Fig., in M059 K cells there is a more fect in a nonhomologous DNA end-joining (NHEJ) than additive effect of combined (X+T) treatment, in the latter cell line [4]. Tyrphostin AG 1478 slowed i.e. radiosensitisation; this effect is absent in M059J cells (close to additive effect at doses up to 1 Gy and protective effect at higher doses). In conclusion, tyrphostin AG 1478 slowes down the DSB rejoining in M059 K and has no effect in M059 J cells. This effect corresponds with a decrease in survival in M059 K but not in M059 J cells subjected to combined (T+X) treatment and suggests a direct relation between EGFR kinase activity, DNA-PK-dependent DSB rejoining and survival. The work was supported by the Polish Ministry of Education and Science statutory grant for the INCT.

References [1]. Amorino G.P., Hamilton V.M., Valerie K., Dent P., Lammering G., Schmidt-Ulrich R.K.: Mol. Biol. Cell, 13, 2233-2244 (2002). [2]. Harari P.M., Huang S.M.: Semin. Radiat. Oncol., 11, 281-289 (2001). [3]. Dittmann K., Mayer C., Fehrenbacher B., Schaller M., Raju U., Milas L., Chen D.J., Kehlbach R., Rodemann H.P.: J. Biol. Chem., 280, 31182-31189 (2005). [4]. Anderson C.W., Dunn J.J., Freimuth P.I., Galloway A.M., Allalunis-Turner M.J.: Radiat. Res., 156, 2-9 (2001). Fig. Survival ratio after combined (X+T) treatment to that [5]. Grądzka I., Buraczewska I., Sochanowicz B., Szumiel after X-irradiation alone (see text for explanations). I.: Eur. J. Biochem., 271 (Suppl. 1, Pt1), 1-12 (2004). RADIOBIOLOGY 107 DECREASED PERSISTENCE OF γH2AX FOCI IN X-IRRADIATED xrs6 CELLS TREATED WITH SIRTUIN INHIBITOR Maria Wojewódzka, Marcin Kruszewski, Irena Szumiel

In the preceding reports, we described the effect With the use of an anti-γH2AX antibody with of sirtuin inhibitor, GPI 19015 treatment on the a fluorescent tag, a pattern of γH2AX foci can be repair of DNA double strand breaks (DSB) and revealed a few minutes after irradiation. The foci survival in CHO-K1 and xrs6 cells [1]. In CHO-K1 are markers of DSB and allow to directly count the cells a relatively weak effect was noted (using the DSB number per nucleus (review in [3]). As shown neutral comet assay) at the 15 min repair interval. in Figs.1 and 2, in xsr6 cells GPI 19015 treatment In contrast, in the DSB repair (nonhomologous causes a faster disappearance of foci than in the end-joining – NHEJ) defective mutant cell line, xrs6, inhibitor-untreated cells. In CHO-K1 cells there the increase in the rate of DSB repair was more pro- is no effect of the inhibitor, in agreement with the nounced, especially in G1 phase of the cell cycle. weak effect on DSB rejoining estimated with the The cells were treated with sirtuin inhibitor 200 μM comet assay. As stated previously, the possible rea- GPI 19015 at 37oC for 1 h and X-irradiated with 10 son of this effect may lay in the impaired DNA-PK Gy without medium change. Applying the same ex- (DNA-dependent protein kinase) dependent non- perimental schedule, we determined the number of homologous end-joining (D-NHEJ) in xrs6 cells: γH2AX foci in both cell lines, using the foci method DSB repair in these cells has to rely on the ho- as described in [2]. mologous recombination repair or DNA-PK in- Control Irradiation 1 Gy Irradiation 1 Gy 0 h 4 h

CHO-K1

CHO-K1+GPI

xrs6

xrs6+GPI

Fig.1. Photographs of histone γH2AX foci in control cells and cells irradiated with 1 Gy X-irradiation. Time-dependent decrease of the histone γH2AX foci number in untreated and inhibitor-treated CHO-K1 and xrs6 cells also is presented in Fig.2. 108 RADIOBIOLOGY

Fig.2. Time-dependent decrease of the histone γH2AX foci number in untreated and inhibitor-treated CHO-K1 cells (A) and xrs6 cells (B). The foci numbers are expressed as a percentage of mean initial foci number in irradiated cells. Number of foci in controls was subtracted. Foci in 100 cells were scored for each time interval. dependent (backup) nonhomologous end-joining inhibitor. In: INCT Annual Report 2005. Institute of (B-NHEJ) [4,5]. It can be expected that sirtuin in- Nuclear Chemistry and Technology, Warszawa 2006, hibition increases histone acetylation and thus, pp. 107-108. facilitates the access of repair enzymes to the dam- [2]. Cowell I.G., Durkacz B.W., Tilby M.J.: Biochem. aged DNA sites. Pharmacol., 71, 13-20 (2005). [3]. Pilch D.R., Sedelnikova O.A., Redon C., Celeste A., Supported by the Polish Ministry of Education Nussenzweig A., Bonner W.M.: Biochem. Cell Biol., and Science statutory grant for the INCT. 81, 123-129 (2003). [4]. Wang H., Perrault A.R., Takeda Y., Qin W., Wang M., References Iliakis G.: Nucleic Acids Res., 31, 5377-5388 (2003). [5]. Wang H., Rosidi B., Perrault R., Wang M., Zhang L., [1]. Wojewódzka M., Kruszewski M., Szumiel I.: Backup Windhofer F., Iliakis G.: Cancer Res., 65, 4020-4030 nonhomologous end-joining is the target of sirtuin (2005).

TWO p53 BINDING PROTEINS ARE PRESENT IN LY-R (REPAIR COMPETENT) AND LY-S (REPAIR DEFICIENT) CELLS IN DIFFERENT PROPORTIONS Barbara Sochanowicz, Irena Szumiel

L5178Y-S (LY-S) subline is the longest known cells are deprived of this protein. Therefore, we mammalian radiation sensitive cell line. Although examined the total cell extracts from both closely it is clear that the reason for radiation sensitivity related LY sublines, LY-R (repair competent) and of LY-S cells is an impaired DNA DSB (double strand break) repair, the molecular defect is unknown. LY-S cells show both phenotypic features that are characteristic of cells with a defective NHEJ (nonhomologous end-joining): a pronounced G1 phase radiosensitivity and a slown down DSB repair. Nevertheless, the NHEJ defect in LY-S cells is not due to DNA-PK (DNA-dependent protein kinase), Xrcc4 or ligase IV mutation. Another possible defect concerning autophosphorylation in the so-called ABCDE cluster of serine and threonine residues in the central part of the catalytic subunit has also been eliminated as a reason for impaired repair of DSB (reviewed in [1]). A recent paper [2] pointed to a role of 53BP1 protein in the NHEJ system. 53BP1 (p53 binding protein) is a BRCT domain-containing protein that is rapidly recruited to DSB after X-irradiation. Its function probably consists in acting as a scaffold protein and contributing to ligase IV and Artemis Fig.1. Model of NHEJ pathways according to [2]: (A) the functioning, as shown in Fig.1. Its absence in chicken core NHEJ pathway, (B) ATM/Artemis – dependent DT40 cells was phenotypically manifested as a NHEJ pathway, (C) 53BP1 – dependent pathway. The 53BP1 defect [2] and exactly matched the phenotype of protein contributes to both B and C pathway. Lig IV LY-S cells; hence, there was a possibility that LY-S – ligase IV. RADIOBIOLOGY 109 and two bands in LY-R and LY-S cells. In LY cells the two detected proteins seem to sum up to the same amount. Nevertheless, the band corresponding to 53BP1 of similar molecular weight as that in K562 cells is less abundant in LY-S cells than in LY-R cells. There are no data on 53BP1 isoforms in the literature. The antibody was obtained with the use of a peptide representing a portion of human 53BP1 encoded in part by exons 11 and 12 as immunogen. It reacts with both the human and murine protein. Notwithstanding the possible significance of the presence of two detected proteins expressed in various proportions in LY sublines, it can be stated LY-R LY-S LY-R LY-S K562 μ μ μ that there is no analogy between this observation 60 g 30 g 30 g and that concerning DT40 cells with a DSB repair Fig.2. Western blot showing one band detected with the defect due to lack of 53BP1. Thus, absence of 53BP1 anti-53BP1 antibody in K562 cells and two bands in protein is not a reason of defective DSB repair in LY-R and LY-S cells. Note that in LY cells the two LY-S cells. detected proteins seem to sum up to the same amount but the ratio of band 1 to 2 differs. References LY-S (repair deficient), for 53BP1 protein, using [1]. Szumiel I.: Int. Radiat. Biol., 81 (5), 353-365 (2005). a specific antibody (rabbit polyclonal to 53BP1, [2]. Iwabuchi K., Hashimoto M., Matsui T., Kurihara T., ab36823, Abcam) and Western blotting method. Shimizu H., Adachi N., Ishiai M., Yamamoto K., K562 cells served as a positive control. Tauchi H., Takata M., Koyama H., Date T.: Genes As shown in Fig.2, we detected one protein Cells, 11(8), 935-948 (2006). band with the anti-53BP1 antibody in K562 cells

PREMATURE CHROMOSOME CONDENSATION IN BIOLOGICAL DOSIMETRY AFTER HIGH DOSE GAMMA IRRADIATION Sylwester Sommer, Iwona Buraczewska, Andrzej Wójcik Biological dosimetry is necessary in the case of nor, to the total number of 10 020 cells. Excess frag- radiation accidents or accidental exposures to ion- ments or entities with color junctions, involving 3 izing radiation, especially in the case of lack or fail- painted pairs of chromosomes, were regarded as ure of physical measurements of the dose [1]. aberrations. Analysis of Giemsa-stained dicentrics in human Figure presents the dose-effect curve for total peripheral blood lymphocytes is regarded by the aberrations in chromosomes 2, 8 and 14, scored in International Atomic Energy Agency as the most lymphocytes of 6 patients. There was a clear dose accurate and reliable assay of biological dosimetry – dependence and no saturation of aberration yields [1]. In the case of high radiation doses, problems can occur with obtaining a sufficient number of mitotic cells for analysis [1,2]. The use of drug-induced PCC (premature chromatin condensation) was proposed to overcome this problem [2,3]. Therefore, we decided to determine the frequency of aberrations induced by high doses of radiation in painted chromosomes 2, 8 and 14, both accumulated in mitotic cells and after PCC induction. Human lymphocytes of 6 healthy donors, irradiated with 0, 3, 5, 7 and 10 Gy of γ 60Co were cul- tured in whole blood cultures for 48 h. Twenty four hours after set-up of cultures, colcemid was added to the final concentration of 1 μg/ml to arrest cells in the first mitosis after irradiation. Two hours before the end of cultivation, calyculin A (50 nM) was applied to induce PCC. Lymphocytes were fixed according to the standard procedure. FISH stain- Fig. Dose response curves for total aberration yields de- ing was performed on 3 pairs of chromosomes: 2, termined with the PCC method combined with FISH 8, 14, using directly labeled probes from Oncor, staining after in vitro irradiation of peripheral blood according to the manufacturer’s protocol. At least lymphocytes from 6 donors with 0, 3, 5, 7 and 10 Gy of 150 cells for each dose were analyzed for every do- gamma rays. 110 RADIOBIOLOGY up to the dose of 10 Gy. In spite of relatively low the possibility of analyzing heavily damaged cells values of the mitotic index (except controls) – lower which would be arrested before entering mitosis than 1% – it was possible – due to PCC – to analyze e.g. in the G2 phase checkpoint. We conclude that more than 150 spreads from each slide; this would after establishing suitable calibration curves, simul- not be possible if only cells arrested in metaphase taneous use of PCC and chromosome painting by colcemid block were analyzed. Simultaneous could be a very useful tool for biological dosimetry usage of PCC and whole chromosome FISH al- in the case of high doses of radiation. lowed to score not only excess fragments but also The work was supported by the Polish Ministry the exchange type of aberrations, usually not rec- of Education and Science – grant No. 6 P05A 11920 ognizable in PCC-spreads, because of their poor and statutory grant for the INCT. quality. We could not see any differences between in- References dividual radiosensitivity of donors – there were only slight differences between curves. Such result [1]. Cytogenetic analysis for radiation dose assessment. A confirms our previous report where we also found manual. IAEA, Vienna 2001. Technical Reports Series no difference between donors with respect to ra- No. 405. diation sensitivity [4]. [2]. Gotoh E., Durante M.: J. Cell. Physiol., 209, 297-304 (2006). Our experimental scheme allows to analyze ex- [3]. Kanda R., Minamihisamatsu M., Hayata I.: Int. J. clusively aberrations in cells in G2/M phase and Radiat. Biol., 78, 857-862 (2002). mitosis of the first cycle after irradiation; this is [4]. Sommer S., Buraczewska I., Wojewódzka M., Boużyk E., important, since there is a loss of damaged (aber- Szumiel I., Wójcik A.: Int. J. Radiat. Biol., 81, 741-749 rant) cells during cell division. Also important is (2005). NUCLEAR TECHNOLOGIES AND METHODS NUCLEAR TECHNOLOGIES AND METHODS 113

PROCESS ENGINEERING

METHOD FOR COLLECTION OF NITRATE FROM WATER SAMPLES AND DETERMINATION OF NITROGEN AND OXYGEN ISOTOPE COMPOSITION Małgorzata Derda, Stela Maria Cuna1/, Ryszard Wierzchnicki 1/ National Institute for Research and Development of Isotopic and Molecular Technologies, Cluj-Napoca, Romania Problem associated with anthropogenic nitrogen column with 15 ml of 3 M HCl. The nitrate-bear- contributions to the biosphere and hydrosphere are ing acid eluent was neutralized with Ag2O and fil- increasingly being recognized. Nitrate contamina- tered to remove the AgCl precipitate. The sample tion, often related to agricultural activities, is one containing AgNO3 was split into aliquots in the of the major problems in surface and groundwater ratio 1:2 for δ15N and δ18O analysis. system. Nitrogen availability is one of the main controls on productivity and is an important factor regulat- ing biodiversity. At present, nitrogen input from human sources, chiefly synthetic fertilizers and burning of fossil fuels, approximately equals the input from natural nitrogen fixation. The increased nitrogen input from anthropogenic sources causes eutrophication of lakes, streams, and coastal water- ways, acidification of environments, and degradation of drinking water quality [1]. Nitrogen in terrestrial and aquatic ecosystem cycles among oxidized, reduced, organic and inorganic species, of which the nitrate is relatively abundant and mobile. Nitrogen and oxygen isotope ratios of nitrates provide a powerful tool to investi- Fig. Schematic representation of the procedure for collec- gate nitrate sources and cycling mechanisms. The tion, elution and processing of δ15N and δ18O analysis. analysis of nitrates for both δ15N and δ18O allows improved discrimination among potential sources One portion for δ15N analysis was drying at o and reaction mechanisms [2,3]. 55-65 C to evaporate water and to obtain AgNO3 Our objectives were to develop methods for con- as a solid phase [5]. After drying, the AgNO3 was centrating dissolved nitrates and to prepare them redissolved by adding 2 ml of deionized water. The for nitrogen and oxygen isotope analysis. We have resulting precipitate was pipetted into 3 silver cap- developed ion exchange methods because these sules such that each capsule contained 6-10 μmol methods offer a number of important advantages of NO3. The capsules were drying and after add- over other methods: i) nitrates can be concentrated ing sucrose, δ15N was measured using an EA-IRMS from dilute waters, ii) columns can be loaded in (elemental analyzer-isotope ratio mass specto- the field, iii) many samples may be processed at meter) in continuous flow. Nitrogen isotope values one time. The main disadvantage of this method (δ15N) are reported in per mill (‰), relative to the is time required for collection and preparation of atmospheric air. samples. The portion for δ18O determination was dried

The technical procedure of the method include: and then CO2 was produced by off-line pyrolysis quantitative extraction of nitrates from water with graphite in a vacuum line. The δ18O analysis samples, preparation of other nitrogen and oxygen was carried out using the dual inlet system Delta bearing species for 15N and 18O analysis, and con- plus IRMS. The δ18O values were reported relative version of the nitrate fraction to suitable gases for to the standard VSMOW. nitrogen and oxygen isotopic analysis. The anion exchange resin techniques offer an Samples were prepared by an anion exchange efficient and reliable means of collecting, transport- resin method as shown in Fig. [4]. The nitrate frac- ing, and storing, water samples for nitrogen and tion was collected by passing the water sample oxygen isotope analysis for the nitrate. Multiple through pre-filled, disposable, anion exchange resin samples may be sorbed on columns in field condi- columns. Nitrate fraction was then eluted from the tions using a common and relatively inexpensive 114 PROCESS ENGINEERING equipment. The laboratory preparation of samples References for δ15N analysis requires little technician time per sample (about 30 min) and most of the total time [1]. Vitousek P.M., Aber J.D., Howarth R.W., Likens G.E., required for sample preparation is spent for dry- Matson P.A., Schindler D.W., Schlesinger W.H., Tilman ing and combustion steps. D.G.: Ecol. Appl., 7, 3, 737-750 (1997). The preparation of a sample for δ18O analyses [2]. Amberger A., Schmidt H.L.: Geochim. Cosmochim. Acta, 51, 2699-2705 (1987). is more time-consuming (about 2 h) because of the [3]. Boettcher J., Strebel O., Voerkelius S., Schmidt H.L.: necessity of eliminating non-nitrate, oxygen-bear- J. Hydrol., 114, 413-424 (1990). ing anions and finally extraction of CO2. [4]. Silva S.R., Kendall C., Wilkison D.H., Ziegler A.C., Chang The presented method will be used for moni- C.C.Y., Avanzino R.J.: J. Hydrol., 228, 22-36 (2000). toring water systems and investigation of anthro- [5]. Fukada T., Hiscock K.M., Dennis P.F., Grischek T.: pogenic impact on the condition of Polish rivers. Water Res., 37, 3070-3078 (2003).

THE KINETICS OF TRANS-DICHLOROETHYLENE DECOMPOSITION IN AIR UNDER ELECTRON-BEAM IRRADIATION Yongxia Sun, Andrzej G. Chmielewski, Sylwester Bułka, Zbigniew Zimek, Henrietta Nichipor1/ 1/ Institute of Radiation Physical-Chemical Problems, National Academy of Sciences of Belarus, Minsk, Belarus

In our previous work [1,2], we have experimentally compounds were observed as by-products for studied 1,1-dichloroethylene – 1,1-DCE (H2C=CCl2) trans-DCE degradation in air under EB irradia- and trans-dichloroethylene – trans-DCE (trans- tion using the same analytical method. 1,1-DCE -HClC=CHCl) decomposition in an air mixture and trans-DCE are geometric isomers. Whether under electron-beam (EB) irradiation. It was found their decomposition mechanism in the air mixture that the decomposition efficiency of 1,1-DCE in air under EB irradiation is the same or not is not clear under EB irradiation is higher than trans-DCE in to us. In this work, we made a computer simula- the same range of initial concentration. The degra- tion of trans-DCE degradation in the air mixture dation organic by-product of 1,1-DCE was identi- under EB irradiation, the decomposition mechan- fied as chloroacetyl chloride (CH2ClCOCl) by ism was proposed and compared with 1,1-DCE. means of gas chromatography with a flame ioniz- The computer simulation of trans-DCE degra- ing detector (GC-FID) analysis, while no organic dation in air under EB irradiation was carried out

Fig.1. Scheme of reaction pathways of trans-DCE decomposition and by-products formation. NUCLEAR TECHNOLOGIES AND METHODS 115 by using the computer code “Kinetic” [3] and GEAR method, 320 reactions involving 78 species were considered, five main groups of reactions were included, the rate constants of reactions were mostly taken from the literatures [4,5]. The rate of Wj of j type species generated from matrix with k type molecules was calculated according to equation: ρ ρ Wj = Σ Gjk I k/ where: Gjk – value of j type species from k type ρ matrix, I – dose rate, k – gas phase density of the matrix, ρ – overall density of the gas phase. When fast electrons from electron beams are absorbed 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. These primary species and thermalized secondary electrons cause trans-DCE degradation by complex chemical reactions, a scheme of reaction pathways of trans-DCE decomposition and organic products formation is presented in Fig.1. Based on our calculation results, similar to 1,1-DCE degradation in air under Fig.2. Concentration of trans-DCE vs. dose under EB ir- EB irradiation, Cl– dissociated thermalized second- radiation (solid lines – experimental results [2], ary electron attachment, Cl addition reaction with dashed lines – calculation results). trans-DCE followed by peroxyl radical reactions is a main reaction pathway for trans-DCE degra- Mechanism of trans-DCE degradation in the air dation. Calculated and experimental results of mixture under EB irradiation is similar to 1,1-DCE, trans-DCE degradation in the air mixture vs. dose Cl– dissociated thermalized secondary electron under EB irradiation are presented in Fig.2. The attachment, Cl addition reaction with trans-DCE key reactions which cause trans-DCE or 1,1-DCE followed by peroxyl radical reactions is the main decomposition and products formation in air under reaction pathway for trans-DCE degradation. EB irradiation can be generally written as follows: HCOCl which was not and cannot be detected by – × –9 e + C2H2Cl2 = Cl + C2H2Cl· k1=1.0 10 GC-FID analysis was predicted as a main product Cl– + A+ = Cl + A of trans-DCE degradation based on modelling (A+ is any positive ion in the gas phase) simulation results. OH radical presence increases

C2H2Cl2 + Cl = C2H2Cl3 (k3) decomposition efficiency of trans-DCE less than O2 + C2H2Cl3· = C2H2Cl3(O2)· 10%. 2C2H2Cl3(O2)· = C2H2Cl3(O)· + O2 C2H2Cl3(O)· = CH2ClCOCl + Cl (for 1,1-DCE) References or C H Cl (O) = HCOCl + CHCl (for trans-DCE) 2 2 3 · 2 [1]. Sun Y. et al.: Radiat. Phys. Chem., 61, 353-360 (2001). The rate constant of Cl addition reaction to [2]. Sun Y. et al.: Radiat. Phys. Chem., 68, 843-850 (2003). × –10 3 –1 –1 1,1-DCE (k3a=1.4 10 cm ·molecule ·s ) is [3]. Bugaenko W.L. et al.: Program for modeling of chemical × –11 3 higher than to trans-DCE (k3b=9.58 10 cm ·mol- kinetics. Institute of Theoretical and Experimental ecule–1·s–1), this is the main reason why the decom- Physics, Moscow 1980. Report ITEP No. 50. position efficiency of 1,1-DCE in air under EB ir- [4]. Albritton D.L.: At. Data Nucl. Data, 22, 1-101 (1978). radiation is higher than that of trans-DCE. [5]. http://kinetics.nist.gov/kinetics/index.jsp.

ELECTRON BEAM OF VOCs TREATMENT EMMITTED FROM OIL COMBUSTION PROCESS Anna Ostapczuk, Janusz Licki1/, Andrzej G. Chmielewski 1/ Institute of Atomic Energy, Świerk, Poland

Electron beam (EB) processing has been already in waste-incineration [3] and polycyclic aromatic applied on industrial scale for the treatment of flue hydrocarbons (PAHs) in coal combustion flue gases gas from coal combustion: full-scale EB installa- [4]. It has been observed that the investigated groups tions have been put into operation in Poland [1] of compound change their distribution profile to and China [2] for the removal of acidic pollutants homologues, which are characterized by lower like SO2 and NOx. The technology has been investi- toxicity factor and, as the consequence, the overall gated for volatile organic compounds (VOCs) re- toxicity of flue gas decreased [3-5]. The change of moval from flue gases since the late ’80ies and re- concentration and distribution profile observed in cent research in a pilot plant scale has shown the flue gas treated by EB irradiation can be caused possibility to decompose/detoxify of dioxins stream by three processes: (i) destruction in the oxidation 116 PROCESS ENGINEERING processes [6,7], adsorption on the aerosol surface and (iii) new compound formation in radical process [8]. The experimental work done in the pilot plant on real flue gas has been concentrated on the EB influence on the homologues belonging to one group of compounds. VOCs have been investigated as a single model compound irradiated in a gaseous mixture and as a main decomposition pathway OH radicals – initiated oxidation is proposed [9-10]. The process is analogical to atmospheric chemistry, and VOCs are mineralized and transformed into other organic compounds. Laboratory scale experiments on EB treatment have been performed to investigate the change of the composition of organic fraction of flue gas emitted from oil combustion process. The flue gas (v=5 m3/h) passing the irradiation chamber has been irradiated by EB from an ILU-6 accelerator through a titanium window with a dose ranging from 3.5 to 8.8 kGy. The concentration of organic compounds in flue gas at the inlet and outlet of the irradiation chamber have been compared with Fig. Distribution of PAH, BTX and OAH in the organic the aim to find how EB irradiation influences the fraction of flue gas at the inlet and the outlet of irra- composition of organic fraction of flue gas. The diation chamber; dose D=5.3 kGy, initial VOC con- μ 3 qualitative and quantitative analysis of the concen- centration ci=72.5 g/m . trated extracts was performed by gas chromatography-mass spectrometry (GC-MS) by a Shimadzu dividual compounds like PAHs has been lowered GC-17A gas chromatograph connected with a even by two orders of magnitude. quadropole mass spectrometer Shimadzu QP5050. Simultaneously, an increase of oxygen-contain- Analyzed mixtures were separated on a non-polar ing aromatic compounds (OAH) like phenol, ben- column HP5-MS (Hewlett Packard, 30 m×0.25 mm zaldehydes, benzoid acids and others has been ID×0.25 mm film thickness). observed. OAH is a dominating group of VOCs The composition of the organic fraction of oil present in flue gas, in contast to the composition combustion flue gas has been determined qualita- of flue gas before EB treatment (Fig.). The higher tively and quantitavely in several experimental se- concentration of oxidized compounds and increase

Table. Organic compounds and their concentration level detected in oil combustion gas.

ries with the purpose to establish the key groups of CO content in irradiated flue gas is effected by of emitted compounds. The categories of the de- oxidative decomposition of aromatic compounds. tected organic compounds and their concentration The work has been partially co-finansed by the level are listed in Table. International Atomic Energy Agency (IAEA re- The composition of the organic fraction of flue search contract No. POL 13136) and the Ministry gas has changed after irradiation: the concentra- of Science and Higher Education (agreement No. tion of PAHs and aromatic compounds (BTX) 7/IAEA/2006/0). decreased after irradiation. The average removal efficiency for a dose of 5.3 kGy of these compounds References was 60 and 84%, respectively. Decomposition ra- [1]. Tymiński, B.; Pawelec, A.: Economic evaluation of tio of the investigated compounds increased with electron beam flue gas treatment. In: Radiation treat- dose absorbed. The initial concentration of the in- ment of gaseous and liquid effluents for contaminant NUCLEAR TECHNOLOGIES AND METHODS 117

removal. Proceedings of a technical meeting held in treatment of gaseous and liquid effluents for con- Sofia, Bulgaria, 07-10.09.2005. IAEA, Vienna 2005, taminant removal. Proceedings of a technical meeting pp. 25-34, IAEA-TECDOC-1473. held in Sofia, Bulgaria, 07-10.09.2005. IAEA, Vienna [2]. Mao B.: Process of flue gas desulphuration with elec- 2005, pp. 63-68, IAEA-TECDOC-1473. tron beam irradiation in China. In: Radiation treat- [6]. Biermann H.W., Mac Leod H., Atkinson R., Winer ment of gaseous and liquid effluents for contaminant A.M., Pitts J.N.: Environ. Sci. Technol., 19, 1115 removal. Proceedings of a technical meeting held in (1985). Sofia, Bulgaria, 07-10.09.2005. IAEA, Vienna 2005, [7]. Atkinson R., Arey J., Zielinska B., Aschmann S.M.: pp. 45-51, IAEA-TECDOC-1473. Int. J. Chem. Kinet., 22, 1071 (1990). [3]. Hirota K., Hakoda T., Taguchi M., Takigami M., Kim [8]. Gerasimov G.Ya.: High Energ. Chem., 39, 60 (2005). H.-H., Kojima T.: Environ. Sci. Technol., 37, 3164 [9]. Prager L., Mark G., Mätzing H., Paur H.-R., Schubert (2003). J., Frimmel F.H., Hesse S., Schuchmann H.-P., [4]. Chmielewski A.G., Ostapczuk A., Zimek Z., Licki J., Schuchmann M.N., Sonntag C.V.: Environ. Sci. Kubica K.: Radiat. Phys. Chem., 63, 653-655 (2002). Technol., 37, 379-385 (2003). [5]. Chmielewski A.G., Ostapczuk A., Licki J.: Polycyclic [10]. Hirota K., Mätzing H., Paur H.-R., Woletz K.: aromatic hydrocarbons removal from flue gas by elec- Radiat. Phys. Chem., 45, 649-655 (1995). tron beam treatment – pilot plant tests. In: Radiation

ELECTRON BEAM TREATMENT OF FLUE GAS FROM FUEL OIL COMBUSTION Andrzej G. Chmielewski, Andrzej Pawelec, Bogdan Tymiński, Zbigniew Zimek, Janusz Licki1/, Ahmed A. Basfar2/ 1/ Institute of Atomic Energy, Świerk, Poland 2/ King Abdulaziz City for Science and Technology, Riyadh, Saudi Arabia

During operation of the plant installed at the Po- of the parametric tests indicate that, with the ex- morzany Electric Power Station, the electron beam ception of dose, SO2 and NOx removals depend on flue gas treatment technology has proved its us- the different process conditions. By controlling these ability for industrial applications. The technology conditions it is possible to obtain maximum removal allows for simultaneous removal of both sulphur efficiencies. NOx removal is mostly energy-consum- dioxide (SO2) and nitrogen oxides (NOx) with high ing, while SO2 removal is sensitive to temperature, efficiency. Beside of this the process is wasteless humidity and ammonia stoichiometry. The proper and economically competitive to the conventional selection of the process conditions (gas humidity emission control methods. One of the important – 10-15 vol.%, ammonia stoichiometry – 0.90-0.95 0 advantages is the possibility of application of this and gas temperature – 60-70 C) guarantees high SO2 method for cleaning of flue gas from various, not removal efficiency at low energy consumption. A only coal combustion based, technological pro- dose of 6-9 kGy is sufficient to achieve over 90% cesses. Research on the purification of flue gas SO2 and 70% NOx simultaneous removal from flue from the fuels different than coal was undertaken gas under optimum operating conditions. Higher in the Institute of Nuclear Chemistry and Tech- NOx removal efficiencies require higher energy nology. consumption. No impact of oxygen concentration, The process of treatment of flue gas from fuel in the analyzed range, on the process efficiency was oil combustion was studied. Three types of oil con- observed. The optimal parameters were very simi- taining various amounts of sulphur (oil I – 2.81%, lar for all three grades of oil. This means that the oil II – 2.9% and oil III – 3.1%) were taken for labo- electron beam flue gas treatment technology may ratory experiments. The composition of the flue be applied for any grade of oil. gas depends on burning conditions and oil itself. The by-product is almost a pure mixture of Generally, the basic flue gas parameters were as ammonium sulphate and ammonium nitrate, that follows: makes it a valuable fertilizer. The combination of - volume flow rate – 5 Nm3/h, these two compounds provides a suitable quality

-SO2 concentration – 800-1850 ppmv, material for direct soil application or as a blend- -NOx concentration – 80-190 ppmv, ing component in the standard manufacture of - gas temperature at process vessel – 60-120oC. commercial fertilizer (NPK type). The influence of such factors as irradiation dose, The obtained results correspond with those gas temperature at the inlet to process vessel, am- previously obtained for the experiments conducted monia stoichiometry, gas humidity and oxygen con- with coal combustion flue gases. The above results centration on the process efficiency was studied. prove the possibility of electron beam flue gas

High SO2 and NOx removal efficiency up to 99% treatment technology to be applied for the purifi- for SO2 and 90% for NOx (respectively, 98% and cation of flue gases from different fuel combus- 85% in optimal conditions) was achieved. Results tion process. 118 PROCESS ENGINEERING DOSIMETRY FOR COMBUSTION FLUE GAS TREATMENT WITH ELECTRON BEAM Kishor Mehta1/, Sylwester Bułka 1/ Vienna, Austria The most widely applied systems for coal fired The second best choice would be calorimetry boilers are wet flue gas desulphurization (FGD) us- of flue gas for the determination of average dose. ing lime or limestone as reagent and selective cata- However, there are uncertainties using this method; lytic reduction for NOx reduction. Therefore, it is mainly how adiabatic is the system. The main source still important to develop new treatment methods of uncertainty arises from the contribution of the that do not have these problems. The electron beam walls of the reaction vessel to the temperature rise treatment of flue gas is one of the new technologies. of the flue gas since it is unavoidable that radia-

Its success in significantly reducing SO2 and NOx tion (electrons) will deposit part of its energy in has already been demonstrated in many pilot plants the walls. However, by judiciously matching the and a few full commercial plants. size of the reaction vessel to the beam energy, this There are several advantages in employing ion- uncertainty can be minimized. izing radiation (electrons) for this purpose, includ- The third method, measurement with solid ing [1]: dosimeters, is still less reliable. One can measure - several polluting gases are removed simulta- dose using several dosimeters and calculate some neously with high efficiency; kind of average dose for the entire reaction vessel. - dry system without any wastewater treatment; There are two difficulties in this method. First, to - simple system with easy operation; be very accurate, dose should be measured at a - compact plant, thus easy for retrofitting in an very large number of locations. Second, this is the existing power station; measurement of dose rate, and not dose to gas. One - high energy efficiency, and by-product can be needs then to assume that the residence time of the used as fertilizer. gas is the same through each part of the vessel; This process requires beam power of 300 kW that will be true if it were a plug (segregated) flow. or more, and electron energy in the range of 0.8 to On the other hand, it would be irrelevant if the 1 MeV. Accelerators suitable to fulfill such require- gas flow were turbulent. But that is hardly the case. ments are based on high-power, high-voltage trans- The only method to measure non-uniformity of formers according to the present state-of-the-art dose absorbed in gas is to measure the dose rate at accelerator technology. Industrial linac technology, various locations in the vessel with fixed dosimeters, which was developed for military applications, is such as cellulose tri-acetate (CTA). This informa- being demonstrated now as an appropriate tech- tion then can be used to calculate dose absorbed nical and cost-effective competitive alternative [2]. by different portion of gas as it travels through the The electron beam technology is relatively flexible vessel. However, as mentioned above, one then and adaptable to local conditions. The process can assumes that there is a plug (segregated) flow. On be easily adapted for different removal efficiency the other hand, if the flow were completely turbu- levels and adjusted for use with different fuels. lent, the dose would be uniform to all the gas. Yet

Also, retrofitting of existing facilities to reduce NOx another method is to carry out a detailed Monte and SO2 concentrations to meet low-space require- Carlo simulation of the system. The reliability of ments is an attractive option. the results of such a calculation of course depends Dose and dose distribution in the reaction on the quality of the input data. Thus, we have to vessel of a flue gas treatment facility very strongly know the type of flow of the gas through the vessel: influence the removal efficiency of NOx, and to a plug or turbulent and extent of each. And it is smaller degree of SO2. Thus, it is essential that always prudent then to validate the results with these two parameters are measured and optimized measurements. for better economy of the process. The recent dosimetry related work carried out References by the authors at the Institute of Nuclear Chemis- try and Technology (INCT) lead to conclusion that [1]. Chmielewski A.G., Zimek Z.: Nuclear technology for the best method for measuring average dose to the cleaning coal emissions. In: The environmental chal- gas is through a dosimetry system that relies on lenges of nuclear disarmament. Eds. T.E. Baca, T. Flor- kowski. Kluwer Academic Publishers, The Netherlands the reaction in the gas phase. Such measurements 2000, pp. 139-148. will truly represent the dose absorbed by the flue [2]. Chmielewski A.G., Ostapczuk, Namba H., Tokunaga gas. Thus, it is a matter of selecting a most suit- O., Hashimoto S., Tanaka T., Ogura Y., Doi Y., Aoki able system whose G value is known fairly accu- S., Izutsu M.: Radiat. Phys. Chem., 46, 1103-1106 rately and the product(s) is easily measurable. (1995). NUCLEAR TECHNOLOGIES AND METHODS 119 CATALYTIC CRACKING OF POLYOLEFINE WASTES IN A LARGE LABORATORY INSTALLATION Bogdan Tymiński, Krzysztof Zwoliński, Renata Jurczyk

Recycling of polyolefine wastes by thermal degradation into liquid hydrocarbons is being intensivly studied. Several plants producing a wide hydrocarbon fraction, similar to heavy crude petrol oil from polyolefine wastes, exist in Poland. Previous investigations showed that it is possible, without additional energy consumption, to receive more valuable gasoline and light oil fractions from the same plastic wastes. Lately, we concentrated on checking of quality of wastes on final products. There were made five experiments with the use of different wastes. Experiments were made in a large laboratory installation shown in Fig. Products were withdrawn from five levels at the distillation column and were analyzed in the same way as reported in paper [1,2]. The main results are presented in Table. In the first three experiments the wastes were prepared in our laboratory from relatively clean materials. The next two experiments were made with wastes from a company selecting the wastes. The wastes were in the form of flakes of unknown composition. From Table, it follows that the distillates from these wastes (experiments Nos.4 and 5) contain more heavy fraction and its temperature Fig. Scheme of a large laboratory installation for catalytic of freezing point is higher. In one case, not shown cracking of polyolefine wastes. in Table, the wastes contained a component with a high melting temperature which caused plugging carbons, these temperatures were lower. In the the melter. To avoid this design of the melter was batch distillation it was easy to separate fractions improved. After improvement, the temperature in with a demanded range of boiling points. Both

Table. Main results of decomposition of plastic wastes (PP – polypropylene, PE – polyethylene).

the melter significantly increased and there was methods of distillation give more pure and stable no more problems with plugging of the melter. products [2]. The distillates from the distillation column contain some heavy oil which makes worse the prop- References erties of the gasoline and light oil fraction. For the separation of gasoline and light oil fractions with [1]. Tymiński B., Zwoliński K., Jurczyk R., Darkowski A.: higher purity, the distillates were purified in a batch Investigation of catalysts for cracking of polyethylene wastes into liquid hydrocarbons. In: INCT Annual and continuous distillation process. In the continu- Report 2005. Institute of Nuclear Chemistry and Tech- ous distillation process, the temperature in the nology, Warszawa 2006, pp. 113-114. o boiler was 360 C and the gasoline fraction collected [2]. Tymiński B., Zwoliński K., Jurczyk R.: Prace Naukowe at temperatures 230 to 170oC and the light oil frac- Instytutu Inżynierii Ochrony Środowiska Politechniki tion – at temperatures 200 to 270oC. During distil- Wrocławskiej, 81, Seria konferencje 12, 263-268 (2006), lation of the fractions containing more light hydro- in Polish. 120 PROCESS ENGINEERING ECONOMICAL COMPARISON OF ABSORPTION AND MEMBRANE METHODS APPLIED FOR THE ENRICHMENT OF METHANE IN BIOGAS Marian Harasimowicz1/, Grażyna Zakrzewska-Trznadel1/, Weronika Ziółkowska2/, Andrzej G. Chmielewski1,2/ 1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland 2/ Faculty of Chemical and Process Engineering, Warsaw University of Technology, Poland

Raw biogas contains about 55-65% methane (CH4), Laboratory experiments with the use of gas sepa- 30-45% carbon dioxide (CO2), traces of hydrogen ration membranes from polyimide showed a great sulphide (H2S) and fractions of water vapour. En- potential for membrane permeation as a separa- richment of methane in biogas from anaerobic dition method of gaseous components of biogas [2,3]. gestion in fermentation tanks or landfills to obtain At common concentration of methane, a single fuel of higher calorific value can be achieved by re- stage unit seems sufficient to achieve 94% enrich- moving carbon dioxide and other gaseous impuri- ment, and multistage systems are not required. For ties like hydrogen sulphide. Elimination of carbon lower methane concentrations (<60%), the stan- dioxide from the flue gas helps in increasing its calo- dard gas GZ-50 can be produced by a multistage

Table 1. The comparison of the capabilities of absorption and membrane methods.

rific value as well as in eliminating the greenhouse separation. The high permeability of the polyimide gas, CO2. Carbon dioxide thus generated can be membranes to water vapour and hydrogen sulphide, utilized as an effective refrigerant. common impurities of gas produced in biomass Current technologies to purify off-gas and in- fermentation process, makes them useful for biogas crease its caloric value have been primarily limited processing without special pretreatment. to physicochemical methods such as chemical sepa- Preliminary economic evaluations proved that ration, membrane separation, cryogenic separation the application of membranes is reasonable. Table as well as adsorption. Chemical methods are based 1 performs the production abilities of the absorp- on absorption under elevated pressure (in water, tion method carried in a Benfield type apparatus.

30% solution of potassium carbonate (K2CO3), At the same flow rate of biogas, the absorption solution of monoethyloamine, etc.). Other methods method produces 40% more of methane than are based on adsorption in which a vital role plays membrane permeation. The productivity of the a suitable adsorbent material [1]. membrane system is reduced by methane losses

Table 2. A comparison of energy and reagents consumption in two methods: absorption and membrane separation. NUCLEAR TECHNOLOGIES AND METHODS 121 that are equal ca. to 84 000 Nm3 per year. However, the membrane installation is simple, compact and the expenses related to methane losses are compen- does not need complex control equipment like sated by the lower costs of materials consumption. chemical methods. Despite of high costs of the The chemical method is more energy-consuming, membrane modules for gas separation, the total uses more reagents like potassium carbonate, acti- capital costs of the membrane installation are vator (DEA) and corrosion inhibitor (KVO3). In lower than for the Benfield installation. this method, in some parts of installation waste Comparison of the operational costs is also heat can be utilized, that reduces the total energy favourable for membrane permeation. Even consumption. though the membrane method consumes much In Table 2, the consumption of energy and re- energy for gas compression, it does not use the agents is presented. The energy consumption for expensive reagents, which are necessary for chemi- absorption is reduced by waste energy utilized in cal process. some parts of installation. The work proved that the absorption method The investment costs of both methods are listed can be superseded by membrane separation. Thanks in Table 3. The tentative cost evaluation showed to the development of material science that produces modern high selective materials and new Table 3. Economy of two processes: absorption and mem- achievements in process engineering, separation brane separation for methane enrichment – a com- of gaseous components of biogas are reliable. Both parison. selectivity and efficiency of membranes are sufficient to produce gas of appropriate parameters of standard gas GZ-50. References [1]. Sarkar S.C., Bose A.: Energ. Convers. Manage., 38, Suppl. 1, 105-110 (1997). [2]. Harasimowicz M., Orluk P., Zakrzewska-Trznadel G., Chmielewski A.G.: Application of polyimide membrane from biogas purification and enrichment. In: Proceedings of the 5th European Meeting on Chemical Industry and Environment, EMChIE 2006, Vienna, Austria, 03-05.05.2006, pp. 617-622. [3]. Harasimowicz M., Ziółkowska W., Zakrzewska-Trzna- del G., Chmielewski A.G.: Economical comparison of absorption and membrane methods applied for enrich- that the membrane method is more economical ment of methane biogas. In: Proceedings of the XXI than the absorption method. Both capital and op- ARS SEPARATORIA, Toruń, Poland, 03-06.07.2006, erational costs are lower for the membrane pro- pp. 52-54. cess than for chemical absorption. Additionally,

STUDY OF BOUNDARY-LAYER PHENOMENA IN MEMBRANE PROCESSES Grażyna Zakrzewska-Trznadel, Agnieszka Miśkiewicz, Marian Harasimowicz, Ewa Dłuska1/, Stanisław Wroński1/, Agnieszka Jaworska1/, Cornel Cojocaru2/ 1/ Faculty of Chemical and Process Engineering, Warsaw University of Technology, Poland 2/ ”Gh.Asachi” Technical University of Iaºi, Romania Pressure-driven membrane filtration is an import- is important to keep appropriate hydrodynamic ant process for separation of colloids and particu- conditions in the apparatus that avoid continuous late matter from liquid suspensions in many fields building-up of the cake layer which results in in- of engineering and applied science. There are many crease of the resistance and reduction of the per- examples of application of pressure-driven mem- meate flux. The term of concentration polarization brane processes in nuclear technology. Such pro- describes the tendency of the solute to accumu- cesses like reverse osmosis, ultrafiltration or micro- late in the membrane-liquid interface. It is import- filtration can be used for liquid radioactive waste ant to suppress the concentration polarization by processing, cleaning reactor waters, boric acid re- adjusting the flux on the level that avoid the bound- covery and separation of isotopes. The pressure- ary level development or by promoting the turbu- -driven membrane filtration process can operate lence by all available means. For understanding of at either cross-flow or dead-end flow mode. In case permeate flux decline mechanisms and predicting of dead-end filtration the resistance increases with of the permeate flow rate, the development of formation of the cake on the membrane surface, mathematical models and tools for simulations and while in cross-flow process the deposition continues optimization are of great importance. until the cake adhesion is balanced by shearing The hybrid membrane process for removal of forces of the liquid passing over the membrane. It cobalt ions, the main components of the liquid 122 PROCESS ENGINEERING radioactive wastes produced in Poland, was run in ΔPK the ultrafiltration unit equipped with a membrane Jv = (2) μδ contactor with a central rotor. Helical Couette- Taylor flow was expected to promote the turbu- where: K – cake permeability, δ – thickness of the lence and vortices in the apparatus that resulted cake layer. in good transport parameters. Before filtration, From comparison of eqations (1) and (2), the thickness of the residual deposit layer can be estimated. The cake thickness determined for different process conditions, assuming K=10–17 m2, was in a 0.035-0.186 mm range for dynamic conditions. The thickness showed a marked influence of rotation: the δ values decreased with increasing rotation frequency in the helical-flow membrane apparatus. The influence of rotation on the separation efficiency was not observed. In experimental conditions at rotation frequency W=1000-1500 rpm and for ion to polymer concentration ratio

CCo2+/Cpolymer=1/4, the retention factors higher than 90% were achieved. The models for simulation and optimization Fig.1. Permeate flux vs. time. Cobalt removal in hybrid pro- of cross-flow filtration developed from theory of cess: sorption on activated carbon (AC)-ultrafiltra- concentration polarization and response surface tion. methodology (RSM) were elaborated. The regression analysis in order to find empirical models for cobalt ions were complexed by soluble chelating fitting the experimental data of flux decline was polymers like polyacrylic acid derivatives or employed. The models were determined by mini- 2 adsorbed on activated carbon seeds dispersed in mization of the residual variance Sres: n the solution. In both cases the improvement of fil- 1 2 SJtJ2exper() min tration conditions and increase of permeate flux res =−→∑()jj (3) through the membrane were observed when dy- n − 2 j=1 namic conditions were applied (Figs.1-2). There The experimental data of the kinetics of flux decline were fitted well by polynomial equation of type:

−123 Jt()=+ a01 a t + at 2 + at 3 + at 4 + at 5(4) Two responses derived from kinetic curves of flux decline were used: the average permeate flux cal-

culated by integration of J(t) function from t1=1 min up to tn=180 min as follows: 1 tn <>=JJtdt() (5) t ∫ n t1 where J(t) means the regression functions determined by regression analysis, and the cumulative Fig.2. Permeate flux vs. time. Cobalt removal in hybrid pro- flux decline defined as cess: complexation by polyacrylic acid (PAA)-ultra- n ⎛⎞Jt( 1 ) − Jt( i ) filtation. S = (6) FD ∑⎜⎟ i=2 ⎝⎠Jt()1 was evidence that by promoting the turbulence the resistance of boundary layer and the resistance of the deposit accumulated on the membrane surface were reduced. Permeate flux, Jv, can be expressed as a function of total membrane-cake resistance by the equation: ΔP J v = (1) μ()Rm + Rδ where: ΔP – transmembrane pressure, μ – viscosity of the liquid.

Membrane resistance, Rm, was estimated from water permeability and cake layer resistance Rδ – from the total resistance determined in experiments. On the other hand, permeate flux can be described by the relationship analogical to the Fig.3. Permeate flux vs. time for optimal conditions: Δ * * 2 * equation of the filtration through the sediments: P =0.19 bar, QR=54 L/m h and W =2480 rpm. NUCLEAR TECHNOLOGIES AND METHODS 123 The cumulative flux decline defined by equation ditions, the check out experiment was carried out (6) gives information about all experimental points to determine the permeate flux vs. time (Fig.3). The in flux decline curve for the time interval studied, initial flux decline was observed in the time interval i.e. 1 min≤t≤180 min. By means of the multiple 1 min≤t≤60 min; after that a slight increase of flux linear regression method, the empirical models of was recognized for t>60 min. This means that in cross-flow filtration, which gave the information optimal operating conditions the vortices created about the influence of hydrodynamic parameters by Taylor flow led to self-cleaning effect of the upon J and SFD were developed. The cumulative membrane surface for t>60 min. For all experi- flux decline and average permeate flux were used ments concerning the polymer-assisted cross-flow as the objective functions in optimization by the ultrafiltration process carried out in the helical Lagrange multiplier method using MathCAD soft- membrane module, the average value of the rejec- ware. The calculated optimal values in terms of action coefficient was 91.54% with a standard devia- Δ * * tual operating variables were P =0.19 bar, QR=54 tion of 4.06%. L/m2h and W*=2480 rpm. For these operation con-

A STUDY OF STABLE ISOTOPE COMPOSITION IN MILK Ryszard Wierzchnicki, Małgorzata Derda

Isotope ratio mass spectrometry (IRMS) methods Correlation between the stable isotope compo- play a very important role in food authenticity and sition 18O/16O, 13C/12C, 15N/14N and δD in milk com- origin control. The measurements of bioelements ponents was analyzed. The variability of the pa- (hydrogen, nitrogen, carbon, oxygen, and sulfur) rameters related to environmental factors like: composition provide a very sensitive tool to food geology, climate and anthropogenic factors was control. The isotopic methods of origin and authen- studied (Fig.). ticity control were recently implemented in Euro- pean Union for wine, juice, and honey. The aim of our study is to explore the relationship between isotopic composition of milk and its origin (regional, seasonal). The stable isotope composition of food is strictly connected with environmental conditions (climate, geographical position and included pollutants). The bases for this study are isotopic effects (biological, physical and chemical) which are responsible for different isotopic composition in nature: Fig. Factors determining the water isotopic composition soil, air and water. The effect of differentiation of of dairy products – a schematic way from the farm to isotope composition is connected with different the consumer. composition of cow diet (maize, grass etc.) and different composition of drinking water for cows Finally, on the basis of the collected results a [1-3]. Seasonal and regional variations of cow diet map of isotopic parameters distribution will be composition cause seasonal and regional variations drawn. The information about the relation be- of isotopic composition of milk and finally dairy tween the isotopic compositions and the regional products (Table). and seasonal factors will be an important research

Table. Chemical components of milk and their important isotopic composition.

In the frame of the project, many samples of result of this project. In the future, on the data milk and dairy products from main regions of milk base of authentic value of stable isotope composi- production were gained. The collected samples tion, the method for origin control of milk and were measured by the use of IRMS DELTAplus dairy products will be proposed. (Finnigan, Germany), connected with peripheral The study was supported by the Polish Minis- units as: GasBench, H/Device and Elementar try of Science and Higher Education in the frame Analizer (ThermoFinnigan). of project No. 2P06T03928. 124 PROCESS ENGINEERING

References [3]. Renou J.P., Deponge Ch., Gachon P., Bonnefoy J.C., Coulon J.B., Garel J.P., Verite R., Ritz P.: Food Chem., [1]. Rossmann A., Haberhauer G., Hölzl S., Horn P., Pichl- 85, 63-66 (2004). mayer F., Voerkelius S.: Eur. Food Res. Technol., 211, 32-40 (2000). [2]. Knobe N., Vogl J., Pritzkow W., Panne U., Fry H., Lochotzke H.M., Preiss-Weigert A.: Anal. Bioanal. Chem., 386, 104-108 (2006).

INTERLABORATORY TESTS FOR 3H MEASUREMENTS IN WATER SAMPLES Wojciech Sołtyk, Jolanta Walendziak, Jacek Palige Successive observation and measurements of 3H samples of water with 3H concentration in an in- contents in water samples has been realized in terval of 0-20 TU. Poland in a few laboratories starting since 1967. The In test VI participated 86 laboratories and 6 measurement of this kind is being performed in samples of water with 3H concentration in an in- the Institute of Nuclear Chemistry and Technology terval of 0-25 TU and with one unknown sample (INCT) since 1999 and is connected with the ob- with a concentration of about 500 TU were mea- servations of 3H concentration changes in surface sured.

Table 1. Results of test V.

and underground waters in the surrounding of the The results of tests are presented in Tables 1 coal mine “Bełchatów”. About 240 3H measure- and 2. ments are realized each year. The real concentration, Cr, is defined as the The results of these measurements are used for the mean value – the result of averaging all data ob- diagnosis of environmental processes occurring in tained by the test participants whose result Ci ful- δ the open lignite mine area. filled the condition |Ci – Cr|<2 . The International Atomic Energy Agency The measured concentration is the result obtained (IAEA) organizes from time to time (every 5 years) in the INCT laboratory with an error of ±0.5 TU. Table 2. Results of test VI.

interlaboratory tests for checking the correctness The results of the test realized by the IAEA in of data obtained in the laboratories which are reg- 2005, for the moment, were not published. istered in the IAEA – laboratories net. The data obtained in the INCT laboratory in- The INCT laboratory participated in the tests dicate sufficient agreement with the interlaboratory organized in 1994 (test V), 2000 (test VI) and 2005. results especially with those for higher 3H concen- In test V participated 91 laboratories from nu- tration. merous countries which measured the same 4

MODELLING FOR GROUNDWATER FLOW IN THE OPENCAST BEŁCHATÓW AREA Robert Zimnicki The groundwater flow modelling is one of the most dence time in ground could be forecasted by com- important steps in characterizing transport and puter simulation of flow processes. properties of contaminants in industrial area like Modelling for the Bełchatów opencast area coal-mine. The majority of processes based on natu- started in 2006. Simulation was done using Modflow ral raw material exploitation causes a significiant software based on the application of the finite ele- environment destruction. The majority of problems ment method for the solution of appropriate 3D concerning water quality like salinity or organic pol- flow equation system for porous media. The Darcy lutant contents, water interchange and their resi- law was applied for filtration velocity description. NUCLEAR TECHNOLOGIES AND METHODS 125

Fig. Scheme of exploitation area.

At the beginning, data concerning porosity of the vity for all area 5 m2/day were preset. Rain param- materials, boundary conditions for a certain part of eter is equal to 0.0016 m/day. opencast, like salt dome, outer dump, first driving Actually the model is being verified. The sensi- area, were collected. The applied model consist of tivities of applied procedures on boundary condi- six layer describing three principal geological plies tions changing is tested [1]. (Mesozoic, Quaternary and Cenozoic). The scheme of exploitation area is presented in Fig., where the References principal mine objects are indicated. [1]. Zimnicki R., Owczarczyk A., Chmielewski A.G.: Obser- The Bełchatów model consist of 680x360x6 cells, wacja zmian hydrochemicznych wód podziemnych w re- in reality, the dimensions are 34 000 m length and jonie powstającej odkrywki węgla brunatnego. In: Ma- 18 000 m width. Step size between bend is 50 m. teriały z IV Ogólnopolskiej Konferencji Naukowo-Tech- The porosity for sand is equal to 45%, granite – nicznej “Postęp w inżynierii środowiska”, Bystre near 0.7% and total as 10% were sets. The transmissi- Baligród, Poland, 21-23.09.2006, pp. 521-529 (in Polish).

TRACER AND CFD INVESTIGATIONS OF SEDIMENTATION PROCESSES IN RECTANGULAR SETTLER Jacek Palige, Andrzej Dobrowolski, Sylwia Ptaszek, Andrzej G. Chmielewski Wastewater treatment process is realized in dif- Many researches concerning the sludge sedi- ferent apparatus such as equalizers, aeration tanks, mentation process were carried out [1-3]. Actually, settlers and final sedimentation basins. The treat- few methods are used for investigations of settlers. ment efficiency strongly depends on the work of a The tracer method is used for the determination secondary settler. of residence time distribution (RTD) function and

Fig.1. Scheme of a secondary settler and experimental results of spatial sludge ceoncentration distribution: A – in profiles at 8, 24 and 37 m from the wastewater input as a function of depth; B – 1 and 2 m below the water table in the axis of the settler. 126 PROCESS ENGINEERING

Fig.2. Distribution of axial velocity component in planes orthogonal to the settler axis at distances: 6, 15, 25, 30 and 38 m from the wastewater input. computational fluid dynamics (CFD) [4-6] for ob- ocity was 3 cm/min. Using the CFD codes, the sedi- taining the water flow structure inside a settler mentation process of monodisperse sludge with tank. input concentration 2 kg/m3 and flow rate of fluid In this work, the results of tracer investigations 0.041 m3/s was simulated. Numerical 3D simulations and CFD simulations for an industrial rectangular of the sedimentation process with numerical code settler with immersed input (width 10 cm in all of FLUENT software application were carried out settler width) are presented. Volume of unit under using the Euler-granular scheme and standard k-ε investigation was V=1050 m3 (length L=41.5 m, model of flow turbulence for a mixture of water height H=3÷4 m), flow rate of wastewater q=160 and sludge. m3/h, output of sewage in the settler was realized The characteristic backflow, up to 30 m in settler by overflow. For this inflow structure, the sediment (Fig.2) for this construction of inflow, was observed concentrations have been measured 1 and 2 m near the surface and bottom of the tank. below the water table in the axis of the settler and Numerical sludge concentration distribution as a in profiles at 8, 24, 37 m from the wastewater in- function of depth in the axis of the settler are pre- put as a function of depth. The scheme of the set- sented in Fig.3. tler and the distribution of sediment inside the A satisfactory agreement of numerical and experi- settler are presented in Fig.1. mental curves of concentration sludge distribution The velocity of sludge sedimentation was de- was observed in profiles 1 and 2. In profile 3, a termined in laboratory tests. The value of this vel- large decrease of sludge concentration obtained in numerical simulation is connected with the fact that, for example, the sludge drift in the bottom and scrapper movement in real settler tank is not taken into account. References [1]. White D.A., Verdone N.: Chem. Eng. Sci., 55, 2213-2222 (2000). [2]. Berres S., Buger R., Tory E.M.: Chem. Eng. J., 111, 105-117 (2005). [3]. Burger R., Karlsen K.H., Towers J.D.: Chem. Eng. J., 111, 119-134 (2005). [4]. Krebs P., Armbruster M., Rodi W.: Gaz, Woda Tech. Sanit., 11 (2000), in Polish. [5]. Palige J., Dobrowolski A., Owczarczyk A., Chmielew- ski A.G., Ptaszek S.: Inż. Ap. Chem., 42, 72-75 (2003), in Polish. [6]. Palige J., Owczarczyk A., Ptaszek S.: Inż. Ap. Chem., Fig.3. Profiles of sludge concentration in the axis of the set- 44, 24-26 (2005), in Polish. tler as a function of depth (8, 24, 37 m from the wastewater input).

NATIVE AND TRANSPLANTED Pleurozium schreberi (Brid.) Mitt. AS BIOINDICATOR OF NITROGEN DEPOSITION IN A HEAVY INDUSTRY AREA OF UPPER SILESIA Grzegorz Kosior1/, Aleksandra Samecka-Cymerman1/, Andrzej G. Chmielewski, Ryszard Wierzchnicki, Małgorzata Derda, Alexander J. Kempers2/ 1/ Department of Ecology and Nature Protection, Wrocław University, Poland 2/ Department of Environmental Sciences, Radboud University of Nijmegen, the Netherlands

During the period of 90 days, an assay was carried the most polluted industrial region of Poland in the out with the moss Pleurozium schreberi trans- Upper Silesia (Poland). Within the same period also planted from an uncontaminated control site to samples of native Pleurozium schreberi growing in NUCLEAR TECHNOLOGIES AND METHODS 127 the industrial region were collected together with better nitrogen accumulator in the less polluted the same species from an unpolluted control site. parts of the area showing a relation between the Concentrations of total nitrogen in soil, nitrate and δ15N signature and the tissue nitrogen concentra- + – ammonia in rainfall, nitrogen in mosses as well as tion to the ratio NH4 N/NO3N after 45 days of ex- lead and zinc as pollution markers in mosses were posure. The same species transplanted into the measured. The natural abundance of 15N was de- more polluted sites of the industrial area did not termined in transplanted, native and control Pleu- reach the level of nitrogen of native species within rozium schreberi. The examined soils from the pol- 90 days of exposure and showed a relation to at- luted sites were contaminated with high levels of mospheric nitrogen deposition only after 90 days nitrogen and also the concentrations of lead and of exposure. Therefore, it may be concluded that zinc in mosses seriously exceeded the levels of these the transplanted moss needs at least 90 days in its elements in plants from the control sites. The in- new environment to give indications for polluting put of atmospheric ammonium nitrogen by deposi- nitrogen compared to the indications obtained tion significantly exceeded that of the nitrate nitro- from the native mosses. Therefore, the transplants gen at all sites. Established correlations confirmed were worse indicators of nitrogen deposition in a general suitability of the examined moss species heavy polluted areas compared to those in less for at least a rough estimation of the nitrogen in- polluted areas. put. The transplanted Pleurozium schreberi was a 128 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS

MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS

IDENTIFICATION OF LEAD WHITE OF THE 15th CENTURY GDAŃSK PANEL PAINTINGS BY MEANS OF INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS Ewa Pańczyk, Justyna Olszewska-Świetlik1/, Lech Waliś 1/ Faculty of Fine Arts, Nicolaus Copernicus University, Toruń, Poland

Connection between the content of trace elements its production can be determined on the way of ex- in lead white and the place, time and technology of tensive studies carried out on sample paintings rep- Table. Description of the analyzed samples. NUCLEAR TECHNOLOGIES AND METHODS 129 resenting different periods in history and various ing their structure and state of preservation of the countries [1-5]. More sensitive detection methods original layers, After removal of protective coat- currently applied in neutron activation analysis ing with a scalpel under a microscope, a sample of (NAA), and first of all, high-resolution gamma the white was taken directly to a quartz ampoule. spectrometry allow to increase the number of de- The sampling spots were selected so that they had tectable elements and to more accurately deter- not shown admixtures of other pigments as indi- mine their concentrations in the lead white [2]. A cated by UV luminescence tests. Detailed descrip- more complete distribution pattern of trace ele- tion of the paintings is presented in Table. 1-6 ments permits also to take into account the ele- samples from each object, with a mass from 0.1 to ments that were not present in original paints in a 1 mg were collected. given period of history. This is particularly impor- The analysis of lead white samples was carried tant for elimination of the impurities accidentally out using the instrumental neutron activation introduced into paint during creation of a paint- analysis (INAA) method without chemical sepa- ing. The objective of the work are systematic stud- ration, using standards of analyzed elements. The ies on the lead white in Polish painting. The pre- samples were packed together with standards of sented results of analyses constitute merely a part such elements as Na, K, Sc, Cr, Mn, Fe, Co, Ni, of broader studies on lead white produced in 15th Cu, Zn, Ga ,Ge, As, Se, Br, Rb, Sr, Zr, Mo, Ru, and 16th centuries. The following work contains Ag, Cd, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, the results of researches of the chosen set of panel Tb, Dy, Ho, Er, Yb, Lu, Hf, Ta, W, Ir, Au, Hg, Th paintings of Gdańsk from the second half of the and 238U. Also attached were the standards of gold 15th century. A set of 16 pieces of panel painting, and scandium evaporated onto a piece of alu- most of which were taken from the important shrine minium foil. They played the role of the thermal of Gdańsk – the Church of the Blessed Virgin Mary neutron flux monitor. – were the object of the research. Additionally, the Irradiation of the samples was carried out in the study of the retable from the Parish Church at MARIA reactor at Świerk, in a channel with 8*1013 Wróblewo, an altar from the St. Peter and St. Paul n/cm2s thermal neutron flux. The irradiation time church at Hel and Grudziądz Polyptych from the was 24 h with subsequent 8-hour cooling. Then, Castle of the Teutonic Knights at Grudziądz were the irradiated samples were unpacked and washed taken. The workshop of these three panel paint- in 1:1 hydrochloric acid solution and rinsed in al- ings is closely connected to Gdańsk painting tradi- cohol to remove surface contaminations. tion. Only a part of works of art remained until our Measurements of activity of samples and stan- times [6]. Those that were preserved, in most cases dards prepared in such a way were carried out us- constitute only a part of retables (panels of poly- ing an HP germanium detector with an active vol- ptychs, predellas). ume of 80 cm3 and an energy resolving power of All the samples were taken from paintings sub- 1.95 keV for the 1333 keV peak from 60Co. The jected to a routine maintenance work after reveal- detector cooperates with a S100 Canberra analyzer,

Fig. Dendrogram of 56 lead white samples taking from 19 panel paintings (number of features is 28) – standardized variables. 130 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS controlled by IBM/PS-2. The analysis of complex per and manganese and a higher content of sliver gamma radiation spectra was carried out using and antimony than lead white from regions south micro-SAMPO and Gene 2000 programs. The to Alps and is more similar to lead white applied measurements were repeated six times within three in Northern Europe [4,5,7]. The results of the con- months after irradiation. The measurement time ducted analyses revealed features characteristic of varied between 300 and 10 000 s. Thirty two ele- painting technique of Gdańsk of the second half ments were identified and determined in the ana- of 15th century. lyzed samples. Ultimately, 28 elements were selected for References multiparameter statistical analysis aimed at iden- [1]. Perlman I., Asaro F., Michel H.V.: Annu. Rev. Nucl. tifying the degree of similarity of analyzed paint- Sci., 22 (1972). ings. [2]. Sayre E.V.: Advan. Activ. Anal., 2 (1972). The clustering analysis using STATISTICA [3]. Fleming S.J.: Authenticity in art. London 1975. (StatSoft) program was carried out to identify the [4]. Houtman J.P., Turkstra J.: Neutron activation analysis similarity degree of analyzed objects. The cluster- and its possible application for age determination of ing analysis was carried out for standardized vari- paintings. In: Proceedings of the Conference on Radio- ables. chemical Methods of Analysis, Salzburg, Austria 1964. The results of clustering analysis for all the IAEA, Vienna 1965, vol.1. tested 19 panel paintings (56 samples of lead white) [5]. Lux F., Braunstein L.: Z. Anal. Chem., 221 (1966), in German. are presented in Fig., which clearly shows division [6]. Olszewska-Świetlik J.: Technologia i technika gdań- into four groups. Based on to date quantitative skiego malarstwa tablicowego drugiej połowy XV wie- analysis of the trace elements in lead white col- ku. Toruń 2005, in Polish. lected from paintings from the 15th-19th century, [7]. Pańczyk E., Ligęza M., Waliś L.: Nukleonika, 37, 29 it can be concluded that lead white from the stud- (1992). ied panel paintings shows a lower content of cop-

ELEMENTAL COMPOSITION AND PARTICLE MORPHOLOGY OF LEAD WHITE PIGMENTS Bożena Sartowska, Ewa Pańczyk, Lech Waliś The analysis of pigments on artworks is of major For the last twenty centuries, lead white has significance in art conservation as it leads to detailed been one of the most frequently used pigment. Its characterization of materials and is thus important purity is directly related with the development of for dating and authentication, as well as for poss- methods of production and purification of lead. ible conservation or restoration of artwork. Pigment Owing to this fact, it is possible to distinguish the analysis can be a challenging problem due to the groups of the artists by whom the painting has been complexity of materials analyzed because one may created by determining trace elements present in have to identify several different pigments used in the lead white used. In addition, it is possible to multicomponent mixtures and in different paint identify repainted fragments and conservation layers. The problem becomes even more demand- steps made which is of great importance to art his- ing for artworks in which sampling is either ex- torians. The variation seen in trace element com- tremely limited or even forbidden. Several analyti- positions according to region and time, proper cal techniques for identification of pigments have authentication would require compiling a library been in use for many years such as scanning elec- of analyses of carefully documented paintings to tron microscopy (SEM), energy-dispersive X-ray compare statistically the painting in question. Such (EDX), X-ray diffraction (XRD), X-ray fluor- work can confidently contribute to the reassign- escence (XRF), Fourier-transform infrared spec- ment of dates and the placement of objects in their troscopy (FT-IR), UV-visible absorption, particle- correct historical context [1-4]. -induced X-ray emission (PIXE), proton-induced The lead white of commerce that has been used gamma-ray emission (PIGE), Rutherford back- in painting is the basic carbonate 2PbCO3·Pb(OH)2. scattering spectroscopy (RBS), instrumental neu- Lead carbonate hydroxide is chemically equivalent tron activation analysis (INAA) and prompt gamma to the naturally occurring hydrocerrusite, however, activation analysis (PGAA) [1-3]. the mineral equivalent is extremely rare and con- Natural and synthetic pigments are subject to sequently rarely used as a pigment source. During various geological, mining and manufacturing pro- the Roman period, lead white was well-known his- cesses, which are unique to each manufacturer. torically as a synthetic pigment that is made from Understanding of the manufacturing process of metallic lead and vinegar. Lead white was com- common pigments allows the forensic scientist to monly adulterated with other white pigments, par- understand how trace elements may become in- ticularly chalk, baryte and kaolinite to cut cost [4]. corporated into the final product, and validity of The goal of the described work is the compari- the concept of using their association pattern in son of trace element patterns and particle mor- the paint as a provenance establishment tech- phology of contemporary lead white pigments and niques. Bologna chalk which was used very often as an NUCLEAR TECHNOLOGIES AND METHODS 131 admixture to lead white specially in grounding of elements at a level of ppb or even better in a wide paints, with lead white pigment taken from the range of materials. In the 1950’s there was no tech- panel painting of Crucifixion Triptych (Gać Śląska, nique that could compete with this method. At dating on 1440/1450) which belongs to the so-called present, though there are other methods with com- Silesian Painting School. We used two methods: parable sensitivity, neutron activation analysis INAA for determination of trace elements and SEM (NAA) still offers new capabilities thanks to the for revealed morphology of investigated pigments. development of electronics and availability of in- The activation analysis is one of the modern creasingly technologically advanced instruments. instrumental analytical methods. Since 1950 it has This results in enhanced precision, accuracy and been an important technique used to analyze trace repeatability [1,3].

Table. Composition of lead white and chalk samples [ppm]. 132 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS A B

Fig.1. Pigments: A – calcite CaCO3, B – lead white 2PbCO3·Pb(OH)2. The analysis of lead white samples was carried mixture in this contemporary paint. In original, out using the INAA method without chemical lead white taken from the Crucifixion Triptych con- separation, using standards of analyzed elements. tained a higher concentration of copper and lower The samples were packed together with standards of silver than in contemporary pigments. [3]. Also attached were the standards of gold and The same four different kinds of pigments were scandium evaporated onto a piece of aluminium investigated by means of SEM: powder of CaCO3 foil. They played the role of the thermal neutron – calcite, powder of 2PbCO3·Pb(OH)2 – lead white flux monitor. pure pigment (Poland), oil colour form Grumbacher Irradiation of the samples was carried out in N.Y. and original lead white pigment taken from the MARIA reactor at Świerk, in a channel with the panel painting of the Crucifixion Triptych with 8x1013 n/cm2s thermal neutron flux. The irradiation linseed oil binder. time was 24 h with subsequent 8-hour cooling. Mea- Powders of pigments and small pieces of paints surements of radioactivity of samples and standards were fixed at the microscopic tables using the con- were carried out using an HP germanium detector ductive glue (Quick Drying Silver Paint, Agar Scien- with an active volume of 80 cm3 and an energy re- tific Ltd.). The surfaces of the samples were coated solving power of 1.95 keV for the 1333 keV peak with a thin layer of metal to reduce the charging from 60Co. The detector cooperates with a S100 which takes place during SEM observations [5]. Canberra analyzer, controlled by IBM/PS-2. The They were covered with a thin layer (less than 10 analysis of complex gamma radiation spectra was nm) of gold using a vacuum evaporator JEE-4X carried out using micro-SAMPO and Gene 2000 (JEOL, Japan). Observations were carried out us- programs. The measurements were repeated six ing scanning electron microscope DSM 942 (Zeiss, times within three months after irradiation. The Germany). measurement time varied between 300 and 10 000 Powder of CaCO3 consists of agglomerates of s. Thirty two elements were identified and deter- needle-shape grains (Fig.1A). Needles-grains with mined in the analyzed samples. The results of this different sizes are in the shape according to the analysis are presented in Table. theoretical calcite orthorhombic crystal system [6]. It follows from the comparison of the data sets Powder of lead white consists of agglomerates obtained for the investigated samples that the oil of hexahedron plate-shape grains (Fig.1B). The colour from Grumbacher N.Y. firm characterized sizes of these plates are: the diagonal – about 2.4 a very high concentration of zinc which is an ad- μm and the thickness – about 0.3 μm. The shape A B

Fig.2. Oil colour (Grumbacher N.Y.): A – surface, B – brittle fracture. NUCLEAR TECHNOLOGIES AND METHODS 133 A B

Fig.3. Lead white from the panel painting Crucifixion Triptych with linseed oil binder: A – bulk sample, B – dispersed particles x20 000, C – dispersed particles x5000. of the observed plates are in good agreement with oil paint from Gać Śląska shows a spherical shape the theoretical hexagonal crystallographic lattice of the pigment particles dispersed in used oil. of 2PbCO3·Pb(OH)2 [6]. In this work, it was demonstrated that a com- The Grumbacher N.Y. oil colour was in the dried bined method approach, performed directly on the form as a bulk material. Pieces of this paint have artwork and small samples, is able to identify the the smooth surface without cracks and inclusions. materials that were used to manufacture artefacts. Visible grains are fixed in the matrix. Diameter of The consequence of these findings, in relation to the single grain is less than 1.1 mm (Fig.2A). Sur- dating and authenticating the investigated artefact, face of brittle fracture shows a lot of cracks and are consistent with the art historical observations. voids, free pieces of material could be distinguished. According to our experience, the NAA and Much smaller particles (about 0.3 μm) fixed in the SEM methods are a powerful tool to identify and matrix are visible at the fracture (Fig.2B). characterize the pigments. The sample of lead white from the Crucifixion Triptych was in the form of some small particles of References dried paint. Their surfaces are rough with voids [1]. Houtman J.P., Turkstra J.: Neutron activation analysis and inclusions (Fig.3A). The interesting objects – and its possible application for age determination of groups of the spherical particles are also observed. paintings. In: Proceedings of the Conference on The spheres are in different sizes: from less than Radiochemical Methods of Analysis, Salzburg 1964. 0.3 μm in diameter (Fig.3B) to rather big – 17.6 IAEA, Vienna 1965, vol.1. μm in diameter (Fig.3C). This shape is the result [2]. Lux F., Braunstein L.: Z. Anal. Chem., 221 (1966), in of the pigment formation: the particles of solid German. [3]. Pańczyk E., Ligęza M., Waliś L.: Nukleonika, 37, 29 (1992). phase of 2PbCO3·Pb(OH)2 are dispersed in the liquid phase of used oil [7]. [4]. Eastugh N., Walsh E., Chaplin T., Siddall R.: Pigment Scanning electron microscopy is a useful tool compendium. Elsevier 2004. for investigations of the morphology of pigments [5]. Goldstein I.J.: Electron microscopy and X-ray microanalysis. A text for biologist, material scientists and and paints. The investigated pigments consist of geologists. Plenum Press, New York 1992, 820 p. small particles with the shape in accordance with [6]. Poradnik fizykochemiczny. Praca zbiorowa. WNT, the theoretical shape of crystallized CaCO3 and Warszawa 1974, 1985 p. (in Polish). 2PbCO3·Pb(OH)2. The investigated paints show [7]. Spychaj T., Spychaj S.: Farby i kleje wodorozcieńczalne. the pigment particles fixed in the oil matrix. The WNT, Warszawa 1996, 323 p. (in Polish). 134 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS ULTRAVIOLET BLUE FLUORESCENCE OF CENTRAL EUROPEAN BAROQUE GLASS (FURTHER RESULTS) Jerzy Kunicki-Goldfinger, Joachim Kierzek, Piotr Dzierżanowski1/ 1/ Faculty of Geology, Warsaw University, Poland About 1200 colourless glass vessels originated Analyses by wavelength dispersive spectrometry mainly from central European areas and dated to in the EPMA system were carried out using 17th and 18th centuries were analyzed by the use Cameca SX-100 at the Electron Microprobe Labo- of energy dispersive X-ray fluorescence (EDXRF) ratory, Faculty of Geology, Warsaw University. analysis and examined under UV-C radiation. Standards were oxides and minerals. Corning B, These observations were carried out to distinguish C, D, and NIST 610, 612, among others, were used the items that show blue fluorescence, which is as secondary standards. associated with the presence of lead in glass. The The obtained results have confirmed that blue colour of fluorescence was determined with the fluorescence of baroque central European vessel naked eye. Also, small samples were taken from glass is connected to the presence of lead in glass. the 88 examined objects. They were analyzed by There is no border PbO concentration that cause the use of electron probe microanalysis (EPMA). the phenomenon. The PbO concentration even The project constitutes a continuation of our below 0.2% can cause the bright blue fluorescence. previous paper [1]. On the other hand, in this range slightly below A band with the dominant line of 253.7 nm 0.5% of PbO, a few examined glasses did not show (usually denoted as UV-C) was applied. Commer- the fluorescence at all. These vessels are attributed cially available sources of the UV-C radiation were to unknown Polish and/or Russian factories run used (two low pressure TUV 15 V mercury lamps, by the end of the 18th century. manufactured by Philips). They were installed in a The presence or absence of blue fluorescence special chamber for safe observation of the phe- does not seem to depend on the concentration of nomenon. The total radiation intensity in the Mn and Fe, thought the relative ratios of Pb, Mn chamber amounted to 8.257x10–4 W/cm2 (for the and Fe influence the changes of glass fluorescence wavelength range of 200-398 nm), with a single under UV-C in the case of such small lead con- dominant peak of 2.503x10–4 W/cm2 for a wave- centrations. length of 254 nm. When the PbO content is higher (over 0.5%), Energy dispersive X-ray fluorescence was used glass shows this fluorescence independently of the in a surface manner. The 109Cd and 241Am radio- kind of glass matrix composition. There is one ex- isotope annular sources were applied to excite the ception found and it concerns a few vessels attrib- elements in the glass. X-ray spectra were measured uted to Zechlin (or Potsdam), Brandenburgia using Si(Li) and a planar HPGe detectors. The live (Fig.1). It should be underlined that not all glasses time of the measurements was 600 s. The analyzed from this glass centre behave in this way; other

Fig.1. Triangular diagrams for the variables Pb, Mn, and Fe. The variables have been transformed in such a way that the sum of their values is constant for each case. area of glass amounted to approximately 2 cm2. examples also containing lead show the blue fluor- No quantitative chemical analysis was carried out escence. We do not know the reason of it. by the use of EDXRF. Only PbO contents were es- Three groups of leaded central European glass, timated. which show blue fluorescence under UV-C radia- NUCLEAR TECHNOLOGIES AND METHODS 135 <0.4. 5 O 2 Table. Chemical composition of 21 glasses analyzed by the use EPMA [wt%]. < – below detection limit. For all samples: P 136 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS tion, have been distinguished (tentatively marked highest PbO concentration reaching c. 2%. “B” is A, B, and C) (Fig.2). “A” is white (chalk) glass with crystal glass. The PbO content did not exceed 6%. “C” is also crystal glass, but with the PbO content over 6%. These groups differ from one another in the chemical composition as a consequence of the application of determined recipes and raw materials. Chemical composition of 21 glasses with the highest PbO concentration analyzed by the use of EPMA (in wt%) are presented in Table. The items have been sorted according to their lead content and the presence of blue colour of their fluorescence is indicated. The PbO level in the remaining 67 glasses, also examined by the use of EPMA, remains below 0.04% and they did not show blue fluorescence. It can be seen that the glasses with PbO content over about 0.2-0.3% show this distinct blue fluorescence. Though, there are two exceptions and both vessels were produced in Zechlin. According to our previously published results, we can now divide leaded crystal central European glass from the 18th century into two groups, B and C. The further conclusion is that all glasses that belong to group C showed blue fluorescence. Among the glasses from group B, we have found a few exceptions. We have also found a few examples with very low lead content (or with its concentration below the detection limit) that exhibit weak pale-blue fluorescence. This phenomenon is caused probably by the presence of other kind of fluorescent centre in glass than lead. Spectroscopy seems to be undoubtedly needed for further studies on this phenomenon. The project has been carried out at the Institute of Nuclear Chemistry and Technology in Warsaw within the frameworks of a few separated projects since 1998. The following museums made the vessels available for examination: the National Museums (Gdańsk, Cracow, Poznań, Warsaw, Wrocław), the Royal Castle in Warsaw, the Wawel State Art Col- lection, the Czartoryski Museum and the Jagiellon- ian University Museum (Cracow), the District Mu- seums (Jelenia Góra, Rzeszów, Tarnów), the Łań- cut Castle Museum, Museum in Nieborów and Arkadia, the Museum-Palace in Wilanów, the His- torical Museum of Warsaw and private collectors. Fig.2. The scatter plots for PbO [wt%] and, respectively References Rb, Y and Zr. Rb, Y and Zr contents are expressed in arbitrary units. Three groups of leaded glass have [1]. Kunicki-Goldfinger J.J., Kierzek J.: Glass Technol., been distinguished. 43C, 111-113 (2002).

LATE 17th CENTURY GLASS VESSELS FROM EILAND – TECHNOLOGICAL APPROACH Jerzy Kunicki-Goldfinger, Martin Mádl1/, Piotr Dzierżanowski2/ 1/ National Museum & Institute of Art History, Academy of Sciences of Czech Republic, Prague, Czech Republic 2/ Faculty of Geology, Warsaw University, Poland

We know relatively little about glass production ous technologies and manufacturing processes that in the second half of the 17th century, when vari- would later become commonplace were still being NUCLEAR TECHNOLOGIES AND METHODS 137 developed and tested. In the catalogs of European acteristics and distinct properties have been dis- glass collections, we find only a few objects that can cussed elsewhere [2]. be reliably dated between the 1650s and the 1690s, We took small samples of glass from the three with the exception of enameled glass that derives vessels and analyzed them by wavelength-disper- from the Renaissance tradition. sive spectrometry with electron-probe microanaly- This article draws attention to several luxury sis (EPMA). The samples for analysis were col- objects that are intriguing because of their crizzled lected with a diamond point. They came from the glass and forming and finishing techniques. We have pontil mark of the goblet of Matthias Helfried von managed to date these objects with considerable Plönstein; from the bowl of the jug of Marie Adel- precision. At the same time, we have attempted to heid, Countess Thun; and from the stem of the gob- situate them in the broader context of European let with the coat of arms of the Lodron family. The glass production, and specifically to link them with samples were mounted in blocks of epoxy resin, the important Hessian glassmaker Georg Gunde- polished to 0.25 μm, and coated with a layer of lach and his heretofore little-known work in Bohe- carbon. The analyses were carried out using a mia. Cameca SX-100 equipped with three simulta- Our primary method for the identification of neously working spectrometers (PET, LIF, TAP objects has been art-historical analysis, augmented crystals, and PC2 for boron) at the Electron Micro- by chemical analysis of the selected samples. Three probe Laboratory (Faculty of Geology, Warsaw objects attracted our special attention. One of them University). The measurement conditions were as is a goblet of Matthias Helfried von Plönstein dec- follows: (i) for main constituents – 15 kV, 6 nA, 20 orated with a prelate’s coat of arms in the glass col- μm beam diameter, counting time 20 s for each lection of the Prague City Museum (inv. no. 137 969). element; (ii) for minor and trace constituents (with The next object that deserves our attention is a gob- fixed concentration of main constituents) – 20 kV, let of Christoph Lodron and Catharina von Spaur 100 nA, 80 μm beam diameter, counting time 20-60 bearing the coat of arms of the Lodrons in the col- s; and (iii) for boron (with fixed concentration of lection of the Museum of Applied Arts in Prague main and minor constituents) – 5 kV, 100 nA, 20 (inv. no. 4 462). Another vessel that can be linked μm beam diameter, counting time 20 s. The stan- with the Thun court and perhaps also with the glass- dards were oxides and minerals. Corning reference works in Eiland is a small jug of Marie Adelheid, glass D, CRM-glasses 4001 and 4002 (Glass Insti- Countess Thun with the motif of the Virgin and tute, Hradec Králové, Czech Republic), and NIST Child in the collection of the Department of Czech CRM-glasses 610 and 612 were used as secondary History of the National Museum in Prague (inv. no. standards. H2 – 6 579). The results are presented in Table (Nos.1, 2, The main goal of this part of our study was to and 11). For comparison, we include the results of identify the technology used in the manufacture of chemical analyses of luxury glasses manufactured the three glass vessels. We assumed that this would in central Europe from the late 17th through the contribute important complementary information 18th centuries. Because there are almost no pub- to the study of the provenance and dating of the lished chemical analyses of central European luxury objects. baroque glasses from the late 17th century, we have Two preliminary assumptions have been made relied mainly on examples from the first half of in writing this section. First, we use the term “glass” the 18th century and on two vessels from about to mean only the material, not the object, and we 1700 that were specially examined for our study. characterize this “glass” exclusively in terms of its They are shown in Table as Nos.3 and 4. Both chemical composition. Second, when interpreting glasses are crizzled. The analyses were also car- the chemical composition, we consider only the ried out using EPMA, under the same conditions. likely intention of the glassmaker, assuming that The presence of certain chemical components this composition reflects, at least to some extent, and their concentrations in all of the glasses in the recipe used. This method of analysis differs Table provide clues to their provenance and dat- from an assessment of the optical quality of the ing. The near absence of MgO and P2O5, as well as glass that is made with the naked eye, since the the presence of As2O3, suggests that the glass was latter involves an examination of the final prod- melted from batches containing potash (and/or uct, which does not always reflect the glassmaker’s saltpeter) as a flux, arsenic, and other ingredients. intention. In some instances, glass that was intended Saltpeter and arsenic began to be used in the pro- to be of particularly fine quality emerged from the duction of certain types of colorless vessel glass in manufacturing process as an inferior material, and central Europe probably not earlier than in the the reverse also happened. second half of the 17th century. We use the terms “crystal glass”, “white glass” The glasses in Table are grouped into three sets (also referred to as “chalk glass”), and “ordinary according to composition. The first set consists of glass” in referring to the chemical composition of six examples of central European crystal glass dat- the glass. These terms correspond to the three types ing from the late 17th century and about 1700. It of glass compositions developed by the Venetians: includes the goblet of Matthias Helfried von Plön- cristallo, vitrum blanchum, and vetro commune [1]. stein and the goblet with the coat of arms of the These three basic formulas for colorless glass were Lodron family. These examples are distinguished used during the period under discussion, and they by their uniquely low concentration of CaO, which are known from documentary sources. Their char- is significantly below one weight percent (<1%), 138 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS <0.03, ZnO<0.03. 3 O 2 <0.01, Y 2 O<0.07, ZrO 2 <0.4, Rb 3 <0.4, SO 5 O 2 All results are for colorless glasses. Nos.1-4, 6, 8, and 10 crizzled. + – found but not quantified; < below detection limit. For all samples: P Table. Chemical composition of luxury vessel glass from central Europe, late 17th and 18th centuries [wt%]. Column 3: NM – National Museum, MAA Museum of Applied Arts, MP Palace. NUCLEAR TECHNOLOGIES AND METHODS 139 and five of these vessels have relatively high levels The second set contains four objects from the of B2O3. The EPMA system used for the analyses first half of the 18th century. They were made in allowed us to quantify boron oxide only when its Dresden, Zechlin, Naliboki, and an unidentified concentration exceeded about 0.7-1%, depending German glasshouse. The composition of this later on the glass matrix. Because of this, in certain cases, crystal glass is distinguished by a higher CaO con- boron could be found but not quantified. tent (which does not go much above 5% in any of The low CaO content suggests that calcium the discussed examples). The other characteristic could have been introduced to the glass as con- features of the chemical composition of this glass tamination or as a minor constituent of certain raw are its significant PbO content and the lack of, or materials (possibly potash or wine stone). If this markedly lower concentration of, B2O3. type of crystal glass was made without adding cal- The four examples of white glass in the third cium as a raw material, it may be considered a suc- set, which date from the late 17th century to the cessor to Venetian cristallo. Another possible ex- end of the 18th century, originated in Bohemia, planation is that chalk was added as an ingredient Germany, and Poland. Their composition is char- in very small quantities. Chalk appears in lists of acterized by a lack of B2O3 and a significantly raw materials used during this period, but we do higher CaO concentration (ranging from 7.5 to not know if it was used in the production of this 9.5%). particular type of glass. The higher concentration White glass and crystal glass may generally be of B2O3 seems to be a characteristic only of crystal distinguished by calculating variables from the glass, and documentary sources from the period alkaline and alkaline earth oxide concentrations, confirm that borax was used in the production of as shown in Fig.1. This plot clearly shows that crystal glass. Five of these six early examples of crys- baroque crystal glass and white glass followed the

Fig.1. Venetian soda-ash glass (vitrum blanchum and cristallo) and the late 17th and 18th century central European potassium glass (white glass and crystal) shown in a scatter plot for the variables calculated from the alkaline and alkaline earth oxide concentrations. The three vessels that are considered to be Eiland products are indicated by arrows [2,4]. tal glass are known to have been manufactured in tradition of Venetian cristallo and vitrum blanchum, Bohemian and German centers. The vessel from respectively. Altmünden is dated to about 1710, and it differs In Figure 1, we can also observe the division of from the other glasses in this set in its possible lack baroque crystal glass into the earliest formulation, of B2O3 and its high PbO content. It may thus be which is characterized by a virtual lack of CaO (a seen as a later variation of this early crystal glass group of points in the lower right corner of the plot), formula. It appears that lead compounds were and later formulations. The same division can be introduced as separate raw materials in central seen even more distinctly in Fig.2, which is a plot

European colorless vessel glass formulas not ear- of As2O3 and CaO concentrations. Based on this lier than about 1700 [3]. plot, we can tentatively conclude that levels of these 140 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS

Fig.2. Crystal and white glass from various central European glasshouses (late 17th and 18th centuries). The three vessels

that are considered to be Eiland products are marked as black squares. Scatter plot for As2O3 and CaO concentrations. oxides gradually increased in crystal glass from the ogy, stylistic features, iconography, and the tech- time its manufacture in this part of Europe began nology used in their manufacture. Both vessels are in the late 17th century. exceptional in their decorative features and the We conclude that the goblet of Matthias Hel- quality of their glass. Their chemical composition fried von Plönstein and that with the coat of arms represents an early phase in the development of of the Lodron family are made of crystal glass from crystal glass in central Europe. Based on histori- the earliest known phase of its development in cal research, we can date the goblets quite securely central Europe, while the jug of Marie Adelheid, about 1675, while chemical analysis confirms that Countess Thun is an example of white glass. Both they were probably produced in the late 17th cen- of the goblets are crizzled, and it is well known that tury. We can be fairly sure that the goblets were crystal glass is particularly susceptible to crizzling made with the same technology, in the same fac- [5,6]. tory, and by the same glassmaker. The Eiland glass- The glasses from which these two goblets were works and Georg Gundelach are the strongest can- made have very similar chemical compositions, and didates, although the lack of comparative material they may therefore be considered as products of the makes this attribution uncertain. same glasshouse and made during the same period. As for the jug of Marie Adelheid, Countess In this article, these glasses are tentatively attributed Thun, we can say only that it was made of white to the Eiland glassworks. However, we can neither glass after 1688. This dating, unlike that of the exclude nor confirm the same attribution for the goblets, is based solely on stylistic analysis and his- jug of Marie Adelheid, Countess Thun. Moreover, torical research. The jug differs from the two gob- the chemical composition of this glass affords no lets both technologically and stylistically. clues to its dating. We cannot rule out the same attribution for all Because of the lack of published chemical analy- three vessels. However, we did not find any clear ses of Bohemian luxury vessel glasses from the late evidence indicating that the jug was manufactured 17th century, as well as any known object that can in the same glasshouse as the goblets. This remains be securely attributed to the Eiland glasshouse, all an open question [7]. conclusions concerning the dating and attribution of the three vessels discussed in this article must References remain a working hypothesis. [1]. Moretti C., Toninato T.: Rivista della Stazione Speri- It is very encouraging that the art-historical and mentale del Vetro, 1, 31-40 (1987), in Italian. technological studies we conducted produced such [2]. Kunicki-Goldfinger J., Kierzek J., Dzierżanowski P., Kasprzak A.J.: Central European crystal glass of the similar results. On some points, our findings were e complementary, enabling us to offer bolder hypoth- first half of the eighteenth century. In: Annales du 16 eses. However, a consistently wide margin of un- Congres de l’Association Internationale pour l’Histoire du Verre (London 2003). AIHV, Nottingham 2005, pp. certainty has to be taken into account, as is usual 258-262. for this type of research. [3]. Kunicki-Goldfinger J., Kierzek J., Kasprzak A.J., Two of the objects discussed in this article – the Dzierżanowski P., Małożewska-Bućko B.: Lead in goblet of Matthias Helfried von Plönstein and the Central European 18th-century colorless vessel glass. Lodron goblet – show many similarities in typol- In: Archäometrie und Denkmalpflege – Kurzberichte NUCLEAR TECHNOLOGIES AND METHODS 141

2003 (Berlin). Etnologischen Museum Staatliche Conference “Cultural Heritage Research: A Pan-Euro- Museen zu Berlin, Berlin 2003, pp. 56-58. pean Challenge”, Cracow, Poland, 16-18.05.2002. Ed. [4]. Verità M.: Rivista della Stazione Sperimentale del R. Kozłowski. Institute of Catalysis and Surface Vetro, 15, 1, 17-29 (1985), in Italian. Chemistry, Polish Academy of Sciences and European [5]. Kunicki-Goldfinger J., Kierzek J., Małożewska-Bućko Communities, Cracow 2003, pp. 301-304. B., Kasprzak A.: Glass Technol., 43C, 364-368 (2002). [7]. Mádl M., Kunicki-Goldfinger J.: J. Glass Stud., 48, [6]. Kunicki-Goldfinger J.: Preventive conservation 255-277 (2006), (the full text of the article, which com- strategy for glass collections: identification of glasses prises both historical and technological approaches). susceptible to crizzling. In: Proceedings of the 5th EC

WATER SOLUBLE SILICA BIOCIDES CONTAINING QUATERNARY AMMONIUM SALTS Andrzej Łukasiewicz, Dagmara K. Chmielewska, Lech Waliś

Silica biocides insoluble in water obtained by coat- insoluble in water materials C(SiO2-QAC): binds + ing a carrier (TiO2, dolomite etc.) with an ammo- acid dyes effectively, binds Ag from water and nium salt (QAC – quaternary N-alkylammonium zero-valent silver atoms obtained due to UV irra- compound) and water glass (WG) stabilized by diation. sulphuric acid have been described previously [1-3]. s-SiO2-QAC can be also incorporated into fabrics Many scientific papers on the synthesis of silica and similar materials. materials with the application of acid or basic Investigations of biocidal properties of soluble hydrolysis of alcoholic solution of tetraethoxysilan materials s-SiO2-QAC and their binding with dif- (Si(OEt)4) have been published [4,5]. Nanosol, which ferent carriers as well as structural investigation can be connected with other materials creating are being continued. nanogel, can be obtained by this procedure. On the basis of the earlier developed technol- References ogies, we have elaborated a method for the syn- [1]. Łukasiewicz A., Krajewski K.J., Gajewska J., Chmiele- thesis of water soluble silica materials containing wska D.: Właściwości biocydowe nowych materiałów quaternary alkylammonium salts (s-SiO2-QAC). dla budownictwa modyfikowanych IV-rzędową solą Example: 20 ml of 50% aqueous solution of N-alkiloamoniową związaną z krzemionką. In: Czwarto- benzalkonium chloride (Aldrich) was dissolved in rzędowe sole amoniowe. Wydawnictwo Instytutu Tech- nologii Drewna, Poznań 2005, pp. 432-437 (in Polish). 20 ml of Si(OEt)4 (Aldrich), then 100 ml of isopro- panol was added and the mixture was stirred. Next, [2]. Łukasiewicz A., Chmielewska D., Waliś L., Krajewski 10 ml of 0.04% HCl or 0.02% H SO was added K.: Ekologia, 29, 3, 36-37 (2005), in Polish. 2 4 [3]. Chmielewska D.K, Łukasiewicz A., Michalik J., Sar- and the mixture stayed at room temperature until towska B.: Nukleonika, 51, Suppl. 1, 69-72 (2006). the next day. Properties of the hydrolyzate indicate [4]. Mahltig B., Haufe H., Bottcher H.: J. Mater. Chem., complete hydrolysis of Si(OEt)4 and binding of 41, 15, 4385-4398 (2005). silica with QAC. The hydrolyzate is bound quan- [5]. Haufe H., Thron A., Fiedler D., Mahltig B., Bottcher titatively with carrier C (e.g. TiO2, dolomite) and H.: Surf. Coat. Int. B: Coat. Trans., 88, 1, 55-60 (2005). the product indicates properties characteristic of

THE ROLE OF CARBON, CHROMIUM AND NITROGEN IN AUSTENITIZATION OF UNALLOYED AND ALLOYED STEELS BY INTENSE PLASMA PULSES Jerzy Piekoszewski1,2/, Ludwik Dąbrowski3/, Bożena Sartowska1/, Lech Waliś1/, Michał Kopcewicz4/, Justyna Kalinowska4/, Marek Barlak2/, Jacek Stanisławski2/, Zbigniew Werner2/, Adam Barcz5/ 1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland 2/ The Andrzej Sołtan Institute for Nuclear Studies, Świerk, Poland 3/ Institute of Atomic Energy, Świerk, Poland 4/ Institute of Electronic Materials Technology, Warszawa, Poland 5/ Institute of Physics, Polish Academy of Sciences, Warszawa, Poland

In our previous works it was shown that normal to study how the alloying elements such as carbon, γ γ and so-called expanded austenite phases ( N , C) chromium and nitrogen influence the efficiency of can be formed not only in the stainless steel but austenitization of steels treated by argon and ni- also in carbon steels and even in the pure α-iron if trogen plasma pulses [3]. The steel samples con- they are treated with high intensity nitrogen plasma tained initially 2.5-4.2 at.% C, 0.12-14 at.% Cr and pulses [1,2]. The purpose of the present work was about 1 at.% N after the nitrogen plasma treatment 142 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS were used in the investigations. The pulses were - Presence of carbon strengthens the efficacy of generated by rod plasma injector type of genera- chromium in austenite formation. tor described in detail in [4]. This work was financed by the Polish Ministry The energy density of plasma pulses was about of Education and Science for scientific projects 5 Jcm-2, pulse duration – about 1 μs and numer of under contract No. 1147/T08/2005/29. pulses – 3. The energy was high enough to melt the near surface layer, so the used element was doped References to the liquid metal. The samples were examined [1]. Sartowska B., Piekoszewski J., Waliś L., Szymczyk W., by conversion electron Mössbauer spectroscopy Stanisławski J., Nowicki L., Ratajczak R., Kopcewicz (CEMS), X-ray diffraction (XRD) and secondary- M., Kalinowska J., Barcz A., Prokert M.: Vacuum, 78, -ion mass spectroscopy (SIMS) techniques. The 181-186 (2005). main results of the detailed analysis of the experi- [2]. Piekoszewski J., Sartowska B., Waliś L., Werner Z., Kopcewicz M., Prokert F., Stanisławski J., Kalinowska mental data can be summarized as follows: J., Szymczyk W.: Nukleonika 49, 2, 57-60 (2004). - Both nitrogen and carbon alone are capable of [3]. Gavriljuk V.G., Berns H.: High nitrogen steels. Struc- forming normal and expanded austenite phases ture, properties, manufacture, applications. Springer- γ γ N and C. -Verlag, Berlin Heilderberg 1999, 376 p. - Of all three alloying elements: carbon, chromium [4]. Werner Z., Piekoszewski J., Szymczyk W.: Vacuum, 63, and nitrogen, nitrogen is most effective in auste- 701-708 (2000). nitization of both carbon and alloyed steels. - Presence of nitrogen weakens the efficacy of carbon and chromium in austenite formation.

THERMAL STABILITY OF THE PHASES FORMED IN THE NEAR SURFACE LAYERS OF CARBON STEEL BY NITROGEN PULSED PLASMA TREATMENT Bożena Sartowska1/, Jerzy Piekoszewski1,2/, Lech Waliś1/, Jacek Stanisławski2/, Lech Nowicki2/, Renata Ratajczak2/, Michał Kopcewicz3/ 1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland 2/ The Andrzej Sołtan Institute for Nuclear Studies, Świerk, Poland 3/ Institute of Electronic Materials, Warszawa, Poland

The intense pulsed plasma beams were used for trolled temperature and flow of the ambient gas – carbon steel surface modification. The energy den- argon. The heat treatment parameters were: tem- sity of the pulse was high enough to melt the near perature between 100 to 300oC with a step of 50oC surface region of the substrate and nitrogen was in- for 1 h. In the investigating samples nitrogen re- troduced into the liquid alloy. The nitrogen expanded tained a dose of 1.2x1017 cm–2. The standard devia- austenite – γN (austenite in which iron atoms have tion σ=2x1016 cm–2. one or more nitrogen atoms in the nearest neigh- Relative changes of the determined parameters bourhood) was found in the near-surface region of characterizing properties of the material are defined carbon steel and significant increase of hardness as: and tribological properties were observed [1]. The [(AM – IM)/IM] x 100% formation of nitrogen expanded austenite does not where AM and IM are the values of the investigated follow the equilibrium phase Fe-N diagram [2,3]. parameter for annealed and initial material, respec- At elevated temperature, the interstitial atoms can tively. be released from the lattice and diffuse. Therefore, After annealing, the relative surface nitrogen the stability under maximum operating tempera- concentration changes depending on the anneal- tures must be determined and it must be known ing temperature (Fig.1). The surface nitrogen con- how long a component can be used under specific centration increased up to temperature of about thermal load before undesirable properties occur. Carbon steel 1C45 with 0.52 wt% C and heat treated with the standard procedures was used for investigations. The plasma pulses were generated in a rod plasma injector (RPI) [4]. The samples were irradiated with five nitrogen plasma pulses at an energy density of about 5 J cm–2. The samples were characterized by: nuclear reaction analysis (NRA) 14N(d,α)12C for the determination of retained nitrogen dose and conversion electron Mössbauer spectroscopy (CEMS) for quantitative analysis of the identified phases. The annealing processes Fig.1. Changes of surface nitrogen concentration as a re- were carried out using a tube furnace, with con- sult of annealing the modified samples. NUCLEAR TECHNOLOGIES AND METHODS 143 150oC and decreased for annealing at higher tem- contain any of austenite stabilizing element shows peratures. The main reason for this fact could be the lowest (150oC) onset temperature of nitrogen releasing of the interstitial nitrogen atoms from expanded austenite decomposition. the nitrogen expanded austenite lattice at elevated temperature. It is likely that up to 150oC, nitrogen diffuses towards the surface. At a temperature higher than 150oC, the nitrogen atoms have higher energy and can diffuse to the bulk of the sample as well [5]. As a result of surface modification process, we obtained thin (about 1.5 μm) layers with the presence of the identified phases α-Fe (ferrite and/or γ martensite), 0 (austenite in which iron atoms have no nitrogen or carbon atoms in the nearest neigh- γ γ bourhood), expanded austenities C, N (austenities in which iron atoms have one or more carbon or nitrogen atoms in the nearest neighbourhood) and nitrides. CEMS results obtained for the heat-treated Fig.3. Changes of the nitrogen expanded austenite pres- samples are presented in Fig.2. The phases trans- ence in the modified surface layer of different kinds o formation process started at annealing at 150 C. of steels as the result of annealing the samples. γ γ γ The content of all austenities ( 0, C and N) decreases with temperature, while the contents of In conclusions: The surface nitrogen concen- α-Fe phases and nitrides increase. Decrease of the tration in the top layer of modified carbon steel austenitic phases content above 150oC has a rapid started its decreasing from 150oC due to releasing the interstitial nitrogen atoms from fcc (face centered cubic) nitrogen expanded austenite lattice and their diffusion into the surface and bulk of the samples. The significant changes of the content of identified phases started at 150oC. The austenities transformed to the α-Fe phases. The nitrides are formed at the expense of nitrogen released from the fcc expanded austenite lattice. The modification effects in unalloyed steel 1C45 induced by the intense nitrogen plasma pulses are stable to the temperature of about 150oC. This is the application limit, but below this temperature a material can be used without losing its required properties. Fig.2. Changes of the identified phases contents as the result of annealing modified samples. This work was financed by the Polish Ministry of Education and Science for scientific projects character and these phases are no more present under contract No. 1147/T08/2005/29. above 250oC. The content of α-Fe phases increases by a factor of 2 at 300oC annealing. It is obvious References that this increase is of the expense of austenitic [1]. Sartowska B., Piekoszewski J., Waliś L., Szymczyk W., phases decomposition. For the same reason, we Stanisławski J., Nowicki L., Ratajczak R., Kopcewicz observed also an increase of nitrides content by a M., Kalinowska J., Barcz A., Prokert F.: Vacuum, 78, factor of about 2. Released interstitial nitrogen 181-186 (2005). atoms become available for the nitrogen phases [2]. Williamson D.L., Oztruk O., Glick S., Wei R., Wilbur formation [5]. P.J.: Nucl. Instrum. Meth. Phys. Res. B, 59/60, 737-741 The presence and stability of nitrogen expanded (1991). austenite determined in our experiments in steel [3]. Gavriljuk V.G., Berns H.: High nitrogen steels. Struc- 1C45 are compared with the data reported in the ture, properties, manufacture, applications. Springer- literature describing the alloyed steels: austenitic -Verlag, Berlin Heilderberg 1999, 376 p. X6 (0.08% C, 17-19% Cr, 9-12% Ni) and ferritic [4]. Werner Z., Piekoszewski J., Szymczyk W.: Vacuum, 63, 701-708 (2000). X10 (0.12% C, 17-19% Cr) [6] (Fig.3). As it is seen, γ [5]. Briglia Th., Terwagne G., Bodart F., Quaeyhaegenes the N phase is the most stable in X6 steel contain- C., D’Haen J., Stals L.M.: Surf. Coat. Technol., 80, ing both chromium and nickel alloying elements. 105-108 (1999). It is less stable in chromium containing X10 steel [6]. Jirásková Y., Blawert C., Schneeweiss O.: Phys. Status with the onset temperature of 250oC. As it could Solidi A, 175, 537-548 (1999). have been expected, our sample which does not 144 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS ELECTRON-BEAM IRRADIATION OF PVDF MEMBRANES AS A METHOD FOR OBTAINING BRITTLE FRACTURES FOR SEM OBSERVATIONS Bożena Sartowska, Oleg Orelovitch1/, Andrzej Nowicki 1/ Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, Dubna, Russia

Specific template – track membranes can be used highest purity, strength, and resistance to solvents, to obtain the nano- and microstructures [1]. It is im- acids, alkalies and heat. It is commonly used in the portant for these applications to know geometry chemical, semiconductor, medical and defense in- parameters of the pores like sizes, shape and their dustries. A fine powder grade is also used as the inner surface morphology [2]. A scanning electron principal ingredient of high-end paints for metals. microscopy technique (SEM) was used for the in- PVDF is exhibiting efficient piezoelectric and pyro- vestigations of surface and fracture of membrane. electric properties. These characteristics make it The proper preparation of samples for SEM ob- useful in sensor and battery applications [6,7]. servations is very important in order to prevent de- The samples of PVDF membranes were irradi- struction the structure of the membrane during frac- ated with electron beam at the Institute of Nuclear ture preparation. The breaking membrane samples Chemistry and Technology (INCT) using different at the liquid nitrogen temperature (77 K) did not doses. The mechanical properties: tensile strength A B

Fig.1. The fractures of PVDF membrane: A – initial, fractured in liquid nitrogen; B – irradiated with electron beam up to a dose of 603 kGy. allow us to obtain undistorted cross-section. The and elongation at break of the initial and irradiated use of other methods of sample preparation as elec- materials were tested using a universal testing ma- tron beam, gamma rays or UV irradiation allows chine Instron 5565 (Instron Co., England) in the us to make them more brittle [3-5]. Preliminary INCT. Membranes surface and fracture observations results of investigations of polyvinylidene fluoride were made using SEMs: JSM 840 (Jeol, Japan) and (PVDF) membranes after electron-beam irradia- DSM 942 (Zeiss, Germany). The samples were fixed tion are presented here. using a conductive glue and then coated with a thin Polyvinylidene fluoride is a highly non-reactive layer of gold to reduce the charging which takes a and thermoplastic fluoropolymer. This is the rea- place during SEM observation. son to find new methods of destruction of this type Figure 1A presents the fractures of the investi- of polymer foils or membranes for the cleavage gated PVDF membrane produced using the method production for SEM fracture investigations. Its use with liquid nitrogen. The deformation of polymeric is generally reserved for applications requiring the material is clearly seen, so the observation of the

Fig.2. Results of mechanical strength measurements of PVDF membrane: A – initial, B – after electron-beam irradiation up to a dose of 603 kGy. NUCLEAR TECHNOLOGIES AND METHODS 145 shape and inner geometry of the channels is diffi- In conclusion: using the irradiation with elec- cult or even impossible. Figure 1B presents the frac- tron beams, we can obtain a better SEM image of tures of a PVDF membrane subjected to the elec- polymeric membrane fractures than obtained with tron-beam irradiation up to a dose of 603 kGy. The liquid nitrogen. plastically deformed parts of the material are not visible. The shape and sizes of channels are clearly References seen, so the pores can be observed, measured and [1]. Sartowska B., Wawszczak D., Buczkowski M., Starosta characterized. W.: Radiat. Meas., 40, 2-6, 790-793 (2005). Figure 2 presents the results of mechanical [2]. Apel P.Yu.: Radiat. Meas., 34, 559-566 (2001). strength measurements. According to these dia- [3]. Orelovitch O.L., Apel P.Yu., Sartowska B.: Mater. grams, we can determine the main parameters of Chem. Phys., 81, 349-351 (2003). material tensile properties: elongation at breake [4]. Orelovitch O.L., Apel P.Yu.: Microsc. Anal., 82, 11-13 [%] and tensile stress [MPa]. The strength of the (2003). membrane decreases significantly after electron- [5]. Orelovitch O.L., Apel P.Yu., Sartowska B.: J. Microsc., -beam irradiation. The elongation at breake (ten- 224, 100-102 (2006). [6]. Zhang Q.M., Bharti V., Kavarnos G., Schwartz M.: sile strain) of irradiated membrane was only about Poly(vinylidene fluoride) (PVDF) and its copolymers. 1% at the 13 MPa of tensile stress, while for the In: Encyclopedia of smart materials. John Wiley & Sons, initial material these parameters were 25% at the 2002, pp. 807-825. 35 MPa, respectively. This means that the investi- [7]. Vinogradov A., Schwartz M.: Piezoelectricity in poly- gated material became more brittle and the mem- mers. In: Encyclopedia of smart materials. John Wiley brane breaks without distortion of its channel struc- & Sons, 2002, pp. 780-792. ture and we obtain the cleavage without plastic deformations.

SELECTED PROPERTIES OF POLYPYRROLE NANOSTRUCTURES DEPOSITED IN TRACK-ETCHED MEMBRANE TEMPLATES Marek Buczkowski, Wojciech Starosta, Bożena Sartowska, Danuta Wawszczak Polypyrrole (PPy) belongs to conducting polymers poly(ethylene terephthalate) (PET) films [4]. In or- which are the most stable in typical environmental der to prepare samples for measurements, proper conditions and seems to be very interesting material for nanotechnology [1-4]. Presented results A are a continuation of investigations carried out earlier. The first subject was connected with: deposition of PPy nanotubules on track-etched membranes (TMs) and determination of the kinetics of their wall thickness growth for time of deposition longer than 7 min [4]. The second subject was connected with measurements of electrical parameters of PPy nanotubules deposited into TMs [5]. In this work, the results are connected with: PPy nanotubules formed in TM templates for times of polymerization shorter than 5 min, determination of permeability of deposited nanotubules and covering of such structures with a thin copper layer. The template-based synthesis of PPy was carried out into pores of TMs made of 10 μm thick B

Fig.2. Nanotubules formed in pores of TM membrane (0.2 Fig.1. A scheme of the mould for PPy nanotubules deposi- μm pore size) after 2 min (A) and 3 min (B) of poly- tion in TMs membranes. merization process. 146 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS

Table 1. Dependence of PPy layer thickness on TM vs. time of polymerization for both sides of a membrane sample (pore size – 1.3 μm).

allowed to determine nanotubules wall thickness and thickness of the PPy layer on membrane surfaces. Selected SEM photographs (Fig.2) show fractures of the samples in liquid nitrogen in case of time of polymerization, respectively 2 and 3 min. Dependence of nanotubule wall thickness vs. time of polymerization is shown in Fig.3 (for times equal to or longer than 7 min; results are taken from pre- Fig.3. Kinetic curve of PPy nanotubules growth into pores vious work). It is seen that the first stage of the of the TM (initial pore size – 1.3 μm). speed of nanotubules formation is higher than in the next stage. This speed is equal to 20.3 nm/min solutions were introduced to both sides of a mem- and is 1.7 times higher than in the next stage. Thick- brane disc (for certain period of time) that had ness of PPy layers on the template surfaces for dif- been mounted in a plexiglas mould (Fig.1). As a ferent times of polymerization is given in Table 1.

Table 2. Permeability of nanotubules deposited on pores of TMs 0.2 μm at an air pressure of 0.5 bar.

result of such procedure, discs 20 mm in diameter The value of permeability is an important par- covered with PPy have been obtained (outer diameter in some applications, for instance, in micro- ameter of samples was 30 mm). filtration devices. Permeability for samples with

Table 3. Permeability of nanotubules deposited on pores of TMs 1.3 μm at an air pressure of 0.5 bar.

Scanning electron microscopy (SEM) measure- different wall thickness of nanotubules in TMs with ments by using a Zeiss-Leo DS942 microscope pore diameters 0.2 and 1.3 μm was determined at A B

Fig.4. The copper layer sputtered on the membrane surface by using a glow vacuum discharge: (A) membrane pore size – 0.2 μm, (B) membrane pore size – 1.3 μm. NUCLEAR TECHNOLOGIES AND METHODS 147 an air pressure of 0.5 bar. For TMs with a pore size with PPy nanotubules: TM membrane with pores of 0.2 μm, the initial permeability was equal to 0.70 0.2 μm (Fig.4A) and 1.3 μm (Fig.4B). The thick- l/(min·cm2). Values of the permeability for differ- ness of copper layers was similar in both cases: 0.7 ent wall thickness of PPy nanotubules deposited and 1.2 μm, respectively, but the structure of these in such pores are given in Table 2. It was calculated layers was different. In case of smaller size of the that by decreasing the internal pore diameter 6.3 pores in template, the surface of the copper layer times (from 200 to 32 nm), the permeability de- was smoother. creased 2.9 times. The authors would like to thank Mr Adam Le- For TMs with a pore size of 1.3 μm, the initial ciejewicz – head of the “Surftec” s.c. for the copper permeability was equal to 14.8 l/(min· cm2). For dif- sputtering of membrane samples by using glow ferent wall thickness of PPy nanotubules deposited vacuum discharge. in pores, the permeability is given in Table 3. In this case, decreasing of the internal pore diameter References 6.6 times (from 1300 to 198 nm) caused decreas- [1]. Nakata M., Kise H.: Polym. J., 25, 91 (1993). ing of the permeability 10.4 times. [2]. Kohli P., Martin C.R.: Curr. Pharm. Biotechnol., 15, Attempts were taken up concerning the cover- 441-450 (2004). ing of samples with deposited PPy nanotubules by [3]. Zhitariuk N.J. et al.: Nucl. Instrum. Meth. Phys. Res. thin metallic layer. This is important matter be- B, 105, 204-7 (1995). cause samples with deposited PPy can be applied [4]. Starosta W., Buczkowski M., Sartowska B., Wawszczak D.: Nukleonika, 51, Suppl. 1, S35-S39 (2006). as sensors and in such case it is necessary to intro- [5]. Buczkowski M., Wawszczak D., Starosta W.: Electrical duce electrical connection with an outer circuit. parameters of polypyrrole nanotubules deposited inside Introductory experiments were carried out with track-etched membrane templates. In: INCT Annual glowing sputtering of copper (in the “Surftec” s.c., Report 2004. Institute of Nuclear Chemistry and Tech- Warszawa). SEM photographs (Fig.4) show the nology, Warszawa 2005, pp. 93-94. sputtered copper layer in case of two types of samples

SOL-GEL-DERIVED HYDROXYAPATITE AND ITS APPLICATION TO SORPTION OF HEAVY METALS Andrzej Deptuła, Jadwiga Chwastowska, Wiesława Łada, Tadeusz Olczak, Danuta Wawszczak, Elżbieta Sterlińska, Bożena Sartowska, Marcin Brykała, Kenneth C. Goretta1/ 1/ Argonne National Laboratory, USA

Hydroxyapatite (HA, Ca10(PO4)6(OH)2) is the ma- (1.7 M) with 85% H3PO4, followed by emulsifica- jor inorganic constituent of biological hard tissues tion in dehydrated 2-ethyl-1-hexanol. Drops of such as bones and teeth. Owing to its structure and emulsion were gelled by extraction of water with chemical composition this material also shows a this solvent. Details of the laboratory equipment high capacity for ion exchange. The properties of (50 g/h) and microspheres formation have been synthetic hydroxyapatites depend greatly on the described [12,16,17]. For synthesis of the powder method of their preparation. In most published for the monoliths, we modified the sol-gel process work, hydroxyapatites obtained by precipitation described in [15], using inexpensive CaO and H3PO4 methods have been studied. These hydroxyapatites as starting ingredients. In brief, 28.054 g of CaO have been examined as new inorganic cation ex- was dissolved in 150 mL of deionized water and changers [1-6] and anion exchangers [7,8]. Teams 44 g of ASC was dissolved in 500 mL of deionized from Argonne National Laboratory have studied water. The solutions were blended with 20 mL of engineering aspects of HA and use of various concentrated H3PO4 and 150 mL of deionized phosphates for containment of radioactive waste water. The pH was adjusted to 7 by addition of

[9-11]. NH4OH. Evaporation was followed by drying at The principal goal of this work was a study of room temperature (RT) and final heating of mono- adsorption of heavy metal ions on HA microspheres liths in air for 2 h soak at 900oC. The sedimenta- and monolithic ceramics to address the possibility tion rate of the spherical powders of HA was ap- of application to separation of various metal ions proximately 20 times greater than for irregularly from water and liquid wastes. Hydroxyapatite in the shaped powders of similar size distribution. The form of microspheres was prepared by a proprietary resulting spherical powders and monoliths are sol-gel method [12,13]. For fabrication of HA mono- shown in Fig.1. liths, we applied a second proprietary method. The On the basis of published information [16], we synthesis processes consisted of preparation of sols estimate the cost of producing HA microspheres with the use of a very strong complexing agent – by our method for a projected scale of 1 kg h–1 to ascorbic acid (ASC) [14,15]. be approximately 170 USD/kg. This price is com- Synthesis parable to those for irregularly shaped commer- Starting sols were prepared by ultrasonic mix- cial HA powders (Sigma Chemical Company (art. ing of concentrated solutions of calcium acetate C 4507) = 180 USD/kg; Merck (index 11.1701) = 148 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS

A B

------3cm ------

Fig.1. Sol-gel-derived HA produced in the forms of microspheres (A) and fired monolith (B).

150 USD/kg). Merck also offers microspheres (di- μ It may be concluded that a greater number of ameter 75-100 m) at approximately 1700 USD/kg. Ca cations than P anions release into solution when For column-based sorption experiments, powder pH decreases, which results in a decrease in the fractions of approximately 200 mesh were separated Ca/P mole ratio in the solid phase. These results by sedimentation. The concentrations of stock sol- –1 correspond with measurements of the solubility of utions of metals were 1 mg cm . The solutions were HA reported elsewhere [5,18]. prepared by dissolving metallic compounds in 1 M Batch sorption experiments HCl. A test water solution of the following com- The influence of pH on the sorption of the se- position [mg dm–3] was used: Na+ – 15; K+ – 4; Mg2+ 2+ – 2– 2+ lected elements, and the sorption kinetics for Cu(II) – 20; Ca – 55; Cl – 125; SO4 – 80; Zn – 0.2; 2+ 2+ 2+ 2+ 2+ 2+ and Ni(II), were studied by the batch method. A Cd , Pb , Ni , Co , Cu , and Mn – 0.1. solution for each element, containing 100 μg of the Solubility of hydroxyapatite element, was adjusted to a suitable pH by addition Solubility was estimated under conditions simi- of HCl or NaOH and transferred into a 50 cm3 lar to those of metal sorption: 0.2 g of HA was separatory funnel. The final volume of the solution shaken with 20 mL of solution of suitable pH for 3 o was 20 cm . Then 0.5 g of the HA was added and 30 min at 20 C. The solution was then filtered off. mechanically shaken for 30 min. The solution was Ca was measured by atomic absorption spectro- filtered then and the sorbent was washed twice with metry (AAS) and P by spectrophotometry, as 2 cm3 portions of a solution of the same pH. The phosphoromolybdate with reduction to blue. Mea- washings were combined with the filtrate. The con- surements of the Ca and P eluted by solutions of centration of each element studied was determined pH within the range of 0-9 revealed that the solu- by AAS with flame atomization or by spectrophoto- bility of HA increased with decreasing pH (Fig.2). metry. The amount of the element retained on the The amount of Ca eluted by 1 M HCl from 1 g of sorbent was calculated from the difference between HA was ca. 0.5 mg Ca, which corresponds to 12 the amounts in the original solution and in the fil- mmole per one mole HA. The solubility decreased trate. with increasing pH, e.g. from 2.7 to 0.8 mmole Ca For kinetic studies, similar experiments were per one mole HA for pH=5-9. The concentration performed for two elements – Cu(II) and Ni(II) – of P in the solutions was much lower than that of at a suitable pH and a shaking time within a 5-30 Ca: the P eluted by 1 M HCl was equal to ca. 0.067 –1 min interval. The retention capacities for Cu(II) mg g HA (2.2 mmole per mole). and Pb(II) were also determined by the batch method. Detailed conditions of these experiments are shown in Table; amount of sorbent – 0.5 g,

Table. Estimations of retention capacity of elements on HA.

Fig.2. Solubility (as concentration, c) of HA at various pH levels. NUCLEAR TECHNOLOGIES AND METHODS 149 volume of liquid phase – 20 cm3, original concen- then washed with 10 cm3 of solution of the same tration of metal – 0.5 mg cm–3. pH. The washings were combined with the efflu- Column sorption experiments ent. The element studied was determined in the A glass column, 4 mm inner diameter, was filled combined solution. with 0.5 or 1 g HA and conditioned with a solution The test water samples, 100 or 200 cm3 each, of a suitable pH. A sample containing 100 μg of were adjusted to pH=5. The solution was then the element studied, adjusted to a suitable acidity, passed at the flow rate of 0.5 cm3 min–1 through was passed through the column under pressure at the column filled with 1.0 g of HA (previously a flow rate of 0.3-2.2 cm3 min–1. The column was washed with water, pH=5). The efficiency of sorp-

Fig.3. Retention of elements in solutions of various pH (pH measured before sorption); monolithic HA was used in only three sets of experiments (top three plots). 150 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS tion was checked by determining the metal con- posed as a mechanism for ion removal; ion exchange centration in the elutant, with the use of the AAS was not observed, but it could not be completely method with flame atomization. ruled out. The kinetic sorption was rapid: equilibrium was The amount of Ca2+ released during the sorp- attained within a few minutes. The effect of shak- tion can be used as an indicator of either ion ex- ing time was established for Cu(II) and Ni(II). change or ion adsorption. If ion exchange takes Obtained data indicated that the equilibrium of place, the molar ratio between the divalent metal sorption process is attained in 5 min. This rapid cation retained in the solid phase and Ca released equilibration is in contrast to the previously reported into the solution must be close to one. If this ratio work with HA, for which the times for attaining is less than one, then some adsorption must have the equilibrium were much longer (1-48 h) [4,5] and taken place. even 20 days [3]. In the present work, for both Ca/Cu and Ca/Ni, The main results of our experiments are shown the molar ratio was equal to 0.3. These results sug- in Fig.3, as the dependence of sorption upon the gest that for the HA materials studied the predomi- pH of the original solution. The pH of the solution nant process in the sorption of metal cations was after sorption increased, probably owing to a par- surface adsorption, possibly accompanied by ion tial dissolution of HA. The retention of most ele- exchange. ments studied was approximately 94-100%, in the Synthetic HA synthesized by sol-gel methods – most suitable acidity ranges. Only the MnO4 ions and produced in the form of microspheres or ir- exhibited low retention; the maximum was 47% in regularly shaped powders that were processed into a 1 M H2SO4 solution. The sorption of Cr(VI), monoliths offered the possibility for separation of which was present in solution as anions, and that various metal cations and anions. In contrast to HAs of Sb(V), As(V), and Mo(VI), which have ampho- previously reported upon, the sorption kinetics was teric character with a predominance of acidic prop- fast; equilibrium of sorption was attained within a erties, probably followed anion exchange between few minutes. the hydroxyl ions of the lattice and the metal an- The cost to produce these materials in irregu- ions in the solution. larly shaped powders (monoliths) was estimated to The optimum conditions for the column probe more than 10 times lower than spherical powders cess were established for Cu(II). The influences and HA powders now offered commercially. of flow rate and sample volume on the sorption The mechanism of cation sorption on the HA efficiency were determined. The process of sorp- was determined to be primarily ion adsorption, tion was carried out under pressure in the glass possibly accompanied by ion exchange. The HA column filled with 0.5-1 g of HA. It was found that studied is a suitable material for the separation of flow rates to 2.5 mL min–1 and sample volumes to the group of metals studied from natural waters. 200 mL did not deteriorate the efficiency of Cu However, retention capacity was not high (3 mg sorption. of Cu and 10 mg of Pb per 1 g of HA), which would The sorption responses of the group of diva- be a disadvantage for possible applications of the lent metal ions (Cu, Cd, Pb, Ni, Co, and Mn) from HA as, for example, a filter material to sewage treat- the artificially prepared test water were also studied ment. The retention capacity for U(VI) of mono- by a dynamic method. Under the conditions estab- lithic HA was much better for spherical HA, ap- lished (pH – 5, flow rate – 0.5 cm3 min–1, sample proximately 3 times higher. We recommend that volume – 100 cm3, 1 g of HA), all of the metals the monolithic form HA should be examined for studied were quantitatively adsorbed. immobilization of U from nuclear wastes. Retention capacity of hydroxyapatite The conditions and the results of determina- References tion of the retention capacity for Cu(II), Pb(II), and U(VI) are show in Table. It can be concluded [1]. Suzuki T., Hatsushika T., Hayakawa Y.: J. Chem. that the capacities of HA materials that were Soc., Faraday Trans., 77, 1059 (1981). studied were rather low, equal to 3 mg of Cu2+, 10 [2]. Suzuki T., Hatsushika T., Miyake M.: J. Chem. Soc., mg of Pb2+, and 12 mg of U(VI) per 1 g of HA. Faraday Trans., 78, 3605 (1982). [3]. Suzuki T., Ishigaki K., Miyake M.: J. Chem. Soc., The retention capacity of the monolithic HA was Faraday Trans., 80, 3157 (1984). significantly higher: for U(VI) it was approximately [4]. Reichert J., Binner J.G.P.: J. Mater. Sci., 31, 1231 three times higher than the values that were ob- (1996). tained for spherical HA. [5]. Jeanjean J., Fedoroff M., Faverjon F., Vincent U., Discussion – mechanism of sorption Corset J.: J. Mater. Sci., 31, 6156 (1996). The sorption of metal cations can be achieved [6]. Jeanjean J., Vincent U., Fedoroff M.: J. Solid State mainly in two ways: ion exchange and ion adsorp- Chem., 108, 68 (1994). tion. The ion exchange mechanism is generally [7]. Wright G.: Ann. Chim. Fr., 5, 39 (1970). believed to take place in the case of sorption of [8]. Young R.A.: In: Proceedings of the 2nd International heavy metals on HAs [2,3,5]. Moreover, Xu et al. Congress on Phosphorus Compounds (IMPHOS). Paris 1980, p. 73. [19] proposed that the most important sorption [9]. Singh D.,. Wagh A.S, Cunnane J., Mayberry J.: J. mechanism may be surface complexation and co- Environ. Sci. Health A, 32, 527 (1997). precipitation, possibly accompanied by ion exchange [10]. Singh D., de la Cinta Lorenzo-Martin M., Routbort and solid-state diffusion. Furthermore, in the work J.L, Gutiérrez-Mora F., Case E.D.: Int. J. Appl. by Reichert and Binner [4], ion adsorption was pro- Ceram. Technol., 2, 247 (2005). NUCLEAR TECHNOLOGIES AND METHODS 151

[11]. Goretta K.C., Singh D., Tlustochowicz M., Cuber preparing of high temperature superconductors. Polish M.M., Burdt M.L., Jeong S.Y., Smith T.L.,. Wagh A.S., Patent No. 172618 (1997). Routbort J.L.: Mater. Res. Soc. Symp. Proc., 556, 1253 [16]. Deptuła A, Łada W., Olczak T., Sartowska B., (1999). LeGeros R.Z., LeGeros J.P.: Complex sol-gel process [12]. Deptuła A., Łada W., Olczak T., Borello A., Alvani (CSGP) preparation of calcium phosphate bioma- C., Di Bartolomeo A.: J. Non-Cryst. Solids, 147&148, terials (powders, monoliths, fibres). In: Bioceramics 537 (1992). 11. Eds. R.Z. LeGeros, J.P. LeGeros. World Scientific, [13]. Alvani C., Borello A., Deptula A., Lorenzini L., Orru’ Singapore 1998, p. 743. L.: Method for preparing of irregularly shaped and [17]. Deptula A., Chmielewski A.G.,. Wood T.E.: Sol-gel spherical powders of calcium phosphates, especially ceramic beads and bubbles – a historical perspective, Ca-hydroxyapatite. Italian Patent 01245400 (1994). modern fabrication and cost analysis. In: 9th CIMTEC [14]. Deptuła A, Łada W., Olczak T., LeGeros R.Z., Proceedings. Part D. Ed. P. Vincenzini. Techna, Faenza LeGeros J.P.: Method for preparing of calcium phos- 1999, p. 771. phates layers, especially hydroxyapatites. Polish Patent [18]. Verbeek R.M.H., Steyaer H., Thun H.P., Verbeek F.: No. 180602 (2000). J. Chem. Soc., Faraday Trans., 76, 209 (1980). [15]. Deptuła A., Łada W., Olczak T., Lanagan M.T., [19]. Xu Y., Schwartz F., Traina S.J.: Environ. Sci. Technol., Dorris S.E., Goretta K.C., Poeppel R.B.: Method for 28, 1472 (1994).

PHYSICAL AND CHEMICAL PROPERTIES OF YTTERBIUM

DOPED KY(WO4)2 NANOCRYSTALS Andrzej Deptuła, Mieczysław T. Borowiec1/, Vladimir P. Dyakonov1/, Wiesława Łada, Tadeusz Olczak, Danuta Wawszczak, Pavlo Aleshkevych1/, Wiktor Domuchowski1/, Tetyana Zayarnyuk1/, Marek Barański1/, Henryk Szymczak1/, Marcin Brykała 1/ Institute of Physics, Polish Academy of Sciences, Warszawa, Poland

Nanocrystalline materials can offer several alter- drying takes place under vacuum conditions. The natives to the classic bulk laser crystals. Sol-gel drawback of the prolonged drying time is related methods are used for producing homogeneous to the risk that the SI process might disappear. As samples at low temperatures. can be seen in the upper part of Fig.1, sample The mechanism of selfignition B6Pw-1 extracted from the running furnace at Sol-gel methods are used for producing homo- 230oC is black in colour. Further heating to 300oC geneous samples at low temperatures. Novel syn- produced a white powder with only small gray in- thesis of carbon-free nanocomposites of KYW and clusions, indicating that SI has occurred. After a KYW:Yb (1 mol%) was elaborated by introduc- final treatment at 550oC, sample B6Pw-2 is snow- ing a selfignition (SI) step. The SI mechanism is -white. In contrast, sample B6Pw-4 heated slowly very complex and strongly related to the drying and (lower part of Fig.1) does not exhibit SI and, under heating conditions. Obviously the SI step can be the same firing conditions, became deep gray in- easily obtained without a drying step. However, a dicating high carbon content. controlled drying step is necessary in order to avoid Final thermal treatment parameters have been the foaming effect which causes a 10-20 fold in- selected on the basis of differential thermal analy-

Fig.1. Samples of KY(WO4)2 gels is various stages of the thermal treatment. Fig.2. The representative TG (thermogravimetry) and DTA crease of the powder volume. This effect can be traces of the gel samples B27 (650oC, 5 h, 2oC/min, 3+ o o suppressed if the drying time is increased and the SI) and KY(WO4)2+Yb , 650 C, 5 h, 2 C/min, SI). 152 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS sis – DTA (Fig.2). As can be seen (line a) at 230oC, resonance lines, meaning the absence of paramag- the samples extracted from the running furnace netic centra in this sample (very high “spectral” are black. But farther heating results in selfignition. purity). On the other hand, the spectrum of the The sample taken out immediately after SI is white, B8Yb sample exposes wide resonance absorption. only with small gray inclusions. However, after This absorption is a result of the superposition of final treatment the sample is snow-white. In con- the single resonance lines of the Yb ions averaging trast, a sample heated slowly (line b) does not ex- on angles (Fig.4). hibit SI and, after the same firing conditions is IR spectra of KY(WO4)2 nanocomposites deeply gray, indicating a high carbon content. The infrared (IR) spectra of the synthesized XRD and ESR investigations of nanocrystals samples were obtained from a KBr pellet using a The expected monoclinic phase C2/c of the KYW nanocomposites was confirmed using X-ray

Fig.5. The IR spectra of B6Pw-2 sample (KY(WO4)2, SI – 550oC, 10 h).

Fig.3. X-ray spectrum for samples B27. BRUKER-EQUINOX 55 spectrometer. For semi- -quantitative evaluation of the carbonate content diffraction (XRD) technique (Fig.3). Unit cell in the synthesized materials it was necessary to use parameters and size of grain L for various samples admixtures of Na2CO3 powder. Table. Lattice parameters of decarbonized nanocomposites.

are presented in Table. The electron spin resonance In the gels dried at 230oC (B6Pw-1 and B6Pw-3), (ESR) spectrum of the B6Pw-2 sample shows no only a very weak and broad -Me-(=)O band was observed in the range 600-1000 cm–1. A very strong band near 1400 cm–1 (assigned to σOH) indicates the presence of (Me)-OH groups. These, together with σ –1 ν molecular H2O bonds ( , 1600 cm ; , 2900-3600 cm–1) form a gel network (hydrogen bonds and -O- bridging bonds). Nitrate and carbonate bands were not observed. The absence of bands characteristic of organic substances (e.g. C-H bands at 2800-3000 cm–1 related to ascorbic acid, ASC, and products of its decomposition), indicated that the ASC decomposition at this temperature is complete. This is a very important result if compared to other sys-

tems (e.g. LiNixCo1-xO2), where carbonates remained after ASC decomposition and strongly hydrated the final compounds. The lack of organic compounds (no –C-H bands) in the KYW and KYW:Yb Fig.4. The EPR spectra for samples B6Pw-2 (KY(WO4)2, o samples clearly indicates that the morphology of SI – 550 C, 10 h) and B8Yb (KY(WO4)2+1%mol Yb, SI – 550oC, 10 h). the dried gels is responsible for the occurrence of NUCLEAR TECHNOLOGIES AND METHODS 153 the SI process. From the IR spectra (Fig.5), it tals. The IR spectra of synthesized samples were seems that high-purity double tungstate structures obtained. can be easily obtained by introducing an SI step. This work was supported by the Eueopean Union The best example is sample B6Pw-2. (project DT-CRYS, NMP3-CT-2003-505580) and

The good quality nanocomposites of KY(WO4)2 the Polish State Committee of Scientific Research and KY(WO4)2+1%mol Yb have been synthesized. (KBN) (decision of project No. 72/E-67/SPB/6 Electron spin resonance studies in the X band have PR/DIE 430/2004-2006). been performed on KYW and KYW:Yb nanocrys-

SAXS STUDY OF XERO- AND AERO-GELS FORMED FROM MONOSACCHARIDE GELATORS Helena Grigoriew, Dagmara K. Chmielewska The processes of gel drying produce xero- or aero- work does not collapse and the aero-gel is highly -gels, depending on the method used. The method porous. Both processes can be complex and many- of xero-gel production is lyophilization or frozen- -staged [1]. -drying, i.e. evaporation of the solvent at low press- The weak, physical gels, as it is known, can dis- ure, from the frozen gelator skeleton. If there is no integrate upon touching. So, the process of drying collapse, the gelator structure, with an enormous can be expected as having a more essential influ- surface area and a very small pore size, is main- ence on their structure. tained. But such drying process is accompanied The main goal of this work was to check, using with unhindered shrinkage that can lead to struc- the small angle X-ray scattering (SAXS) method, tural collapse of the gelator network structure, re- the influence of drying on monosaccharide gel sulting in formation great, compact, surface-type structure and to consider the rightness of applica- clusters. The aero-gel is produced by careful drying tion of microscopic results to the description of a wet gel in various environments, often in super- wet monosaccharide gels structure. -critical conditions, and/or with solvent exchange. The gel, formed from a methyl-4,6-O-benzy- The gel does not shrink, so the fragile gelator net- lidene-α-D-glucopyranoside gelator with diphenyl

Fig.1. Fractal curves for weaker apolar gels: A – wet, B – xero, C – aero. The straight-line parts of the curves are marked by lines with their slopes. 154 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS ether as a solvent, was prepared [2]. The gelator is and, after normalization, to subtraction of the an example of one of the smallest monosaccharide background which was the USAXS signal due to molecule, which is apolar as well as the solvent is. the solvent in the capillary. To obtain a wide range So, very weak mutual interactions in the gel struc- of scattering angles (USAXS-SAXS), each sample ture can be expected. The next gel was built of me- was measured at two different sample-detector dis- thyl-4,6-O-(p-nitrobenzelidene)-α-D-glucopyrano- tances (4 and 12 m), and both measurements were side gelator with water as a solvent. Both materials joined, using OTOKO program, to get one curve are polar and the gelator molecule size is not very over the whole range. small among monosaccharides. This gel structure For weak glucose gel, G, the first slope of log-log is expected to be stronger than the first one. Both curve (Fig.1A), of dm=1.6 is generated by loose, gelators were prepared by us according to [2,3]. The mass fractal built according to DLCA (diffraction gels were prepared in the same way, as used in our limited cluster aggregation) mechanism. The sur- earlier works [4,5]: a mixture composed of a gelator face fractal slope of ds=2.9, (ds=6 – slope) means and a solvent was heated in a closed, capped tube very uneven and developed surface. From the until the gelator dissolved. The gelator concen- fractal curve, also two sizes, typical of fractal struc- tration was in the range 1-1.5% [g/mL]. Aero-gels ture can be evaluated: at Guinier crossover – radius were produced by leaving the obtained gels in open of gyration of fractal aggregate, Rg=109 nm and vessels till they become dry. Xero-gels were pro- at Porod crossover – size of primary particle, a=10 duced by frozen-drying of the gels in a Labconco nm. lyph.lock 1l apparatus at about -50oC and 10 mm The essential change of fractal curve for xero- Hg. -gel (Fig.1B) seems to be caused by drying-induced The wet gel samples for SAXS measurements stress that results in collapse and formation of were prepared by putting them in thin-walled cap- large-scale morphological features. Their size is too illaries ( Hilgenberg, 2 mm diameter, 0.01 mm wall large to be visible by X-rays, and small-s scatter- ≈ thickness), then sealed. ing is related to surface fractal with dimension ds 2, The measurements were carried out at the characteristic of smooth, sharp interface. After this ULTRA-SAXS BW-4 wiggler beamline, Hasy- surface fractal range, for bigger angles, the cross- lab-DESY synchrotron, BW4 beamline. The col- over is showed, at 17 nm, and then mass fractal lected ultra small angle X-ray scattering (USAXS) range, of dm=2.45. The same run of aero-gel fractal measurements were subjected to pie integration, curve (Fig.1C) is observed, also with crossover at

Fig.2. Fractal curves for stronger polar gels: A – wet, B – xero, C – aero. The straight-line parts of the curves are marked by lines with their slopes. NUCLEAR TECHNOLOGIES AND METHODS 155 17 nm. Only the followed mass range slope is Visible three ranges of the fractal curve (Fig.2C) smaller and is equal to dm=1.8, i.e. there is more are related to a small primary particle, smaller than loose structure. in the wet P gel (a=63 nm in comparison with So, in our case, the collapse takes place not only a=160 nm), of very uneven surface (in compari- at the xero-gel formation, where it is due to a strong son with very smooth one). The particles form shrinkage during emptying fractal structure from loose fractal generated by DLCA mechanism, and maintaining it solvent molecules, but also at aero- not dense by RLCA mechanism. Such structure is -gel formation, where the evaporated solvent mol- not a modification of the previous wet gel struc- ecules are replaced by their vapor and finally by ture and must be formed during drying from the air, so stresses should be much smaller. These ob- beginning. This behavior could be explained by the servation confirmed a big weakness of monosac- Ostwald ripening [1] including dissolutions and charide gel structure. precipitations, and the resulting structure is formed Whereas, for a stronger para-glucose gel with by these competing interactions. water, P, the fractal curve (Fig.2A) begins, the part All dried gels, xero-gels and aero-gels, obtained generated by mass fractal of dm=2.9 is much denser by us from the monosaccharide gels, are of essen- than for G gel, built according to another, RLCA tially changeable structures in comparison with the (reaction limited cluster aggregation) mechanism. related wet gels. The Porod bend at 160 nm and then surface fractal References of ds=2.05 means that the primary particle is much greater, than for G gel, and of smooth surface. This [1]. Brinker C.J., Scherer G.W.: Sol-gel science: The can be expected, because the polarity of both gel physics and chemistry of sol-gel processing. Academic constituents can activate enthalpic forces that favor Press, Boston 1990. a large scale phase separation [1]. [2]. Sakurai K., Jeong Y., Koumoto K., Friggeri A., The log-log curve of related P xero-gel (Fig.2B) Okamoto S., Inoue K., Shinkai S.: Langmuir, 19, 8211 is close to the curve, obtained for G xero-gel with (2003). [3]. Gronwald O., Sakurai K., Luboradzki R., Kimura T., long, straight-line segment of surface fractal with Shinkai S.: Carboch. Res., 331, 307 (2001). close interface. This run of the curve suggest a simi- [4]. Grigoriew H., Luboradzki R., Cunis S.: Langmuir, 20, lar collapse as caused by G-xero-gel formation. 7374 (2004). But for the P aero-gel there is no similarity with [5]. Grigoriew H., Luboradzki R., Gronkowski J.: J. Non- the G aero-gel structure. No collapse is observed. -Cryst. Solids, 352, 3052 (2006). 156 NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS

NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS

MEASUREMENT OF 222Rn AND 220Rn WITH SINGLE SCINTILLATION CELL Bronisław Machaj, Piotr Urbański, Jakub Bartak Quite often there exists a need for measurement of radon 222Rn and thoron 220Rn concentration in air. Such continuous measurements can be done with two scintillation cells (Lucas cells) [1] connected in series and air flow forced through the cells. Be- tween the first and the second cell a delay of air flow is so placed that thoron with its 55 s half-life disintegrates. The first cell detects radon and thoron, the second radon only. From these two readings, concentration of radon and thoron can be determined. Another method of measurement of radon and thoron is spectrometry of alpha radiation of decay products [2]. The alpha radiation of 218Po (6.0 MeV) is used for measurement of 222Rn, and 216Po (6.78 MeV) alpha radiation for measurement of 220Rn. The aim of the presented investigations was the Fig.2. Simulated alpha activity deposited on the walls of development of a gauge model for measurement Lucas cell when 1 dis/min of 220Rn is flowing through of radon and thoron with a single Lucas cell. A the cell during 10 min. Decay series of 220Rn→ gauge for measurement of radon concentration in 216Po→212Pb→212Bi was simulated. Alpha activity of air, MR-1, employing the Lucas cell as alpha ra- 220Rn+216Po+212Bi(212Po) against time is shown in diation detector was developed earlier. Additional this Fig. function for measuring thoron concentration in air should widen its applications. the air flow is switched off. Count rate is measured Thoron laden and radon laden air are forced at two time intervals from 1 to 10 min and from 20 to flow at a rate of 1 dm3/min through the Lucas to 30 min. The time intervals are a compromise cell for a period of 10 min, simultaneously count between the length of measuring cycle and the rate from the Lucas cell is measured. After 10 min, random errors that are made smaller with increasing counting time. The relation between the count

Fig.1. Simulated alpha activity deposited on the walls of Lucas cell when 1 dis/min of radon is flowing through Fig.3. Measured count rate against time (broken line) the cell during 10 min. The curve in the period 1-10 and simulated count rate corresponding to real min is disturbed due to air flow (lower deposition of (reference) radon concentration – 53.09 dis/min 218 222 →218 → Po inside the cell). Decay series of Rn Po (continuous line). n1=sum(r(1:10))=683 counts, 214 →214 214 Pb Bi ( Po) was simulated. Alpha activity of n2=sum(r(20:20))=1287 counts, from y=m\n: 222Rn+218Po+214Po against time is shown in this Fig. 222Rn=56.0 dis/min, 220Rn=-1.85 dis/min. NUCLEAR TECHNOLOGIES AND METHODS 157 y = m·ε\n = |A| [dis/min] (3) |B|

where n =|n1| |n2| Employing Cramer rules, concentration of radon and thoron can be given in a more convenient form for microprocessor processing: A = (-0.000049·n + 0.0435·n )/ε [dis/min] 1 2 (4) B = (0.0548·n1 – 0.0305·n2)/e

Fig.4. Measuring arrangement for thoron: AP – air pump 1 dm3/min, TS – thoron source, AF – air filter, LC – Lucas cell, MR-1 – radon radiometer, pgc – black rubber pipe. numbers n1 and n2 at the two time intervals and the alpha activity deposited inside on the walls of the cell are given by: ε n1=(m11·A+m12·B)· ε (1) n2=(m21·A+m22·B)· where: A – radon alpha activity, B – thoron alpha activity, ε – deposition and detection efficiency.

The coefficients m11...m22 are determined from the simulated activity of alpha radiation [3-5] (Figs.1 and 2). The coefficients m11, m12 are equal to the total (sum) alpha activity at 1-10 min interval from radon and thoron, respectively, and m , m to the Fig.5. Measured count rate against time (broken line) and 21 22 simulated alpha count rate corresponding to refer- total alpha activity at an interval of 20-30 min from ence thoron concentration – 1323 dis/min (continu- radon and thoron. After computation of the coef- ous line). n1=25635 counts, n2=48.6 counts; from ficients, the m matrix of coefficients is equal to: y=m\n: 222Rn=0.8 dis/min, 220Rn=1404 dis/min. m = |12.80 18.25| |22.98 0.0218| Random error due to fluctuations of count number and equation (1) can be rewritten as: calculated from the relation for propagation of ε n1 = (12.80·A + 18.25·B)· errors: ε (2) n2 = (22.98·A + 0.0218·B)· 22222∂∂yy Concentration of radon A and thoron B computed s(y)=+ ( ) s(n)12 ( ) s(n) (5) from equations (2) is given by matlab function: ∂∂nn12

Table. Results of radon and thoron measurement.

The mean ratio of columns 4/6, for measurements mr62...mr65, is 1.003, which means that the computed concentration y=m\n of radon is correct. The ratio of columns 5/7, for measured mr53, mr147, mr150 is 1.04, which means that the computed concentration y=m\n of thoron is too high by 4%. This error can be corrected by dividing the thoron concentration from y=m\n by 1.04. Negative values of “cross talk” from radon concentration into thoron concentration for measurements of mr62...mr65 can be neglected (no negative concentration exists). “Cross talk” from the thoron concentration into radon concentration is <1.5% of the indicated radon concentration. 158 NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS is equal to 0.209 dis/min for 222Rn and 0.234 dis/min is equal to 1323 dis/min. Computed thoron con- for 220Rn at ε=1 and radon and thoron concentra- centration from y=m\n is equal to 1404 dis/min. tion equal to 1 dis/min. Results of a series of measurements are given in Radon laden air was forced to flow 1 dm3/min, Table. within 10 min, across an air filter through the Lucas Measurements and computations carried out cell φ54x74 mm (0.17 dm3) that was installed in an confirm that radon and thoron concentration in MR-1 radon monitor and was placed inside a radon air can be measured with a single Lucas cell. Al- chamber with known radon concentration. Simul- though the investigations were done on the as- taneously, pulse count rate of the Lucas cell was sumption of detection efficiency ε=1, however, the measured in the time period up to 220 min. The method is valid also for ε different from 1. measured count rate (broken curve) is shown in Fig.3. The simulated count rate (smooth curve) References corresponds to the reference radon concentration [1]. Coleman R.L.: A method for concurrent and continu- which is equal to 53.09 dis/min at ε=1. Computed ous measurement of Rn-222 and Rn-220 using scintil- radon concentration from y=m\n is 56.0 dis/min. lation cell. Oak Ridge National Laboratory Report Similarly, thoron was forced to flow through the No. ORNL/TM-2002/37. Lucas cell (Fig.4), and count rate was measured. [2]. Rad7. Electronic radon detector. Durridge Company. Thoron source was ventilated until radiation equi- www.durridge.com. [3]. Machaj B., Bartak J.: Nukleonika, 43, 2, 175-184 librium was reached and the outlet of thoron source (1996). was connected to an air filter at the moment of start- [4]. Machaj B., Urbanski P.: Nukleonika, 47, 1, 39-42 232 ing count rate measurement. The U source is an (2002). 228 old source and is in radiation equilibrium with Th [5]. Machaj B., Urbanski P.: Nukleonika, 49, 3, 123-129 and 224Ra. (2004). The measured and simulated count of thoron is given in Fig.5. The reference concentration at ε=1

DOSIMETRIC GATE DSP-15 Edward Świstowski, Jan Mirowicz, Piotr Urbański, Jan Pieńkos

A common procedure of checking if personnel ware allows for programming parameters of the involved in handling open radioisotopes is not gate such as permissible contamination level, time contaminated is installment of a dosimetric gate of measurement, date and time setting etc. The [1-3] and obligatory checkup of all the employees. gauge program allows also for quick checkup of A new dosimetric gate DSP-15 was developed in proper operation of the gate. the Department of Radioisotope Instruments and The principle of operation of the gate is illus- Methods, Institute of Nuclear Chemistry and Tech- trated in a block diagram in Fig.1. Fifteen propor- nology. The gate is designed for fast radioactive contamination measurement of the personnel leaving the area under dosimetric control where open radioisotope sources are handled. The contamination is measured by proportional counters for beta and gamma radiation located in the gate. Addition- ally, the gate is equipped with a local monitor dis- playing the state of the gate and measuring results of the last measurement. In case contamination of a person or a passage of an unauthorized person through the gate takes place, this incident is detected by an acoustic alarm. The gate is also equipped with relays (contacts closed or open) that can, e.g. block the exit of a contaminated person. Automatic registration of staff is accomplished by means of a proximity card presented against a card reader of the gate. The gate is prepared for operation in the monitoring system. Each measur- Fig.1. Block diagram of DSP-15: S1-S15 – proportional ing result is sent immediately to an external com- counter LND 49741, W1-W15 – charge preamplifier, puter of the monitoring network, and is stored is E1-E15 – pulse discriminator, PLI1-PLI15 – pro- the gate memory. Three modes of operation can be grammable pulse counter, CZK – card reader, RS232 – serial port RS232, RS485 – serial port RS485, USB programmed: a) obligatory contamination mea- – universal series bus, GL – loudspeaker, M – gate surements of persons entering and leaving the area monitor, uP – microprocessor system, IR bra – IR under control, b) no obligatory contamination mea- control of a person presence in the gate, IR in – IR surement of persons entering and leaving the area control at the input to the gate, IR out – IR control under control, c) obligatory contamination checkup at the exit from the gate, IR S1 – IR control of S1 of persons leaving the area under control. The soft- (left hand), IR S4 – IR control of S4 (right leg). NUCLEAR TECHNOLOGIES AND METHODS 159 tional counters for measurement of beta and gamma radiation are used in the gate. Four counters S1...S4 serve for measurement of contamination of legs and hands. Five counters S6...S10 located at the front column are used for measurement of contamination of front clothes of a person, and another five counters S11...S15 placed at the rear column are used for measurement of back clothes of a person. Each measuring channel contains charge preamplifier, pulse discriminator and pulse counter under the control of microprocessor system. The gate card reader CZK serves for reading identification number of the person and for reading two special cards SETTINGS and DOSIMETRY. When SETTING card is read out a menu is displayed allowing for setting measuring parameters of the gate. Present- ing DOSIMETRY card against card reader mode of operation of the gate is selected and the gate is made ready for contamination measurements. Measurement of contamination starts when identification card of a person is presented against the card reader. Measuring results are stored in the memory of the gate, are displayed on the screen of a local monitor M, and are sent to an external Fig.2. A general view of the gate. computer through a serial port RS485. A universal series bus USB connects a laptop to the gate that The main parameters of the gate are following: enables to read out measuring results stored in the - contamination detected – beta and gamma radia- gate memory. tion; Number of registered pulses by the probes - radiation detector – LND 49741, proportional S1...S15, that are proportional to the contamina- counter, xenon filled, 3 mg/cm2 window, 115 cm2 tion, are compared with the permissible (pro- area; grammed) level of contamination. In case when - sensitivity for 60Co – 600 cps/mR/h; excessive contamination is detected, the counter - background measuring time – 1 s; that detected the contamination is shown, alarm - contamination measuring time – 1...9 s program- in sounded and the exit from the area under con- mable; trol is blocked. - memory capacity – 500 measurements stored in The gate is equipped with IR (infrared) controls memory. to check if a person the contamination of whom is to be measured is present inside the gate, and if his References legs and hands are in correct position. Addition- [1]. Sirius-4 serries. Hand and foot surface contamination ally there are two other IR controls at the entrance monitors. www.canberra.com/products/575.asp. and exit from the gate (entrance and exit from the [2]. Argos-2. Whole body beta or alpha + beta surface con- area under control). The gate is also equipped with tamination moniotor. Hand and foot surface contami- movement and dusk sensors for automatic switch- nation monitors. www.canberra.com/products/566.asp. ing on light. A general view of the gate is shown in [3]. Dosimetric stand SD-50B. http://www.zami.com.pl. Fig.2.

GAMMA THIN LAYER CHROMATOGRAPHY ANALYZER SC-05 Edward Świstowski, Bronisław Machaj, Ewa Kowalska, Jan Pieńkos, Ewa Gniazdowska

Thin layer chromatography (TLC) is a technique pounds and the result of analysis can be shown in very often used in chemistry for identifying com- the form of diagrams. pounds, determining their purity, and following the A gamma TLC analyzer, type SC-05, was de- progress of reactions. It is also a good method for veloped and was constructed in the Department optimization of the solvent system for a given sep- of Radioisotope Instruments and Methods, Institute aration problem [1]. TLC technique is faster and of Nuclear Chemistry and Technology (INCT). A simpler than column chromatography and requires general view of the analyzer is shown in Fig.1. It is samples of much lower volume. Analysis of com- a laboratory instrument, with small dimensions pounds that are labelled with isotopes emitting whose parameters allow for its wide application in gamma or beta radiation can be measured with chemical and pharmaceutical laboratories, employ- analyzers equipped with sensitive radiation detec- ing radioactive isotopes, and in nuclear medicine. tors [2]. Such analyzers enables fast and accurate The analyzer can analyze strips 20 cm long with an scanning of prepared strips with investigated com- isotope labelled compound deposited on the strip. 160 NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS Gamma isotopes: 125I, 131I, 111In, 188Re, 99mTc and others with radiation energy 15-510 keV can be analyzed. The radiation is collimated with a Pb slot collimator 2.5x25 mm, 20 mm thick. An NaI(Tl) φ25x25 mm scintillator is used as radiation detector. Linear stage with the strip analyzed is moved in relation to the detector in 1 mm steps by a step motor. Counting time of one step is programmed in the range: 0.5, 1, 3, 6 s. The measuring result of each step is displayed on the analyzer display, and is stored in the analyzer memory. The measuring

Fig.1. A general view of gamma TLC analyzer SC-05. results stored in the memory are sent through a serial port to an external computer. Up to 50 dia- Fig.2. TLC carried out to check the progress of a grams can be stored in the memory. Three fixed 99m 125 131 99m S3( TcO)SPh complex formation [S3=S(CH2CH2SH)2]: windows for I, I, Tc and one programmable A – TLC of pertechnetate obtained from a 99Mo/99mTc window in the range 15-510 keV are accessible for generator-Amersham (heptavalent technetium), B the user. The measuring results stored in the memory – TLC of 99mTcO-ethylene glycol complex (penta- can be called from the memory and can be reviewed valent technetium), C – TLC of intermediate com- on analyzer display in the form of a diagram together plex 99mTcO-thiophenol, D – TLC of mixed-ligand 99m with the date, time and parameters of the measure- complex S3( TcO)SPh. ment. A fragment of the diagram (peak) can be selected and the number of counts in the selected One of the SC-05 analyzers was installed in the fragment is automatically displayed. Department of Radiochemistry of the INCT where To ensure stable operation of measuring chan- it is used for routine investigations. Example chro- nel of the analyzer, automatic gain control circuit matograms achieved with the help of the analyzer is used. Light emitting diode (LED) is used as ref- are shown in Fig.2. erence signal. During gain control process, the amplitude of LED pulse is measured and the high References voltage of photomultiplier tube is changed until a [1]. http://www.raytest.de/radiochromatography/products/ correct pulse amplitude is achieved. Automatic Rita-Star. gain control is activated after mains voltage is [2]. http://www.chem.ucla.edu/~bacher/General/30BL/ switched on, and later before start of analysis of a tips/TLC1.html. new strip.

INVESTIGATION OF DUST POLLUTION IN ASSEMBLING HALL OF TV SETS Jan Pieńkos, Piotr Urbański

It is well known that airborne dust pollution has a lution was set, and dust concentration in the air is harmful influence on human being health. Because measured. The smaller is the diameter of the dust of that, a maximum permissible level of dust pol- particles, the more deeply the particles can pen- NUCLEAR TECHNOLOGIES AND METHODS 161 etrate into the lung. Average daily permissible level of measuring results to an external PC computer. of dust concentration in ambient air with particle Operation of the dust monitor was controlled by diameter <10 μm is set to 50 μg/m3. the stuff of the Institute of Nuclear Chemistry and Air dust pollution is important not only from Technology (INCT) and the measuring results were the point of view of human being protection. It is also available by the INCT, although the distance also important from the point of view of clean air of assembling hall from Warsaw was more than 200 km. Work in the assembling hall was carried out

Fig.1. Localization of dust monitor in the assembling hall. that is required in some industries. On request of Fig.2. Dust concentration inside assembling hall. a producer of TV set, measurements of dust concentration were measured inside assembling hall in two shifts from 6 to 22 h. Measuring results for to investigate what is the dust pollution and how it the first 4.5 days, illustrating how high was the dust varies. The AMIZ-2004G monitor for automatic concentration in μg/m3, and how the dust concen- measurement of airborne dust pollution of ambi- tration varied within these days are shown in Fig.2. ent air was used to investigate the dust concentra- Similar dust concentration and similar variations tion in the air. The dust monitor was located in the of dust concentration were observed in the remain- middle of the assembling hall between the trans- ing days of investigations. On analyzing the diagram porters moving the TV sets (Fig.1). The principle of dust concentration, the following observations of operation of the monitor employs attenuation can be made: of beta radiation from 147Pm by the dust deposited - Dust concentration during work hours is high, on an air filter to determine the mass of dust. Vol- single readings reaching up to 150 μg/m3, and ume of the air from which the dust is deposited on the average 80-100 μg/m3. At night, when there the filter is proportional to the time of deposition was no work activity the dust concentration was (the flow of air through the filter is kept constant). much lower and fell to less than 50 μg/m3, and Dust concentration is the ratio of the dust mass to on Sunday even to 30 μg/m3. the volume of air. The measurements were carried - It is up to the producer of TV sets to decide if out in the period of seven days. Total dust air inlet the recorded levels of dust concentration can be was installed in the dust monitor. Thus, all the dust accepted as sufficiently low, or appropriate steps particles without limitation of their diameter were should be undertaken to decrease the dust con- deposited on the air filter. The monitor was set to centration. continuous automatic mode of operation with 1 h - The dust monitor AMIZ-2004G proved to be dust deposition on the air filter. The measuring an appropriate instrument for checkup measure- results were stored in the monitor memory. The dust ments of dust concentration inside of some in- monitor was equipped with wireless transmission dustrial halls.

COMMERCIAL APPLICATION OF ELECTRON BEAM ACCELERATORS AT R&D AND SERVICE CENTER Andrzej G. Chmielewski, Wojciech Migdał, Zbigniew Zimek, Iwona Kałuska, Sylwester Bułka

Two pilot plant installations have been built at the type, 2 MeV and 20 kW beam power (supported Institute of Nuclear Chemistry and Technology by the International Atomic Energy Agency – (INCT) to carry out R&D studies, to evaluate tech- IAEA, 1988); nical and economical requirements for industrial - demonstration facility for flue gas treatment facilities and to provide radiation processing ser- with flow rate up to 20 000 Nm3/h, with two elec- vice on a semi-industrial scale: tron accelerators ELV 3A type 0.7 MeV and 50 - pilot plant installation for polymer modification, kW beam power each (supported by the IAEA), equipped with an electron accelerator ILU-6 located at the power station “Kawęczyn” (1991); 162 NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS and two industrial plants: Actually, permission by the Ministry of Health - radiation sterilization plant equipped with a in Poland was granted for irradiation of the fol- microwave linac ELEKTRONIKA 10/10 with lowing kind of products: potatoes, onions, garlic, electron energy of 10 MeV and an average beam mushrooms, spices and dried vegetables. power of 15 kW (1993); The role of the plant is to promote food irra- - food irradiation plant with two 10 MeV electron diation technology in Poland by: accelerators: PILOT with 1 kW and ELEKTRONI- - development of new radiation technologies for KA 10/10 with 10 kW of beam power (1992) [1]. the preservation and hygienization of food prod- The commercial irradiation plant was built to ucts; satisfy growing demands for irradiation service. A - development of radiation technologies for the facility equipped with the electron accelerator hygienization of natural components utilized in ELEKTRONIKA 10/10 was put into operation at the cosmetic industry; the INCT in 1993. The accelerator was manufac- - development of radiation technologies for the tured in NPO “Toriy” (Moscow, Russia). 10 MeV hygienization of natural product utilized in the electron energy and up to 15 kW average beam pharmaceutical industry; power is applied for radiation processing This ac- - development and standardization of control sys- celerator is based on the running wave accelerat- tem for electron beam processing of food and ing section and is placed vertically to avoid bend- other products; ing magnet and beam power losses related to its - organization of local (national) and/or interna- application and a high average power magnetron tional workshops and symposia devoted to tech- was used as a source of microwave energy. nical, technological and economical aspects of The microprocessor controlled roller and belt food irradiation. conveyor system is used to carry boxes with typical Figure 2 shows the block diagram of the accel- size 580x460x200 mm. The speed of the conveyor erator installation at the plant for food irradiation. section located at the irradiation chamber, where In both irradiation plants a computer system has a stainless steel belt was applied, can be varied con- been installed which assures delivery of the desired tinuously within the range 0.3-7 m/min. Additional dose of electrons 9.0-9.5 MeV by controlling accel- equipment for two-sided irradiation can be used erator parameters with the use of an analog-digital when necessary. The rubber belts are used for trans- steering system and collecting data under technol- porting boxes between basement and ground levels. ogical conditions. Basing on the dose measurements Continuous monitoring of electron beam parameters at the adjusted parameters and actual conveyor and speed of the conveyor were foreseen to fulfil speed, the system calculates the dose on-line that routine monitoring requirements. Upgraded accel- is stored at computer hard disc. erator control system for delivering required dose and data acquisition for sterilization process have been implemented. Figure 1 shows the block diagram of the accelerator installation with pointed out devices being under computer control. In Poland till the end of 50s of the XX century, the research activities in the field of food irradiation were rather of basic research type. Practical applications of food irradiation on a commercial scale started in plant in 1993. The plant was established in the scope of government programme and was equipped with two linear electron accelerators: PILOT (10 MeV, 1 kW) and ELEKTRONIKA (10 MeV, 10 kW) [2,3]. Fig.2. Block diagram of the accelerator installation at the plant for food irradiation. Electron Gun * The system enables simultaneous on-line con- Accelerating trol of irradiation parameters dedicated to food Section products in agreement with the EC Directives

Magnetron 1999/2/EC, 1999/3/EC and Decree of the Ministry of Health dated 15.01.2003 and to medical devices HV Pulse Power Supply RF Power Vacuum Generator Scanning in agreement with ISO 13485 and ISO 11137. Pump Coils * Dosimetric systems used in both plants are * Scanning traceable by the accreditated Laboratory for Mea- Horn surements of Technological Doses. EB Extraction* In conclusion, two plants (one for sterilization Control System Interfaces Motor Window Console & Steering and the second for food irradiation) equipped with Signal Processing Conveyor linear accelerators 10 MeV, 10 kW have been op- * Most important signal sources erated for more than ten years. Technical and for irradiation process status evaluation economical feasibility of the electron beam tech- Fig.1. Block diagram of the accelerator installation at the nology for these applications have been demon- plant for radiation sterilization. strated. NUCLEAR TECHNOLOGIES AND METHODS 163 Quality assurance and quality control proce- References dures following all ISO and EN standards are fully [1]. Zimek Z., Rzewuski H., Migdal W.: Nukleonika, 40, implemented. The accredited laboratory for tech- 3, 93-113 (1995). nological dosimetry, beside routine laboratories [2]. Migdal W., Walis L., Chmielewski A.G.: Radiat. Phys. led to the establishment of high level quality control Chem., 42, 1-3, 567-570 (1993). system. [3]. Migdal W., Maciszewski W., Gryzlow A.: Radiat. Phys. Well prepared and implemented technical, eco- Chem., 46, 4-6, 749-752 (1995). nomical and quality systems are inseparably conditions for the establishment of food irradiation and sterilization facilities.

ELECTRON GUN FOR 10 MeV, 10 kW ELECTRON ACCELERATOR Zygmunt Dźwigalski, Zbigniew Zimek

Main assembly of new electron accelerator which used as a source of electrons in this particular struc- is under construction at the Institute of Nuclear ture. The triode electron gun was designed and made Chemistry and Technology is standing wave accel- by the accelerator manufacturer “Toriy” company erating structure operated at a frequency of 2856 (Moscow, Russia). MHz. The accelerating structure was provided by Electron gun construction modification is necess- “Lepton JSCo” company (St. Petersburg, Russia) ary to meet the requirements for standing wave struc-

Table. Electron beam parameters.

under the technical cooperation project supported ture applied in a new accelerator. The following by the International Atomic Energy Agency. Elec- modifications were introduced in vacuum area of tron beam emitted from an electron gun is intro- the triode electron gun: duced to the first resonator area of the accelerat- - enlargement of the distance “L” between the ing structure. The electron beam parameters should cathode and the grid from 1 to 3.6 mm (Fig.1); be compatible with electrical specification of the - enlargement of the distance “A” between the structure (Table). Table contains the data related grid and the anode from 20 to 35 mm (Fig.1); to parameters of the electron beam which is introduced in the first resonator area of “Elektronika 10/10” accelerator. In that case the accelerating structure is designed for travelling wave operating mode at a frequency of 1863 MHz. The triode electron gun with a spherical impregnated cathode is

Fig.1. Electron gun – distances between electrodes. Fig.2. Electron gun – additional element. 164 NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS - additional element whose shape beam dimensions was incorporated (Fig.2). The modification should allow to obtain desirable shape of the electron beam shown in Fig.3. Shapes of the equipotential lines are congenial to real shapes of the lines in the electron beam area,

Fig.4. Electron gun – silicon rubber insulator and additional insulator. The electron gun main insulator, made from silicon rubber, operating in air, could be not sufficient in the new working environment at the highest electrical strength. Electrical strength of the insulator is too low, especially in long-term exploitation. Due to that, additional insulating part, made from acrylic glass or epoxy glass will be in- Fig.3. Electron gun – equipotential lines and electron tra- corporated (Fig.4). The glass ring will be connected jectories. constantly with the main insulator. Electrical strength of such a modified insulator will be much higher but the lines differ from the real ones and far from than 50 kV. the beam area. It is due to the accepted mathematical model. THE INCT PUBLICATIONS IN 2006 165

THE INCT PUBLICATIONS IN 2006

ARTICLES

1. Apel P.Yu., Blonskaya I.V., Dmitriev S.N., Orelovitch O.L., Sartowska B. Structure of polycarbonate track-etch membranes: origin of the “paradoxical” pore shape. Journal of Membrane Science, 282, 393-400 (2006). 2. Asmus K.-D., Hug G.L., Bobrowski K., Mulazzani G., Marciniak B. Transients in the oxidative and H-atom-induced degradation of 1,3,5-trithiane. Time-resolved studies in aqueous solution. Journal of Physical Chemistry A, 110, 9292-9300 (2006). 3. Bartłomiejczyk T., Iwaneńko T., Wojewódzka M., Woliński J., Zabielski R., Kruszewski M. Differential action of ghrelin and leptin, a human metabolism and energy regulators, on the lymphocyte susceptibility to oxidative stress. Journal of Physiology and Pharmacology, 57, Suppl. 2, 118 (2006). 4. Bartłomiejczyk T., Iwaneńko T., Wojewódzka M., Woliński J., Zabielski R., Kruszewski M. Ghrelin administration sensitizes blood mononuclear cells to oxidative stress. Journal of Physiology and Pharmacology, 57, Suppl. 2, 119 (2006). 5. Bartoś B., Bilewicz A. Effect of crown ethers on Sr2+, Ba2+, and Ra2+ uptake by tunnel-structure ion exchangers. Solvent Extraction and Ion Exchange, 24, 261-269 (2006). 6. Barysz M., Kędziera D., Leszczyński J., Bilewicz A. Structure and hydrolysis of the heavy alkaline earth cations: relativistic studies. International Journal of Quantum Chemistry, 106, 2422-2427 (2006). 7. Bilewicz A., Bartoś B., Misiak R., Petelenz B. Separation of 82Sr from rubidium target for preparation of 82Sr/82Rb generator. Journal of Radioanalytical and Nuclear Chemistry, 268, 3, 485-487 (2006). 8. Bojanowska-Czajka A., Drzewicz P., Kozyra Cz., Nałęcz-Jawecki G., Sawicki J., Szostek B., Trojanowicz M. Radiolytic degradation of herbicide 4-chloro-2-methyl phenoxyacetic acid (MCPA) by γ-radiation for environmental protection. Ecotoxicology and Environmental Safety, 65, 265-277 (2006). 9. Bojanowska-Czajka A., Drzewicz P., Nałęcz-Jawecki G., Sawicki J., Trojanowicz M. Zastosowanie promieniowania jonizującego do degradacji wybranych pestycydów w wodach i ściekach (Application of ionizing radiation to the decomposition of selected pesticides in waters and sewages). Postępy Techniki Jądrowej, 49, 1, 26-31 (2006). 10. Bonilla F.A, Skeldon P., Thompson G.E., Piekoszewski J., Chmielewski A.G., Sartowska B., Stanisławski J. Corrosion resistant Ti-Pd surface alloys produced by high intensity pulsed plasma beams. Part 2. Depo- sition by pulsed implantation doping mode with palladium implantation using a MEVVA source. Surface and Coatings Technology, 200, 4684-4692 (2006). 11. Bonilla F.A, Skeldon P., Thompson G.E., Piekoszewski J., Chmielewski A.G., Sartowska B., Stanisławski J., Bailey P., Noakes T.C.Q. Corrosion resistant Ti-Pd surface alloys produced by high intensity pulsed plasma beams. Part 1. Depo- sition by pulsed erosion and vacuum evaporation/pulsed implantation doping modes. Surface and Coatings Technology, 200, 4674-4683 (2006). 166 THE INCT PUBLICATIONS IN 2006

12. Brzóska K., Iwaneńko T., Wojewódzka M., Woliński J., Kruszewski M. Differential action of human metabolism regulators on the lymphocyte susceptibility to oxidative stress. Acta Biochimica Polonica, 53, Suppl. 1, 172 (2006). 13. Brzóska K., Kruszewski M., Szumiel I. Nonhomologous end-joining deficiency of L5178Y-S cells is not associated with mutation in the ABCDE autophosphorylation cluster. Acta Biochimica Polonica, 53, 1, 233-236 (2006). 14. Brzóska K., Męczyńska S., Kruszewski M. Iron-sulfur clusters proteins: electron transfer and beyond. Acta Biochimica Polonica, 53, 4, 685-691 (2006). 15. Brzóska K., Męczyńska S., Kruszewski M. Non-haem iron proteins: new functions of old pals. Acta Biochimica Polonica, 53, Suppl. 1, 112 (2006). 16. Chmielewska D.K., Łukasiewicz A., Michalik J., Sartowska B. Silica materials with biocidal activity. Nukleonika, 51, Suppl. 1, s69-s72 (2006). 17. Chmielewski A.G. Worldwide developments in the field of radiation processing of materials in the down of 21st century. Nukleonika, 51, Suppl. 1, s3-s9 (2006). 18. Chmielewski A.G., Licki J., Pawelec A., Tymiński B., Zimek Z. Operational experience of the industrial plant for electron beam flue gas treatment. Ecological Chemistry and Engineering, 13, 10, 1057-1063 (2006). 19. Chmielewski A.G., Palige J., Zakrzewska-Trznadel G. Izotopy widzą wszystko (Isotopes see everything). Almanach Ekologii, 122-124 (2006). 20. Chmielewski A.G., Tymiński B., Pawelec A., Palige J., Dobrowolski A. Modelowanie przepływu gazu w reaktorze do oczyszczania spalin metodą radiacyjną z użyciem metod CFD (Modelling of gas flow in a reactor for electron beam flue gas treatment using CFD methods). Prace Naukowe Instytutu Inżynierii Chemicznej PAN, 7, 59-71 (2006). 21. Chwastowska J., Danko B. Analiza materiałów środowiskowych (Analysis of environmental materials). Ekologia, 4, 38-39 (2006). 22. Cieśla K., Salmieri S., Lacroix M. γ-Irradiation influence on the structure and properties of calcium caseinate-whey protein isolate based films. Part 1. Radiation effect on the structure of proteins gels and films. Journal of Agricultural and Food Chemistry, 54, 6374-6384 (2006). 23. Cieśla K., Salmieri S., Lacroix M. γ-Irradiation influence on the structure and properties of calcium caseinate-whey protein isolate based films. Part 2. Influence of polysaccharide addition and radiation treatment on the structure and functional properties of the films. Journal of Agricultural and Food Chemistry, 54, 8899-8908 (2006). 24. Cieśla K., Salmieri S., Lacroix M. Modification of the properties of milk protein films by gamma radiation and polysaccharide addition. Journal of the Science of Food and Agriculture, 86, 908-914 (2006). 25. Dalivelya O., Savina N., Kuzhir T., Buraczewska I., Wojewódzka M., Szumiel I. Effects of an antimutagen of 1,4-dihydropyridine series on cell survival and DNA damage in L5178Y murine sublines. Nukleonika, 51, 3, 141-146 (2006). 26. Danilczuk M., Lund A., Sadło J., Yamada H., Michalik J. Conduction electron spin resonance of small silver particles. Spectrochimica Acta A, 63, 189-191 (2006). THE INCT PUBLICATIONS IN 2006 167

27. Danilczuk M., Pogocki D., Lund A., Michalik J. EPR and DFT study on the stabilization of radiation-generated methyl radicals in dehydrated Na-A zeolite. Journal of Physical Chemistry B, 110, 24492-24497 (2006). 28. Danko B., Samczyński Z., Dybczyński R. Analytical scheme for group separation of the lanthanides from biological materials before their determination by neutron activation analysis. Chemia Analityczna, 51, 527-539 (2006). 29. Dembiński W., Herdzik I., Skwara W., Bulska E., Wysocka A.I. Isotope effects of gallium and indium in cation exchange chromatography. Nukleonika, 51, 4, 217-220 (2006). 30. Deperas-Kamińska M., Szumiel I., Wójcik A. Elementy radiologii dla pilota Pirxa (Elements of radiobiology for pilot Pirx). Kosmos, Problemy Nauk Biologicznych, 55, 4, 337-345 (2006). 31. Deptuła A., Chwastowska J., Łada W., Olczak T., Wawszczak D., Sterlińska E., Sartowska B., Goretta K.C. Sol-gel-derived hydroxyapatite and its application to sorption of heavy metals. Advances in Science and Technology, 45, 2198-2203 (2006). 32. Deptuła A., Dubarry M., Noret A., Gaubicher J., Olczak T., Łada W., Guyomard D.

Atypical Li1.1V3O3 prepared by a novel synthesis route. Electrochemical and Solid-State Letters, 9, 1, A16-A18 (2006). 33. Deptuła A., Łada W., Olczak T., Chmielewski A.G.

Application of Pt/Al2O3 catalysts produced by sol-gel process to uranyl ion reduction. Nukleonika, 51, Suppl. 1, s79-s82 (2006). 34. Filipczak K., Woźniak M., Ulański P., Olah L., Przybytniak G., Olkowski R.M., Lewandow- ska-Szumieł M., Rosiak J.M. Poly(ε-caprolactone) biomaterial sterilized by e-beam irradiation. Macromolecular Bioscience, 6, 261-273 (2006). 35. Filipiuk D., Fuks L., Majdan M. Biosorpcja jako metoda usuwania i odzysku metali ciężkich z wodnych ścieków przemysłowych (Biosorption as a new method for sequestering heavy metals in industrial aqueous effluents). Przemysł Chemiczny, 85, 6, 417-422 (2006). 36. Fuks L., Filipiuk D., Majdan M. Transition metal complexes with alginate biosorbent. Journal of Molecular Structure, 792-793, 104-109 (2006). 37. Fuks L., Polkowska-Motrenko H. Interlaboratory comparison of the determination of 137Cs and 90Sr in water, food and soil: preparation and characterization of test materials. Nukleonika, 51, Suppl. 2, s27-s31 (2006). 38. Głuszewski W. Nowe zakłady produkcji polietylenu PE i polipropylenu PP (New works for the production of polyethylene (PE) and polypropylene (PP). Postępy Techniki Jądrowej, 49, 2, 40-43 (2006). 39. Głuszewski W. Rak płuca. Wczesne wykrycie = dłuższe życie (Lung cancer. Early detection=longer life) Postępy Techniki Jądrowej, 50, 4, 29-31 (2006). 40. Głuszewski W., Panta P.P., Kubera H. Wpływ promieniowania jonizującego na właściwości materiałów opakowaniowych (Effect of ionizing radiation on the properties of packaging materials). Opakowanie, 9, 24-26 (2006). 168 THE INCT PUBLICATIONS IN 2006

41. Głuszewski W., Zagórski Z.P. Zastosowanie chromatografii gazowej (GC) w badaniach modyfikacji radiacyjnej polipropylenu (Ap- plication of gas chromatography to the investigation of radiation chemistry of polypropylene). Czasopismo Techniczne. Mechanika, 6, 190-192 (2006). 42. Głuszewski W., Zagórski Z.P. Zdolności przerobowe akceleratorów IChTJ do obróbki radiacyjnej (Production capacity of the INCT accelerators for radiation processing). Kauczuki Naturalne i Syntetyczne, 3, 28-30 (2006). 43. Gniazdowska E., Kraus W., Emmerling F., Spies H., Stephan H. Tetrabutylammonium bis(2-amidobenzenethiolato-κ2S,N)oxorhenate(V). Acta Crystallographica E 62, m1197-m1199 (2006). 44. Grądzka I. Mechanizmy i regulacja programowanej śmierci komórek (Mechanisms and regulation of the programmed cell death). Postępy Biochemii, 52, 2, 157-165 (2006). 45. Grigoriew H., Luboradzki R., Gronkowski J. USAXS studies of monosaccharide gels. I. Dependence of the glucofuranose-based gel structure on the gelator concentration. Journal of Non-Crystalline Solids, 352, 3052-3057 (2006). 46. Gryz M., Starosta W., Leciejewicz J. Bis(μ-pyridazine-3,6-carboxylato-κ4N,O:N’,O’)-bis[diaquazinc(II)]. Acta Crystallographica E, 62, m3470-m3472 (2006). 47. Gryz M., Starosta W., Leciejewicz J. trans-Diaquabis(pyridazine-3-carboxylato-κ2N,O)-magnesium(II) dihydrate. Acta Crystallographica E, 62, m123-m124 (2006). 48. Grzesiuk W., Nieminuszczy J., Kruszewski M., Iwaneńko T., Płazińska M., Bogdańska M., Bar-Andziak E., Królicki L., Grzesiuk E. DANN damage and its repair in lymphocytes and thyroid nodule cells during radioiodine therapy in patients with hyperthyroidism. Journal of Molecular Endocrinology, 37, 527-532 (2006). 49. Khayet M., Mengual J.I., Zakrzewska-Trznadel G. Direct contact membrane distillation for nuclear desalination. Part II: experiments with radioactive solutions. International Journal of Nuclear Desalination, 2, 1, 56-73 (2006). 50. Konarski P., Ćwil M., Piekoszewski J., Stanisławski J.

SIMS characterisation of superconductive MgB2 layers prepared by ion implantation and pulsed plasma treatment. Applied Surface Science, 252, 7078-7081 (2006). 51. Kornacka E., Kozakiewicz J., Legocka I., Przybylski J., Przybytniak G., Sadło J. Radical processes induced in poly(siloxaneurethaneureas) by ionising radiation. Polymer Degradation and Stability, 91, 2182-2188 (2006). 52. Kornacka E., Kozakiewicz J., Przybytniak G. Odporność radiacyjna aromatycznych poliuretanów przeznaczonych do zastosowań medycznych (Ra- diation resistance of aromatic polyurethanes for medical applications). Inżynieria Biomateriałów, 58-60, 143-145 (2006). 53. Kornacka E.M., Przybytniak G., Święszkowski W. Wpływ stopnia krystaliczności na stabilność radiacyjną UHMWPE (The influence of crystallinity on radiation stability of UHMWPE). Inżynieria Biomateriałów, 58-60, 146-149 (2006). THE INCT PUBLICATIONS IN 2006 169

54. Krejzler J., Narbutt J., Foreman M.R.St J., Hudson M.J., Casensky B., Madic C. Solvent extraction of Am(III) and Eu(III) from nitrate solution using synergistic mixtures of n-tridentate heterocycles and chlorinated cobalt dicarbollide. Czechoslovak Journal of Physics, 56, Suppl. D, D459-D467 (2006). 55. Lankoff A., Banasik A., Duma A., Ochniak E., Lisowska H., Kuszewski T., Góźdź S., Wójcik A. A comet assay study reveals that aluminium induces DNA damage and inhibits the repair of radiation-induced lesions in human peripheral blood lymphocytes. Toxicology Letters, 161, 27-36 (2006). 56. Lankoff A., Bialczyk J., Dziga D., Carmichael W.W., Grądzka I., Lisowska H., Kuszewski T., Góźdź S., Piorun I., Wójcik A. The repair of gamma-radiation-induced DNA damage is inhibited by microcystin-LR, the PP1 and PP2A phosphate inhibitor. Mutagenesis, 21, 1, 83-90 (2006). 57. Lankoff A., Bialczyk J., Dziga D., Carmichael W.W., Lisowska H., Wójcik A. Inhibition of nucleotide excision repair (NER) by microcystin-LR in CHO-K1 cells. Toxicon, 48, 957-965 (2006). 58. Lankoff A., Wójcik A., Fessard V., Meriluoto J. Nodularin-induced genotoxicity following oxidative DANN damage and aneuploidy in HepG2 cells. Toxicology Letters, 164, 239-248 (2006). 59. Liniecki J., Wójcik A. 20 lat po awarii w Czarnobylu. Co dziś wiemy o następstwach zdrowotnych? (20 years after the Chernobyl accident. What we know today about the radiological consequences?) Postępy Techniki Jądrowej, 49, 1, 2-8 (2006). 60. Lisowska H., Lankoff A., Wieczorek A., Florek A., Kuszewski T., Góźdź S., Wójcik A. Enhanced chromosomal radiosensitivity in peripheral blood lymphocytes of larynx cancer patients. International Journal of Radiation Oncology, Biology, Physics, 66, 4, 1245-1252 (2006). 61. Łyczko K., Narbutt J., Paluchowska B., Maurin J.K., Persson I. Crystal structure of lead(II) acetylacetonate and the structure of the acetylacetone solvated lead(II) ion in solution studies by large-angle X-ray scattering. Dalton Transactions, 3972-3976 (2006). 62. Mádl M., Kunicki-Goldfinger J.J. Eiland: Georg Gundelach and the glassworks on the Dìèin Estate of count Maximilian Thun-Hohenstein. Journal of Glass Studies, 48, 225-247 (2006). 63. Majkowska A., Bilewicz A. Formation kinetics and stability of some TRI and tetraaza derivative complexes of scandium. The Quarterly Journal of Nuclear Medicine and Molecular Imaging, 50, Suppl. 1 to issue 1, 45 (2006). 64. Markowicz S., Niedzielska J., Kruszewski M., Ołdak T., Gajkowska A., Machaj E.K., Skurzak H., Pojda Z. Nonviral transfection of human umbilical cord dentritic cells is feasile, but the yield of dendritic cells with transgene expression limits the application of this method in cancer immunotherapy. Acta Biochimica Polonica, 53, 1, 203-211 (2006). 65. Męczyńska S., Lewandowska H., Kruszewski M. The role of lysosomal iron in dinitrosyl iron complexes formation. Acta Biochimica Polonica, 53, Suppl. 1, 192 (2006). 66. Orelovitch O.L., Apel P.Yu., Sartowska B. New methods of track membrane treatment in the preparation of samples for further observation with scanning electron microscopy. Journal of Microscopy, 224, 100-223 (2006). 67. Palige J., Dobrowolski A., Owczarczyk A., Chmielewski A.G., Ptaszek S. Badania znacznikowe i CFD procesu sedymentacji osadu w osadniku prostokątnym (Tracer and CFD investigations of sedimentation processes in a rectangular settler). Inżynieria i Aparatura Chemiczna, 6a, 181-182 (2006). 170 THE INCT PUBLICATIONS IN 2006

68. Palige J., Dobrowolski A., Owczarczyk A., Chmielewski A.G., Ptaszek S. Badania znacznikowe i CFD struktury przepływu ścieków w osadnikach prostokątnych dla różnych geometrii napływu i wypływu ścieków (Tracer and CFD investigations of flow structure for two wastewater inputs and outputs configurations in rectangular settler). Inżynieria i Aparatura Chemiczna, 5a, 104-107 (2006). 69. Pawlukojć A., Natkaniec I., Bator G., Sobczyk L., Grech E., Nowicka-Scheibe J. Low frequency internal modes of 1,2,4,5-tetramethylbenzene, tetramethylpyrazine and tetramethyl-1,4-benzo- quinone INS, Raman, infrared and theoretical DFT studies. Spectrochimica Acta Part A, 63, 766-773 (2006). 70. Pawlukojć A., Sawka-Dobrowolska W., Bator G., Sobczyk L., Grech E., Nowicka-Scheibe J. X-ray diffraction, inelastic neutron scattering (INS) and infrared (IR) studies on 2:1 hexamethylbenzene (HMB)-tetracyanoethylene (TCNE) complex. Chemical Physics, 327, 311-318 (2006). 71. Peimel-Stuglik Z., Fabisiak S. Solid state “self-calibrated” EPR-dosimeters – advantageous and shortcomings. Spectrochimica Acta Part A, 63, 855-860 (2006). 72. Podrez-Radziszewska M., Bąkowski D., Lachowicz M., Głuszewski W., Dudziński W. Charakterystyka twardości i właściwości wytrzymałościowych UHMWPE po napromieniowaniu wiązką elektronów (Characterization of hardness and strength properties UHMWPE after irradiation with an electron beam). Inżynieria Materiałowa, 2, 75-78 (2006). 73. Polkowska-Motrenko H., Chajduk E., Dybczyński R. Selective separation of trace amounts of selenium using extraction chromatography and its determination by neutron activation analysis in biological samples. Chemia Analityczna, 51, 581-591 (2006). 74. Polkowska-Motrenko H., Dybczyński R. Activities of the INCT, Warsaw, in the domain of quality assurance for inorganic analysis. Journal of Radioanalytical and Nuclear Chemistry, 269, 2, 339-345 (2006). 75. Prager M., Pietraszko A., Sobczyk L., Pawlukojć A., Grech E., Seydel T., Wischnewski A., Zamponi M. X-ray diffraction and inelastic neutron scattering study of 1:1 tetramethylpyrazine chloranilic acid complex: temperature, isotope, and pressure effects. The Journal of Chemical Physics, 125, 194525-1-11 (2006). 76. Premkumar T., Govindarajan S., Starosta W., Leciejewicz J. Diaquatetrakis(pyrazine-2-carboxylato-κ2O,N)-thorium(IV) trihydrate. Acta Crystallographica E, 62, m98-m100 (2006). 77. Pruszyński M., Bilewicz A. 211At-Rh(16-S4-diol) complex as a precursor for astatine radiopharmaceuticals. The Quarterly Journal of Nuclear Medicine and Molecular Imaging, 50, Suppl. 1 to issue 1, 44 (2006). 78. Pruszyński M., Bilewicz A., Wąs B., Petelenz B. Formation and stability of astatide-mercury complexes. Journal of Radioanalytical and Nuclear Chemistry, 268, 1, 91-94 (2006). 79. Przybytniak G., Kornacka E., Ryszkowska J., Bil M., Rafalski A., Woźniak P., Lewandowska-Szu- mieł M. Influence of radiation sterilization on poly(ester urethanes) designed for medical applications. Nukleonika, 51, Suppl. 1, s121-s128 (2006). 80. Sadlej-Sosnowska N., Ocios A., Fuks L. Selectivity of similar compounds’ identification using IR spectrometry: β-Lactam antibiotics. Journal of Molecular Structure, 792-793, 110-114 (2006). 81. Sadło J., Michalik J., Kevan L. EPR and ESEEM study of silver clusters in ZK-4 molecular sieves. Nukleonika, 51, Suppl. 1, s49-s54 (2006). THE INCT PUBLICATIONS IN 2006 171

82. Sadło J., Michalik J., Stachowicz W., Strzelczak G., Dziedzic-Gocławska A., Ostrowski K. EPR study on biominerals as materials for retrospective dosimetry. Nukleonika, 51, Suppl. 1, s95-s100 (2006). 83. Samczyński Z. Ion exchange behavior of selected elements on Chelex 100 resin. Solvent Extraction and Ion Exchange, 24, 781-794 (2006). 84. Sartowska B., Piekoszewski J., Waliś L., Stanisławski J., Nowicki L., Ratajczak R. Characterization of the near-surface layers of carbon steels modified by interaction with intense pulsed plasma beams: scanning electron microscopy investigations. Journal of Microscopy, 224, 114-116 (2006). 85. Sastry M.D., Gustafsson H., Danilczuk M., Lund A. Dynamical effects and ergodicity in the dipolar glass phase: evidence from time-domain EPR and 4– phase memory time studies of AsO4 in Rb1-x(NH4)xH2PO4 (x = 0, 0.5, 1). Journal of Physics: Condensed Matter, 18, 4265-4284 (2006). 86. Sawka-Dobrowolska W., Bator G., Czarnik-Matusewicz B., Sobczyk L., Pawlukojć A., Grech E., Nowicka-Scheibe J., Rundlöf H. X-ray and neutron diffraction, IR and INS spectroscopic and DFT theoretical studies on the tetramethylpyrazine-1,2,4,5-tetracyanobenzene complex. Chemical Physics, 327, 237-246 (2006). 87. Schlick S., Bosnjakovic A., Danilczuk M. Direct ESR and spin trapping methods for the study of radicals in PEMS and model compounds exposed to oxygen radicals. Abstracts of Papers of the American Chemical Society, Division of Fuel Chemistry, 51, 2, 688-689 (2006). 88. Sommer S., Deperas-Kamińska M., Wójcik A., Szumiel I. Indywidualna promieniowrażliwość chromosomów i odcisk palca promieniowania. Otwarte pytania w dziedzinie dozymetrii biologicznej (Individual radiosensitiveness of chromosomes and fingerprint of radiation. Open questions in the field of biological dosimetry). Postępy Techniki Jądrowej, 49, 1, 16-21 (2006). 89. Starosta W., Buczkowski M., Sartowska B., Wawszczak D. Studies on template-synthesized polypyrrole nanostructures. Nukleonika, 51, Suppl. 1, s35-s39 (2006). 90. Starosta W., Leciejewicz J. catena-Poly[[aquacalcium(II)]bis(μ-1H-imidazole-4-carboxylato)-κ4N,O:O,O’; κ3O,O’:O’]. Acta Crystallographica E, 62, m2648-m2650 (2006). 91. Starosta W., Leciejewicz J., Premkumar T., Govindarajan S. Crystal structures of two Ca(II) complexes with imidazole-4,5-dicarboxylate and water ligands. Journal of Coordination Chemistry, 59, 5, 557-564 (2006). 92. Stupińska H., Iller E., Zimek Z., Kopania E., Palenik J., Milczarek S. Otrzymywanie mikrokrystalicznej celulozy z zastosowaniem ekologicznych metod depolimeryzacji celulozy. Część I. Degradacja radiacyjna (Obtaining of microrystalline cellulose with the ecological method of cellulose depolymerization. Part I. The radiational degradation). Przegląd Papierniczy, 8, 475-481 (2006). 93. Sun Y., Chmielewski A.G., Bułka S., Zimek Z. Influence of base gas mixture on decomposition of 1,4-dichlorobenzene in an electron beam generated plasma reactor. Plasma Chemistry and Plasma Processing, 26, 347-359 (2006). 94. Szumiel I. Epidermal growth factor receptor and DNA double strand break repair: the cell’s self-defence. Cellular Signalling, 18, 1537-1548 (2006). 95. Trojanowicz M. Analytical applications of carbon nanotubes: a review. Trends in Analytical Chemistry, 25, 5, 480-489 (2006). 172 THE INCT PUBLICATIONS IN 2006

96. Trojanowicz M., Wójcik L., Szostek B., Korczak K., Bojanowska-Czajka A., Drzewicz P., Ma- sar M., Kaniansky D. Application of capillary electrophoresis in analysis of perfluorinated carboxylic acids. Organohalogen Compounds, 68, 2531-2534 (2006). 97. Trybuła Z., Kempiński W., Andrzejewski B., Piekara-Sady L., Kaszyński J., Trybuła M., Pieko- szewski J., Stanisławski J., Barlak M., Richter E.

Superconducting regions and Kondo effect of MgB2 formed by implantation of magnesium ions into boron substrate. Acta Physica Polonica A, 109, 4-5, 657-660 (2006). 98. Tymiński B., Zwoliński K., Jurczyk R. Badania w skali wielkolaboratoryjnej rozkładu odpadów poliolefin na produkty ciekłe (Research on waste polyolefine degradation into liquid products). Prace Naukowe Instytutu Inżynierii Ochrony Środowiska Politechniki Wrocławskiej z. 81, Seria: Konferencje z. 12, 263-267 (2006). 99. Tymiński B., Zwoliński K., Jurczyk R. Degradation of polyolefine wastes into liquid fuels. Nukleonika, 51, Suppl. 1, s95-s100 (2006). 100. Urbański P., Bartak J., Jakowiuk A., Świstowski E., Machaj B., Kowalska E., Pieńkos J. Nowe urządzenia do promieniowania jonizującego (New instruments for measurements of ionizing radiation). Ekopartner, 11, 24-25 (2006). 101. Urbański P., Bartak J., Jakowiuk A., Świstowski E., Machaj B., Kowalska E., Pieńkos J. Urządzenia promieniowania jonizującego (Instruments of ionizing radiation). Ekologia, 6, 42-43 (2006). 102. Wierzchnicki R. Izotopy stabilne w kontroli pochodzenia żywności (Stable isotopes in the control of food authencity). Postępy Techniki Jądrowej, 49, 1, 22-25 (2006). 103. Wojewódzka M., Buraczewska I., Szumiel I., Grądzka I. DNA double-strand break rejoining in radioadapted human lymphocytes: evaluation by neutral comet assay and pulse-field gel electrophoresis. Nukleonika, 51, 4, 185-191 (2006). 104. Wojewódzka M., Kruszewski M., Ołdak T., Bartłomiejczyk T., Goździk A., Szumiel I. Inhibition of poly(ADP-ribose)polymerase does not affect the recombination events in CHO xrs6 and wild type cells. Radiation and Environmental Biophysics, 45, 277-287 (2006). 105. Wojewódzka M., Szumiel I. Ogniska histonu γ-H2AX. Marker pęknięć podwójnoniciowych DNA (γ-H2AX histone foci – marker of DNA double strand breaks). Postępy Techniki Jądrowej, 49, 3, 15-18 (2006). 106. Wójcik A., Bochenek A., Lankoff A., Lisowska H., Padjas A., Szumiel I., von Sonntag C., Obe G. DNA interstrand crosslinks are induced in cells prelabelled with 5-bromo-2’-deoxyuridine and exposed to UVC radiation. Journal of Photochemistry and Photobiology B: Biology, 84, 15-20 (2006). 107. Wójcik A., Szumiel I., Liniecki J. Hormeza czy to zjawisko powszechne i powszechnie nieznane? (Hormesis, a common phenomenon and commonly unknown?) Postępy Techniki Jądrowej, 49, 2, 34-39 (2006). 108. Yordanov N.D., Fabisiak S., Lagunov O. Effect of the shape and size of dosimeters on the response of solid state/EPR dosimetry. Radiation Measurements, 41, 257-263 (2006). 109. Zagórski Z.P. Radiation chemistry of radioactive waste to be stored in the salt mine repository. Nukleonika, 51, Suppl. 2, s87-s92 (2006). THE INCT PUBLICATIONS IN 2006 173

110. Zagórski Z.P. Radiation induced dehydrogenation of organics: from amino acids, to synthetic polymers, to bacterial spores. Indian Journal of Radiation Research, 3, 2-3, 89-93 (2006). 111. Zakrzewska-Trznadel G. Membrane processes for environmental protection: application in nuclear technology. Nukleonika, 51, Suppl. 1, s101-s111 (2006). 112. Zakrzewska-Trznadel G. Tritium removal from water solutions. Desalination, 200, 737-738 (2006). 113. Zhydachevskii Ya., Suchocki A., Sugak D., Luchechko A., Berkowski M., Warchoł S., Jakieła R.

Optical observation of the recharging processes of manganese ions in YalO3:Mn crystals under radiation and thermal treatment. Journal of Physics: Condensed Matter, 18, 5389-5403 (2006). 114. Zimek Z. Chemia i technika radiacyjna (Radiation chemistry and technology). Postępy Techniki Jądrowej, 50, 4, 14-20 (2006). 115. Zimek Z., Przybytniak G., Kałuska I. Radiation processing of polymers and semiconductors at the Institute of Nuclear Chemistry and Tech- nology. Nukleonika, 51, Suppl. 1, s129-s132 (2006). 116. Zimek Z., Przybytniak G., Nowicki A., Mirkowski K. Zastosowanie techniki radiacyjnej do otrzymywania napełniaczy bentonitowych i ich mieszanek z poli- propylenem (Application of radiation technique to obtain bentonite fillers and their mixtures with polypropylene). Inżynieria Materiałowa, 6, 1333-1336 (2006).

BOOKS

1. Chmielewski A.G., Kang C.M., Kang C.S., Vujic J.L. Radiation technology. Introduction to industrial and environmental applications. Seoul National University Press, Seoul 2006, 274 p.

CHAPTERS IN BOOKS

1. Chiarizia R., Jensen M.P., Borkowski M., Nash K.L. A new interpretation of third-phase formation in the solvent extraction of actinides by TBP. In: Separation for the nuclear fuel cycle in the 21st century. G.L. Lumetta, K.L. Nash, S.B. Clark, J.I. Friese (eds). ACS Symposium Series no. 933. American Chemical Society, Washington, DC 2006, pp. 135-150. 2. Chmielewski A.G., Sun Y. Air emission and off-gas treatment technologies – overview. In: Ochrona powietrza w teorii i praktyce. Tom 1. Red. J. Konieczyński. Instytut Podstaw Inżynierii PAN, Zabrze 2006, pp. 9-16. 3. Deptuła A., Goretta K.C., Olczak T., Łada W., Chmielewski A.G., Jakubaszek U., Sartowska B., Alvani C., Casadio S., Contini V. Preparation of titanium oxide and metal titanates as powders, thin films, and microspheres by novel inorganic sol-gel process. In: Nanoparticles and nanostructures in sensors and catalysis. Chuan-Jian Zhong, N.A. Kotov, W. Daniell, F.P. Zamborini (eds). Materials Research Society Symposium Proceedings vol. 900E. MRS, Warrendale 2006, pp. 0900-O09-10.1-10.6. 4. Jakowiuk A., Świstowski E., Urbański P., Pieńkos J., Machaj B., Salwa J. System monitoringu zapylenia powietrza (Wireless system for air dust concentration monitoring). 174 THE INCT PUBLICATIONS IN 2006

In: Ochrona powietrza w teorii i praktyce. Tom 2. Red. J. Konieczyński. Instytut Podstaw Inżynierii PAN, Zabrze 2006, pp. 119-127. 5. Pruszyński M., Bilewicz A. Binding of 131I to rhodium(III) complexes: model studies on attaching 211At to metal complexes. In: Application of radiotracers in chemical, environmental and biological sciences. S. Lahiri, D. Layak, A. Mukhopadhyay (eds). Saha Institute of Nuclear Physics, Kolkata 2006. Vol. 2, pp. 20-22. 6. Sun Y., Chmielewski A.G., Bułka S., Zimek Z. Organic pollutants treatment from air using electron beam technology. In: Ochrona powietrza w teorii i praktyce. Tom 1. Red. J. Konieczyński. Instytut Podstaw Inżynierii PAN, Zabrze 2006, pp. 253-257. 7. Zimek Z. Economic benefits of radiation processing applied in Poland. In: A study on economical benefits of industrial applications of radiation and radioisotopes. Report of Consultants Meeting, Vienna 6-9 December 2004. IAEA, Vienna 2006, pp. 56-63.

THE INCT REPORTS

1. INCT Annual Report 2005. Institute of Nuclear Chemistry and Technology, Warszawa 2006, 235 p. 2. Zakrzewska Trznadel G. Procesy membranowe w technologiach jądrowych (Membrane processes in nuclear technologies). Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria A nr 1/2006, 191 p. 3. Zakrzewska Trznadel G. Procesy membranowe w technologiach jądrowych – wybrane zagadnienia modelowania transportu masy oraz projektowania systemów rozdzielania (Membrane processes in nuclear technologies – selected issues of mass tansport modeling and separation systems design). Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria A nr 2/2006, 80 p. 4. Polkowska-Motrenko H., Dybczyński R., Chajduk E., Danko B., Kulisa K., Samczyński Z., Sypu- ła M., Szopa Z. Polish reference material: Corn Flour (INCT-CF-3) for inorganic trace analysis – preparation and certification. Institute of Nuclear Chemistry and Technology, Warszawa 2006. Raporty IChTJ. Seria A nr 3/2006, 47 p. 5. Polkowska-Motrenko H., Dybczyński R., Chajduk E., Danko B., Kulisa K., Samczyński Z., Sypu- ła M., Szopa Z. Polish reference material: Soya Bean Flour (INCT-CBF-4) for inorganic trace analysis – preparation and certification. Institute of Nuclear Chemistry and Technology, Warszawa 2006. Raporty IChTJ. Seria A nr 4/2006, 51 p. 6. Herdzik I. ICP-MS jako metoda oznaczania stosunków izotopowych galu, indu i talu w badaniach efektów izotopowych w układach chromatograficznych (ICP-MS as the method of the determination of gallium, indium and tallium isotope ratios in the studies of isotope effects in the chromatography systems). Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria A nr 5/2006, 19 p. 7. Pawlukojć A. Badania widm oscylacyjnych, w obszarze niskich częstości, wybranych kompleksów molekularnych z prze- niesieniem ładunku oraz ich składników metodą nieelastycznego rozpraszania neutronów termicznych (The investigations of low frequency oscillation spectra of selected charge transfer molecular complexes and their compounds by inelastic thermal neutron spectroscopy). Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria A nr 6/2006, 100 p. 8. Chmielewski A.G. Packaging for food irradiation. Institute of Nuclear Chemistry and Technology, Warszawa 2006. Raporty IChTJ. Seria B nr 1/2006, 26 p. THE INCT PUBLICATIONS IN 2006 175

9. Polkowska-Motrenko H., Dudek J., Chajduk E., Sypuła M., Sadowska-Bratek M. Badania biegłości ROŚLINY 6 – oznaczanie zawartości As, Cd, Cu, Hg, Pb, Se i Zn w grzybach suszonych (maślak sitarz) (Proficiency test PLANT 6 – determination of As, Cd, Cu, Hg, Pb, Se and Zn in dry mushroom powder (Suillus bovinus)). Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria B nr 2/2006, 22 p. 10. Zimek Z., Dźwigalski Z., Warchoł S., Roman K., Bułka S. Modernizacja Stacji Sterylizacji Radiacyjnej wyposażonej w akcelerator elektronów ELEKTRONIKA 10/10. Część I (Upgrading of Radiation Sterilization Facility equipped with electron accelerator ELEKTRONIKA 10/10. Part I). Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria B nr 3/2006, 28 p. 11. Malec-Czechowska K., Laubsztejn M., Strzelczak G., Stachowicz W. Wykrywanie napromieniowania farmaceutyków zawierających składniki pochodzenia roślinnego metodą pomiaru termoluminescencji oraz metodą spektroskopii elektronowego rezonansu paramagnetycznego (Detection of irradiation in herbal pharmaceuticals with the use of thermoluminescence and electron paramagnetic resonance spectroscopy). Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria B nr 4/2006, 18 p. 12. Mehta K., Bułka S. Dosimetry for combustion flue gas treatment with electron beam. Institute of Nuclear Chemistry and Technology, Warszawa 2006. Raporty IChTJ. Seria B nr 5/2006, 26 p. 13. Lewandowska-Siwkiewicz H., Kruszewski M. Dinitrozylowe kompleksy żelaza w układach biologicznych (Dinitrosyl iron complexes in biological systems). Instytut Chemii i Techniki Jądrowej, Warszawa 2006. Raporty IChTJ. Seria B nr 6/2006, 36 p.

CONFERENCE PROCEEDINGS

1. Bojanowska-Czajka A., Drzewicz P., Trojanowicz M., Nałęcz-Jawecki G., Sawicki J., Zimek Z., Nichipor H. Analityczne badania radiolitycznej degradacji wybranych pestycydów (Analytical control of radiolytical decomposition of selected pesticides). Dla miasta i środowiska – IV konferencja: Problemy unieszkodliwiania odpadów, Warszawa, Poland, 27.11.2006, pp. 23-26. 2. Chmielewski A.G. Practical applications of radiation chemistry. Physical chemistry. Proceedings of the 8th international conference on fundamental and applied aspects of physical chemistry, Belgrade, Serbia, 26-29.09.2006. Vol. 1, pp. 38-46. 3. Chmielewski A.G., Pawelec A., Tymiński B., Zimek Z.

Parametric analysis of the electron beam process for SO2 and NOx removal. V European meeting on chemical industry and environment, 3-5.05.2006, Vienna, Austria. W. Höflinger (ed.). Vienna University of Technology, Vienna. Vol. I, pp. 598-606. 4. Chmielewski A.G., Sun Y., Bułka S., Zimek Z. Chlorinated organic compounds decomposition in air in an electron beam generated plasma reactor. The First Central European Symposium on Plasma Chemistry, Gdańsk, Poland, 28-31.05.2006. Pro- ceedings, [3] p. 5. Dybczyński R. The position of NAA among the methods of inorganic trace analysis in the past and now. Proceedings of the enlargement workshop on neutron measurement, evaluations and applications NEMEA-2, Bucharest, Romania, 20-23.10.2004. A.J.M. Plompen (ed.). Report EUR 22136 EN. Insti- tute for Reference Materials and Measurements, Luxemburg [2006], pp. 85-88. 6. Harasimowicz M., Orluk P., Zakrzewska-Trznadel G., Chmielewski A.G. Application of polyimide membranes for biogas purification and enrichment. V European meeting on chemical industry and environment, 3-5.05.2006, Vienna, Austria. W. Höflinger (ed.). Vienna University of Technology, Vienna. Vol. I, pp. 617-625. 176 THE INCT PUBLICATIONS IN 2006

7. Harasimowicz M., Ziółkowska W., Zakrzewska-Trznadel G., Chmielewski A.G. Economical comparison of absorption and membrane methods applied for enrichment of methane in biogas. “Ars Separatoria 2006”: Proceedings of the XXI International Symposium on Physico-Chemical Methods of Separation, Toruń, Poland, 2-5.07.2006. J. Ceynowa, R. Wódzki (eds.). Nicolaus Copernicus University, Toruń 2006, pp. 52-54. 8. Łyczko M., Schibli R., Narbutt J. Substitution of imidazole and bombesin for water in aquatricarbonyl(n-methyl-2-piridenecarbothioamide) technetium(I) cation. [2+1] approach. Technetium, rhenium and other metals in chemistry and nuclear medicine. Proceedings of the 7th Inter- national symposium on technetium in chemistry and nuclear medicine, Italy, 6-9.09.2006. U. Mazzi (ed.) SGE Editoriali, Padova 2006, pp. 335-336. 9. Owczarczyk A., Palige J., Dobrowolski A., Chmielewski A.G., Ptaszek S. CFD and RTD methods for industrial wastewater treatment plants settler investigation. V European meeting on chemical industry and environment, 3-5.05.2006, Vienna, Austria. W. Höflinger (ed.). Vienna University of Technology, Vienna. Vol. I, pp. 96-103. 10. Polkowska-Motrenko H., Dobkowski Z. Rola porównań międzylaboratoryjnych w procesie doskonalenia systemu zarządzania (Role of ILC in the advancement of management system). XII Sympozjum: Doskonalenie systemu zarządzania w laboratorium, Gdańsk-Sobieszowa, Poland, 21-23.05.2006. (I tura). Materiały sympozjum, pp. 73-78. 11. Polkowska-Motrenko H., Dobkowski Z. Rola porównań międzylaboratoryjnych w procesie doskonalenia systemu zarządzania (Role of ILC in the advancement of management system). XII Sympozjum: Doskonalenie systemu zarządzania w laboratorium, Ustroń, Poland, 10-12.09.2006. (II tura), pp. 85-90. 12. Samczyński Z., Łyczko M., Dybczyński R., Narbutt J. 99m + Ion exchange studies on the organometallic aqua-ion fac-[ Tc(CO)3(H2O)3] in acidic aqueous solutions. Technetium, rhenium and other metals in chemistry and nuclear medicine. Proceedings of the 7th Inter- national symposium on technetium in chemistry and nuclear medicine, Italy, 6-9.09.2006. U. Mazzi (ed.). SGE Editoriali, Padova 2006, pp. 125-126. 13. Zagórski Z.P. Radiation induced dehydrogenation of organics: from amino acids, to synthetic polymers, to bacterial spores. Proceedings of Trombay Symposium on Radiation and Photochemistry, Mumbai, India, 5-9.01.2006. Vol. I: Invited talks, pp. 97-99. 14. Zakrzewska-Trznadel G., Harasimowicz M., Miśkiewicz A., Chmielewski A.G., Dłuska E., Wroń- ski S., Jaworska A. Reducing the fouling and boundary layer phenomena in membrane processes for radioactive wastes treatment. “Ars Separatoria 2006”: Proceedings of the XXI International Symposium on Physico-Chemical Methods of Separation, Toruń, Poland, 2-5.07.2006. J. Ceynowa, R. Wódzki (eds.). Nicolaus Copernicus University, Toruń 2006, pp. 140-141. 15. Zimnicki R., Owczarczyk A., Chmielewski A.G. Obserwacja zmian parametrów hydrochemicznych wód podziemnych w rejonie powstającej kopalni odkrywkowej węgla brunatnego (Investigations of groundwater composition and hydrological condition changes in area of formation of an open-cast lignite mine). Postęp w inżynierii środowiska. IV Ogólnopolska konferencja naukowo-techniczna, Rzeszów-Bystre k. Baligrodu, Poland, 21-23.09.2006. Pod red. J.A. Tomaszka, pp. 521-529.

CONFERENCE ABSTRACTS

1. Bobrowski K., Hug G.L., Hörner G., Marciniak B., Pogocki D., Schöneich C. Sulfide radical cation chemistry in cyclic dipeptides. 20th International Symposium on Radical Ion Reactivity: ISRIR 2006, Rome, Italy, 2-6.07.2006, IL14, [1] p. THE INCT PUBLICATIONS IN 2006 177

2. Bobrowski K., Hug G.L., Pogocki D., Hörner G., Marciniak B., Schöneich C. Stabilization of sulfide cations: mechanisms relevant to oxidation of peptides and proteins containing methionine. The 1st Asian-Pacific Symposium on Radiation Chemistry, Shanghai, China, 17-21.09.2006. Conference abstract book, pp. 58-59. 3. Bobrowski K., Hug G.L., Pogocki D., Marciniak B., Schöneich C. Stabilization of sulfide radical cations through complexation with the peptide bond. RADAM’06: Radiation Damage in Biomolecular Systems, Groningen, The Netherlands, 6-9.06.2006, [1] p. 4. Bojanowska-Czajka A., Drzewicz P., Trojanowicz M. Analityczne badania radiolitycznej degradacji karbendazymu (Analytical control of carbendazim decomposition by gamma irradiation). ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006. Streszczenia, p. 21. 5. Brzóska K., Kruszewski M., Szumiel I. Defect in double-stranded DNA breaks repair in L5178Y-S cells is not associated with alterations in the autophosphorylation sites of DNA-dependent protein kinase. The 10th Anniversary of Gliwice Scientific Meetings, Gliwice, Poland, 17-18.11.2006, p. 37. 6. Celuch M., Enache M., Pogocki D. Acid-base catalysis of singlet oxygen-induced oxidation of alkylthiocarboxylic acids. 12th International Conference on Physical Chemistry - Romphyschem-12, Bucharest, Romania, 6-8.09.2006. Abstract book, p. 60. 7. Celuch M., Enache M., Pogocki D. Reakcje jednoelektronowego utleniania kwasów alkilotiokarboksylowych (Reactions of one-electron oxidation of alkylthiocarboxylic acids). ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006. Streszczenia, p. 24. 8. Chajduk E., Dybczyński R. Nowa metoda oznaczania śladowych ilości As w materiałach biologicznych za pomocą radiochemicznej neutronowej analizy aktywacyjnej (Determination of trace amounts of arsenic in biological samples by RNAA). XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, S8-P20, p. 200. 9. Chajduk E., Polkowska-Motrenko H., Dybczyński R. Konstruowanie metod o najwyższej randze metrologicznej dla oznaczania Se w materiałach biologicznych za pomocą RNAA (A new, high accuracy RNAA method for selenium determination in biological materials). ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006. Streszczenia, p. 25. 10. Chajduk E., Polkowska-Motrenko H., Dybczyński R. Metoda definitywna oznaczania selenu w matrycach biologicznych (Definitive method for selenium determination in biological materials). VI Sesja przeglądowa analityki żywności, Warszawa, Poland, 17.11.2006. Materiały sesji, p. 17. 11. Chmielewski A.G. Industrial scale processing of flue gases from electric and heat power plants. Workshop on the Plasma-Assisted Combustion and Plasma-Aftertreatment of Combustion Flue Gases for Power Industry, Gdańsk, Poland, 28-31.05.2006. Book of abstracts, p. 13. 12. Chmielewski A.G. Industrial applications of electron beam flue gas treatment – from laboratory to the practice. 11th Tihany Symposium on Radiation Chemistry, Eger, Hungary, 26-31.08.2006. Program and abstracts, p. 50. 13. Chmielewski A.G. Technologiczne aspekty chemii radiacyjnej (Technological aspects of radiation chemistry). XLIX Zjazd PTChem i SIPChem, Gdańsk, Poland, 18-21.09.2006. Materiały zjazdowe, S12, W-1, p. 283. 178 THE INCT PUBLICATIONS IN 2006

14. Chmielewski A.G. Water pollutants degradation by electron beam. The First Central European Symposium on Plasma Chemistry, Gdańsk, Poland, 28-31.05.2006. Book of abstracts, p. 17. 15. Chmielewski A.G., Chmielewska D.K., Sampa M.H. Prospects and challenges in application of gamma and electron beam processing of nanomaterials. IRaP 2006: 7th International Symposium on Ionizing Radiation and Polymers, Antalya, Turkey, 23-28.09.2006. Book of abstracts, p. 44. 16. Chmielewski A.G., Haji-Saeid M., Ramamoorthy N. Fostering new developments in radiation processing and IAEA’s role. 14th International Meeting on Radiation Processing, Kuala Lumpur, Malaysia, 26.02.-3.03.2006. Con- ference abstracts book, [1] p. 17. Chmielewski A.G., Migdał W., Świętosławski J., Jakubaszek U., Tarnowski T. Chemical-radiation degradation of natural oligo-aminopolysaccharides and product agricultural applications. 14th International Meeting on Radiation Processing (IMRP), Kuala Lumpur, Malaysia, 26.02.-3.03.2006. Conference abstracts book, p. 198. 18. Chmielewski A.G., Sun Y., Bułka S., Zimek Z. Chlorinated organic compounds decomposition in air in an electron beam generated plasma reactor. The First Central European Symposium on Plasma Chemistry, Gdańsk, Poland, 28-31.05.2006. Book of abstracts, p. 55. 19. Chmielewski A.G., Sun Y., Bułka S., Zimek Z. Dosimetric methods for laboratory scale VOC treatment. The Workshop on dosimetry for radiation applications in technologies for environment pollution control, Warszawa, Poland, 5.04.2006, p. 4. 20. Chwastowska J., Skwara W., Sterlińska E., Dudek J., Pszonicki L. Oznaczanie kadmu, ołowiu, miedzi i bizmutu w wodach mineralnych metodą GF-AAS po wydzieleniu za pomocą ekstrakcji do fazy stałej (Determination of cadmium, lead, copper and bismuth in mineral waters by GF-AAS after preconcentration on dithizone sorbent). Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały XV Poznańskiego konwersatorium analitycznego, Poznań, Poland, 20-21.04.2006, p. 115. 21. Chwastowska J., Skwara W., Sterlińska E., Dudek J., Pszonicki L. Sorbent chelatujący z ditizonem, własności analityczne i możliwości zastosowania (Chelating sorbent with dithizon – analytical property and possibility of use). Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały XV Poznańskiego konwersatorium analitycznego, Poznań, Poland, 20-21.04.2006, p. 114. 22. Chwastowska J., Skwara W., Sterlińska E., Dudek J., Pszonicki L. Własności analityczne i możliwości zastosowania sorbentu chelatującego z ditizonem (Analytical properties and applications of dithizone sorbent). XI Konferencja: Zastosowanie metod AAS, ICP-AES, ICP-MS w analizie środowiskowej – Thermo Electron, Warszawa, Poland, 9-10.11.2006, PO-03, p. 22. 23. Chwastowska J., Skwara W., Sterlińska E., Dudek J., Pszonicki L. Zastosowanie ekstrakcji do fazy stałej przy oznaczaniu metali ciężkich metodą GF-AAS (Application of solid-phase extraction for determination of heavy metals by GF-AAS). XI Konferencja: Zastosowanie metod AAS, ICP-AES, ICP-MS w analizie środowiskowej – Thermo Electron, Warszawa, Poland, 9-10.11.2006, PO-04, p. 23. 24. Cieśla K., Eliasson A.-C. DSC studies of retrogradation and amylose-lipid complex transition taking place in gamma irradiated wheat starch. IRaP 2006: 7th International Symposium on Ionizing Radiation and Polymers, Antalya, Turkey, 23-28.09.2006. Book of abstracts, p. 45. 25. Cieśla K., Lundqvist H., Eliasson A.-C. Surface tension and WAXS diffraction studies of binding cetyltrimethyl-ammonium bromide to gamma irradiated and nonirradiated potato starch. XIV International Starch Convention Cracow-Moscow, Cracow, Poland, 20-24.06.2006, pp. 66-67. THE INCT PUBLICATIONS IN 2006 179

26. Cieśla K., Rahier H. Gamma irradiation effect on interaction of potato starch with lipids and surfactants studied by DSC. ESTAC 9: 9th European Symposium on Thermal Analysis and Calorimetry, Kraków, Poland, 27-31.08.2006, p. 26. 27. Cieśla K., Sartowska B., Królak E. Gamma irradiation influence on structure of potato starch gels studied by SEM. XIV International Starch Convention Cracow-Moscow, Cracow, Poland, 20-24.06.2006, pp. 106-107. 28. Cieśla K., Vansant E.F. Physico-chemical changes taking place in gamma irradiated bovine globulins studied by thermal analysis. ESTAC 9: 9th European Symposium on Thermal Analysis and Calorimetry, Kraków, Poland, 27-31.08.2006, p. 37. 29. Danko B., Dybczyński R., Kulisa K., Samczyński Z. Oznaczanie lantanowców w próbkach biologicznych za pomocą neutronowej analizy aktywacyjne i chromatografii jonów (Determination of the lanthanides in biological samples by NAA and IC). XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, S8-P23, p. 200. 30. Danko B., Dybczyński R., Kulisa K., Samczyński Z. Schemat wydzielania frakcji lantanowców z materiałów pochodzenia roślinnego oraz środowiskowego (A scheme for the separation of lanthanide fraction from materials of biological and environmental origin). Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały XV Poznańskiego konwersatorium analitycznego, Poznań, Poland, 20-21.04.2006, p. 136. 31. Dybczyński R. Contribution of NAA to the certification of reference materials for inorganic trace analysis. NEMEA-3: 3rd Workshop on Neutron Measurements, Evaluations and Applications, Borovets, Bul- garia, 25-28.10.2006. Book of abstracts, p. 19. 32. Dybczyński R. Neutronowa analiza aktywacyjna i jej znaczenie dla zapewnienia jakości wyników analitycznych w nieorganicznej analizie śladowej (Neutron activation and its significance for the assurance of the quality of analytical results in inorganic trace analysis). XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, S12-W2, p. 283. 33. Dybczyński R. Zarys historii, zastosowania i znaczenie materiałów odniesienia w nieorganicznej analizie śladowej (Historical outline of the application and significance of reference materials in inorganic trace analysis). Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały XV Poznańskiego konwersatorium analitycznego, Poznań, Poland, 20-21.04.2006, p. 147. 34. Dybczyński R., Danko B., Polkowska-Motrenko H., Samczyński Z. Metody definitywne oparte na radiochemicznej neutronowej analizie aktywacyjnej i ich miejsce w metro- logii chemicznej (Definitive methods based on radiochemical neutron activation and their position in chemical metrology). Ogólnopolska konferencja naukowa: Jakość w chemii analitycznej, Warszawa, Poland, 23-24.11.2006, [1] p. 35. Dybczyński R., Danko B., Polkowska-Motrenko H., Samczyński Z. The place of highly accurate methods by RNAA in metrology. 15th Radiochemical Conference, Mariánské Lázne, Czech Republic, 23-28.04.2006. Booklet of abstracts, p. 84. 36. Dybczyński R., Kulisa K. Wpływ temperatury na proces rozdzielania w chromatografii jonowymiennej i chromatografii pasma chromatograficznego (Influence of temperature on the separation process in ion exchange chromatography and ion chromatography and the mechanism of band spreading). VII Konferencja chromatograficzna: chromatografia i techniki pokrewne a zdrowie człowieka, Białystok, Poland, 10-13.10.2006, pp. 19-20. 37. Filipczak K., Ulanski P., Przybytniak G., Olah L., Rosiak J.M. Some observations on the effect of ionizing radiation on poly(ε-caprolactone). 180 THE INCT PUBLICATIONS IN 2006

11th Tihany Symposium on Radiation Chemistry, Eger, Hungary, 26-31.08.2006. Program and abstracts, p. 91. 38. Filipczak K., Ulanski P., Przybytniak G., Rosiak J.M. Studies on the free radical chemistry of poly(ε-caprolactone). IRaP 2006: 7th International Symposium on Ionizing Radiation and Polymers, Antalya, Turkey, 23-28.09.2006. Book of abstracts, p. 125. 39. Fuente J. De la, Sobarzo-Sánchez E., Bobrowski K. Spectroscopic characterization of radicals species from 2,3-dihydro-oxoisoaporphines generated by flash photolysis and pulse radiolysis. XVIII International Conference on Physical Organic Chemistry, Warsaw, Poland, 20-25.08.2006, p. 57. 40. Fuks L. Pt(II) chloride complexed by tetrahydrofurylthiourea or tetrahydrotiophenylthiourea: structural and biological features. 3rd Central European Conference: Chemistry towards biology – CHTB 2006, Kraków, Poland, 8-12.09.2006, P-8, [1] p. 41. Giglio J., León E., Rey A., Künstler J.-U., Gniazdowska E., Decristoforo C., Pietzsch H.-J. 99mTc-labelled RGD-peptides using the „4+1” mixed-ligand approach. Technetium, rhenium and other metals in chemistry and nuclear medicine. 7th International Sympo- sium, Italy, 6-9.09.2006. U. Mazzi, A. Nadali (eds). Abstracts, 3AP12, p. 46. 42. Głuszewski W., Zagórski Z.P. Chemia radiacyjna mieszanin polimerowych PP/PS (Radiation chemistry of PP/PS polymer mixtures). ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006. Streszczenia, p. 34. 43. Głuszewski W., Zagórski Z.P. Radiation effects on PP/PS blends as a model of protection effects by aromatics. IRaP 2006: 7th International Symposium on Ionizing Radiation and Polymers, Antalya, Turkey, 23-28.09.2006. Book of abstracts, p. 128. 44. Głuszewski W., Zagórski Z.P. Zjawiska ochronne w chemii radiacyjnej polimerów (Protective phenomena in the radiation chemistry of polymers). 9. Spotkanie Inspektorów Ochrony Radiologicznej, Dymaczewo Nowe, Poland, 20.05.-2.06.2006. Materiały konferencyjne, pp. 15-16. 45. Grądzka I., Sochanowicz B., Buraczewska I., Szumiel I. Participation of the EGF receptor in the response to X-irradiation in human glioma M059 K and J cells. The 10th Anniversary of Gliwice Scientific Meetings, Gliwice, Poland, 17-18.11.2006, p. 42. 46. Grodkowski J., Kocia R., Mirkowski J. Radioliza impulsowa przejściowych widm absorpcyjnych p-terfenylu w cieczy jonowej bis[(trifluoro-

metylo)sulfonylo] imidzie metylotributyloamoniowym (R4NNTF2) (Pulse radiolysis of intermediate absorption spectra of p-terphenyl in ionic liquid methyltributylammonium bis[(trifluoromethyl)sulfonyl]imide). ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006. Streszczenia, p. 56. 47. Gryz M., Starosta W., Leciejewicz J. Crystal structure of zinc(II) pyrazolate trihydrate. 48. Konwersatorium krystalograficzne, Wrocław, Poland, 29-30.06.2006. Streszczenia komunikatów, A-22, p. 71. 48. Gryz M., Starosta W., Leciejewicz J. Monomeric molecules in the crystal structures of magnesium(II) and zinc(II) structures with imidazole-4-carboxylate and water ligands. 48. Konwersatorium krystalograficzne, Wrocław, Poland, 29-30.06.2006. Streszczenia komunikatów, A-23, pp. 72-73. 49. Herdzik I. Separacja izotopów galu i indu z wykorzystaniem chromatografii jonowymiennej (Separation of gallium and indium isotopes using ion-exchange chromatography). THE INCT PUBLICATIONS IN 2006 181

ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006. Streszczenia, p. 40. 50. Kałuska I., Lazurnik V.T., Lazurnik V.M., Popov G.F., Rogov Y.V., Zimek Z. The features of electron dose distribution in circular objects: comparison of Monte Carlo simulation predictions with dosimetry. 14th International Meeting on Radiation Processing (IMRP), Kuala Lumpur, Malaysia, 26.02.-3.03.2006. Conference abstracts book, p. 206. 51. Kciuk G., Hug G., Mirkowski J., Bobrowski K. Intramolecular electron transfer in dipeptides containing tyrosine. 11th Tihany Symposium on Radiation Chemistry, Eger, Hungary, 26-31.08.2006. Program and abstracts, p. 10. 52. Kciuk G., Hug G., Mirkowski J., Bobrowski K. Radiation-induced oxidation of dipeptides containing tyrosine and methionine: influence of amino acid sequence, pH and conformation. 12th International Conference on Physical Chemistry – Romphyschem-12, Bucharest, Romania, 6-8.09.2006. Abstract book, p. 61. 53. Kciuk G., Hug G., Mirkowski J., Bobrowski K. Utlenianie dipeptydów zawierających reszty tyrozyny i metioniny: badania metodą radiolizy impulsowej (Oxidation of dipeptides containing tyrosine and methionine; studies by pulse radiolysis). ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006. Streszczenia, p. 52. 54. Kocia R., Grodkowski J., Mirkowski J. Pulse radiolysis study of the formation the p-terphenyl radical anion in the ionic liquid methyltributyl-

ammonium bis[(trifluoromethyl)sulfonyl]imide (R4NNTf2). 12th International Conference on Physical Chemistry - Romphyschem-12, Bucharest, Romania, 6-8.09.2006. Abstract book, p. 116. 55. Kornacka E.M., Przybytniak G., Rafalski A., Kozakiewicz J. Radiation induced effects in segmented poly(siloxaneurethane) ureas based on aliphatic and aromatic diisocyanates. 11th Tihany Symposium on Radiation Chemistry, Eger, Hungary, 26-31.08.2006. Program and abstracts, p. 77. 56. Kornacka E.M., Przybytniak G., Święszkowski W. Influence of crystallinity on radiation stability of PE. Workshop on Biotribology, COST 533, Warszawa, Poland, 6.10.2006, pp. 8-9. 57. Krejzler J., Narbutt J., Foreman M.R.St J., Hudson M.J., Casensky B., Madic C. Solvent extraction of Am(III) and Eu(III) from nitrate solution using synergistic mixtures of n-tridentate heterocycles and chlorinated cobalt dicarbollide. 15th Radiochemical Conference, Mariánské Lázne, Czech Republic, 23-28.04.2006. Booklet of abstracts, p. 212. 58. Kruszewski M., Iwaneńko T., Woliński J., Wojewódzka M. Differential action of human metabolism and energy regulators on the lymphocyte susceptibility to ionizing radiation. III International and VI Cuban Mutagenesis, Teratogenesis and Carcinogenesis Workshop, Havana, Cuba, 25-27.09.2006, p. 8. 59. Kruszewski M., Iwaneńko T., Woliński J., Wojewódzka M. Ghrelin, a natural ligand for the GHS receptor, sensitizes blood mononuclear cells to oxidative stress. III International and VI Cuban Mutagenesis, Teratogenesis and Carcinogenesis Workshop, Havana, Cuba, 25-27.09.2006, p. 30. 60. Kruszewski M., Iwaneńko T., Woliński J., Zabielski R., Wojewódzka M. Ghrelin, a natural ligand for the growth hormone secretagogue receptor, sensitizes blood mononuclear cells to oxidative stress. The 10th Anniversary of Gliwice Scientific Meetings, Gliwice, Poland, 17-18.11.2006, p. 45. 182 THE INCT PUBLICATIONS IN 2006

61. Kruszewski M., Lewandowska H., Męczyńska S., Sochanowicz B., Sadło J. Differential action of permeable and non-permeable iron chelators on formation on dinitrosyl iron complexes in vivo. 16th International Conference on Chelators (ICOC), Limassol, Cyprus, 25-31.10.2006, p. 32. 62. Kulisa K., Dybczyński R., Danko B., Samczyński Z. Wstępne wydzielanie grupy lantanowców z materiałów biologicznych i środowiskowych i ich oznaczanie za pomocą chromatografii jonów (Preliminary separation of the lanthanides as a group from biological and environmental materials and their determination by ion chromatography). VII Konferencja chromatograficzna: chromatografia i techniki pokrewne a zdrowie człowieka, Białystok, Poland, 10-13.10.2006, p. 97. 63. Łyczko K., Starosta W. The structures of lead(II) complexes with tropolone. ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006. Streszczenia, p. 67. 64. Łyczko M. Trikarbonylkowe kompleksy technetu(I) z lipofilowymi ligandami bidentnymi (Tricarbonyl complexes of technetium(I) with bidentate lyophylic ligands). ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006. Streszczenia, p. 68. 65. Łyczko M., Schibli R., Narbutt J. Substitution of imidazole and bombesin for water in aquatricarbonyl(n-methyl-2-piridenecarbothioamide) technetium(I) cation. 2+1 approach. Technetium, rhenium and other metals in chemistry and nuclear medicine. 7th International Sympo- sium, Italy, 6-9.09.2006. U. Mazzi, A. Nadali (eds). Abstracts, 3AP14, p. 47. 66. Maddukuri L., Christiansen M., Dudzińska D., Zaim J., Obutulowicz T., Komisarski M., Wójcik A., Kusmierek J., Stevnsner T., Bohr A., Tudek B. Cockayane syndrome group B protein in involved in repairing of DNA adducts induced by trans-4-hydroxy-2-nonenal. The 10th Anniversary of Gliwice Scientific Meetings, Gliwice, Poland, 17-18.11.2006, p. 47. 67. Majkowska A., Bilewicz A. Formation kinetics and stability of some TRI and tetraaza derivative complexes of scandium. ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006. Streszczenia, p. 72. 68. Marciniak B., Hug G.L., Hörner G., Bobrowski K. Reactive intermediates in the photo-oxidation of sulfur-containing organic compounds. 20th International Symposium on Radical Ion Reactivity: ISRIR 2006, Rome, Italy, 2-6.07.2006, IL3, [1] p. 69. Męczyńska S., Lewandowska H., Kruszewski M. The role of lysosomal iron in ·NO signaling. ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006. Streszczenia, p. 77. 70. Męczyńska S., Lewandowska-Siwkiewicz H., Kruszewski M. Interaction of dinitrosyl iron complexes with DNA. The 10th Anniversary of Gliwice Scientific Meetings, Gliwice, Poland, 17-18.11.2006, p. 49. 71. Narbutt J., Krejzler J. Heteroleptic complexes of Am(III) and Eu(III) with a triazinylbipyridine derivative. Multiple regression analysis of solvent extraction data. 37th International Conference on Coordination Chemistry (ICCC), Cape Town, South Africa, 13-18.08.2006. D.J. Robinson, I.M. Robinson (eds.). Oral abstracts, p. 222. 72. Narbutt J., Krejzler J. Oddzielanie trójwartościowych aktynowców od lantanowców w odpadach promieniotwórczych z prze- robu wypalonych paliw jądrowych (Separation of trivalent actinides from lanthanides in radioactive wastes from reprocessing of spent nuclear fuels). XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, S12-W4, p. 284. THE INCT PUBLICATIONS IN 2006 183

73. Ostapczuk A. Electron beam application for volatile organic compounds removal. The Workshop on dosimetry for radiation applications in technologies for environment pollution control, Warszawa, Poland, 5.04.2006, p. 5. 74. Pawlukojć A., Starosta W., Leciejewicz J., Natkaniec I., Nowak D. The molecular structure and dynamics of 2-aminopyridine-3-carboxylic acid by X-ray diffraction, inelastic neutron scattering, infrared, Raman spectroscopy and from first principles calculations. V Workshop on investigations at the IBR-2 pulsed reactor, Dubna, Russia, 14-17.06.2006. Programme and abstracts, p. 58. 75. Polkowska-Motrenko H. Badania biegłości laboratoriów oznaczających pierwiastki toksyczne w żywności (Proficiency testing of laboratories determining toxic elements in food). XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, p. 221. 76. Polkowska-Motrenko H., Chajduk E., Dybczyński R. Oznaczanie selenu w materiałach biologicznych za pomocą metody definitywnej opartej na radiochemicznej neutronowej analizie aktywacyjnej (Determination of selenium in biological samples by definitive method based on RNAA). Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały XV Poznańskiego konwersatorium analitycznego, Poznań, Poland, 20-21.04.2006, p. 90. 77. Polkowska-Motrenko H., Dybczyński R. Działalność Instytutu Chemii i Techniki Jądrowej w dziedzinie zapewnienia jakości w nieorganicznej analizie śladowej (Activities of the Institute of Nuclear Chemistry and Technology in the domain of quality assurance for inorganic trace analysis). VI Sesja przeglądowa analityki żywności, Warszawa, Poland, 17.11.2006. Materiały sesji, p. 13. 78. Polkowska-Motrenko H., Dybczyński R. Program badań biegłości ROŚLINY – oznaczanie zawartości As, Cd, Cu, Hg, Se, Pb i Zn w żywności pochodzenia roślinnego (PT scheme: PLANTS – determination of As, Cd, Cu, Hg, Se, Pb and Zn in food of plant origin). Ogólnopolska konferencja naukowa: Jakość w chemii analitycznej, Warszawa, Poland, 23-24.11.2006, [1] p. 79. Polkowska-Motrenko H., Dybczyński R., Chajduk E., Danko B., Kulisa K., Samczyński Z., Sypu- ła M., Szopa Z. Nowe polskie atestowane materiały odniesienia: Mąka Kukurydziana INCT-CF-3 i Mąka Sojowa INCT-SBF-4 dla potrzeb nieorganicznej analizy śladowej – przygotowanie i atestacja (New Polish CRMs: Corn Flour INCT-CF-3 and Soya Bean Flour INCT-SBF-4 for the purpose of inorganic trace analysis – preparation and certification). Ogólnopolska konferencja naukowa: Jakość w chemii analitycznej, Warszawa, Poland, 23-24.11.2006, [1] p. 80. Polkowska-Motrenko H., Dybczyński R., Chajduk E., Danko B., Kulisa K., Samczyński Z., Sypu- ła M., Szopa Z. Nowe polskie certyfikowane materiały odniesienia dla potrzeb nieorganicznej analizy śladowej: Mąka Kukurydziana INCT-CF-3 i Mąka Sojowa INCT-SBF-4 (New Polish certified reference materials: Corn Flour INCT-CF-3 and Soya Beam Flour INCT-SBF-4 for inorganic trace analysis). XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006, S8-K40, p. 194. 81. Polkowska-Motrenko H., Fuks L., Sypuła M. Badania biegłości laboratoriów monitorujących skażenia promieniotwórcze kraju (Proficiency testing of laboratories monitoring country radionuclide contamination). XLIX Zjazd PTChem i SITPChem, Gdańsk, Poland, 18-22.09.2006. Materiały zjazdowe, p. 289. 82. Polkowska-Motrenko H., Sadowska-Bratek M. Badanie trwałości materiałów odniesienia metodą NAA (Studies of the stability of reference materials by the NAA method). Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały XV Poznańskiego konwersatorium analitycznego, Poznań, Poland, 20-21.04.2006, p. 92. 83. Przybytniak G., Kornacka E.M., Kozakiewicz J. Radical processes in segmented poly(siloxaneurethaneureas) induced by ionizing radiation. 184 THE INCT PUBLICATIONS IN 2006

IRaP 2006: 7th International Symposium on Ionizing Radiation and Polymers, Antalya, Turkey, 23-28.09.2006. Book of abstracts, p. 160. 84. Przybytniak G., Kornacka E., Mirkowski K., Nowicki A., Rafalski A. Radiation degradation of blends polypropylene/poly(ethylene-co-vinyl acetate). 11th Tihany Symposium on Radiation Chemistry, Eger, Hungary, 26-31.08.2006. Program and abstracts, p. 16. 85. Rafalski A., Przybytniak G., Kornacka E., Mirkowski K., Nowicki A. Influence of copolymers on radiation resistance of polypropylene blends. XVII International Conference on Physical Organic Chemistry, Warszawa, Poland, 20-25.08.2006, p. 80. 86. Ramamoorthy N., Haji-Saeid M., Chmielewski A.G., Chupov A. IAEA’s support to radiation processing technology practices in developing countries. 14th International Meeting on Radiation Processing, Kuala Lumpur, Malaysia, 26.02.-3.03.2006. Con- ference abstracts book, [1] p. 87. Sadło J., Michalik J., Danilczuk M., Turek J. Silver clusters in molecular sieves. E-MRS 2006 Fall Meeting, Warszawa, Poland, 4-8.09.2006. Book of abstracts, p. 71. 88. Samczyński Z., Łyczko M., Dybczyński R., Narbutt J. Badania trikarbonylkowych kompleksów technetu(I) metodą chromatografii jonowymiennej i elektro- forezy bibułowej (Investigations of tricarbonyl complexes of technetium(I) by ion exchange chromatography and paper electrophoresis). VII Konferencja chromatograficzna: chromatografia i techniki pokrewne a zdrowie człowieka, Białystok, Poland, 10-13.10.2006, pp. 72-74. 89. Samczyński Z., Łyczko M., Dybczyński R., Narbutt J. 99m + Ion exchange studies on the organometallic aqua-ion fac-[ Tc(CO)3(H2O)3] in acidic aqueous solutions. Technetium, rhenium and other metals in chemistry and nuclear medicine. 7th International Sympo- sium, Italy, 6-9.09.2006. U. Mazzi, A. Nadali (eds). Abstracts, 3AP26, p. 18. 90. Starosta W., Leciejewicz J. The crystal structure of a calcium(II) complex with pyridazine-3-carboxylate and water ligands. 48. Konwersatorium krystalograficzne, Wrocław, Poland, 29-30.06.2006. Streszczenia komunikatów, B-27, p. 161. 91. Starosta W., Leciejewicz J. Three-dimensional polymeric molecular pattern in the crystal structure of a Ca(II) complex with pyrazine-2,3,5,6-tetracarboxylate and water ligands. 48. Konwersatorium krystalograficzne, Wrocław, Poland, 29-30.06.2006. Streszczenia komunikatów, B-28, pp. 162-163. 92. Trojanowicz M., Drzewicz P., Bojanowska-Czajka A., Nałęcz-Jawecki G., Sawicki J. Radiolytic removal of selected pesticides from industrial wastes. SETAC Asia/Pacific 2006. Growth with a limit: the integration of ecosystem protection for human health benefits, Peking, China, 18-20.09.2006. Abstracts, [1] p. 93. Trojanowicz M., Szydłowska D., Campas M., Marty J.-L. Determination of microcystins in surface waters using amperometric screen-printed biosensor with immobilized protein phosphatase and high-performance liquid chromatography. SETAC Asia/Pacific 2006. Growth with a limit: the integration of ecosystem protection for human health benefits, Peking, China, 18-20.09.2006. Abstracts, [1] p. 94. Turek J., Michalik J. Rodniki srebroorganiczne (Organosilver radicals). ChemSession’06: III. Warszawskie seminarium doktorantów chemików, Warszawa, Poland, 19.05.2006. Streszczenia, p. 108. 95. Wierzchnicki R., Derda M. Stable isotopes composition in milk origin control. 3rd Central European Congress on Food, Sofia, Bulgaria, 22-24.05.2006. Book of abstracts, p. 209. THE INCT PUBLICATIONS IN 2006 185

96. Wojewódzka M., Kruszewski M., Buraczewska I., Xu W., Massuda E., Zhang J., Szumiel I. Sirtuin inhibition increases the rate of DNA-PK-independent double-strand break repair. III International and VI Cuban Mutagenesis, Teratogenesis and Carcinogenesis Workshop, Havana, Cuba, 25-27.09.2006, p. 31. 97. Wojewódzka M., Kruszewski M., Buraczewska I., Xu W., Massuda E., Zhang J., Szumiel I. Type III histone deacetylases inhibition increases the rate of DNA-PK-independent DSB repair. The 10th Anniversary of Gliwice Scientific Meetings, Gliwice, Poland, 17-18.11.2006, p. 61. 98. Zagórski Z.P. Prebiotic chemical raw material for life. 4th International School on Complexity: Basic questions about the origin of life, Cerice, Italy, 2-5.10.2006, p. 26. 99. Zagórski Z.P. Pulse radiolysis of solids. Pune University Workshop on Radiation and Photochemistry (PUWORP-2006), Pune, India, 10-11.01.2006, [1] p. 100. Zagórski Z.P. Role of ionizing in contribution to homochirality as the signature of life. 4th International School on Complexity: Basic questions about the origin of life, Cerice, Italy, 2-5.10.2006, p. 51. 101. Zimek Z. Characteristics and capabilities of X-ray converters applied in radiation processing. 11th Tihany Symposium on Radiation Chemistry, Eger, Hungary, 26-31.08.2006. Program and abstracts, p. 35. 102. Zimek Z. Dosimetric method for industrial scale flue gas treatment. The Workshop on dosimetry for radiation applications in technologies for environment pollution control, Warszawa, Poland, 5.04.2006, p. 6. 103. Zimek Z., Chmielewski A.G. Implementation of high power electron accelerators for environmental protection. RuPAC 2006: XXth Russian Conference on Charged Particle Accelerators, Novosibirsk, Russia, 10-14.09.2006. Abstracts brochure, p. 109. 104. Zimek Z., Dźwigalski Z., Warchoł S., Bułka S., Roman K. Upgrading of accelerator facility for radiation sterilization. RuPAC 2006: XXth Russian Conference on Charged Particle Accelerators, Novosibirsk, Russia, 10-14.09.2006. Abstracts brochure, p. 108. 105. Zimek Z., Przybytniak G., Nowicki A., Mirkowski K. Modification of bentonite fillers using ionizing radiation. E-MRS 2006 Fall Meeting, Warszawa, Poland, 4-8.09.2006. Book of abstracts, p. 113.

SUPPLEMENT LIST OF THE INCT PUBLICATIONS IN 2005

CHAPTERS IN BOOKS

1. Dalivelya O., Savina N., Buraczewska I., Grądzka I., Szumiel I. Effects of an antimutagen of 1,4-dihydropyridine series on cell survival in X-irradiated murine L5178Y sublines. In: Molekularnaya i prikladnaya genetika. Institut Genetiki i Citologii Nacional’noj Akademii Nauk Belarusi, Minsk 2005. Naucnye trudy, Tom 1, p. 292. 186 NUKLEONIKA

NUKLEONIKA THE INTERNATIONAL JOURNAL OF NUCLEAR RESEARCH

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

CONTENTS OF No. 1/2006 Proceedings of the 2nd IAEA Research Co-ordination Meeting of the Co-ordinated Research Project on Dense Magnetized Plasma, 1-3 June 2005, Kudowa Zdrój, Poland 1. Foreword A. Malaquias 2. Dense magnetized plasma and its applications: a view of the 3-year activity of the IAEA Co-ordinated Research Programme V.A. Gribkov, A. Malaquias 3. Development of diagnostic tools for Plasma Focus derived X-ray source E. Angeli, C. Bonifazzi, A. Da Re, M. Marziani, A. Tartari, M. Frignani, S. Mannucci, D. Mostacci, F. Rocchi, M. Sumini 4. Dense Plasma Focus as a powerful source of monochromatic X-ray radiation A.V. Dubrovsky, V.A. Gribkov, Yu.P. Ivanov, L. Karpiński, M.A. Orlova, V.M. Romanova, M. Scholz, I.V. Volobuev 5. Production of negative hydrogen ions using a low-pressure reflex discharge source E.I. Toader 6. Development of a large beam facility B.H. Oh, S.R. In, K.W. Lee, S.H. Jeong, C.S. Seo, D.H. Chang 7. Experimental study of a small gas-puff Z-pinch device C.M. Luo, X.X. Wang, X.B. Zou 8. D(3He,p)4He and D(d,p)3H fusion in a small plasma focus operated in a deuterium helium-3 gas mixture S.V. Springham, T.H. Sim, R.S. Rawat, P. Lee, A. Patran, P.M.E. Shutler, T.L. Tan, S. Lee 9. PF-6 – an effective plasma focus as a source of ionizng radiation and plasma streams for application in material technology, biology and medicine V.A. Gribkov, A.V. Dubrovsky, M. Scholz, S. Jednorog, L. Karpiński, K. Tomaszewski, M. Paduch, R. Miklaszewski, V.N. Pimenov, L.I. Ivanov, E.V. Dyomina, S.A. Maslyaev, M.A. Orlova 10. Colored-noise-induced anomalous transport in periodic structures T. Laas, A. Sauga, R. Mankin, A. Ainsaar, Ü. Ugaste, A. Rekker 11. Surface and bulk processes in materials induced by pulsed ion and plasma beams at Dense Plasma Focus devices V.N. Pimenov, S.A. Maslyaev, L.I. Ivanov, E.V. Dyomina, V.A. Gribkov, A.V. Dubrovsky, M. Scholz, R. Miklaszewski, Ü.E. Ugaste, B. Kolman 12. Status of a mega-joule scale Plasma-Focus experiments M. Scholz, B. Bieńkowska, M. Borowiecki, I. Ivanova-Stanik, L. Karpiński, W. Stępniewski, M. Paduch, K. Tomaszewski, M. Sadowski, A. Szydłowski, P. Kubeš, J. Kravárik 13. High kinetic energy dense plasma jet A.V. Voronin, V.K. Gusev, Yu.V. Petrov, N.V. Sakharov, K.B. Abramova, K.G. Hellblom NUKLEONIKA 187

CONTENTS OF No. 2/2006 1. The quantum diffusion of carbon in α-iron in low temperature L. Dąbrowski, A. Andreev, M. Georgiev 2. Investigation of low temperature diffusion of carbon in martensite by Mössbauer spectroscopy and X-ray diffraction A. Jabłońska, L. Dąbrowski, J. Suwalski, S. Neov 3. Surface structure changes of InP and GaAs single crystals irradiated with high energy electrons and swift heavy ions A.Yu. Didyk, F.F. Komarov, L.A. Vlasukova, V.N. Yuvchenko, A. Hofman 4. Preparation of [61Cu]DTPA complex as a possible PET tracer A.R. Jalilian, P. Rowshanfarzad, M. Sabet, M. Kamalidehghan 5. Production of [103Pd]Bleomycin complex for targeted therapy A.R. Jalilian, Y. Yari-Kamrani, M. Sadeghi 6. Gamma-ray beam attenuation to assess the influence of soil texture on structure deformation L.F. Pires, O.O.S. Bacchi, N.M.P. Dias 7. A radiographic facility at the Sołtan Institute for Nuclear Studies (SINS) at Świerk, Poland J. Bigolas, W. Drabik, E. Pławski, A. Wysocka-Rabin 8. Air aerosol sampling station AZA-1000 at Polish Polar Station in Hornsund, Spitsbergen B. Mysłek-Laurikainen, M. Matul, S. Mikołajewski, H. Trzaskowska, Z. Preibisz, I. Garanty, M. Kubicki, P. Rakowski, T. Krynicki, M. Stefański

CONTENTS OF No. 3/2006 1. Effects of an antimutagen of 1,4-dihydropyridine series on cell survival and DNA damage in L5178Y murine sublines O. Dalivelya, N. Savina, T. Kuzhir, I. Buraczewska, M. Wojewódzka, I. Szumiel 2. Production and quality control of 66Ga radionuclide M. Sabet, P. Rowshanfarzad, A.R. Jalilian, M.R. Ensaf, A.A. Rajamand 3. Development of [66Ga]oxine complex; a possible PET tracer A.R. Jalilian, P. Rowshanfarzad, M. Sabet, A. Rahiminejad-Kisomi, A.A. Rajamand 4. Computation of concentration changes of heavy metals in the fuel assemblies with 1.6% enrichment by ORIGEN code for VVER-1000 M. Rahgoshay 5. Monte-Carlo simulation of a neutron source generated with electron linear accelerator A. Wasilewski, S. Wronka 6. Investigation of high-dose irradiation effects on polystyrene calorimeter response F. Ziaie, A. Noori 7. Influence of temperature on breakdown voltage of 10 MeV electron beam irradiated LDPE and HDPE M. Borhani, F. Ziaie, M.A. Bolorizadeh, G. Mirjalili

CONTENTS OF No. 4/2006 1. Obituary Professor Barbara Hołyńska (1930-2006) 2. DNA double-strand break rejoining in radioadapted human lymphocytes: evaluation by neutral comet assay and pulse-field gel electrophoresis M. Wojewódzka, I. Buraczewska, I. Szumiel, I. Grądzka 3. Influence of 137Cs and 90Sr on vegetative and generative organs of Lepidium sativum L. and Tradescantia clone 02 D. Marèiulionienë, B. Lukšienë, D. Kiponas, D. Montvydienë, G. Maksimov, J. Darginavièienë, V. Gavelienë 4. Preparation and biodistribution of [201Tl](III)vancomycin complex in normal rats A.R. Jalilian, M.A. Hosseini, A. Karimian, F. Saddadi, M. Sadeghi 5. Production, quality control and initial imaging studies of [82mRb]RbCl for PET studies P. Rowshanfarzad, A.R. Jalilian, M. Kiyomarsi, M. Sabet, A.R. Karimian, S. Moradkhani, M. Mirzaii 6. Isotope effects of gallium and indium in cation exchange chromatography W. Dembiński, I. Herdzik, W. Skwara, E. Bulska, A.I. Wysocka 188 NUKLEONIKA

7. Production and separation of manganese-54 from alpha-irradiated V2O5 target M. Kłos, M. Bartyzel, B. Petelenz 8. Design, construction and performance of a pressure chamber for water retention curve determination through traditional and nuclear methods L.F. Pires, O.O.S. Bacchi

SUPPLEMENT No. 1/2006 Proceedings of the 2nd Polish-Japanese Workshop on Materials Science “Materials for Sustainable Development in the 21st Century”, 12-15 October 2005, Warsaw, Poland 1. Foreword J. Michalik, K. Halada 2. Worldwide developments in the field of radiation processing of materials in the down of 21st century A.G. Chmielewski

3. Design of high quality doped CeO2 solid electrolytes with nanohetero structure T. Mori, J. Drennan, D.R. Ou, F. Ye 4. Structure and properties of nanomaterials produced by severe plastic deformation Z. Pakieła, H. Garbacz, M. Lewandowska, A. Drużycka-Wiencek, M. Suś-Ryszkowska, W. Zieliński, K.J. Kurzydłowski

5. Synthesis of nanostructured tetragonal ZrO2 of enhanced thermal stability A. Adamski, P. Jakubus, Z. Sojka 6. Studies on template-synthesized polypyrrole nanostructures W. Starosta, M. Buczkowski, B. Sartowska, D. Wawszczak 7. Structural characterization of room-temperature synthesized fullerene nanowhiskers K. Miyazawa, J. Minato, T. Mashino, S. Nakamura, M. Fujino, T. Suga 8. EPR and ESEEM study of silver clusters in ZK-4 molecular sieves J. Sadło, J. Michalik, L. Kevan 9. Properties of novel silicon nitride-based materials K. Itatani 10. Development of environmental purification materials with smart functions H. Yamada, Y. Watanabe, K. Tamura 11. Silica materials with biocidal activity D.K. Chmielewska, A. Łukasiewicz, J. Michalik, B. Sartowska 12. High pressures studies on hydrides of selected manganese alloys H. Sugiura, S.M. Filipek, V. Paul-Boncour, I. Marchuk, R.-S. Liu, S.I. Pyun

13. Application of Pt/Al2O3 catalysts produced by sol-gel process to uranyl ion reduction A. Deptuła, W. Łada, T. Olczak, A.G. Chmielewski 14. Hybrid atomization method suitable for production of fine spherical lead-free solder powder K. Minagawa, H. Kakisawa, S. Takamori, Y. Osawa, K. Halada 15. Degradation of polyolefine wastes into liquid fuels B. Tymiński, K. Zwoliński, R. Jurczyk 16. EPR study on biominerals as materials for retrospective dosimetry J. Sadło, J. Michalik, W. Stachowicz, G. Strzelczak, A. Dziedzic-Gocławska, K. Ostrowski 17. Membrane processes for environmental protection: applications in nuclear technology G. Zakrzewska-Trznadel 18. Advanced processing for recycling of iron scrap with impurities Y. Osawa, S. Takamori, K. Minagawa, H. Kakisawa, K. Halada 19. Influence of radiation sterilization on poly(ester urethanes) designed for medical applications G. Przybytniak, E. Kornacka, J. Ryszkowska, M. Bil, A. Rafalski, P. Woźniak, M. Lewandowska-Szumieł 20. Radiation processing of polymers and semiconductors at the Institute of Nuclear Chemistry and Tech- nology Z. Zimek, G. Przybytniak, I. Kałuska

SUPPLEMENT No. 2/2006 Proceedings of the IV All-Polish Conference on Radiochemistry and Nuclear Chemistry, 9-11 May 2005, Kraków-Przegorzały, Poland NUKLEONIKA 189

1. Preface L. Fuks 2. Thermochromatographic separation of 206,208Po from a bismuth target bombarded with protons B. Wąs, R. Misiak, M. Bartyzel, B. Petelenz 3. Carbon isotope effects in the studies of the mechanism of action of tyrosine phenol-lyase W. Augustyniak, R. Kański, M. Kańska 14 4. Synthesis of ring labeled [1’- C]-L-tyrosine R. Kański, W. Augustyniak, M. Kańska 5. Tritium kinetic isotope effects on enzymatic decomposition of L-tryptophan E. Boroda, R. Kański, M. Kańska 6. Self-absorption correction in gamma-ray spectrometry of environmental samples – an overview of methods and correction values obtained for the selected geometries P. Jodłowski 7. Interlaboratory comparison of the determination of 137Cs and 90Sr in water, food and soil: preparation and characterization of test materials L. Fuks, H. Polkowska-Motrenko 8. Studies on concentration of some heavy metals and strontium 90Sr and cesium 137Cs isotopes in bottom sediments of selected lakes of Łęczyńsko-Włodawskie Pojezierze J. Solecki, M. Reszka, S. Chibowski 9. Determination of the sediment deposition rates in the Kuwait Bay using 137Cs and 210Pb A.Z. Al-Zamel, F. Bou-Rabee, M.A. Al-Sarawi, M. Olszewski, H. Bem 10. Radionuclides of iron (55Fe), nickel (63Ni), polonium (210Po), uranium (234U, 235U, 238U) and plutonium (238Pu, 239-240Pu, 241Pu) in Poland and Baltic Sea environment B. Skwarzec, D.I. Strumińska, A. Boryło 11. Investigation of the influence of high humidity and exposure duration on the measurement results of radon concentration by means of PicoRad system in the CLOR calibration chamber O. Stawarz, M. Karpińska, K. Mamont-Cieśla 12. Accumulation properties of Norway spruce (Picea abies) for different radionuclides E. Tomankiewicz, J.W. Mietelski, P. Gaca, S. Błażej 13. Spatial 137Cs distribution in forest soil A. Dołhańczuk-Śródka, T. Majcherczyk, M. Smuda, Z. Ziembik, M. Wacławek 14. Isotope effects on selected physicochemical properties of nitromethane and 1-pentanol A. Makowska, J. Szydłowski 15. Radiation chemistry of radioactive waste to be stored in the salt mine repository Z.P. Zagórski

SUPPLEMENT No. 3/2006 Proceedings of the 18th International Conference on Nucleus-Nucleus Collisions, 4-9 August 2005, Budapest, Hungary 1. Preface J. Pluta 2. Freeze-out and anisotropic flow in microscopic models L.V. Bravina, K. Tywoniuk, E.E. Zabrodin, G. Burau, J. Bleibel, C. Fuchs, A. Faessler – – 3. Can thermal model explain Λ/p puzzle? L.V. Bravina, M.S. Nilsson, K. Tywoniuk, E.E. Zabrodin 4. Rapidity distributions of strange particles in Pb-Pb at 158 A GeV G.E. Bruno on behalf of the NA57 Collaboration 5. Elliptic flow at RHIC with NeXSPheRIO R.P.G. Andrade, F. Grassi, Y. Hama, T. Kodama, O. Socolowski Jr., B. Tavares 6. Effect of hadronic rescattering on the elliptic flow after the hydrodynamics model G.L. Ma, Y.G. Ma, B.H. Sa, X.Z. Cai, Z.J. He, H.Z. Huang, J.L. Long, W.Q. Shen, C. Zhong, J.H. Chen, J.X. Zuo, S. Zhang, X.H. Shi 7. Systematic study of directed flow at RHIC energies A.C. Mignerey for the PHOBOS Collaboration 190 NUKLEONIKA

8. The azimuthal anisotropy of electrons from heavy flavor decays in s NN = 200 GeV Au-Au collisions by PHENIX S. Sakai for the PHENIX Collaboration

9. Influence of the non-flow effects and fluctuations on the v2 measurements at RHIC X. Zhu, M. Bleicher 10. Freeze-out process with in-medium nucleon mass S. Zschocke, L.P. Csernai, E. Molnár, J. Manninen, A. Nyiri 11. Non-identical particle correlations in central Pb+Au collisions at 158 A GeV D. Antończyk for the CERES Collaboration 12. Charge balance functions and the transverse flow P. Bożek

13. Preliminary results on direct photon-photon HBT measurements in s NN = 62.4 GeV and 200 GeV Au+Au collisions at RHIC D. Das, G. Lin, S. Chattopadhyay, A. Chikanian, E. Finch, T.K. Nayak, S.Y. Panitkin, J. Sandweiss, A.A. Suaide, H. Zhang for the STAR Collaboration

14. Baryon-baryon correlations in Au+Au collisions at s NN = 62 GeV and s NN = 200 GeV, measured in the STAR experiment at RHIC H.P. Gos for the STAR Collaboration 15. Charge transfer fluctuations as a QGP signal S. Jeon, L. Shi, M. Bleicher 16. Strangeness conservation and pair correlations of neutral kaons with close momenta in inclusive processes V.L. Lyuboshitz, V.V. Lyuboshitz 17. Obtaining the specific heat of hadronic matter from CERN/RHIC experiments A. Mekjian

18. The evolution of correlation functions from low to high pT in PHENIX: from HBT to jets J.T. Mitchell for the PHENIX Collaboration 19. Effect of hard processes on momentum correlations in pp and pp– collisions G. Paić, P.K. Skowroński 20. A survey of multiplicity fluctuations in PHENIX J.T. Mitchell for the PHENIX Collaboration

21. How to measure specific heat using event-by-event average pT fluctuations M.J. Tannenbaum for the PHEHIX Collaboration 22. A statistical model analysis of yields and fluctuations in 200 GeV Au-Au collisions G. Torrieri, S. Jeon, J. Rafelski 23. Proposition of numerical modelling of BEC O.V. Utyuzh, G. Wilk, Z. Włodarczyk 24. Transverse momentum distributions and string percolation study in p+p, d+Au and Au+Au collisions

at sNN = 200 GeV B.K. Srivastava, R.P. Scharenberg, T.J. Tarnowsky for the STAR Collaboration

Information INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY NUKLEONIKA Dorodna 16, 03-195 Warszawa, Poland phone: (+4822) 504-11-32; fax: (+4822) 811-15-32; e-mail: [email protected] Abstracts and full texts are available on-line at http://www.ichtj.waw.pl/ichtj/general/nukleon.htm INTERVIEWS IN 2006 191

INTERVIEWS IN 2006

1. Chmielewski Andrzej G. Niedzicki W.: Sylwetki uczonych (Profiles of scientistis). TVP, Program 1, 20.09.2006. 2. Chmielewski Andrzej G. Truszczak D.: Osiągnięcia nauki (Achievements of science). Polskie Radio, Program 1, 20.09.2006. 3. Chmielewski Andrzej G. Giurla S.: A tecnologia avança e a humanidade agradece (High-tech serving the people). Brasil Nuclear, 11, 29, 20-22 (2006). 4. Chmielewski Andrzej G. Łoś P.: Akceleratory elektronów w ochronie środowiska (Application of electron accelerators in environmental protection). Radio dla Ciebie, 30.10.2006. 192 THE INCT PATENTS AND PATENT APPLICATIONS IN 2006

THE INCT PATENTS AND PATENT APPLICATIONS IN 2006

PATENTS

1. Sposób otrzymywania paliw ciekłych z odpadów tworzyw sztucznych, zwłaszcza odpadów poliolefinowych i urządzenie do realizacji tego sposobu (Method for obtaining liquid fuels from wastes of plastics, particularly of polyolefines, and a facility to realize the method) A.G. Chmielewski, J. Jerzy, T. Siekierski, B. Tymiński, K. Zwoliński Polish Patent No. 191891 2. Sposób usuwania lotnych zanieczyszczeń organicznych gazowych takich jak wielopierścieniowe węglowodory aromatyczne z przemysłowych gazów odlotowych (Method for elimination of gaseous organic impurities such as polycyclic aromatic hydrocarbons from industrial flue gases) A.G. Chmielewski, A. Ostapczuk, K. Kubica, J. Licki Polish Patent No. 192519 3. Sposób zwiększenia efektywności oczyszczania promieniotwórczych ścieków nisko i średnio aktywnych zatężanych metodą odwróconej osmozy (Method for enhancement of purification effectiveness of low and medium level radioactive wastes concentrated by reverse osmosis) A.G. Chmielewski, M. Harasimowicz, B. Tymiński, G. Zakrzewska-Trznadel Polish Patent No. 193649

PATENT APPLICATIONS

1. Detektor do pomiaru stężenia produktów rozpadu radonu w powietrzu (Detector for measuring the concentration of radon decay products in air) B. Machaj, J. Bartak P 378974 2. Sposób otrzymywania dwuwolframianu itrowo-potasowego oraz nanokompozytu tego dwuwolframianu dotowanego iterbem (Method for obtaining ittrium-potassium ditungstate and a nanocomposite of this compound doped with ytterbium) A. Deptuła, W. Łada, T. Olczak, D. Wawszczak, M. Borowiec, H. Szymczak, W. Diakonow, M. Barański P 379537 (with the Institute of Physics, Polish Academy of Sciences) 3. Sposób otrzymywania napełniaczy o strukturze montmorylonitu (Method for obtaining fillers of montmorillonite structure) Z. Zimek, I. Legocka, K. Mirkowski, A. Nowicki, G. Przybytniak P 379779 4. Sposób otrzymywania terapeutycznych ilości radionuklidu 177Lu (Method for obtaining therapeutic quantities of the 177Lu radionuclide) A. Bilewicz, E. Iller P 379829 5. Sposób wytwarzania mikrokrystalicznej celulozy (Method for obtaining microcrystalline cellulose) H. Stupińska, J. Palenik, E. Kopania, D. Wawro, D . Ciechańska, G. Krzyżanowska, E. Iller, Z. Zimek P 380328 (with the Institute of Biopolymers and Chemical Fibres, and the Pulp and Paper Research Institute) CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2006 193

CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2006

1. REGIONAL TRAINING COURSE “APPLICATION OF MONTE CARLO MODELING METHODS FOR DOSIMETRY CALCULATION IN RADIATION PROCESSING” IN THE FRAME OF THE TECHNICAL COOPERATION PROJECT RER/8/010 “QUALITY CONTROL METHODS AND PROCEDURES FOR RADIATION TECHNOLOGY”, 3-7 APRIL 2006, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology, International Atomic Energy Agency Organizing Committee: I. Kałuska, M.Sc., Z. Zimek, Ph.D., Prof. A.G. Chmielewski, Ph.D., D.Sc. OPENING J. Michalik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) A. Chupov (International Atomic Energy Agency, Vienna, Austria) H. Sampa (International Atomic Energy Agency, Vienna, Austria) LECTURES • New development in constuction and operation of radiation processing plants A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; Warsaw Uni- versity of Technology, Poland) • The use of dosimetry in process validation and facility qualification A. Kovacs (Institute of Isotopes and Surface Chemistry, Budapest, Hungary) • The role of Monte Carlo methods in industrial radiation application J. Mittendorfer (MEDISCAN, Austria) • Physical and mathematical methods for simulation of radiation processing V. Lazurik (Kharkov State University, Ukraine) • Models of an irradiation process for EB technologies (numerical code RT-Office) G. Popov (Kharkov State University, Ukraine) • Software for EB processing: ModeRTL, ModeDF, ModeCEB G. Popov (Kharkov State University, Ukraine) • Architecture of RT-Office software V. Lazurik (Kharkov State University, Ukraine) • The use of dosimetry and interpretation of dosimetry data K. Mehta (International Atomic Energy Agency, Vienna, Austria) • Calorimeters and alanine, CTA, PVC foil dosimeters Z. Stuglik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Dosimetry system for EB irradiation A. Kovacs (Institute of Isotopes and Surface Chemistry, Budapest, Hungary) • Introduction to intercomparison experiments Z. Stuglik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Uncertainty in dose measurements K. Mehta (International Atomic Energy Agency, Vienna, Austria) • Uncertainty evaluation of computer programs based on Monte Carlo method for dose calculations J. Mittendorfer (MEDISCAN, Austria) • Validation of radiation sterilization process I. Kałuska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • X-ray application for radiation processing Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Radiation processing of polymers A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; Warsaw Uni- versity of Technology, Poland) 194 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2006

• Simulation of irradiation process on radiation-technological lines (RTL) with scanned beam; software ModeRTL V. Lazurik, G. Popov (Kharkov State University, Ukraine) • Evaluation of intercomparison experiments K. Mehta (International Atomic Energy Agency, Vienna, Austria), A. Kovacs (Institute of Isotopes and Surface Chemistry, Budapest, Hungary) • Comparison of the experimental results with simulation predictions V. Lazurik (Kharkov State University, Ukraine), G. Popov (Kharkov State University, Ukraine), Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), I. Kałuska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Simulation of irradiation process of multi-layer circular objects such as wire, cables, tubing, pipes with scanned beam G. Popov (Kharkov State University, Ukraine) • Examples of some actual problems solutions in radiation processing V. Lazurik (Kharkov State University, Ukraine), G. Popov (Kharkov State University, Ukraine) SPECIAL LECTURES – technical visit to the Institute of Nuclear Chemistry and Technology • Film Dose Reader CD-02 B. Machaj (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Radiation facilities at the Institute of Nuclear Chemistry and Technology] Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Sadło (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), I. Kałuska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), S. Bułka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • The experimental validation of simulation predictions for dose mapping in heterogeneous targets irradiation with scanned EB I. Kałuska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), S. Bułka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), Z. Stuglik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), G. Popov (Kharkov State University, Ukraine) • Biological dosimetry in human biomonitoring M. Kruszewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), K. Brzozowska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), T. Bartłomiejczyk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), A. Wójcik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

2. THE WORKSHOP “DOSIMETRY FOR RADIATION APPLICATION IN TECHNOLOGIES FOR ENVIRONMENT POLLUTION CONTROL” IN THE FRAME OF THE MARIE CURIE HOST FELLOWSHIPS FOR THE TRANSFER OF KNOWLEDGE: ADVANCED METHODS FOR ENVIRONMENT RESEARCH AND CONTROL (AMERAC), 5 APRIL 2006, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology LECTURES • Overview of dosimetry methods for radiation technologies for environment preservation K. Mehta (International Atomic Energy Agency, Vienna, Austria) • Application of dosimetry for wastewater treatment – Brazilian experience M.H.O Sampa (International Atomic Energy Agency, Vienna, Austria), P.R. Rela (Instituto de Pesquisas Energéticas e Nucleares (IPEN), São Paulo, Brazil), C.L. Duarte (Instituto de Pesquisas Energéticas e Nucleares (IPEN), São Paulo, Brazil), C.S. Rela (Instituto de Pesquisas Energéticas e Nucleares (IPEN), São Paulo, Brazil), F.E. Costa (Instituto de Pesquisas Energéticas e Nucleares (IPEN), São Paulo, Brazil) • Dosimetry for wastewater treatment tests – Italian experience M. Lavalle (Institute for Organic Synthesis and Photoreactivity (ISOF), National Research Council (CNR), Bologna, Italy) • Dosimetric methods for industrial scale flue gas treatment Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Dosimetric methods for laboratory scale VOC treatment A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; Warsaw Uni- versity of Technology, Poland), Y. Sun (Institute of Nuclear Chemistry and Technology, Warszawa, CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2006 195

Poland), S. Bułka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), Z. Zimek (Insti- tute of Nuclear Chemistry and Technology, Warszawa, Poland) • Electron beam application for volatile organic compounds removal A. Ostapczuk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

3. THE WORKSHOP “METHODS OF ENVIRONMENTAL RESEARCH” IN THE FRAME OF THE MARIE CURIE HOST FELLOWSHIPS FOR THE TRANSFER OF KNOWLEDGE: ADVANCED METHODS FOR ENVIRONMENT RESEARCH AND CONTROL (AMERAC), 10 AUGUST 2006, WARSZAWA, POLAND Organized by the Institute of Nuclear Chemistry and Technology LECTURES • The use of stable isotopes of carbon to study the sources and sinks of some greenhouse gases (CO2, CH4) in air S.M. Cuna (National Institute for Research and Development of Isotopic and Molecular Technologies, Cluj-Napoca, Romania) • Design of novel membranes and their application for desalination by membrane distillation M. Khayet Souhaimi (University Complutense of Madrid, Spain) • Modelling and optimization of experimental processes in environmental engineering using Response Surface Methodology (RSM) C. Cojocaru (”Gh.Asachi” Technical University of Iaºi, Romania) DISCUSSION: conclusions, recommendations Moderator: A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland; Warsaw University of Technology, Poland)

4. SYMPOZJUM „CHEMIA I TECHNIKA RADIACYJNA: WYZWANIA I MOŻLIWOŚCI – JUBILEUSZ 80-LECIA PROF. DR HAB. ZBIGNIEWA P. ZAGÓRSKIEGO” (SYMPOSIUM ON CHEMISTRY AND RADIATION TECHNIQUES: CHALLENGE AND POSSIBILITIES – JUBILEE OF THE 80th ANNIVERSARY OF Prof. ZBIGNIEW P. ZAGÓRSKI, Ph.D., D.Sc. (17 OCTOBER 2006, WARSZAWA, POLAND) Organized by the Institute of Nuclear Chemistry and Technology LECTURES • Laudation L. Waliś (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Mayer (Institute of Applied Radiation Chemistry, Łódź, Poland), Z. Zimek (Institute of Nuclear Chemistry and Technol- ogy, Warszawa, Poland) • Przyszłość chemii radiacyjnej, jak ją widziano w roku 1946 (Future of radiation chemistry as was seen in 1946) Z.P. Zagórski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Znane i nieznane aspekty pierwszych etapów działania promieniowania jonizującego w biopolimerach i polimerach syntetycznych (Known and unknown aspects of primary stages of ionizing radiation treatment of biopolymers and synthetic polymers) G. Przybytniak (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Pomiary odległości metodą EPR (Distance measurements by the EPR method) J. Michalik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Wolne rodniki w związkach o znaczeniu biologicznym (Free radicals in biological important compounds) K. Bobrowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Ciecze jonowe – rozpuszczalniki przyszłości? (Ionic liquids – solvents of future?) J. Grodkowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Relaksacja elektronów pułapkowanych w etanolu oraz mieszaninach etanol-woda i etanol-metanol w tem- peraturze 10-77 (100) K (Relaxation of trapped electrons in ethanol and ethanol-methanol mixtures at a temperature of 10-77 (100) K) J.P. Suwalski (Institute of Applied Radiation Chemistry, Łódź, Poland) • Obecne i przyszłe zastosowania technik radiacyjnych w przetwórstwie polimerów (Present and future applications of radiation processing in polymer modification) A. Rafalski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) 196 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2006

• Antologia dozymetrii radiacyjnej dużych dawek (Antology of high dose radiation dosimetry) P. Panta (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Radiacyjna modyfikacja elastomerów (Radiation modification of elastomers) W. Głuszewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Chemia i technika radiacyjna - i co dalej? (Radiation chemistry and radiation processing – what the next thing?) Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

5. IV KONFERENCJA „PROBLEMY UNIESZKODLIWIANIA ODPADÓW” (IV CONFERENCE ON PROBLEMS OF WASTE DISPOSAL), 27 NOVEMBER 2006, WARSZAWA, POLAND Organized by the Warsaw University of Technology, Plant for Utilization of Solid Municipal Wastes (Warszawa), Institute of Nuclear Chemistry and Technology, Gdańsk University of Technology Organizing Committee: M. Obrębska, Ph.D., A. Polak, M.Sc. OPENING Jerzy Bałdyga (Warsaw University of Technology, Poland) Session IA. NAUKOWO-TECHNICZNA (SCIENCE AND TECHNOLOGY) Chairman: A. Biń (Warsaw University of Technology, Poland) • Przemysłowe testy współspalania komunalnych osadów ściekowych z węglem w kotle pyłowym (Com- bustion of municipal sludge with coal in a dust boiler – industrial tests) R. Wasilewski (Institute for Chemical Processing of Coal, Zabrze, Poland), S. Stelmach (Institute for Chemical Processing of Coal, Zabrze, Poland), J. Zuwała (Institute for Chemical Processing of Coal, Zabrze, Poland) • Współspalanie odpadów, biomasy i paliw kopalnych w kotłach energetycznych (Combustion of wastes, biomass and fossil fuels in energetic boilers) H. Karcz (Wrocław University of Technology, Poland), M. Krzysztof (ZBUS Combustion, Głowno, Poland), K. Folga (ZBUS Combustion, Głowno, Poland) • Wykorzystanie odpadowej biomasy do oczyszczania roztworów wodnych (Application of waste biomass for purification of water solutions) K. Bratek (Wrocław University of Technology, Poland), W. Bratek (Wrocław University of Technology, Poland) Session IB. SAMORZĄDOWO-EKONOMICZNO-PRAWNA (MUNICIPAL-ECONOMIC-LAWFUL) Chairman: P. Grzybowski (Warsaw University of Technology, Poland) • EUROVIX – biotechnologie dla życia (EUROVIX – Biotechnologies for life) K. Łuczak (EUROVIX S.r.l., Italy) • Dlaczego powinniśmy spalać odpady? (Why we should incinerate the wastes?) G. Wielgosiński (Technical University of Łódź, Poland) Session IIA. NAUKOWO-TECHNICZNA (SCIENCE AND TECHNOLOGY) Chairman: R. Zarzycki (Technical University of Łódź, Poland) • Analityczne badania radiolitycznej degradacji wybranych pestycydów (Radiolytical degradation of selected pesticides – analytical investigations) A. Bojanowska-Czajka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), P. Drzewicz (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), M. Trojanowicz (Institute of Nuclear Chemistry and Technology, Warszawa; Warsaw University of Technology, Poland), G. Nałęcz-Jawecki (Medical University of Warsaw, Poland), J. Sawicki (Medical University of Warsaw, Poland), Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), H. Nichipor (Institute of Radia- tion Physical-Chemical Problems, National Academy of Sciences of Belarus, Minsk, Belarus) • Unieszkodliwianie odpadów drobiarskich poprzez fermentacje metanową (Disposal of poultry wastes by methane fermentation) A. Zawadzka (Technical University of Łódź, Poland), K. Sikora-Łępicka (Technical University of Łódź, Poland) • Opracowanie sposobu zmniejszenia zrzutu azotu amonowego w ścieku technologicznym (A method for the reduction of ammonia in technological wastewater) J. Zieliński (Institute of Industrial Organic Chemistry, Warszawa, Poland), K. Zwierzyński (Institute of Industrial Organic Chemistry, Warszawa, Poland), M. Lewandowska (Institute of Industrial Organic Chemistry, Warszawa, Poland) CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2006 197

Session IIB. SAMORZĄDOWO-EKONOMICZNO-PRAWNA (MUNICIPAL-ECONOMIC-LAWFUL) Chairman: G. Wielgosiński (Technical University of Łódź, Poland) • Spalać czy składować? (To incinerate or to storage on landfill sites) J. Kaznowski (SPEC S.A., Warszawa, Poland) • Eliminacja przykrych zapachów w oczyszczalniach ścieków (Elimination of stench in wastewater treatment) M. Szatkowski (Westrand Polska, Warszawa, Poland) Session IIIA. NAUKOWO-TECHNICZNA (SCIENCE AND TECHNOLOGY) Chairman: M. Obrębska (Warsaw University of Technology, Poland) • Przetwarzanie poużytkowych opakowań z poli(tereftalanu etylenu) na węgiel aktywny (Processing of used PET packaging into active carbon) A. Świątkowski (WAT Military University of Technology, Warszawa, Poland), A. Padée (Warsaw Agri- cultural University, Poland) • Analiza własności ciekłych produktów termicznej depolimeryzacji polipropylenu (Properties of liquid products of polypropylene degradation) P. Grzybowski (Warsaw University of Technology, Poland) • Problemy związane z upłynnianiem odpadów poliolefin (Problems of liquefaction of polyolefine wastes) B. Tymiński (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), R. Jurczyk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) 198 Ph.D./D.Sc. THESES IN 2006

Ph.D./D.Sc. THESES IN 2006

Ph.D. THESES

1. Hanna Lewandowska-Siwkiewicz, M.Sc. Powstanie, struktura i przemiany dinitrozylowych kompleksów żelaza w modelowych układach biologicznych (Formation, structure and interactions of dinitrosyl iron complexes in model biological systems) supervisor: Assoc. Prof. Marcin Kruszewski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, 23.02.2006

D.Sc. THESES

1. Grażyna Zakrzewska-Trznadel, Ph.D. Procesy membranowe w technologiach jądrowych (Membrane processes in nuclear technologies) Technical University of Łódź EDUCATION 199

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 programme are: • radiation chemistry and biochemistry, • chemistry of radioelements, • isotopic effects, • radiopharmaceutical chemistry, • analytical methods, • chemistry of radicals, • application of nuclear methods in chemical and environmental research, material science and protection of historical heritage. The candidates accepted for the mentioned programme can be employed in the Institute. The candidates can apply for a doctorial scholarship. The INCT offers accommodation in 10 rooms in the guesthouse for Ph.D. students not living in Warsaw. During the four-year Ph.D. programme the students participate in lectures given by senior staff from the INCT, Warsaw University and the Polish Academy of Sciences. In the second year, the Ph.D. students have teaching practice in the Chemistry Department of Warsaw University. 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 Education and Science, are: • submission of a formal dissertation, summarizing original research contributions suitable for publication; • final examination and public defense of the dissertation thesis. In 2006, the following lecture series were organized: • “Fundalmentals of coordination chemistry” – Prof. Jerzy Narbutt, Ph.D., D.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland); • “Spectrometry mass techniques (ICP MS, electrospray MS, MALDI MS) in analytical chemistry” – Prof. Ryszard Łobiński, Ph.D. (Centre National de la Recherche Scientifique – CNRS, Pau, France); • “Radiation technologies and nuclear techniques in environmental protection” – Prof. Andrzej G. Chmie- lewski, Ph.D., D.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa; Warsaw University of Technology, Poland). The qualification interview for the Ph.D. programme takes place in the mid of October. Detailed information can be obtained from: • Head: Assoc. Prof. Aleksander Bilewicz, Ph.D., D.Sc. (phone: (+4822) 504 13 57, e-mail: [email protected]); • Secretary: Dr. Ewa Gniazdowska (phone: (+4822) 504 10 74 or 504 11 78, e-mail: [email protected]).

TRAINING OF STUDENTS

Number of Institution Country Period participants

AGH University of Science and Technology Poland 3 2 weeks

one-day ChalmersUniversity of Technology Sweden 21 practice

European Union France 1 2 months 200 EDUCATION

Number of Institution Country Period participants

European Union Romania 1 3 months

Forschungszentrum Dresden-Rossendorf Germany 3 2 weeks Institute of Radiopharmacy

International Atomic Energy Agency Egypt 1 3 months

International Atomic Energy Agency Jordan 1 1 month

International Atomic Energy Agency Vietnam 1 3 months

Poland Technical School of Chemistry 2 1 month (Warszawa)

University of Zurich Switzerland 1 1 week Institute of Chemistry

Warsaw University Poland 1 2 months

Warsaw University of Technology one-day Poland 6 Faculty of Chemical and ProcessEngineering practice

Warsaw University of Technology Poland 2 1 month Faculty of Chemistry

Warsaw University of Technology Poland 1 1 month Faculty of Electronicsand Information Technology

Warsaw University of Technology Poland 5 1 month Faculty of MaterialsScience and Engineering

Warsaw University of Technology one-day Poland 27 Faculty of Physics practice RESEARCH PROJECTS AND CONTRACTS 201

RESEARCH PROJECTS AND CONTRACTS

RESEARCH PROJECTS GRANTED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN 2006 AND IN CONTINUATION

1. Neutron activation analysis and ion chromatography as a tool for reliable lanthanides determination in biological and environmental samples. supervisor: Bożena Danko, Ph.D. 2. The chemical isotope effects of gallium, indium and thallium in ligand exchange and red-ox reactions. supervisor: Wojciech Dembiński, Ph.D. 3. Comparative analysis of telomere length, chromosomal aberration frequency and DNA repair kinetics in peripheral blood lymphocytes of healthy donors and cancer patients. supervisor: Prof. Andrzej Wójcik, Ph.D., D.Sc. 4. Oxidation of thioether by organic complexes of copper. Processes of potential importance for patho- genesis of some neurodegenerative diseases. supervisor: Assoc. Prof. Dariusz Pogocki, Ph.D., D.Sc. 5. New methods of the study and reduction of fouling in processes of micro- and ultrafiltration of liquid radioactive waste. supervisor: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc. 6. Modelling of the dispersion of pollutants and studying their transport in natural water receivers using stable isotopes as tracers. supervisor: Andrzej Owczarczyk, Ph.D./Jacek Palige, Ph.D. 7. Influence of gamma irradiation on starch properties: starch interaction with water and lipids, starch-lipid films. supervisor: Krystyna Cieśla, Ph.D. 8. Changes of sulphur isotope ratio in the products of coal combustion and flue gas desulphurization processes. supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. 9. Process of nanostructure formation of small-molecule organic gels using synchrotron methods. supervisor: Assoc. Prof. Helena Grigoriew, Ph.D., D.Sc. 10. Analytical studies of products of degradation of selected chlorophenols and pesticides caused by ionizing radiation. supervisor: Prof. Marek Trojanowicz, Ph.D., D.Sc. 11. Studies of coordination of magnesium and zinc ions in their complexes with the azine dicarboxylate ligands. supervisor: Prof. Janusz Leciejewicz, Ph.D., D.Sc. 12. Stable isotope applications to quality and origin control of milk and milk products. supervisor: Ryszard Wierzchnicki, Ph.D. 13. Protection phenomena in radiation chemistry of polypropylene. supervisor: Prof. Zbigniew P. Zagórski, Ph.D., D.Sc. 14. Modification of the near surface layer of carbon steels with intense argon and nitrogen plasma pulses. supervisor: Prof. Jerzy Piekoszewski, Ph.D., D.Sc. 15. Pilot plant for thermocatalytic degradation of polyolefine and polystyrene wastes into liquid fuels. supervisor: Bogdan Tymiński, Ph.D. 202 RESEARCH PROJECTS AND CONTRACTS

16. Cheap and non-toxic dosimeter for measurement of absorbed dose in radiation processing of fluidized beds and fluid streams. supervisor: Zofia Stuglik, Ph.D. 17. Analytical studies of decomposition of selected pesticides using ionizing radiation. supervisor: Prof. Marek Trojanowicz, Ph.D., D.Sc. 18. Complexes of astatine-211 with metals as potential precursors of radiopharmaceuticals. supervisor: Assoc. Prof. Aleksander Bilewicz, Ph.D., D.Sc. 19. The role of pirin in regulation of NF-κB signalling in response to oxidative stress. supervisor: Assoc. Prof. Marcin Kruszewski, Ph.D., D.Sc. 20. Examination of the antimutagenic effects of 1,4-dihydropyridine on mammalian cells after exposure to X-rays. supervisor: Prof. Irena Szumiel, Ph.D., D.Sc.

RESEARCH PROJECTS ORDERED BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION IN 2006

1. Radiation processing application to form nanofillers with different structure including hybrid and functionalized. PBZ-KBN-095/T08/2003 supervisor: Zbigniew Zimek, Ph.D. 2. Mutual interactions between nutritional components in steering of development of the intestinal im- munological system. PBZ-KBN-093/P06/2003 supervisor: Assoc. Prof. Marcin Kruszewski, Ph.D., D.Sc.

IAEA RESEARCH CONTRACTS IN 2006

1. Application of ionizing radiation for removal of pesticides from ground waters and wastes. 12016/RO principal investigator: Prof. Marek Trojanowicz, Ph.D., D.Sc. 2. Radiation resistant polypropylene for medical applications and as a component of structural engineering materials. 12703/RO principal investigator: Zbigniew Zimek, Ph.D. 3. Electron beam for VOCs treatment emitted from oil combustion process. 13136/RO principal investigator: Anna Ostapczuk, M.Sc.

IAEA TECHNICAL CONTRACTS IN 2006

1. Methyl bromide generator type ABC with accesories for transportation and labeling with radioactive gaseous methyl bromide. RAF4016-92242C

EUROPEAN COMMISSION RESEARCH PROJECTS IN 2006

1. FP6 Integrated Project European research program for the partitioning of actinides from high active wastes issuing the reprocessing of spent nuclear fuels (EUROPART). FP6-508854 RESEARCH PROJECTS AND CONTRACTS 203

2. FP5 Research Training Network: Sulfur radical chemistry of biological significance: the protective and damaging roles of thiol and thioether radicals (SULFRAD). principal investigator: Prof. Krzysztof Bobrowski, Ph.D., D.Sc. RTN-2001-00096 under FP5 3. FP6 Marie Curie Host Fellowships for the Transfer of Knowledge: Advanced methods for environment research and control (AMERAC). principal investigator: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc. MTKD-CT-2004-509226 4. FP6 Marie Curie Host Fellowships for the Transfer of Knowledge: Chemical studies for design and production of new radiopharmaceuticals (POL-RAD-PHARM). principal investigator: Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc. MTKD-CT-2004-509224 5. European cooperation in the field of scientific and technical research. COST D27 – Prebiotic chemistry and early evolution. Role of radiation chemistry in the origin of life on Earth. supervisor: Prof. Zbigniew Zagórski, Ph.D., D.Sc. 6. European cooperation in the field of scientific and technical research. COST P9 – Radiation damage in biomolecular systems (RADAM). Mechanisms of radiation damage transfer in polypeptide molecules. supervisor: Prof. Krzysztof Bobrowski, Ph.D., D.Sc.

OTHER FOREIGN CONTRACTS IN 2006

1. Laboratory scale experimental analysis of electron beam treatment of flue gases from combustion of liquid petroleum oils. Contract with King Abdulaziz City for Science and Technology, Atomic Energy Research Institute, Saudi Arabia 2. Feasibility study for electron beam flue gas treatment at oil fired boiler. Contract with King Abdulaziz City for Science and Technology, Atomic Energy Research Institute, Saudi Arabia 3. The realization and delivery of nickel electrodes coated with magnesium doped lithium cobaltite. Research contract with ENEA, the Italian Agency for New Technologies, Energy and Environment 204 LIST OF VISITORS TO THE INCT IN 2006

LIST OF VISITORS TO THE INCT IN 2006

1. Agorastos Nikos, University of Zurich, Switzerland, 21-26.05. 2. Ajji Zaki, Atomic Energy Commission of Syria, Damascus, Syria, 07-12.05. 3. Araya Ramiro, Universidad de Chile, Chile, 19-27.08. 4. Bekmuratov Timur, Institute of Nuclear Physics, National Nuclear Centre of the Republic of Kazakhstan, Almaty, Kazakhstan, 05.04. 5. Belchior Ana, Instituto Nacional de Engenharia e Technologia Industrial (INETI), Sacavém, Portugal, 05.04. 6. Belgaya Tamas, Institute of Isotope and Surface Chemistry, Budapest, Hungary, 16-20.10. 7. Botelho Maria Luisa, Nuclear and Technological Institute (ITN), Sacavém, Portugal, 05.04. 8. Bznuni Surik, Nuclear and Radiation Safety Center of Armenian Nuclear Regulatory Authority, Yerevan, Armenia, 05.04. 9. Cabalka Martin, Nuclear Research Institute, Øež, Czech Republik, 05.04. 10. Chorniy Anton, Kharkov State University, Ukraine, 05.04. 11. Chukalov Sergey, Institute of Nuclear Physics, National Nuclear Center of the Republic of Kazakhstan, Almaty, Kazakhstan, 28-29.06. 12. Cojocaru Corneliu, “Gh. Asachi” Technical University of Iaºi, Romania, 04.07.-04.10. 13. Cuna Stela, National Institute for Research and Development of Isotopic and Molecular Technologies, Cluj-Napoca, Romania, 18.07.-18.09. 14. Dalivelya Olga, Institute of Genetics and Cytology, National Academy of Sciences of Belarus, Minsk, Belarus, 03-21.07. 15. Demski Mikhail, The D.V. Efremov Scientific Research Institute of Electrophysical Apparatus (NIIEFA), St. Petersburg, Russia, 01-06.10. 16. Drapkin Valery, St. Petersburg Instruments Ltd., Russia, 22-29.04. 17. Duc Ho Minh, Institute for Nuclear Science and Techniques, Vietnam Atomic Energy Commission (VAEC), Hanoi, Vietnam, 02-14.10. 18. Enache Mirela, Institute of Physical Chemistry “I.G. Murgulescu”, Romanian Academy, Bucharest, Romania, 01.01.-31.03. 19. Fuente Julio de la, Universidad de Chile, Chile, 08-27.08. 20. Fulop Marko, Institute of Preventive and Clinical Medicine, Bratislava, Slovakia, 05.04, 26-27.10. 21. Georgescu Rodica-Maria, Horia Hulubei National Institute of Physics and Nuclear Engineering, Bucharest, Romania, 05.04. 22. Gryzlov Anatolij, NPO “Toriy”, Moscow, Russia, 20.06.-05.07, 18-24.09. 23. Gürtler Sylvia, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany, 17-29.09. 24. Houeé-Levin Chantal, Université Paris-Sud, France, 17-18.02. 25. Hug Gordon L., University of Notre Dame Radiation Laboratory, USA, 03-06.01, 17-18.02, 28.09.-01.10. 26. Hustuc Aleksandru, National Scientific Center of Applied Preventive Medicine, Chisinau, Moldavia, 05.04. 27. Ivanov A., The D.V. Efremov Scientific Research Institute of Electrophysical Apparatus (NIIEFA), St. Petersburg, Russia, 22-28.10. 28. Jafarov Yadigar, Institute of Radiation Problems, Azerbaijan National Academy of Sciences, Baku, Azerbaijan, 05.04. 29. Kasztovszky Zsolt, Institute of Isotope and Surface Chemistry, Budapest, Hungary, 16-20.10. 30. Khalil Luai Ahmad, Jordan Atomic Energy Commission, Amman, Jordan, 08.10.-09.11. 31. Khayet Souhaimi Mohamad, University Complutense of Madrid, Spain, 03.07.-29.08. 32. Kim Jinkyu, EB-Tech Co., Ltd., Daejeon, Korea, 19-24.08. 33. Kovacs Andras, Institute of Isotope Research, Hungarian Academy of Sciences, Budapest, Hungary, 05.04. LIST OF VISITORS TO THE INCT IN 2006 205

34. Knyazev Mikhail, St. Petersburg Instruments Ltd., Russia, 22-29.04, 07-12.08, 07-12.11. 35. Krpan Katarina, Rudjer Boskovic Institute, Zagreb, Croatia, 05.04. 36. Kuenstler Jens-Uwe, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany, 26.06.-26.07. 37. Lazurik Valentina, Kharkiv National University, Ukraine, 02-07.04. 38. Lavalle Marco, Institute for the Organic Synthesis and Photoreactivity, National Research Council of Italy (ISOF-CNR), Bologna, Italy, 02-09.04. 39. Le Minh Tuan, Research and Development Center for Radiation Technology, Vietnam Atomic Energy Commission (VINA GAMMA), Ho Chi Minh City, Vietnam, 07.05.-08.08. 40. Lebeda Ondrei, Nuclear Physics Institute, Academy of Sciences of the Czech Republic, Øež, Czech Republic, 18.03-18.05. 41. Lebedev Vjacheslav, Joint Institute for Nuclear Research, Dubna, Russia, 13-20.08. 42. Letournel Eric, VIVIRAD SA, France, 12-13.12. 43. Lyssukin Sergey, Institute of Nuclear Physics, Almaty, Kazakhstan, 28-29.06. 44. Łobiński Ryszard, Centre National de la Recherche Scientifique – CNRS, France, 05.04.-05.06. 45. März Peter, EPR Division, Bruker Biospin GmbH, Silberstreifen, Germany, 20-25.11. 46. Mehta Kishor, International Atomic Energy Agency, United Nations, 28.02.-28.04. 47. Mozziconazzi Olivier, France, 01.01.-28.02. 48. Neves Maria, Instituto Tecnologico e Nuclear, Sacavém, Portugal, 04.09.-04.11. 49. Nichipor Henrietta, Institute of Radiation Physical-Chemical Problems, National Academy of Sciences of Belarus, Minsk, Belarus, 17-28.07, 01-04.10. 50. Novikova Galina, National Research Restoration Centre of Ukraine, Kiev, Ukraine, 01-07.08. 51. Pawlukojć Andrzej, Joint Institute for Nuclear Research, Dubna, Russia, 17-19.09. 52. Pietzsch Juergen Hans, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany, 05-10.04. 53. Politkovskij Fiodor, NPO “Toriy”, Moscow, Russia, 20.06-05.07. 54. Popov Genadiv, Kharkiv State University, Ukraine, 05.04, 06-08.11. 55. Ramirez Trajano, National Technological University, Quito, Ecuador, 11-12.09. 56. Romanova Irina, Institute of Genetics, Academy of Sciences of Moldavia, Chisinau, Moldavia, 05.04. 57. Redaelli Renato, Universita degli Studi di Milano, Italy, 31.10.-02.11. 58. Rieck Stefanie, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany, 17-29.09. 59. Ritter Alina, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany, 17-29.09. 60. Said Amr El-Hag Ali, National Center for Radiation Research and Technology, Cairo, Egypt, 04.04.-29.06. 61. Saidi Mouldi, National Center for Nuclear Sciences and Technologies, Tunis, Tunisia, 16.05.-16.07. 62. Sampa Maria Helena, International Atomic Energy Agency, United Nations, 05.04. 63. Savina Natalya, Institute of Genetics and Cytology, National Academy of Sciences of Belarus, Minsk, Belarus, 03-21.07. 64. Sheyno Igor, Institute of Biophysics, State Scientific Center, Moscow, Russia, 05.04. 65. Skarnemark Gunnar, Chalmers University of Technology, Göteborg, Sweden, 06.08.-05.09. 66. Smolko Edvardo, Irradiation Processing Laboratory, Centro Atomico Buenos Aires, Argentina, 07-11.09. 67. Spies Hartmut, Institute of Radiopharmacy, Forshungszentrum Dresden-Rossendorf, Germany, 18.03.-18.04. 68. Svinin Mikhail, The D.V. Efremov Scientific Research Institute of Electrophysical Apparatus (NIIEFA), St. Petersburg, Russia, 22-28.10. 69. Taroyan Sargis, Yerevan Physics Institute, Yerevan Armenia, 05.04. 70. Tereshatov Evgeny, Joint Institute for Nuclear Research, Dubna, Russia, 13-20.08. 71. Tsrunchev Tsvetelin, National Centre of Radiobiology and Radiation Protection (NCRRP), Sofia, Bulgaria, 05.04. 72. Weissabel Robert, Slovak Office of Standards, Metrology and Testing, Bratislava, Slovakia, 26-27.10. 206 THE INCT SEMINARS IN 2006

THE INCT SEMINARS IN 2006

1. Ewelina Chajduk, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Prace nad konstruowaniem metod o najwyższej randze metrologicznej do oznaczania Se i As w materiałach biologicznych za pomocą RNAA (High-accuracy RNAA methods for the determination of Se i As in biological samples) 2. Prof. Zbigniew Florjańczyk (Warsaw University of Technology, Poland) Polimery hybrydowe (Hybrid polymers) 3. Michał Gryz, M.Sc. (Office for Registration of Medicinal Products, Medical Devices and Biocides, War- szawa, Poland) Cynk i magnez w procesach biologicznych (Zinc and magnesium in biological processes) 4. Gabriel Kciuk, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Wpływ grup funkcyjnych aminokwasów na mechanizmy reakcji rodnikowych w peptydach zawierających tyrozynę (The influence of the amino acid functional groups on the mechanism of radical reactions in peptides containing tyrosine) 5. Monika Łyczko, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Trikarbonylkowe kompleksy technetu(I) z amidowymi pochodnymi kwasu pikolinowego i tiopikolinowego jako prekursory radiofarmaceutyków (Tricarbonyl technetium(I) complexes with amide derivatives of picolinic and thiopicolinic acid as potential radiopharmaceuticals) 6. Prof. Józef Mayer (Technical University of Łódź, Poland) Reakcje jonowe w poli(chlorku winylu) (Ionic reactions in polyvinyl chloride) 7. Sylwia Męczyńska, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Wpływ ·OH i ONOO– na konformację i aktywność białek zawierających żelazo (The influence of nitric oxide and peroxynitrite on conformation and activity of the iron proteins) 8. Dr. Maria Neves (Instituto Tecnologico e Nuclear, Sacavém, Portugal) Radiation in medicine and biology 9. Sławomir Ostrowski, M.Sc. (Industrial Chemistry Research Institute, Warszawa, Poland) Mechanizm reakcji wydłużania łańcucha i właściwości fizykochemiczne związków alkiloaromatycznych. Badania metodami chemii obliczniowej (Mechanism of chain elongation reactions and physicochemical properties of alkylaromatic compounds. Studies using calculation chemistry methods) 10. Wojciech Ozimiński, M.Sc. (National Institute of Public Health, Warszawa, Poland) Tautometria pięcioczłonowych pierścieni heterocyklicznych zawierających trzy heteroatomy. Badania obliczeniowe (Tautomerism of five-membered heterocyclic rings containing three heteroatoms. Calcu- lation studies) 11. Sylwia Ptaszek, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Zastosowanie znaczników i CFD do badania dynamiki przepływu w oczyszczalni ścieków (Application of tracers and CFD for the study of flow dynamics in wastewater treatment plant) 12. Dr. Tomasz Szreder (Institute of Dyes and Organic Products, Zgierz, Poland) Indywidua przejściowe generowane radiacyjnie w cieczach jonowych: badania wykorzystujące piko- sekundowy akcelerator elektronów w Narodowym Laboratorium w Brookhaven (USA) (Radiationally generated transients in ionic liquids: investigations using picosecond electron accelerator in the Brook- haven National Laboratory (USA)) 13. Dr. Daniel Tedder (Georgia Institute of Technology, USA) Efficient strategies for partitioning actinides from alkaline wastes 14. Jerzy Turek, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Budowa i oddziaływania rodników srebroorganicznych. Badania EPR i DFT (Structure and interaction of organosilver radicals. EPR and DFT study) 15. Dr. Grażyna Zakrzewska-Trznadel (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Procesy membranowe w technologiach jądrowych (Membrane processes in nuclear technologies) LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2006 207

LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2006

LECTURES

1. Bilewicz A. Influence of relativistic effect on hydrolysis of heavy cations. First International Symposium on Hydration and Hydroxo Complexation of Cations, Minsk, Belarus, 05-06.10.2006. 2. Bobrowski K. Protection of tyrosine in Met-enkephalin against oxidation by blocking the amine function. CNR Conference “Free Radicals in Chemical Biology”, Bologna, Italy, 30.06.2006. 3. Bojanowska-Czajka A., Drzewicz P., Trojanowicz M. Analityczne badania radiolitycznej degradacji karbendazymu (Analytical control of carbendazim decomposition by gamma irradiation). III Warszawskie Seminarium Doktorantów Chemików ChemSession’06, Warszawa, Poland, 19.05.2006. 4. Brzozowska K. Wypadek radiacyjny w Białostockim Ośrodku Onkologicznym (The radiological accident in the Białystok Oncological Center). II Krakowsko-Poznańskie Studenckie Seminarium Fizyki Biomolekularnej i Medycznej, Poznań, Poland, 22-25.02.2006. 5. Brzozowska K., Wójcik A. Wpływ temperatury na poziom mikrojąder indukowanych promieniowaniem jonizującym w ludzkich limfo- cytach krwi obwodowej (Influence of temperature on radiation-induced micronuclei in human peripheral blood lymphocytes). II Krakowsko-Poznańskie Studenckie Seminarium Fizyki Biomolekularnej i Medycznej, Poznań, Poland, 22-25.02.2006. 6. Brzóska K. Piryna: nowy element regulacji sygnalizacji szlaku NFκB (Piryn: a new regulatory element of the NFκB signaling pathway). Sympozjum “Rola żelaza w organizmie”, Warszawa, Poland, 25.11.2006. 7. Chmielewski A.G. Techniki i technologie jądrowe w zastosowaniach przemysłowych (Application of radiation and nuclear technologies in industry). Seminarium Naukowe “Technika jądrowa w służbie społeczeństwa”, Warszawa, Poland, 30.11.2006. 8. Chmielewski A.G., Kałuska I., Zimek Z., Migdał W., Bułka S. Radiolytic decomposition of pesticide MCPA in various conditions – comparison of experimental data and calculated kinetic model. 14th International Meeting on Radiation Processing, Kuala Lumpur, Malaysia, 26.02.-03.03.2006. 9. Chmielewski A.G., Migdał W., Zimek Z., Kałuska I., Bułka S. Commercial application of an electrom beam accelerator at the R&D and service center. 14th International Meeting on Radiation Processing, Kuala Lumpur, Malaysia, 26.02.-03.03.2006. 10. Dembiński W. Chemia materiałów paliwowych dla reaktorów jądrowych w “Nukleonice” (Chemistry of fuel materials for nuclear reactors in “Nukleonika”). Seminarium z okazji 50-lecia “Nukleoniki”, Warszawa, Poland, 30.06.2006. 11. Kałuska I. Legislation and standardization concerning radiation sterilization process. 208 LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2006

IAEA Course “Economical and Social Benefits of Radiation Processing; Standardization and Legislation Issues Regarding Radiation Processing Implementation in Europe”, Eger, Hungary, 26.08.-02.09.2006. 12. Kałuska I. Dose setting procedures for radiation deactivation and sterilization. IAEA Course “Radiation Deactivation and Sterilization of Biohazards”, Vadodara, India, 28.10.-04.11.2006. 13. Kałuska I. Physical, chemical and biological dose modifying factors. IAEA Course “Radiation Deactivation and Sterilization of Biohazards”, Vadodara, India, 28.10.-04.11.2006. 14. Kałuska I. Dosimetry systems for radiation processing. IAEA Course “Radiation Deactivation and Sterilization of Biohazards”, Vadodara, India, 28.10.-04.11.2006. 15. Kałuska I. Quality assurance in radiation processing. IAEA Course “Radiation Deactivation and Sterilization of Biohazards”, Vadodara, India, 28.10.-04.11.2006. 16. Kruszewski M. Białka żelazowo-siarkowe, nowe funkcje starych klastrów (Iron-sulphur cluster proteins, old pals with new functions). Sympozjum “Rola żelaza w organizmie”, Warszawa, Poland, 25.11.2006. 17. Męczyńska S. Dinitrozylowe kompleksy żelaza: powstawanie i rola w organizmie (Dinitrosyl iron complexes: formation and the role in organisms). Sympozjum “Rola żelaza w organizmie”, Warszawa, Poland, 25.11.2006. 18. Narbutt J. Thermodynamics of solvent extraction of metal ions: fundamentals. Fifth Half-yearly Meeting of EUROPART, Roma, Italy, 26-29.06.2006. 19. Narbutt J. 50 lat radiochemii w “Nukleonice” (50 years of radiochemistry in “Nukleonika”). Seminarium z okazji 50-lecia “Nukleoniki”, Warszawa, Poland, 30.06.2006. 20. Sauerwein W., Malago M., Moss R., Wójcik A., Altieri S., Hampel G., Wittig A., Nievaart V., Collette L., Mauri P., Huiskamp R., Michel J., Daquino G., Gerken G., Bornfeld N., Broelsch C.E. Boron neutron capture therapy (BNCT) for treating disseminated, non-resectable liver metastases. International Workshop on Fast Neutron Therapy, Essen, Germany, 14-16.09.2006. 21. Wójcik A. Aberacje chomosomowe i mikrojądra (Chromosomal aberrations and micronuclei). Kurs Radiobiologii, Kielce, Poland, 20-23.03.2006. 22. Wójcik A. Odczyny popromienne (Post-radiation early and late tissue injuries). Kurs Radiobiologii, Kielce, Poland, 20-23.03.2006. 23. Wójcik A. Hipoksja i jej rola w promieniowrażliwości guzów (Hypoxia and its role in tumor radiosensitivity). Kurs Radiobiologii, Kielce, Poland, 20-23.03.2006. 24. Wójcik A. Percepcja ryzyka dla zdrowia promieniowania jonizującego (Perception of ionizing radiation). Letnia Szkoła Energetyki Jądrowej „Dunaj’06”, Warszawa, Poland, 06.04.2006. 25. Wójcik A., Bochenek A., Lankoff A., Lisowska A., Padjas A., von Sonntag C., Szumiel I., Obe G. DNA interstrand crosslinks are induced in cells prelabelled with BrdU and exposed to UVC radiation. 35th Annual Meeting of European Radiation Research Society – European Radiation Research 2006, Kiev, Ukraine, 22-25.08.2006. 26. Wójcik A., Sommer S., Deperas-Kaminska M., Moss R., Sauerwein W. Effects of high LET (C-12) and low LET (Co-60) irradiation on chromosomal aberrations in peripheral blood lymphocytes. International Workshop on Fast Neutron Therapy, Essen, Germany, 14-16.09.2006. LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2006 209

27. Wójcik A., Wittig A., Sauerwein W. What is the tolerance dose of the liver? International Conference “Innovative Treatment Concepts for Liver Metastases”, Essen, Germany, 07-09.12.2006. 28. Zagórski Z.P. Panspermia revisited? Gordon Research Conference “Origin of Life”, Lewiston, Maine, USA, 23-28.07.2006. 29. Zakrzewska-Trznadel G. Conditioning of biogas from biomass fermentation by membrane method. 7th Framework Programme in Poland, Warszawa, Poland, 16-17.11.2006. 30. Zimnicki R. Sulphur isotopes ratio as a marker of pollutant migration in the ecosystem – opencast mine landfil. 2nd International Workshop “Pathways of pollutants from landfills to air and water-soil systems and mitigation strategies of their impact on the ecosystems”, Kazimierz Dolny, Poland, 17-20.09.2006.

SEMINARS

1. Bilewicz A. Radiofarmaceutyki (Radiopharmaceuticals). Warsaw University, Poland, 16.05.2006. 2. Krzysztof Bobrowski Stabilization of sulfide radical cations in linear and cyclic peptides containing methionine. National Research Council (CNR), Institute for Organic Synthesis and Photoreactivity (ISOF), Bologna, Italy, 24.02.2006. 3. Krzysztof Bobrowski Stabilization of sulfide radical cations: mechanisms relevant to oxidation of peptides and proteins containing methionine. Swiss Federal Institute of Technology – ETH, Zurich, Switzerland, 23.03.2006. 4. Krzysztof Bobrowski Stabilization of sulfide radical cations: mechanisms relevant to oxidation of peptides and proteins containing methionine. University Paris XI, Orsay, France, 12.05.2006. 5. Krzysztof Bobrowski Free radicals in chemistry, biology and medicine: contribution of radiation chemistry. Universidad de Chile, Santiago de Chile, Chile, 13.11.2006. 6. Krzysztof Bobrowski Oxidation of methionine containing peptides: mechanism relevant to biological conditions of oxidative stress. Universidad de Valparaiso, Chile, 20.11.2006. 7. Krzysztof Bobrowski Oxidation of methionine containing peptides: mechanism relevant to biological conditions of oxidative stress. Universidad de Chile, Santiago de Chile, Chile, 22.11.2006. 8. Andrzej G. Chmielewski Electron beam flue gas treatment – the basics. University of Pavia, Italy, 08.05.2006. 9. Andrzej G. Chmielewski Electron beam flue gas treatment – VOC and industrial applications. University of Pavia, Italy, 08.05.2006. 10. Andrzej G. Chmielewski Environmental protection - worldwide developments. University of Pavia, Italy, 08.05.2006. 210 LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2006

11. Adrian Jakowiuk Bezprzewodowe sieci monitoringu z radioizotopowymi czujnikami zapylenia powietrza AMIZ-2004 (Wire- less dust concentration monitoring network based on the radioisotope gauge AMIZ-2004). International Ecological Fair POLEKO, Poznań, Poland, 23.11.2006. 12. Iwona Kałuska Dozymetria procesów radiacyjnych (Dosimetry of radiation processes) Poznań University of Medical Sciences, Poland, 15.03.2006. 13. Andrzej Wójcik Popromienne aberracje chromosomowe: mechanizmy powstawania i biofizyczne modele, czyli badania na pograniczu biologii i fizyki (Radiation induced chromosomal aberrations, on studies on the border of biology and physics). Warsaw University, Poland, 24.02.2006. 14. Andrzej Wójcik Awaria reaktora w Czarnobylu: przyczyny i skutki (Accident of the Chernobyl reactor: causes and results). Polskie Sieci Energetyczne, Warszawa, Poland, 24.04.2006. 15. Andrzej Wójcik Czarnobyl 20 lat po: co wiemy o skutkach dla zdrowia? (Chernobyl 20 years after: what do we know about the health effects?) Świętokrzyska Academy, Kielce, Poland, 26.04.2006. 16. Andrzej Wójcik 20 lat po awarii w Czarnobylu: co dziś wiemy o skutkach zdrowotnych? (20 years after the Czernobyl accident: what do we know today on the health effects?) Świętokrzyska Academy, Kielce, Poland, 26.06.2006. 17. Andrzej Wójcik Cytogenetic markers of individual radiation sensitivity. Gesellschaft für Schwerionenforschung (GSI), Darmstadt, Germany, 25.10.2006. 18. Zbigniew Zimek Electron beam flue gas treatment process. Saudi Aramco, Dhahran, Saudi Arabia, 19.02.2006. 19. Zbigniew Zimek High power electron accelerators for flue gas treatment. Institute of Atomic Energy Research, King Abdulaziz City of Science and Technology, Riyadh, Saudi Arabia, 20.02.2006. 20. Zbigniew Zimek Akceleratory dla techniki jądrowej (Accelerators for nuclear power generation). Polish Nuclear Society, Warszawa, Poland, 30.11.2006. 21. Zbigniew Zimek Electron accelerators for radiation processing. Office of Normalization and Metrology, Bratislava, Slovakia, 13.12.2006. AWARDS IN 2006 211

AWARDS IN 2006

1. Down-regulation of iron regulatory protein 1 activities and expression in superoxide dismutase 1 knock-out mice is not associated with alterations in iron metabolism Second degree group award of the Polish Genetic Society for the best work carried out in Polish laboratories and published in 2005 R.R. Starzyński, P. Lipiński, J.-C. Drapier, A. Diet, E. Smuda, T. Bartłomiejczyk, M.A. Gralak, M. Kruszewski 2. Method for obtaining the Ni/NiO cathodes Bronze medal at the 34th International Exhibition of Inventions, New Techniques and Products of Geneva, Switzerland, 05-09.04.2006 W. Łada, A. Deptuła, T. Olczak, A.G. Chmielewski, A. Moreno 3. Method for obtaining the Ni/NiO cathodes Gold medal at the 55th World Exhibition of Innovation, Research and New Technology “Brussels Eureka 2006”, Belgium, 23-27.11.2006 W. Łada, A. Deptuła, T. Olczak, A.G. Chmielewski, A. Moreno 4. Diploma of the Ministry of Education and Science for the project “Method for obtaining hollow spherical particles from ceramic and metallic materials reduced by hydrogen” A. Deptuła, A.G. Chmielewski, W. Łada, T. Olczak 5. Congratulatory letter of the Ministry of Education and Science for the project “Method for obtaining calcium phosphate layers, especially hydroxyapatite” A. Deptuła, W. Łada, T. Olczak, R.Z. LeGeros, J.P. LeGeros 6. Method for removal of nitrogen oxides from industrial gases. A facility for mixing gases reacting chemically. Method for removal volatile organic impurities such as polycyclic aromatic hydrocarbons from industrial flue gases Gold medal at the 55th World Exhibition of Innovation, Research and New Technology “Brussels Eureka 2006”, Belgium, 23-27.11.2006 A.G. Chmielewski 7. Method for removal of nitrogen oxides from industrial gases. A facility for mixing gases reacting chemically. Method for removal volatile organic impurities such as polycyclic aromatic hydrocarbons from industrial flue gases Special award from the Russian Federal Agency for Science and Invention A.G. Chmielewski 8. First place for the meritorious poster “Application of extraction to the solid phase in the determination of heavy metals by GF-AAS” presented at the XI Conference “Application of AAS, ICP-AES, ICP-MS methods in the environmental analysis”, Warszawa, Poland, 09-10.11.2006 J. Chwastowska, W. Skwara, E. Sterlińska, J. Dudek, L. Pszonicki 9. First degree group award of Director of the Institute of Nuclear Chemistry and Technology for two publications in “Talanta” presenting methods for the determination of platinum, palladium and chromium in trace quantities in environmental samples and speciation analysis of Cr(VI) in the presence of Cr(III) L. Pszonicki, J. Chwastowska, W. Skwara, E. Sterlińska 10. Second degree group award of Director of the Institute of Nuclear Chemistry and Technology for publications in the journals “Biochemical and Biophysical Research Communications”, “Journal of Biological Chemistry” and “Acta Biochimica Polonica” devoted to studies of relations between the metabolism of iron on a cell level and DNA oxidative damage M. Kruszewski, H. Lewandowska, T. Bartłomiejczyk, T. Iwaneńko, B. Sochanowicz 11. Third degree group award of Director of the Institute of Nuclear Chemistry and Technology for the essential contribution to the work on basic studies of secondary periodicity of elements of the block p (group 13) published in “European Journal of Inorganic Chemistry” S. Siekierski, K. Frąckiewicz 212 INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS

INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS

I. DEPARTMENT OF NUCLEAR METHODS OF MATERIALS ENGINEERING 1. Laboratory of Materials Research Activity profile: Studies of the structure and properties of materials and historical art objects. Modi- fication of surface properties of materials by means of intense plasma pulses and ions beams. Syn- thesis and studies of new type of materials with predetermined properties (biocidal, fungicidal, sorptional). Characterization of structural properties of materials using SEM (scanning electron microscopy), X-ray fiffraction (powder and single crystal). Determination of elemental content of environmental and geological samples, industrial waste materials, historic glass objects and other materials by energy dispersive X-ray fluorescence spectrometry using a radioisotope excitation source as well as a low power X-ray tube and using a 2 kW X-ray tube in total reflection geometry. Deter- mination of radioactive isotope content in environmental samples and historical glass objects by gamma spectrometry. • Scanning electron microscope DSM 942, LEO-Zeiss (Germany) Technical data: spatial resolution – 4 nm at 30 kV, and 25 nm at 1 kV; acceleration voltage – up to 30 kV; chamber capacity – 250x150 mm. Application: SEM observation of various materials such as metals, polymers, ceramics and glasses. Determination of characteristic parameters such as molecule and grain size. • Scanning electron microscope equipped with the attachment for fluorescent microanalysis BS-340 and NL-2001, TESLA (Czech Republic) Application: Observation of surface morphology and elemental analysis of various materials. • Vacuum evaporator JEE-4X, JEOL (Japan) Application: Preparation of thin film coatings of metals or carbon. • Gamma radiation spectrometer HP-Ge, model GS 6020; Canberra-Packard (USA) Technical data: detection efficiency for gamma radiation – 60.2%, polarization voltage – 4000 V, energy resolution (for Co-60) – 1.9 keV, analytical program “GENIE 2000”. Application: Neutron activation analysis, measurements of natural radiation of materials. • Gamma spectrometer in low-background laboratory EGG ORTEC Technical data: HPGe detector with passive shield; FWHM – 1.9 keV at 1333 keV, relative efficiency – 92%. • Total reflection X-ray spectrometer Pico TAX, Institute for Environmental Technologies (Berlin, Germany) Technical data: Mo X-ray tube, 2000 W; Si(Li) detector with FHWM 180 eV for 5.9 keV line; analysed elements – from sulphur to uranium; detection limits – 10 ppb for optimal range of analysed elements, 100 ppb for the others. Application: XRF analysis in total reflection geometry. Analysis of minor elements in water (tap, river, waste and rain water); analysis of soil, metals, raw materials, fly ash, pigments, biological samples. • X-ray spectrometer SLP-10180-S, ORTEC (USA) Technical data: FWHM – 175 eV for 5.9 keV line, diameter of active part – 10 mm, thickness of active part of detector – 5.67 mm. Application: X-ray fluorescence analysis. • Coulter Porometer II Coulter Electronics Ltd (Great Britain) Application: Pore size analysis in porous media. • Vacuum chamber for plasma research POLVAC Technika Próżniowa INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS 213

Technical data: dimensions – 300x300 mm; high voltage and current connectors, diagnostic windows. Application: Studies on plasma discharge influence on physicochemical surface properties of polymer films, particularly TEM (track-etched membranes). 2. Laboratory of Diffractional Structural Research Activity profile: X-ray diffraction structural studies on metal-organic compounds originating as degradation products of substances naturally occurring in the environment. Röntgenostructural phase analysis of materials. Studies on interactions in a penetrant-polymer membrane system using small angle scattering of X-rays, synchrotron and neutron radiation. Studies of structural changes occurring in natural and synthetic polymers under influence of ionising radiation applying X-ray diffraction and differential scanning calorimetry. • KM-4 X-ray diffractometer KUMA DIFFRACTION (Poland) Application: 4-cycle diffractometer for monocrystal studies. • CRYOJET - Liquid Nitrogen Cooling System Oxford Instruments Application: Liquid nitrogen cooling system for KM-4 single crystal diffractometer. • HZG4 X-ray diffractometer Freiberger Präzisionsmechanik (Germany) Application: Powder diffractometers for studies of polycrystalline, semicrystalline and amorphous materials. • URD 6 X-ray diffractometer Freiberger Präzisionsmechanik (Germany) Application: Powder diffractometers for studies of polycrystalline, semicrystalline and amorphous materials. 3. Sol-Gel Laboratory of Modern Materials Activity profile: The research and production of advanced ceramic materials in the shape of powders, monoliths, fibres and coatings by classic sol-gel methods with modifications – IChTJ Process or by CSGP (Complex Sol-Gel Method) are conducted. Materials obtained by this method are the fol-

lowing powders: alumina and its homogeneous mixtures with Cr2O3, TiO3, Fe2O3, MgO+Y2O3, MoO3, β β Fe, Mo, Ni and CaO, CeO2, Y2O3 stabilized zirconia, and ’’ aluminas, ferrites, SrZrO3, ceramic superconductors, type YBCO (phases 123, 124), BSCCO (phases 2212, 2223), NdBa2Cu3Ox, their nanocomposites, Li-Ni-Co-O spinels as cathodic materials for Li rechargeable batteries and fuel

cells MCFC, BaTiO3, LiPO4, Li titanates: spherical for fusion technology, irregularly shaped as superconductors and cathodic materials, Pt/WO3 catalyst. Many of the mentioned above systems, as well as sensors, type SnO2, were prepared as coatings on metallic substrates. Bioceramic materials based on calcium phosphates (e.g. hydroxyapatite) were synthesized in the form of powders, monoliths and fibres. • DTA and TGA thermal analyser OD-102 Paulik-Paulik-Erdey, MOM (Hungary) Technical data: balance fundamental sensitivity – 20-0.2 mg/100 scale divisions, weight range – 0-9.990 g, galvanometer sensitivity – 1x10–10 A/mm/m, maximum temperature – 1050oC. Application: Thermogravimetric studies of materials up to 1050oC. • DTA and TGA thermal analyser 1500 MOM (Hungary) Technical data: temperature range – 20-1500oC; power requirements – 220 V, 50 Hz. Application: Thermal analysis of solids in the temperature range 20-1500oC. • Research general-purpose microscope Carl Zeiss Jena (Germany) Technical data: General purpose microscope, magnification from 25 to 2500 times, illumination of sample from top or bottom side. • Metallographic microscope EPITYP-2, Carl-Zeiss Jena (Germany) Technical data: magnification from 40 to 1250 times. Application: Metallographic microscope for studies in polarized light illumination and hardness measurements. • Laboratory furnace CSF 12/13, CARBOLITE (Great Britain) Application: Temperature treatment of samples in controlled atmosphere up to 1500oC with automatic adjustment of final temperature, heating and cooling rate. 214 INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS

II. DEPARTMENT OF RADIOISOTOPE INSTRUMENTS AND METHODS Laboratory of Industrial Radiometry Activity profile: Research and development of non-destructive methods and measuring instruments utilizing physical phenomena connected with the interaction of radiation with matter: development of new methods and industrial instruments for measurement of physical quantities and analysis of chemical composition; development of measuring instruments for environmental protection (dust monitors, radon meters); implementation of new methods of calibration and signal processing (multi- variate models, artificial neural networks); designing, construction and manufacturing of measuring instruments and systems; testing of industrial and laboratory instruments. • Multichannel analyser board with software for X and γ-ray spectrometry Canberra • Function generator FG-513, American Reliace INC

III. DEPARTMENT OF RADIOCHEMISTRY 1. Laboratory of Coordination and Radiopharmaceutical Chemistry Activity profile: Preparation of novel technetium(I, III, V) complexes with chelating ligands (mono- and bifunctional), labelled with 99mTc, as potential diagnostic radiopharmaceuticals or their precursors. Studying of their hydrophilic-lipophilic properties, structure and their interactions with peptides. Also analogous rhenium(I) complexes are synthesised and studied. Novel platinum and palladium complexes with organic ligands, analogs of cisplatin, are synthesised and studied as potential antitumor agents. Solvent extraction separation of trivalent actinides from lanthanides is studied, directed towards nuclear waste treatment. Studies on chemical isotope effects of metal ions – search of correlations between isotope separation factor and structure of species exchanging the isotopes in two-phase chemical systems. (For the research equipment, common for both Laboratories, see below.) 2. Laboratory of Heavy Elements Activity profile: Synthesis of novel macrocyclic complexes of 47Sc, 103m,105Rh and 212Bi radionuclides – potential precursors for therapeutic radiopharmaceuticals. Elaboration of new methods for astatination (211At) of biomolecules via metal complexes. Design of new medically important radionuclide generators, e.g. 82Sr/82Rb, 103Ru/103mRh, 44Ti/44Sc. Structural studies on the complexes and solvates of heavy p-block elements in the solid state and in solution. • Spectrometric set ORTEC Multichannel analyser, type 7150, semiconductor detector Application: Measurements and identification of γ- and α-radioactive nuclides. • Gas chromatograph 610, UNICAM (England) Application: Analysis of the composition of mixtures of organic substances in the gas and liquid state. • High Performance Liquid Chromatography system Gradient HPLC pump L-7100, Merck (Germany) with γ-radiation detector, INCT (Poland) Application: Analytical and preparative separations of radionuclides and/or various chemical forms of radionuclides. • High Performance Liquid Chromatography system Gradient HPLC pump LC-10ADvp, with a UV-VIS detector SPD-10Avp/10AVvp, Shimadzu (Japan) Application: Analytical and preparative separations of radionuclides and/or various chemical forms of radionuclides. • Capillary electrophoresis system PrinCE Technologies with a UV-VIS detector (Bischoff Lambda 1010) and a radiometric detector Activity Gauge type Tc-99m (INCT, Poland) Application: Analytical separation of various radiochemical and chemical species, in particular charged. • Gamma isotope TLC analyzer SC-05 (INCT, Poland) Application: Measurements of gamma radioactivity distribution along thin-layer-chromatography plates and electrophoretic strips. • UV-VIS spectrophotometer DU 68, Beckman (Austria), modernized and computerized Application: Recording of electronic spectra of metal complexes and organic compounds in solution. Analytical determination of the concentration of these compounds. INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS 215 • FT-IR spectrophotometer EQUINOX 55, Bruker (Germany) Application: Measurements of IR spectra of metal complexes and other species in the solid state and in solution.

IV. DEPARTMENT OF NUCLEAR METHODS OF PROCESS ENGINEERING

1. Laboratory for Flue Gases Analysis

Activity profile: Experimental research connected with elaboration of removal technology for SO2 and NOx and other hazardous pollutants from flue gases. • Ultrasonic generator of aerosols TYTAN XLG • Gas chromatograph Perkin-Elmer (USA) • Gas analyser LAND

Application: Determination of SO2, NOx, O2, hydrocarbons, and CO2 concentrations. • Impactor MARK III Andersen (USA) Application: Measurement of aerosol particle diameter and particle diameter distribution. 2. Laboratory of Stable Isotope Ratio Mass Spectrometry Activity profile: Study of isotope ratios of stable isotopes in hydrogeological, environmental, medical and food samples. • Mass spectrometer DELTAplus Finnigan MAT (Bremen, Germany) Technical data: DELTAplus can perform gas isotope ratio measurements of H/D, 13C/12C, 15N/14N, 18O/16O, 34S/32S. Application: For measurements of hydrogen (H/D) and oxygen (18O/16O) in water samples with two automatic systems: H/Device and GasBench II. The system is fully computerized and controlled by the software ISODAT operating in multiscan mode (realtime). The H/Device is a preparation system for hydrogen from water and volatile organic compounds determination. Precision of hydrogen isotope ratio determination is about 0.5‰ for water. The GasBench II is a unit for on-line oxygen isotope ratio measurements in water samples by “continuous flow” techniques. With GasBench II, water samples (0.5 ml) can be routinely analyzed with a precision and accuracy of 0.05‰. The total volume of water sample for oxygen and hydrogen determination is about 2 ml. • Elemental Analyzer Flash 1112 NCS Thermo Finnigan (Italy) Application: For measurement of carbon, nitrogen and sulfur contents and their isotope composition in organic matter (foodstuff and environmental samples). • Gas chromatograph mass spectrometer GC MS-QP 5050A, GC-17A, Shimadzu (Japan) Technical data: capillary column – SPB 5, HP-5MS, SUPELCOWAX™-10. 3. Radiotracers Laboratory Activity profile: Radiotracer research in the field of: environmental protection, hydrology, underground water flow, sewage transport and dispersion in rivers and sea, dynamic characteristics of industrial installations and waste water treatment stations. • Heavy lead chamber (10 cm Pb wall thickness) for up to 3.7x1010 Bq (1 Ci) radiotracer activity preparations in liquid or solid forms • Field radiometers for radioactivity measurements • Apparatus for liquid sampling • Turner fluorimeters for dye tracer concentration measurements • Automatic devices for liquid tracers injection • Liquid-scintillation counter Model 1414-003 ”Guardian”, Wallac-Oy (Finland) Application: Extra low-level measurements of α and β radionuclide concentrations, especially for H-3, Ra-226, Rn-222 in environmental materials, e.g. underground waters, surface natural waters; in other liquid samples as waste waters, biological materials, mine waters, etc. 216 INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS

4. Membrane Laboratory Activity profile: Research in the field of application of membranes for radioactive waste processing, separation of isotopes and gas separation. • Membrane distillation plant for concentration of solutions Technical data: output ~0.05 m3/h, equipped with spiral-wound PTFE module G-4.0-6-7 (SEP GmbH) with heat recovery in two heat-exchangers. • Ultrafiltration plant equipped with replaceable ceramic multichannel modules • US 150 laboratory stand (Alamo Water) for reverse osmosis tests Technical data: working pressure – up to 15 bar, flow rate – 200 dm3/h, equipped with two RO modules. • Laboratory stand with different ceramic replaceable tubular UF modules • Laboratory set-up for small capillary and frame-and-plate microfiltration and membrane distillation module examination (capillary EuroSep, pore diameter 0.2 μm and frame-and-plate the INCT modules) • The system for industrial waste water pretreatment Technical data: pressure – up to 0.3 MPa; equipped with ceramic filters, bed Alamo Water filters with replaceable cartridge (ceramic carbon, polypropylene, porous or fibrous) and frame-and-plate microfiltration module. • Gas separation system equipped with UBE capillary module • Laboratory stand for pervaporation and vacuum membrane distillation tests • Automatic refractometer J357, Rudolph Technologies Inc. (USA)

Technical data: nD=1.29-1.70 , 0-95 BRIX. • Spectrophotometer HACH 2000 (Germany)

V. DEPARTMENT OF RADIATION CHEMISTRY AND TECHNOLOGY

1. Laboratory of Radiation Modified Polymers Activity profile: Modification of polymers by ionising radiation. Radiation-induced radicals in polymers. Optimization of mechanical and chemical properties of biocompatible materials following electron beam and gamma irradiation, biological application of polymers. Nanocomposites and nanofillers modified by ionising radiation. • Extruder PLV-151, BRABENDER-DUISBURG (Germany) Technical data: Plasti-Corder consists of: driving motor, temperature adjustment panel, thermostat, crusher, mixer, extruder with set of extrusion heads (for foils, rods, sleevs, tubes), cooling tank, pelleting machine, collecting device. Application: Preparation of polymer samples. • Equipment for mechanical testing of polymer samples INSTRON 5565, Instron Co. (England) Technical data: high performance load frame with computer control device, equipped with Digital Signal Processing and MERLIN testing software; max. load of frame is 5000 N with accuracy below 0.4% in full range; max. speed of testing 1000 mm/min in full range of load; total crosshead travel – 1135 mm; space between column – 420 mm; the environmental chamber 319-409 (internal dimensions 660x230x240 mm; temperature range – from -70 to 250oC). Application: The unit is designed for testing of polymer materials (extension testing, tension, flexure, peel strength, cyclic test and other with capability to test samples at low and high temperatures). • Viscosimeter CAP 2000+H, Brookfield (USA) Technical data: range of measurements – 0.8-1500 Pa*s, temperature range – 50-235oC, cone rotation speed – 5-1000 rpm, sample volume – 30 μl. Computer controlled via Brookfield CALPCALC® software. Application: Viscosity measurements of liquids and polymer melts. • Differential scanning calorimeter MDSC 2920 CE, TA Instruments Technical data: equipped with liquid nitrogen cooling adapter (LNCA) for 60 l of liquid nitrogen and sample encapsulating press for open or hermetically sealed pans. Module for Modulated DSC™ is included. Working temperature – from -150oC with the LNCA to 725oC. INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS 217

Application: Determines the temperature and heat flow associated with material phase transitions as a function of time and temperature. It also provides quantitative and qualitative data on endother- mic (heat absorption) and exothermic (heat evolution) processes of materials during physical transitions that are caused by phase changes, melting, oxidation, and other heat-related changes. • Processor tensiometer K100C Technical data: supplied with the thermostatable sample vessel. Working temperature is from -10 to +100oC. The height of the sampler carrier is adjusted with the help of a high-precision motor. The balance system is automatically calibrated by a built-in reference weight with a high precision. Resolutions of measurement is 0.01 mN/m. Application: Surface and interfacial tension measurement of liquids – Du Noüy Ring method and Dynamic Wilhelmy method with range 1-1000 mN/m; dynamic contact angle measurements; surface energy calculations on solids, powders, pigments, fibers, etc.; sorption measurements with the Washburn method for determining the surface energy of a powder-form solid. Controlled by LabDesk™ software. • Spectrophotometer UV-VIS UNICAM SP 1800 with linear recorder UNICAM AR 25 Technical data: Wavelength – 190-850 nm. • Equipment for gel electrophoresis System consists of: horizontal electrophoresis apparatus SUBMINI Electrophoresis Mini-System, transilluminator UV STS-20M JENCONS (United Kingdom), centrifuge EBA 12 Hettich/Zen- trifugen, microwave oven KOR 8167 Daewoo. • Melt flow tester ZWICK 4105, Zwick GmbH (Germany) Technical data: temperature of measurements – 150, 190 and 230oC; press load – 2.16 and 5.00 kg; manual operating. Application: Determination of standard values of melt-mass flow rate (MFR) of the thermoplastic materials (polymers) under specified conditions of temperature and load (according to standards: PN-EN ISO 1133:2005, ASTM 1328); comparison of rheological properties of polymers, including filled materials; comparison of degree of degradation; testing of catalogue data. 2. Radiation Sterilization Pilot Plant of Medical Devices and Tissue Grafts Activity profile: Research and development studies concerning new materials for manufacturing single use medical devices (resistant to radiation up to sterilization doses). Elaboration of monitoring systems and dosimetric systems concerning radiation sterilization processing. Introducing specific procedures based on international recommendations of ISO 13485:2003 and ISO 11137:2006 standards. Sterilization of medical utensils, approx. 70 million pieces per year. • Electron beam accelerator UELW-10-10, NPO TORIJ (Moscow, Russia) Technical data: beam energy – 10 MeV, beam power – 10 kW, supply power – 130 kVA. Application: Radiation sterilization of medical devices and tissue grafts. • Spectrophotometer UV-VIS Model U-1100, Hitachi

Technical data: wavelength range – 200-1100 nm; radiation source – deuterium discharge (D2) lamp, and tungsten-iodine lamp. • Spectrophotometer UV-VIS Model SEMCO S/EC Technical data: wavelength range – 340-1000 nm, radiation source – halogen lamp. Application: Only for measurements of dosimetric foils. • Bacteriological and culture oven with temperature and time control and digital reading Incudigit 80L Technical data: maximum temperature – 80oC, homogeneity – ±2%, stability – ±0.25%, thermometer error – ±2%, resolution – 0.1oC. 3. Laboratory of Radiation Microwave Cryotechnique Activity profile: Radiation processes in solids of catalytic and biological importance: stabilization of cationic metal clusters in zeolites, radical reactions in polycrystalline polypeptides, magnetic properties of transition metals in unusual oxidation states; radical intermediates in heterogeneous catalysis. • Electron spin resonance (ESR) Q-band spectrometer Bruker E-500, equipped with continuous flow helium cryostat Oxford Instruments CF935 O and DICE cw ENDOR/TRIPLE unit Bruker E-560 with rf amplifier 10 kHz-220 MHz. 218 INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS • Electron spin resonance (ESR) X-band spectrometer Bruker ESP-300, equipped with: frequency counter Hewlett-Packard 5342A, continuous flow helium cryostat Oxford Instruments ESR 900, continuous flow nitrogen cryostat Bruker ER 4111VT, ENDOR-TRIPLE unit Bruker ESP-351. Application: Studies of free radicals, paramagnetic cations, atoms and metal nanoclusters as well as stable paramagnetic centers. • Spectrophotometer UV-VIS LAMBDA-9, Perkin-Elmer Technical data: wavelength range – 185-3200 nm, equipped with 60 nm integrating sphere. 4. Pulse Radiolysis Laboratory Activity profile: Studies of charge and radical centres transfer processes in thioether model compounds of biological relevance in liquid phase by means of time-resolved techniques (pulse radiolysis and laser flash photolysis) and steady-state γ-radiolysis. • Accelerator LAE 10 (nanosecond electron linear accelerator) INCT (Warszawa, Poland) Technical data: beam power – 0.2 kW, electron energy – 10 MeV, pulse duration – 7-10 ns and about 100 ns, repetition rate – 1, 12.5, 25 Hz and single pulse, pulse current – 0.5-1 A, year of installation 1999. Application: Research in the field of pulse radiolysis. • Gas chromatograph GC-14B, Shimadzu (Japan) Specifications: two detectors: thermal conductivity detectors (TCD) and flame ionization detector (FID). Column oven enables installation of stainless steel columns, glass columns and capillary columns. Range of temperature settings for column oven: room temperature to 399oC (in 1oC steps), rate of temperature rise varies from 0 to 40oC/min (in 0.1oC steps). Dual injection port unit with two lines for simultaneous installation of two columns. Application: Multifunctional instrument for analysis of final products formed during radiolysis of sulphur and porphyrin compounds and for analysis of gaseous products of catalytic reactions in zeolites. • Dionex DX500 chromatograph system Dionex Corporation Specifications: The ED40 electrochemical detector provides three major forms of electrochemical detection: conductivity, DC amperometry and integrated and pulsed amperometry. The AD20 absorbance detector is a dual-beam, variable wavelength photometer, full spectral capability is provided by two light sources: a deuterium lamp for UV detection (from 190 nm) and a tungsten lamp for VIS wavelength operation (up to 800 nm). The GP40 gradient pump with a delivery system designed to blend and pump mixtures of up to four different mobile phases at precisely controlled flow rates. The system can be adapted to a wide range of analytical needs by choice of the chromatography columns: AS11 (anion exchange), CS14 (cation exchange) and AS1 (ion exclusion). Application: The state-of-the-art analytical system for ion chromatography (IC) and high-performance liquid chromatography (HPLC) applications. Analysis of final ionic and light-absorbed products formed during radiolysis of sulphur compounds. The system and data acquisition are controlled by a Pentium 100 PC computer. • Digital storage oscilloscope 6051A Wave Runner, LeCroy Specifications: Bandwidth – 500 MHz; rise time – 750 ps; sample rate - up to 5 Gs/s (by combining 2 channels); acquisition memory – 16 Mpt with 8 Mpt per channel; sensitivity – 2 mV/div to 10 V/div; fully variable, fully programmable; standard ports – 10/100Base-T Ethernet, Parallel, GPiB –IEEE 488.2, USB 2.0 (5), RS-232, SVGA Video Out, Audio in/out; Windows XP Professional operating system. Application: Digital storage oscilloscope (DSO) with high speed and long memory controls pulse radiolysis system dedicated to the nanosecond electron linear accelerator (LAE 10). The multiple time scales can be generated by a computer from a single kinetic trace originating from DSO since the oscilloscope produces a sufficient number of time points (up to 16 M points record length). • Digital storage oscilloscope 9354AL, LeCroy Specifications: Bandwidth DC to 500 MHz; sample rate – 500 Ms/s up to 2 Gs/s (by combining 4 channels); acquisition memory – up to 8 Mpt with 2 Mpt per channel; time/div range – 1 ns/div to 1000 s/div; sensitivity – 2 mV/div to 5 V/div; fully variable, fully programmable via GPIB and RS-232C. Application: Digital storage oscilloscope (DSO) with high speed and long memory controls pulse radiolysis system dedicated to the nanosecond laser flash photolysis. The multiple time scales can INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS 219

be generated by a computer from a single kinetic trace originating from DSO since the oscilloscope produces a sufficient number of time points (up to 8 M points record length). • Digital storage oscilloscope 9304C, LeCroy Specifications: Bandwidth DC to 200 MHz; sample rate – 100 Ms/s up to 2 Gs/s (by combining 4 channels); acquisition memory – up to 200 kpt per channel; time/div range – 1 ns/div to 1000 s/div; sensitivity – 2 mV/div to 5 V/div; fully variable. Application: Digital oscilloscope (DO) is used in pulse radiolysis system dedicated to the nanosecond electron linear accelerator (LAE 10). • Nd:YAG laser Surelite II-10, Continuum (USA) Specifications: energy (mJ) at 1064 nm (650), 532 nm (300), 355 nm (160) and 266 nm (80); pulse width – 5-7 ns (at 1064 nm) and 4-6 ns (at 532, 355 and 266 nm); energy stability – 2.5-7%; can be operated either locally or remotely through the RS-232 or TTL interface. Application: A source of excitation in the nanosecond laser flash photolysis system being currently under construction in the Department. • Potentiostat/Galvanostat VersaStat II Princeton Applied Research (USA) Specifications: Power amplifier compliance voltage single channel – ±20 V, maximum current – ±200 mA, rise time – 100 μs, slew rate – 1 V/μs; system performance: minimum timebase – 100 μs, minimum potential step – 250 μV, noise and ripple <50 μV rms typically, minimum current range – 1 μA (hardware), minimum current range – 100 nA (software), minimum current resolution – 200 pA, drift – vs. time <50 μV/°C vs. time: <200 μV/week. iR compensation: current interrupt 12-bit potential error correction total int. time <50-2000 μs. Accuracy: applied potential – 0.2% of reading ±2 mV, applied current – 0.2% of full-scale current. Computer interface: GPIB IEEE-488, RS-232. Differential electrometer: input bias current <50 pA at 25°C, typically <20 pA at 25°C. Max. voltage range – ±2 V, max. input voltage differential – ±10 V. Bandwidth – -3 dB at>4 MHz. Offset voltage <100 μV. Offset temperature stability <5 μV/°C. Common mode rejection >70 dB at 100 Hz and >60 dB at 100 kHz. Input impedance >1010 Ω, typically 1011 Ω in parallel with <50 pF. 5. Research Accelerator Laboratory Activity profile: Laboratory is equipped with accelerators providing electron beams which make capable to perform the irradiation of investigated objects within wide range of electron energy from 100 keV to 13 MeV and average beam power from 0.1 W do 20 kW, as well as with Co-60 gamma sources with activity 1.9x1010 to 1.3x1014 Bq and dose rate from 0.03 to 1.8 kGy/h. The described above irradiators are completed in a unique in world scale set of equipment which can be applied in a wide range of electron beam and gamma-ray research and radiation processing. • Accelerator ILU-6 INP (Novosibirsk, Russia) Technical data: beam power – 20 kW, electron energy – 0.7-2 MeV. Application: Radiation processing. • Linear electron accelerator LAE 13/9, Institute of Electro-Physical Equipment (Russia) Technical data: electron energy – 10-13 MeV; electron beam power – 9 kW. Application: Radiation processing. • Cobalt source I Issledovatel (Russia) Technical data: 32 sources with an actual activity of 9.2x1013 Bq. Application: Radiation research. • Cobalt source II Mineyola 1000, INR (Świerk, Poland) Technical data: 8 rods with an initial activity of 2.66x1013 Bq; the actual activity is 1.07x1013 Bq. Application: Radiation research. • Electron accelerator AS-2000 (the Netherlands) Technical data: energy – 0.1-2 MeV, max. beam current – 100 μA. Application: Irradiation of materials. • Spectrometer DLS-82E, SEMITRAP (Hungary) Application: Research in radiation physics of semiconductors. 220 INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS

• Argon laser ILA-120, Carl Zeiss (Jena, Germany) Application: Measurements of optical properties. • Spectrometer DLS-81 (Hungary) Application: Measurements of semiconductor properties. • Argon laser LGN-503 (Russia) Application: Measurements of optical properties.

VI. DEPARTMENT OF ANALYTICAL CHEMISTRY 1. Laboratory of Spectral Atomic Analysis Activity profile: atomic absorption and emission spectroscopy, studies on interference mechanisms, interpretation of analytical signals, service analysis. • Atomic absorption spectrometer SH-4000, Thermo Jarrell Ash (USA); equipped with a 188 Controlled Furnace Atomizer (CTF 188), Smith-Heftie background correction system and atomic vapor (AVA-440) accessory. Application: For analyses of samples by flame and furnace AAS. • Atomic absorption spectrometer SP9-800, Pye Unicam (England); equipped with SP-9 Furnace Power Supply, PU-9095 data graphics system, PU-9095 video furnace programmer and SP-9 furnace autosampler. Application: For analyses of samples by flame and furnace AAS. • Atomic absorption spectrometer SOLAR M6 MK II (Thermo Electron Corporation), equipped with: graphite furnace GF 95 with

D2 and Zeeman background correction system, autosampler FS 95 and hydride and cold vapour generator. Application: For analyses of samples by flame and furnace AAS. 2. Laboratory of Neutron Activation Analysis Activity profile: The sole laboratory in Poland engaged for 40 years in theory and practice of neutron activation analysis in which the following methods are being developed: reactor neutron activation analysis (the unique analytical method of special importance in inorganic trace analysis), radiochemical separation methods, ion chromatography. The laboratory is also the main Polish producer of CRMs and the provider for Proficiency Testing exercises. • Laminar box HV mini 3, Holten (Denmark) Technical data: air flow rate 300 m3/h. Application: Protection of analytical samples against contamination. • Ion chromatograph 2000i/SP, Dionex (USA) Technical data: data evaluating program AI-450, ion exchange columns of type Dionex Ion Pac, conductivity detector, UV/VIS detector.

Application: Analyses of water solutions, determination of SO2, SO3 and NOx in flue gases and in air, determination of metals in biological and environmental samples. • HPGe detector, well-type CGW-3223, Canberra, coupled with analog line (ORTEC) and multichannel gamma-ray analyzer TUKAN Application: Instrumental and radiochemical activation analysis. • Coaxial HPGe detector POP-TOP, ORTEC (USA), coupled with analog line (ORTEC) and multichannel gamma-ray analyzer TUKAN • HPGe detector, well-type CGW-5524, Canberra, coupled with multichannel gamma-ray analyzer (hardware and software) Canberra Application: Instrumental and radiochemical activation analysis. • Analytical balance Sartorius BP2 215 Application: For weighing sample of mass >10 mg to 220 g. INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS 221

• Analytical micro-balance Sartorius MC5 Application: Preparation of mono- and multi-elemental standards as well as for weighing small mass samples, less than 10 mg. • Balance WPX 650, RADWAG (Poland) Application: For weighing sample of mass >10 mg to 650 g. • Liquid Scintillation Analyzer TRI-CARB 2900TR, Packard BioScience Company Application: α- and β-ray measurements. • Planetary Ball Mill PM 100, Retsch Application: Grinding and mixing: soft, medium hard to extremly hard, brittle or fibrous materials. • Balance-drier ADS50, AXIS (Poland) Application: Determination of mass and humidity of samples. • Microwave digestion system UnicleverTMII, PLAZMATRONIKA (Poland) Application: Microwave digestion of samples. • Microwave digestion system BM-1S/II, PLAZMATRONIKA (Poland) Application: Microwave digestion of samples. • Homogenizer INCT (Poland) Application: Homogenization of the material used for preparation of CRMs. • Peristaltic pump REGLO ANALOG MS-4/6-100, ISMATEC (Switzerland) Application: Regulation of flow of eluents during elution process. 3. Laboratory of Chromatography Activity profile: Development of HPLC methods for determination of environmental pollutants, application of HPLC and ion-chromatography monitoring of degradation organic pollutants in waters and wastes using ionizing radiation, development of chromatographic methods, preconcentration of organic environmental pollutants, development of chromatographic methods of identification of natural dyes used for ancient textiles. • Apparatus for biological oxygen demand determination by respirometric method and dissolved oxygen measurement method WTW-Wissenschaftlich-Technische Wersttätten (Germany) Application: Analyses of water and waste water samples. • Apparatus for chemical oxygen demand determination by titrimetric method Behr Labor-Technik (Germany) Application: Analyses of water and waste water samples. • Set-up for solid phase-extraction (vacuum chamber for 12 columns and vacuum pump) Application: Analyses of water and waste water samples. • Shimadzu HPLC system consisting of: gradient pump LC-10AT, phase mixer FCV-10AL, diode- -array detector SPD-M10A, column thermostat CTO-10AS Application: Analyses of natural dyes, radiopharmaceuticals, water and waste water samples. • Laboratory ozone generator 301.19, Erwin Sander Elektroapparatebau GmbH (Uetze-Eltze, Germany) Application: Ozone production for degradation of pollutants in waste water samples. 4. Laboratory of General Analysis Activity profile: Preparation and application of new chelating sorbents to the separation of metal traces from environmental materials for their determination by atomic absorption spectrometry, speciation analysis, service analysis. • Spectrophotometer PU8625 Series UV/Visible, Philips Technical data: wavelength range – 200-1100 nm. Application: Measurements of absorbance in spectrophotometric analysis. 222 INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS • Spectrophotometer UV-160, Shimadzu (Japan) Technical data: wavelength range – 200-1100 nm, with automatic baseline correction and graphic printer. Application: Routine spectrophotometric analysis and research works.

VII. DEPARTMENT OF RADIOBIOLOGY AND HEALTH PROTECTION • Equipment for electrophoretic analysis of DNA CHEF III, BIO-RAD (Austria) Application: Analysis of DNA fragmentation as a result of damage by various physical and chemical agents. • Microplate reader ELISA, ORGANON TEKNICA (Belgium) Application: For measurement of optical density of solutions in microplates. • Hybridisation oven OS-91, BIOMETRA (Germany) Technical data: work temperatures from 0 to 80oC; exchangeable test tubes for hybridisation. Application: For polymerase chain reaction (PCR). • Spectrofluorimeter RF-5000, Shimadzu (Japan) Application: For fluorimetric determinations. • Transilluminator for electrophoretic gels Biodoc, BIOMETRA (Great Britain) Application: For analysis of electrophoretic gels. • Laminar flow cabinet NU-437-400E, Nu Aire (USA) Application: For work under sterile conditions. • Liquid scintillation counter LS 6000LL, BECKMAN (USA) Application: For determinations of radioactivity in solutions. • Research microscope universal NU, Carl Zeiss Jena (Germany) Application: For examination of cytological preparations. Comments: Universal microscope for transmission and reflected light/polarised light. Magnifica- tion from 25x to 2500x. Possibility to apply phase contrast. • Incubator T-303 GF, ASSAB (Sweden) Technical data: 220 V, temperature range – 25-75oC. Application: For cell cultures under 5% carbon dioxide. • Incubator NU 5500E/Nu Aire (USA) Technical data: 220 V, temperature range from 18 to 55oC. Application: For cell cultures under 0-20% carbon dioxide. • Laminar flow cabinet V-4, ASSAB (Sweden) Application: For work under sterile conditions. • Image analysis system Komet 3.1, Kinetic Imaging (Great Britain) Application: For comet (single cell gel electrophoresis) analysis. • ISIS 3 Metasystem (Germany) Application: Microscopic image analysis system for chromosomal aberrations (bright field and fluorescence microscopy).

VIII. LABORATORY FOR DETECTION OF IRRADIATED FOOD Activity profile: Detection of irradiated foods. European standards (CEN) adapted as analytical methods to be routinely used in the Laboratory, are based on electron paramagnetic resonance (EPR/ESR) spectroscopy, pulsed photostimulated luminescence (PPSL) and thermoluminescence measurements (TL). The research work is focused mainly on the development of the above three INSTRUMENTAL LABORATORIES AND TECHNOLOGICAL PILOT PLANTS 223

methods and the enlargement of their ability of the detection of irradiation in the variety of foodstuffs. Laboratory is capable to examine food samples by the DNA comet assay (decomposition of single cell) and statistical germination study. The quality assurance system was adapted in the Labo- ratory in 1999 and in 2006 was actualised and documented in agreement with the PN-EN 1SO/IEC 17025:2005 standard. Actually Laboratory possesses Accreditation Certificate of Testing Labora- tory nr AB 262 issued by the Polish Centre for Accreditation and valid until 24.10.2010. • Thermoluminescence reader TL-DA-15 Automated, Risoe National Laboratory (Denmark) Technical data: turntable for 24 samples, heating range – 50÷500oC, heating speed – 0.5÷10.0oC/s, optical stimulated luminescence (OSL) system. Application: Detection of irradiated foods containing silicate minerals, e.g. spices, vegetables shrimps tc, research work on irradiated foods. • Fluorescence microscope OPTIPHOT Model X-2, NIKON (Japan) Technical data: halogen lamp 12 V-100 W LL; mercury lamp 100 W/102 DH; lenses (objectives) CF E Plan Achromat 4x, CF E Plan Achromat 40x, CF FLUOR 20x. Application: Detection of irradiated foods by the DNA comet assay method, research work on apoptosis in mammalian cells, biological dosimetry, analysis of DNA damage in mammalian cells. • Compact EPR spectrometer EPR 10-MINI, St. Petersburg Instruments Ltd. (Russia) Technical data: sensitivity – 3x1010, operating frequency (X band) – 9.0-9.6 GHz, max. microwave power – 80 mW, magnetic field range – 30-500 mT, frequency modulation – 100 kHz. Application: Detection of irradiated foods, bone and alanine dosimetry, research work on irradiated foods and bone tissues. • Pulsed photostimulated luminescence system SURRC (United Kingdom) Technical data: pulsed light source – diodes IR LED; detector – photomultiplier ETL; pulse on and off periods – 15 μs; sample holder – 50 mm diameter disposable Petri dishes; set up – sample chamber and detector head assembly, contol unit, on line computer, optional. Application: Irradiated food screening system.

IX. EXPERIMENTAL PLANT FOR FOOD IRRADIATION 1. Microbiological Laboratory Activity profile: optimization of food irradiation process by microbiological analysis. • Sterilizer ASUE, SMS (Warszawa, Poland) Application: Autoclaving of laboratory glass, equipment, and microbiological cultures. • Fluorescence microscope BX, Olimpus (Germany) Application: Quantitative and qualitative microbiological analysis. 2. Experimental Plant for Food Irradiation Activity profile: Development of new radiation technologies for the preservation and hygienization of food products. Development and standarization of the control system for electron beam processing of food. Development of analytical methods for the detection of irradiated food. Organization of consumer tests with radiation treated food products. • Accelerator ELEKTRONIKA (10 MeV, 10 kW) UELW-10-10, NPO TORIJ (Moscow, Russia) Application: Food irradiation. 224 INDEX OF THE AUTHORS

INDEX OF THE AUTHORS

A Dybczyński Rajmund 73, 85 Dziedzic-Gocławska Anna 30 Aleshkevych Pavlo 151 Dzierżanowski Piotr 134, 136 Antunes Ines 67 Dźwigalski Zygmunt 163 Anuszewska Elżbieta 77 E B Edwards Alan 103 Barański Marek 151 Eliasson Ann-Charlotte 47 Barcz Adam 141 Enache Mirela 25, 27 Barlak Marek 141 Bartak Jakub 156 F Bartłomiejczyk Teresa 101 Bartoś Barbara 67 Ferreri Carla 21 Basfar Ahmed A. 117 Filipiuk Dorota 79 Bilewicz Aleksander 67, 69, 70 Fuente Julio R. De la 22 Bobrowski Krzysztof 19, 21, 22 Fuks Leon 77, 79 Bojanowska-Czajka Anna 52 Borowiec Mieczysław T. 151 G Brykała Marcin 147, 151 Głuszewski Wojciech 39, 41, 49 Brzozowska Kinga 104 Gniazdowska Ewa 159 Brzóska Kamil 99 Goretta Kenneth C. 147 Buczkowski Marek 145 Govindarajan Subbian 93 Bulska Ewa 81 Grądzka Iwona 106 Bułka Sylwester 114, 118, 161 Grigoriew Helena 153 Buraczewska Iwona 109 Grodkowski Jan 23 Gruber Bożena 77 C Gryczka Urszula 42 Celuch Monika 25, 27 Gryz Michał 91, 92, 96 Chajduk Ewelina 82, 85 Guzik Grzegorz P. 56, 63 Chatgilialoglu Chryssostomos 21 Chmielewska Dagmara K. 141, 153 H Chmielewski Andrzej G. 42, 114, 115, 117, 120, Harasimowicz Marian 120, 121 125, 126, 161 Herdzik Irena 81 Chwastowska Jadwiga 89, 147 Houée-Levin Chantal 19 Cieśla Krystyna 44, 47, 49 Cojocaru Cornel 121 I Cuna Stela Maria 113 Iwaneńko Teresa 100, 101, 102 D J Danko Bożena 85 Jaworska Agnieszka 121 Dąbrowski Ludwik 141 Jurczyk Renata 119 Dembiński Wojciech 81 Deperas Joanna 103 Deperas-Kaminska Marta 103, 105 K Deptuła Andrzej 147, 151 Kalinowska Justyna 141 Derda Małgorzata 113, 123, 126 Kałuska Iwona 161 Dłuska Ewa 121 Kamiński Artur 30 Dobrowolski Andrzej 125 Kciuk Gabriel 22 Domuchowski Wiktor 151 Kempers Alexander J. 126 Drzewicz Przemysław 52 Kierzek Joachim 134 Dudek Jakub 82, 89 Kocia Rafał 23 Dyakonov Vladimir P. 151 Kopcewicz Michał 141, 142 INDEX OF THE AUTHORS 225 Kornacka Ewa M. 36 P Kosior Grzegorz 126 Palige Jacek 124, 125 Kowalska Ewa 67, 159 Pańczyk Ewa 128, 130 Kozakiewicz Janusz 36 Pawelec Andrzej 117 Krasavin Eugene A. 105 Pawlukojć Andrzej 94 Krejzler Jadwiga 75 Piekoszewski Jerzy 141, 142 Królak Edward 49 Pieńkos Jan 158, 159, 160 Kruszewska Hanna 77 Pogocki Dariusz 25, 27 Kruszewski Marcin 99, 100, 101, 102, 107 Polkowska-Motrenko Halina 82, 85 Kulisa Krzysztof 85 Premkumar Thatan 93 Kunicki-Goldfinger Jerzy 134, 136 Pruszyński Marek 69 Przybylski Jarosław 36 L Przybytniak Grażyna 33, 36 Laubsztejn Magdalena 60, 63 Pszonicki Leon 89 Leciejewicz Janusz 91, 92, 93, 94, 96 Ptaszek Sylwia 125 Lehner Katarzyna 58, 63 Lewandowska Hanna 99 R Licki Janusz 115, 117 Rahier Hubert 44 Lindholm Carita 103 Ratajczak Renata 142 Lloyd David 103 Romm Horst 103 Lundqvist Henrik 47 Roy Laurence 103 Ł S Łada Wiesława 147, 151 Sadlej-Sosnowska Nina 77 Łukasiewicz Andrzej 141 Sadło Jarosław 27, 28, 30, 99 Łyczko Monika 71, 73 Sadowska-Bratek Monika 82 Samczyński Zbigniew 73, 85 M Samecka-Cymerman Aleksandra 126 Sartowska Bożena 49, 130, 141, 142, 144, 145, 147 Machaj Bronisław 156, 159 Serdiuk Katarzyna 27 Mádl Martin 136 Skarnemark Gunnar 67 Majdan Marek 79 Skwara Witold 81, 89 Majkowska Agnieszka 67, 70 Sobarzo-Sanchez Eduardo 22 Malec-Czechowska Kazimiera 60, 63 Sochanowicz Barbara 99, 106, 108 Mehta Kishor 118 Sołtyk Wojciech 124 Męczyńska Sylwia 99 Sommer Sylwester 109 Michalik Jacek 28, 30 Stachowicz Wacław 56, 58, 60, 63 Migdał Wojciech 42, 161 Stanisławski Jacek 141, 142 Mirkowski Jacek 19, 23 Starosta Wojciech 42, 91, 92, 93, 94, 96, 145 Mirkowski Krzysztof 33 Sterlińska Elżbieta 89, 147 Mirowicz Jan 158 Strzelczak Grażyna 30, 60 Miśkiewicz Agnieszka 121 Sun Yongxia 114 Morand Josselin 103 Sypuła Michał 82, 85 Moss Raymond 103 Szłuińska Marta 103 Mozziconacci Olivier 19, 21 Szopa Zygmunt 85 Szostek Bogdan 52 N Szumiel Irena 106, 107, 108 Narbutt Jerzy 71, 73, 75 Szymczak Henryk 151 Natkaniec Ireneusz 94 Neves Maria 67 Ś Nichipor Henrietta 52, 114 Świstowski Edward 158, 159 Nowak Dorota 94 Nowicki Andrzej 33, 144 T Nowicki Lech 142 Timoshenko Gennady N. 105 Trojanowicz Marek 52 O Turek Janusz 28 Olczak Tadeusz 147, 151 Tymiński Bogdan 117, 119 Olszewska-Świetlik Justyna 128 Orelovitch Oleg 144 U Ostapczuk Anna 115 Urbański Piotr 156, 158, 160 226 INDEX OF THE AUTHORS W Z Walendziak Jolanta 124 Zabielski Roman 101, 102 Waliś Lech 128, 130, 141, 142 Zagórski Zbigniew P. 31, 39, 41 Wawszczak Danuta 145, 147, 151 Zakrzewska-Trznadel Grażyna 120, 121 Werner Zbigniew 141 Zalutsky Michael R. 69 Wierzchnicki Ryszard 113, 123, 126 Zayarnyuk Tetyana 151 Wojewódzka Maria 100, 101, 102, 107 Zimek Zbigniew 33, 52, 114, 117, 161, 163 Woliński Jarosław 100, 101, 102 Zimnicki Robert 124 Wójcik Andrzej 103, 104, 105, 109 Ziółkowska Weronika 120 Wroński Stanisław 121 Zwoliński Krzysztof 119 Wysocka Agnieszka 81