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PL0002050 ISSN 1425-204X

INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY

SL ¥ u 1999

31/ 40 Please be aware that all of the Missing Pages in this document were originally blank pages EDITORS Wiktor Smuiek, Ph.D. Ewa Godlewska-Para

PRINTING Sylwester Wojtas

© Copyright by the Institute of Nuclear Chemistry and Technology, Warszawa 2000 All rights reserved CONTENTS

GENERAL INFORMATION 9 MANAGEMENT OF THE INSTITUTE 11 MANAGING STAFF OF THE INSTITUTE 11 HEADS OF THE INCT DEPARTMENTS 11 SCIENTIFIC COUNCIL (1999-2003) 11

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

RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 17

GENERATION OF RADICAL CATIONS FROM PHENYL, VINYL, AND ALLYL CONTAINING THIOETHERS IN ORGANIC SOLVENTS A. Korzeniowska-Sobczuk, P. Wiśniewski, K. Bobrowski, L. Richter, O. Brede 19 EPR STUDIES OF RADICALS INDUCED BY IONISING RADIATION IN FLUTAMIDE H.B. Ambroż, E. Kornacka, G. Przybytniak 20

THE ROLE OF Cu(I) AND Cu(II) IN DNA DAMAGES H.B. Ambroż, E. Kornacka, G. Przybytniak 21

TEMPERATURE COEFFICIENT OF THE RADIATION YIELD OF THE RADICAL CH3 • CH COf IN CRYSTALLINE ALANINĘ Z.P. Zagórski 22 COMPETITION BETWEEN INTRAMOLECULAR TWO-CENTERED THREE-ELECTRON BONDED (S. • .S)+ AND (S. • .N)+ FORMATION DURING PHOTOOXIDATION OF METHIONINE-CONTAINING PEPTIDES BY THE 4-CARBOXYBENZOPHENONE TRIPLET STATE IN AQUEOUS SOLUTION K. Bobrowski, G.L. Hug, H. Kozubek, B. Marciniak 23

Trp[NH ' +] -Tyr[O ' ] RADICAL TRANSFORMATION IN H-Trp-(Pro)n-Tyr-OH,n = 3-5, SERIES OF PEPTIDES K. Bobrowski, J. Poznański, J. Holcman, K.L. Wierzchowski 25

EPR OF METALS NANOPARTICLES IN MCM-41 MOLECULAR SIEVES J. Michalik, D. Brown, J.-S. Yu, M. Danilczuk, L. Kevan 27

POLY(ETHYLENE TEREPHTHALATE) COMPOSITE MATERIALS - RADIATION EFFECTS J. Sadto, J. Bojarski, G. Strzelczak, J. Michalik 30

FURTHER STUDIES ON IRRADIATION PRODUCTS AND TOXICITY CHANGES IN RADIOLYTIC DECOMPOSITION OF 2,4-DICHLOROPHENOL P. Drzewicz, P.P. Panta, W. Głuszewski, G. Naiqcz-Jawecki, S. Wahyuni, M.H.O. Sampa, S.I. Berrely, M. Trojanowicz 32

RADIATION-INDUCED POLYMERIZATION OF 2-ETHYLHEXYL ACRYLATE FOR MEDICAL APPLICATION P.P. Panta, W. Głuszewski, G. Strzelczak, E.K. Wojtyńska, Z. Zimek 35

EXPERIMENTAL SIMULATION OF SPECTRA OF PEROXIDES ON CHAINS OF POLYPROPYLENE A. Rafalski, Z.P. Zagórski 37 ELECTRON PARAMAGNETIC RESONANCE SPECTROMETRY (EPR) FOR DATING OF PALEOANTHROPOLOGICAL NURAGHI SKELETAL TISSUES W. Stachowicz, J. Sadło, G. Strzelczak, J. Michalik 38

THE CELLULOSE MEMBRANE - WATER INTERACTION STUDIED BY DIFFERENTIA!. SCANNING CALORIMETRY K. Cieśla, H. Rahier, G. Zakrzewska-Trznadel 38

DIFFERENTIAL SCANNING CALORIMETRY STUDIES OF MELTING AND GLASS TRANSITION PROCESSES IN FOOD K. Cieśla, A. Sereno, W. Głuszewski, C. Barbossa 40

EFFECT OF ANNEALING AND IRRADIATION ON THE OPTICAL PROPERTIES OF OXIDE CRYSTAL S.M. Kaczmarek, M. Berkowski, Z. Moroz, S. Warchoł 41 CHANGES IN LUMINESCENCE OF Ce: YAG CRYSTALS UNDER IONIZING RADIATION TREATMENT S.M. Kaczmarek, Z. Moroz, M. Kwaśny, J. Kisielcwski, T. Łukasiewicz, J. Wojtkowska, H. Rzewuski 42

LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES - STATE-OF-THE-ART Z. Stuglik 42

DOSIMETRIC RESPONSES OF SUNNA AND PVC FOIL DOSIMETERS IRRADIATED WITH 10 MeV ELECTRON BEAMS - TIME DEPENDENCE Z. Stuglik 43

INFLUENCE OF BUTADIENE/STYRENE COPOLYMERS ON THE STABILISATION OF POLYPROPYLENE IN ELECTRON BEAM IRRADIATION D. Żuchowska, Z.P. Zagórski, G. Przybytniak, A. Rafalski 44

RADIATION INDUCED DEFECTS IN MONOCRYSTALS AND GLASSES OF LÍ2B4O7 S.M. Kaczmarek, A. Majchrowski, J. Kisielewski, M. Kwaśny, T. Wrońska 47

ANALYTICAL METHODS FOR THE DETECTION OF IRRADIATION IN FOOD COMMODITIES ACCREDITED IN THE 1NCT LABORATORY FOR DETECTION OF IRRADIATED FOODS W. Stachowicz, K. Malec-Czechowska, A.M. Dancewicz, Z. Szot 47

DETECTION OF IRRADIATED FOODS WITH THE USE OF GAS CHROMATOGRAPHY - EXPERIMENTS WITH POULTRY CARCASSES K. Lehner, W. Stachowicz, K. Malec-Czechowska, A.M. Dancewicz, Z. Szot 48

DSC STUDIES OF GELATINIZATION AND AMYLOSE-LIPID COMPLEX DECOMPOSITION OCCURRING IN INITIAL AND GAMMA IRRADIATED WHEAT AND CORN STARCHES K. Cieśla, A.-Ch. Eliasson 49

DECONTAMINATION OF NATURAL HONEY BY IONIZING RADIATION H.B. Owczarczyk, W. Migdał, B. Kędzia, E. Hołderna-Kędzia, D. Madajczyk 51

DECONTAMINATION OF MEDICAL HERBS BY IONIZING RADIATION W. Migdał, H.B. Owczarczyk 51

APPLICATION OF RADIATION TO THE PRODUCTION OF BAITS TO CONTROL CRAWLING INSECTS IN THE URBAN AREA W. Migdał, H.B. Owczarczyk, J. Świętosławski, J. Świętosławski 52

RADIATION EFFECTS IN PVC AND PVC COMPOSITIONS B. Świerz-Motysia, Z. Zimek, J. Bojarski, G. Przybytniak, J. Sadło 54

RADIOCHEMISTRY, STABLE , NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 57

COMPARISON OF AND EFFECTS IN ACETATE/AMALGAM SEPARATION SYSTEM W. Dembiński, M. Poniński, R. Fiedler 59

«-CRYSTALLINE POLYANTIMONIC ACID AS AN ADSORBENT FOR RADIOSTRONTIUM AND ACTINIDES(III), AND AS A PRIMARY BARRIER IN WASTE REPOSITORIES A. Bilewicz, J. Krejzler, J. Narbutt 60

ADSORPTION OF RADIOSTRONTIUM AND ACTINIDE(III) IONS ON A NOVEL ADSORBENT APATITE II J. Krejzler, J. Narbutt 61

ELECTRON CONFIGURATION AND RELATIVISTIC EFFECTS IN d ELECTRON ELEMENTS S. Siekierski 62

THE NEW VALUES OF IONIC RADII OF Rf4"1", Db5+ AND Sg6 + A. Bilewicz 64

STEREOCHEMICAL CHARACTER OF s2 LONE PAIR IN Bi3+ AQUA CATION B. Włodzimirska, A. Bilewicz 64

PECULIARITIES OF THE AQUEOUS RARE EARTH FLUORIDE SYSTEMS T. Mioduski 65

DETERMINATION OF SOME PRECIOUS METALS IN GEOLOGICAL AND ENVIRONMENTAL SAMPLES BY RADIOCHEMICAL NEUTRON ACTIVATION ANALYSIS USING CHELEX 100 ION EXCHANGE RESIN Z. Samczyński, B. Danko, R. Dybczyński 66

MODIFICATION OF , AND BISMUTII BY AND IN ELECTROTHERMAL. ATOMIC ABSORPTION SPECTROMETRY L.Pszonicki.J. Dudek 70 BEHAVIOUR OF AND IN THE PRESENCE OF MODIFIERS IN ELECTROTHERMAL ATOMIC ABSORPTION SPECTROMETRY L. Pszonicki, W. Skwara 71

APPLICATION OF A CHELATING 2-MERCAPTOBENZOTHIAZOLE LOADED RESIN TO THE SEPARATION OF INORGANIC AND ALKYLMERCURY SPECIES IN NATURAL WATERS J. Chwastowska, A. Rogowska, E. Sterlińska 72

SORPTION OF HEAVY METALS ON HYDROXYAPATITES. PART 2 J. Chwastowska, M. Sadowska-Bratek, E. Sterlińska 73

DETERMINATION OF TRANSITION METALS BY ION CHROMATOGRAPHY K. Kulisa, H. Polkowska-Motrenko, R. Dybczyński 74

EFFECT OF THE SAMPLE MINERALIZATION METHOD ON THE ACCURACY OF Co DETERMINATION IN PLANT MATERIALS H. Polkowska-Motrenko, B. Danko, R. Dybczyñski 76

SOL-GEL PROCESS FOR SYNTHESIS OF Ndi osBai 95Cu3Ox SUPERCONDUCTORS FROM Nd, Ba AND Cu ACETATES/AMMONIA/ASCORBIC ACID SYSTEMS A. Deptuta, W. Lada, T. Olczak, K.C. Goretta 78

SYNTHESIS OF LiNii_yCoyO2 POWDERS BY COMPLEX SOL-GEL PROCESS (CSGP) AND THEIR ELECTROCHEMICAL CHARACTERIZATION A. Deptuta, W. Lada, F. Croce, F. Ronci, A. Di Bartolomeo, A. Brignocchi 80

FABRICATION OF L12TÍO3 SPHERICAL MICROPARTICLES BY A CLASSICAL SOL-GEL ROUTE A. Deptuta, T. Olczak, W. Lada, B. Sartowska, A.G. Chmielewski, C. Alvani, S. Casadio 82

PROTON NUCLEAR MAGNETIC RESONANSE STUDIES OF HYDRATION OF OXAALKANES IN BENZENE SOLUTION E. Gniazdowska, P. Dobrowolski, J. Narbutt 85

X-RAY MOLECULAR AND CRYSTAL STRUCTURE OF BIS(PENTANE-2,4-DIONATO)(II) J. Narbutt, B. Paluchowska, J.K. Maurin 86

SMALL AGGREGATES FORMED IN POLYURETHANE-MEMBRANE STRUCTURE DURING SWELLING IN ETHANOL H. Grigoriew, A. Wolińska-Grabczyk, A.G. Chmielewski, H. Amenitsch, S. Bernstorff 88

NEW VIEW ON STRUCTURE OF THE SYSTEM: CELLULOSE-WATER FROM TEMPERATURE TIME-RESOLVED SAXS H. Grigoriew, A.G. Chmielewski, H. Amenitsch 90

NEUTRON SPECTROSCOPY AND AB INITIO STUDY OF BOND DYNAMICS IN L-SERINE A. Pawlukojć, J. Leciejewicz 91

NEUTRON DIFFRACTION STUDY OF INCOMMENSURATE MAGNETIC ORDER IN TbOs2S¡2 AND HoOs2S¡2 M. Kolenda, M. Hofmann, J. Leciejewicz, B. Penc, A. Szytuta 92

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART XXVIII: THE CRYSTAL STRUCTURE OF A FURAN-2-CARBOXYLATE POLYANIONIC COMPLEX 2+ n[Zn(H2O)6] [Zn8Na2(C5H3O5)i8(OH)2]^ B. Paluchowska, J.K. Maurin, J. Leciejewicz 92

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART XXIX: THE CRYSTAL STRUCTURE OF MONOAQUABIS(TRANS-5-METHYLPYRAZINE-2-CARBOXYLATO N,O) (II) TRIHYDRATE H. Ptasiewicz-Bąk, J. Leciejewicz 93

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART XXX: THE CRYSTAL STRUCTURE OF A Ca(II) COMPLEX WITH PYRIDINE-3.4-DICARBOXYLATE LIGAND W. Starosta, H. Ptasiewicz-Bąk, J. Leciejewicz 94

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART XXXI: THE CRYSTAL STRUCTURE OF A Ca(II) COMPLEX WITH PYRIDINE-3,5-DICARBOXYLATE LIGAND W. Starosta, H. Ptasiewicz-Bąk, J. Leciejewicz 95

RADIOBIOLOGY 97

DIFFERENTIAL INACTIVATION OF DNA-DEPENDENT PROTEIN KINASE IN H2O2-TREATED L5178Y-R AND L5178Y-S CELLS B. Sochanowicz, M. Kruszewski, I. Szumiel 99 ERBSTATIN-INDUCED INCREASE IN APOPTOSIS DOES NOT RADIOSENSITIZE L5178Y CELLS I. Buraczewska, A. Gasińska, I. Grądzka, N. Jarocewicz, B. Sochanowicz, I. Szumiel 99

ERBSTATIN-INDUCED ALTERATIONS IN CELL CYCLE DISTRIBUTION IN THE X-IRRADIATED L5178Y CELLS I. Buraczewska, A. Gasińska, I. Szumiel 100

TOTAL TYROSINE PROTEIN KINASE ACTIVITY IN X-IRRADIATED L5178Y CELLS B. Sochanowicz, I. Szumiel 102

APOPTOSIS IN MAMMALIAN CELL LINES WITH DIFFERENT RADIATION SENSITIVITY: COMPARISON AFTER LOW DOSE X-IRRADIATION A. Jaworska, P. De Angelis, I. Szumiel, G. Olsen, J. Reitan 103

CELL CULTURE CONDITIONS AS A CRITICAL FACTOR IN DETERMINATION OF APOPTOSIS: FETAL CALF VERSUS BOVINE SERUM T. Otdak, M. Kruszewski, I. Buraczewska, I. Grądzka 104

X-IRRADIATION OF Gl CHO CELLS INDUCES BOTH TRUE AND FALSE SCE IN BrdU-SUBSTITUTED CELLS BUT ONLY FALSE SCE IN BIOTIN-dUTP-SUBSTITUTED CELLS E. Bruckmann, A. Wójcik, G. Obe 105

DETERMINATION OF DNA DOUBLE STRAND BREAK REPAIR IN HUMAN LYMPHOCYTES BY THE COMET ASSAY M. Wojewódzka, I. Buraczewska, I. Grądzka 106

ANALYSIS OF INVERSIONS AND SISTER CHROMATID EXCHANGES IN CHROMOSOME 3 OF HUMAN LYMPHOCYTES EXPOSED TO X-RAYS A. Wójcik, B. Opalka, G. Obe 107

RADIATION-INDUCED MALFORMATIONS AFTER EXPOSURE OF MURINE GERM CELLS IN VARIOUS STAGES OF SPERMATOGENESIS W.-U. Müller, Ch. Streffer, A. Wójcik, F. Niedereichholz 108

HYDROGEN PEROXIDE-INDUCED DNA DAMAGE IN MEL CELLS OVEREXPRESSING A HEAVY SUBUNIT OF THE HUMAN FERRITIN M. Kruszewski, T. Iwaneńko, T. Żebrowska, P. Lipiński, E. Boużyk 109

NUCLEAR TECHNOLOGIES AND METHODS 111

PROCESS ENGINEERING 113

CONCENTRATION OF LIQUID LOW- AND MEÜIUMACTIVE LEVEL RADIOACTIVE WASTES (LLRW AND MLRW) USING MEMBRANE METHODS A.G. Chmielewski, M. Harasimowicz, B. Tymiński, G. Zakrzewska-Trznadel 113

RADIOTRACER INVESTIGATIONS ON SELECTED CHEMICAL INSTALLATIONS E. Hier 114

DEGRADATION OF VOLATILE ORGANIC COMPOUNDS, EMITTED FROM COAL COMBUSTION BY ELECTRON BEAM TREATMENT A.G. Chmielewski, A. Ostapczuk, Y. Sun, K. Kubica, J. Licki 114

DECOMPOSITION OF 1,1-DICHLOROETHYLENE IN HUMID AIR UNDER ELECTRON BEAM IRRADIATION Y. Sun, T. Hakoda, A.G. Chmielewski, S. Hashimoto, Z. Zimek, S. Bułka, A. Ostapczuk, H. Nichipor 116

ACTIVITIES OF THE LABORATORY OF ISOTOPE RATIO MASS SPECTROMETRY (IRMS) R. Wierzchnicki, M. Derda, A. Mikołajczuk, A. Owczarczyk 117

HYDROCHEMICAL AND ISOTOPE STUDY OF GROUND AND SURFACE WATERS IN THE REGION INFLUENCED BY THE LIGNITE MINE "BEŁCHATÓW" W. Sołtyk, J. Walendziak, A. Owczarczyk 118

RADIOMETRIC STUDY OF GROUND WATER MOTION IN TI IE ELBLĄG ŻUŁAWY AQUIFER W. Sołtyk, J. Walendziak, A. Owczarczyk 120

MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS 121

NEW SILICA SORBENTS BINDING EFFECTIVELY HEAVY METALS FROM WATER A. Łukasiewicz, L. Rowińska, L. Waliś 121

ION ASSISTED PALLADIUM TREATMENTS FOR IMPROVED CORROSION RESISTANCE OF A WINDOW IN THE ELECTRON BEAM DRY SCRUBBER PROCESS S.D. Barson, P. Skeldon, G.E. Thompson, A. Kolitsch, E. Richter, E. Wieser, J. Piekoszewski, A.G. Chmielewski, Z. Werner 122 SURFACE MODIFICATION OF CONSTRUCTIONAL STEELS BY IRRADIATION WITH HIGH INTENSITY PULSED PLASMA BEAMS J. Langner, J. Piekoszewski, Z. Werner, V.l. Tereshin, V.V. Chebotarev, I. Garkusha, L. Waliś, B. Sartowska, W. Starosta, W. Szymczyk, M. Kópcewicz, A. Grabias 123

A LABORATORY-UNIT FIELD TEST OF A PALLADIUM-TREATED TITANIUM FOIL FOR DRY SCRUBBER APPLICATION S.D. Barson, P. Skeldon, O.E. Thompson, J. Piekoszewski, A.G. Chmielewski, J. Licki, B. Sartowska, Z. Werner, E. Richter, E. Wieser 124

EROSION OF ELECTRODES IN THE DPE PROCESS J. Piekoszewski, R. Grötzschel, E. Wieser, J. Stanislawski, Z. Werner, W. Szymczyk, J. Langner 124

STUDY OF ELECTROCHEMICAL PROCESSES USING TRACK ETCHED MEMBRANES M. Buczkowski, D. Wawszczak, W. Starosta, B. Sartowska 125

APPROACH TO ATTRIBUTION OF A 17th-CENTURY ALABASTER ALTAR FROM THE CLARISTS NUNNERY IN KRAKÓW E. Pańczyk, M. Ligęza, L. Waliś 127

INVESTIGATION OF ART OBJECTS WITH THE USE OF TOTAL REFLECTION X-RAY FLUORESCENCE J. Kierzek, J. Kunicki-Goldfinger, B. Małożewska-Bućko 129

DETERMINATION OF AND CONTENT IN A HISTORICAL GLASS VESSEL BY MEASURING ITS NATURAL RADIOACTIVITY J. Kierzek, J. Kunicki-Goldfinger, A. Kasprzak 130

NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS 133

ANEW BACK-SCATTERING COATING THICKNESS GAUGE GlL-99 W. Antoniak, E. Świstowski, P. Urbański 133

RADON PROBE SRDN-2 FOR LONG TERM MEASUREMENTS J. Bartak, J.P. Pieńkos 134

CONTINUOUS MEASUREMENT OF RADON IN AIR WITH LUCAS CELL B. Machaj, P. Urbański 135

AN ATTEMPT TO USE WAVELET TRANSFORM FOR DENOISING XRF SPECTRA A. L'Eplattenier, E. Kowalska, P. Urbański 137

PERFORMANCES OF LAE10 ACCELERATOR WITH A THREE ELECTRODE ELECTRON GUN WITHOUT MESH GRID Z. Dzwigalski, Z. Zimek 138

THE INCT PUBLICATIONS IN 1999 140

THE INCT REPORTS IN 1999 156

NUKLEONIKA 157

THE INCT PATENTS AND PATENT APPLICATIONS IN 1999 162

PATENTS 162 PATENT APPLICATIONS 162

CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1999 163

Ph.D/D.Sc. THESES 167

Ph.D. THESES 167 D.Sc. THESES 167

EDUCATION 168

Ph.D. PROGRAMME IN CHEMISTRY 168 PRACTICAL TRAINING OF STUDENTS 168

RESEARCH PROJECTS AND CONTRACTS 169 RESEARCH PROJECTS GRANTED BY THE POLISH STATE COMMITTEE FOR SCIENTIFIC RESEARCH IN 1999 AND IN PREVIOUS YEARS 169 IMPLEMENTATION PROJECTS GRANTED BY THE POLISH STATE COMMITTEE FOR SCIENTIFIC RESEARCH IN 1999 169 GOVERNMENT STRATEGIC PROGRAMME 170 IAEA RESEARCH CONTRACTS IN 1999 170 IAEA TECHNICAL CONTRACTS IN 1999 170 EUROPEAN COMMISSION RESEARCH PROJECTS IN 1999 170 OTHER FOREIGN CONTRACTS IN 1999 171 LIST OF VISITORS TO THE INCT IN 1999 172 THE INCT SEMINARS IN 1999 175 SEMINARS DELIVERED OUT OF THE INCT IN 1999 177 INDEX OF THE AUTHORS 180 GENERAL INFORMATION

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. The fundamental research on radiobiology, radio- and coordination chemistry and radiation chemistry is continued. The Institute offers academic and research programmes for Ph.D. and D.Sc. thesis in chemistry. Institute is one of the most advanced science and technology centres working on development of technologies and methods in the field of: radiation chemistry and technology, application of nuclear methods in material and process engineering, design and manufacturing of instruments based on nuclear techniques, trace analysis and radioanalytical techniques, environmental research. At this moment, with its nine electron accelerators in operation and with the staff experienced in the field of electron beam applications, the Institute is one of the most advanced centres of science and technology in this domain. The following activity should here be mentioned: • experimental pilot plant for food irradiation, • pilot plant for radiation sterilization of medical devices and transplantations, • pilot plant for radiation modification of polymers, • pilot plant for removal of SO2 and NOX from flue gases. In 1999 the Institute organized: • International Symposium entitled "Creative electrons" concerning radiation chemistry and technology in research and industrial applications; • Technical Review Meeting on industrial demonstration plant for electron beam flue gas (in cooperation with the IAEA); • Training Course on radiation sterilization of medical devices, implant materials, pharmaceutical and cosmetics. Common research projects were performed in the frames of grants from the European Union: • Accreditation for high dose measurement (INCO-Copernicus); • Development of heavy duty reactor window for industrial scale removal of NOX and SO2 from flue gas by electron beam treatment (INCO-Copernicus). The INCT participates in IAEA technical cooperation programmes. The employees of the Institute undertake many expert missions for the IAEA. Since the end of 1997 the INCT has been participating in Government Strategic Programme (SPR-4) "Treatment of radiactive wastes and burnt nuclear fuel". In the frame of this programme the following topics were realized: • Elaboration and studies on novel engineered barriers preventing migration of most toxic from nuclear waste repositories; 10 GENERAI. INFORMATION • Concentration of liquid low- and medium-level radioactive wastes by membrane methods. The INCT, in cooperation with the Institute of Atomic Energy and with the National Museum in Warsaw, has elaborated and implemented a nondistructive method - instrumental neutron acitvation analysis - to determine the time of origin and the provenience of some old paintings. The study allowed to prepare an exhibition entitled "Serenissima. Light of Venice" in the National Museum. The works of Venetian masters from the XlVth to XVIIth centuries, from the Museum's collection, have been exhibited. In the evaluation of scientific and implementation results achieved by academic, scientific and research institutions in the field of chemistry, chemical technology and environmental protection in the years 1995-1997, the Institute, as one of the only two research development units, was classified to I, to the best thirteen scientific units, beside such institutions as universities, technical universities and institutes of the Polish Academy of Sciences. The evaluation was carried out by the Polish State Committee for Scientific Research (KBN) and the total number of the evaluated institutions in the chemistry section was 62. In the year 1999 the Laboratory for Detection of Irradiated Foods has obtained a "Certificate of testing laboratory accreditation". At the Second International Fair of Inventions "Innovation'99" (Gdynia, Poland) the Institute has been awarded with a medal for the industrial waste water clarifier. Two students from Ecole de Mines de Nantes (France), eight fellowship holders from the IAEA were trained at the Institute. A distinction for the Institute's employees was an invitation to contribute to a special issue of the Radiation Physics and Chemistry dedicated to Professor Joseph Silverman on the occasion of his 75th birthday. The Institute is the editor of NUKLEONIKA - a world wide recognized journal for nuclear research. 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. Andrzej G. Chmielewski, Ph.D., D.Sc.

Deputy Director for Administration Edmund Freliszka, M.Sc.

Accountant General Barbara Kaźmirska

HEADS OF THE INCT DEPARTMENTS

Department of Nuclear Methods of Material Department of Analytical Chemistry Engineering Prof. Rajmund Dybczyński, Ph.D., D.Sc. Assoc.Prof. Lech Waliś, Ph.D. Department of Radiobiology and Health Department of Structural Research Protection Wojciech Starosta, M.Sc. Prof. Irena Szumiel, Ph.D., D.Sc.

Department of Radioisotope Instruments Pilot Plant for Food Irradiation and Methods Wojciech Migdał, Ph.D. Prof. Piotr Urbański, Ph.D., D.Sc. Laboratory for Detection of Irradiated Department of Radiochemistry Foods Prof. Jerzy Narbutt, Ph.D., D.Sc. Wacław Stachowicz, Ph.D.

Department of Nuclear Methods of Process Laboratory for Measurements of Technological Engineering Doses Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. Zofia Stuglik, Ph.D.

Department of Radiation Chemistry and Technology Zbigniew Zimek, Ph.D.

SCIENTIFIC COUNCIL (1999-2003)

1. Assoc.Prof. Aleksander Bilewicz, Ph.D., D.Sc. 3. Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology •radiochemistry, inorganic chemistry •chemical and process engineering, nuclear che- mical engineering, isotope chemistry 2. Prof. Krzysztof Bobrowski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 4. Prof. Jadwiga Chwastowska, Ph.D., D.Sc. •radiation chemistry, photochemistry, biophy- Institute of Nuclear Chemistry and Technology sics •analytical chemistry 12 MANAGEMENT OF THE INSTITUTE 5. Jakub Dudek, M.Sc. 20. Prof. Jacek Michalik, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology (Co-chairman) •analytical chemistry Institute of Nuclear Chemistry and Technolog)' •radiation chemistry, surface chemistry, radical 6. Prof. Rajmund Dybczyński, Ph.D., D.Sc. chemistry Institute of Nuclear Chemistry and Technology •analytical chemistry 21. Prof. Jerzy Narbutt, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 7. Prof. Zbigniew Florjańczyk, Ph.D., D.Sc. •radiochemistry Warsaw University of Technology •chemical technology 22. Ewa Pańczyk, M.Sc. Institute of Nuclear Chemistry and Technology 8. Żyta Głębowicz Institute of Nuclear Chemistry and Technology •nuclear physics •staff representative 23. Jan Pawel Pienkos, Eng. 9. Edward IHer, Ph.D. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology •electronics •chemical and process engineering 24. Prof. Leon Pszonicki, Ph.D., D.Sc. 10. Prof. Janusz Jurczak, Ph.D., D.Sc. (Chairman) Polish Academy of Sciences, Institute of Orga- Institute of Nuclear Chemistry and Technology nic Chemistry; University of Warsaw •analytical chemistry •organic chemistry, stereochemistry 25. Zbigniew Samczyński, Ph.D. 11. Iwona Kałuska, M.Sc. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology •analytical chemistry •radiation chemistry 26. Prof. Sławomir Siekierski, Ph.D. 12. Barbara Kaźmirska Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology •physical chemistry, inorganic chemistry •staff representative 27. Prof. Irena Szumiel, Ph.D., D.Sc. 13. Marcin Kraszewski, Ph.D. (Co-chairman) Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology •radiobiology •cellular radiobiology

14. Gabriel Kuc, M.Sc. 28. Prof. Jan Tacikowski, Ph.D. Institute of Nuclear Chemistry and Technology (Co-chairman) •radiation chemistry Insitute of Precision Mechanics 15. Prof. Janusz Lipkowski, Ph.D., D.Sc. •physical metallurgy and heat treatment of me- Polish Academy of Sciences, Institute of Physi- tals cal Chemistry 29. Prof. Marek Trojanowicz, Ph.D., D.Sc. •physico-chemical methods of analysis Institute of Nuclear Chemistry and Technology 16. Prof. Andrzej Łukasiewicz, Ph.D., D.Sc. •analytical chemistry Institute of Nuclear Chemistry and Technology 30. Prof. Piotr Urbański, Ph.D., D.Sc. •material science Institute of Nuclear Chemistry and Technology 17. Kazimiera Malec-Czechowska, M.Sc. •radiometrie methods, industrial measurement Institute of Nuclear Chemistry and Technology equipment, metrology •radiation chemistry 31. Assoc.Prof. Lech Waliś, Ph.D. 18. Prof. Bronisław Marciniak, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Adam Mickiewicz University in Poznań •material science, material engineering •physical chemistry 32. Paweł Wiśniowski, M.Sc. 19. Prof. Józef Mayer, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Łódź Technical University •radiation chemistry, photochemistry, biophy- •physical and radiation chemistry sics MANAGEMENT OF THE INSTITUTE 13 33. Prof. Stanisław Wroński, Ph.D., D.Sc. 35. Wiesław Zieliński, M.Sc. Warsaw University of Technology Institute of Nuclear Chemistry and Technology •chemical engineering •staff representative

34. Prof. Zbigniew Zagórski, Ph.D., D.Sc. 36. Zimek Zbigniew, Ph.D. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology •physical chemistry, radiation chemistry, elec- •electronics, accelerator techniques, radiation trochemistry processing

HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (1999-2003)

1. Prof. Maria Kopeć, Ph.D., D.Sc. 2. Prof. Antoni Dancewicz, Ph.D., D.Sc. Institute of Haematology and Blood Transfusion Institute of Nuclear Chemistry and Technology •haematology, radiobiology •biochemistry, radiobiology 14 SCIENTIFIC STAFF

SCIENTIFIC STAFF

PROFESSORS

1. Ambroż Hanna B. 11. Piekoszewski Jerzy physical and radiation chemistry, biological che- solid state physics mistry, photochemistry 12. Pszonicki Leon 2. Bobrowski Krzysztof analytical chemistry radiation chemistry, photochemistry, biophysics 13. Radoszewski Tomasz 3. Chmielewski Andrzej G. radiometry chemical and process engineering, nuclear che- mical engineering, isotope chemistry 14. Rzewuski Henryk 4. Chwastowska Jadwiga solid state physics analytical chemistry 15. Siekierski Sławomir 5. Dancewicz Antoni physical chemistry, inorganic chemistry biochemistry, radiobiology 16. Szot Zbigniew 6. Dybczyński Rajmund radiobiology analytical chemistry 17. Szumiel Irena 7. Leciejewicz Janusz cellular radiobiology crystallography, solid state physics, material science 18. Trojanowicz Marek 8. Łukasiewicz Andrzej analytical chemistry material science 19. Urbański Piotr 9. Michalik Jacek radiometrie methods, industrial measurement radiation chemistry, surface chemistry, radical equipment, metrology chemistry 20. Zagórski Zbigniew 10. Narbutt Jerzy physical chemistry, radiation chemistry, electro- radiochemistry chemistry

ASSOCIATE PROFESSORS

1. Bilewicz Aleksander 5. Parus Józef radiochemistry, inorganic chemistry analytical chemistry 2. Grigoriew Helena 6. Waliś Lech solid state physics, diffraction research of non- material science, material engineering -crystalline matter 3. Legocka Izabella 7. Wójcik Andrzej polymer technology cytogenetics 4. Mioduski Tomasz 8. Żółtowski Tadeusz lanthanide and actinide chemistry nuclear physics

SENIOR SCIENTISTS (Ph.D.)

1. Borkowski Marian 2. Boużyk Elżbieta chemistry biology SCIENTIFIC STAFF 15 3. Bryl-Sandelewska Teresa 27. Mirkowski Jacek radiation chemistry nuclear and medical electronics 4. Buczkowski Marek 28. Nowicki Andrzej physics organic chemistry and technology, high-tem- perature technology 5. Bukowski Piotr mechanics 29. Owczarczyk Andrzej chemistry 6. Ciesla Krystyna chemistry 30. Owczarczyk Hanna B. biology 7. Danko Bozena analytical chemistry 31. Palige Jacek metallurgy 8. Dembiriski Wojciech chemistry 32. Panta Przemystaw nuclear chemistry 9. Deptuta Andrzej chemistry 33. Pawlukojc Andrzej physics 10. Dobrowolski Andrzej chemistry 34. Pogocki Dariusz radiation chemistry, pulse radiolysis 11. Do Hoang Cuong nuclear physics 35. Polkowska-Motrenko Halina analytical chemistry 12. Dzwigalski Zygmunt high voltage electronics, electron injectors, gas 36. Przybytniak Grazyna lasers radiation chemistry 13. Fuks Leon 37. Ptasiewicz-Bqk Halina chemistry physics 14. Grqdzka Iwona 38. Rafalski Andrzej biology radiation chemistry 15. Grodkowski Jan 39. Skwara Witold radiation chemistry analytical chemistry 16. Harasimowicz Marian 40. Samczyriski Zbigniew technical nuclear physics, theory of elementary analytical chemistry particles 41. Sochanowicz Barbara 17. Iller Edward biology chemical and process engineering 42. Stachowicz Wactaw 18. Jaworska Aiicja radiation chemistry, EPR spectroscopy biology 43. Strzelczak Grazyna 19. Kierzek Joachim radiation chemistry physics 44. Stuglik Zofia 20. Kleczkowska Hanna radiation chemistry biology 45. Szpilowski Stanistaw 21. Krejzler Jadwiga chemistry chemistry 46. Tymiriski Bogdan 22. Kruszewski Marcin chemistry radiobiology 47. Walicka MaJgorzata 23. Krynicki Janusz biology solid state physics 48. WarchoJ Stanislaw 24. Kunicki-Goldflnger Jerzy solid state physics conservator/restorer of art 49. Wqsowicz Tomasz 25. Machaj Bronislaw radiation chemistry, surface chemistry, radical electricity chemistry 26. Migdat Wojciech 50. Wierzchnicki Ryszard chemistry chemical engineering 16 SCIENTIFIC STAFF 51. Wojewódzka Maria 55. Żebrowska Teresa radiobiology biology 52. Wrońska Teresa 56. Zmijewska Wanda chemistry analytical chemistry 53. Zakrzewska-Trznadel Grażyna process and chemical engineering 54. Zimek Zbigniew electronics, accelerator techniques, radiation processing RADIATION CHEMISTRY

AND PHYSICS

RADIATION TECHNOLOGIES RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES PL0001986 19

GENERATION OF RADICAL CATIONS FROM PHENYL, VINYL, AND ALLYL CONTAINING THIOETHERS IN ORGANIC SOLVENTS

Anna Korzeniowska-Sobczuk, Paweł Wiśniowski, Krzysztof Bobrowski, Lothar Richter1', Ortwin Brede»1/ 11 University of Leipzig, Germany Radical cations derived from organic sulphides con- region) is affected by the character of the second taining aromatic and unsaturated substituents have substituent at the thioether function: 760 nm for been the subject of recent studies [1-4] as they play (la), 640 nm for (2a) and 810 nm for (3a), respec- an important role in a variety of chemical processes tively. For the case of the diphenyl sulphide, the extending from those of industrial importance (or- resulting spectra showed the absorption bands at

BuCi BuCI ^ e"

R,=

e" + BuCI Bu' + CI -CH=CH,

R,= (3)

Rj= -CHj-CH=CH5 BuCI+' + \ + BuCI / / R R IP =10.67eV R1=Rj= -CHJ-CH-CHJ (4) BuCI Scheme. ganic synthesis) to the enzymatic oxidations in bio- 340, 500, and 760 nm (Fig.). In contrast to phenyl- logical species. Although a certain amount of infor- -containing sulphides irradiation of diallyl sulphide mation on the nature of the transient species and kinetic parameters formed from the aryl-substituted -S-CH=CH2 (2a) sulphides are available, no similar studies have been performed for the sulphides with unsaturated sub- stituents. Quantitative information on these sys- tems would be of interest since the nature of the species is expected to be influenced by the degree of (3a) delocalization in the aromatic ring and the double bond. The last feature, as it has already been shown in aryl¡ substituted- sulphides, should affect the propensity of the radical cations to form dimers. CH,=CH-CH,-¥-CH,-CH= CH2 (4a) Due to the high ionization potential of halocar- Chart. bons the radical cations derived from organic sul- (4) (in the same experimental conditions) led to the phides are generated as a result of the charge trans- formation of only two strong transient absorption fer from the parental radical cations of the solvent 1 1 1 1 1 1 1 , 1 1 I—'—1 1 (n-butyl chloride) to the solute (organic sulphides) 0.016 (Scheme). The objective of the present study is to provide basic spectral and kinetic behaviour of the o.ou radical cations derived from the corresponding 0.012 f organic sulphides with the aromatic and the unsa- 0.010 turated substituents. q 0.008 When diphenyl sulphide (1), phenylvinyl sul- ¿ s**\ - phide (2), and allylphenyl sulphide (3) were irra- 0.006 ¿J: \\ : diated in N2- and 02-saturated n-butyl chloride 0.0M three transient absorption bands were formed and 0.002 1 assigned to the radical cation-type species (Chart). 0.000 I.I.I. 1— ' • ' t These radical cations exhibit very similar UV 300 400 500 600 700 800 900 spectra, with the strong absorption bands between Wavelength fnm] 320-350 nm and the weaker absorption bands Fig. Transient absorption spectra recorded after pulse irradiation of an N2-saturated n-butyl chloride solution containing 2 between 490-510 nm. However, the location of the mM diphenyl sulphide (•) 50 ns and (•) 750 ns after the third strong absorption band (in the near ÏR pulse (50 Gy). 20 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES

bands with Amax=360 and 550 nm. The kinetic work was supported within the scientific and tech- features at the absorption maxima were found dif- nological cooperation between Poland and Ger- ferent suggesting existence of two types of radical many. cation species. References Preliminary data with higher concentrations (up [1]. Ioele M., Steenken S., Baciocchi E.: J. Phys. Chem. A., lfiL to 50 mM) of sulphides (1, 2, and 3) suggest the 2979-2987 (1997). existence of dimer radical cations. Further experi- [2]. Mohan H., Mittal J.P.: J. Phys. Chem. A.. 1Q1, 10012-1O017 ments are in progress. (1997). [3). Yokoi H., Hatta A., Ishiguro K., Sawaki Y.: J. Am. Chem. This part of work was presented at the In- Soc, 122, 12728-12733 (1998). ternational Workshop on Reactive Intermediates I4),Bauld N.L., Todd Aplin 1, Yueh W., Loinaz A.: J. Am. IWRI'99, August 22-27, 1999, Szczyrk, Poland. This Chem. Soc., 112,11381-11389 (1997).

EPR STUDIES OF RADICALS INDUCED BY IONISING RADIATION

! Is- IN FLUTAMIDE Hanna B. Ambroż, Ewa Kornacka, Grażyna Przybytniak ¡8 Flutamide (2-methyl-N-[4-nitro-3(trifluoromethyl) of radical (I) decays than is formed following pro- ! O phenyl] propanamide, FA) is known as non-ste- cess (II)-»(I). A total concentration of radicals mea- roidal antiandrogen. We have estimated that it is sured directly after irradiation is 1.32xlO17 spins/g moderate sensitive on ionising radiation [1], as 13- i 1 comparing to other 15 drugs, and the population of 12- • paramagnetic species in FA determined 4 and 8 \ weeks following irradiation was average. We now 11- report suggestions concerning a possible structure 10- of the radicals generated in flutamide and the 9- agents influenced on their formation and stabilisa- • 8- tion. •——0 * » W All treatments and measurements were conducted 7- at ambient temperature. Ionising radiation of a dose t 6- of 25 kGy induces in the polycrystalline powder of 5- flutamide two kinds of radicals, which were identified by EPR spectroscopy. A peptide group is probably 4- involved in production of the detected transients. A 3- • Ê dominant singlet, partly saturated at microwave 2- ^ power of 20 mW and characterised by g=2.0043, was assigned to third order centre radical (I), Scheme. Second component of EPR spectrum is time / days anisotropic triplet of g factors equal gj=2.0081, Fig. Kinetics of radical decay; ( •) concentration of all radicals, ( • ) radical (I), ( • ) radical (II), see Scheme. g2=2.0046 and g3=2.0000. It seems to be justified to interpret the signal as absorption exhibited by aryl and decreases of about 40% after 5 months of sto- radical (II) since the values of hyperfine splitting rage. Ai(2Horto)=2.2mT, A2(2Horto)=1.6mT, A3(2Hortü) The population of radicals in flutamide results = 1.5mT, Ai(lHmeta)=0.6mT, A2(lHmeta)=0.6mT from the rate of radical conversion (II)-»(I), sta- and A3(lH ta)=0.6mT are near hfs postulated by me bility of the later product and the efficiency of Kasai for phenyl radical [2]. As the area under the absorption curve is pro-

portional to the number of unpaired spins, the re- c sults of double integration of first derivative EPR <= (¡) signals were compared with those of standard O2N—/ V-NHCOCH(CHj)2 (DPPH) and the number of free radicals per gram \ ff was determined. The sample was stored for 5 (FA) months at room temperature. Kinetics of radical ¡3COCH(CHl)2 decay during first 6 days upon irradiation is pre- sented in Fig. The initial fast reduction of radical Scheme. concentrations lasts no longer than 1 day. After this microcrystalline matrices for trapping paramagnetic of time, the amount of substance (I) slightly species. increases, probably due to reaction (iii), Scheme. This indicates that in the beginning formation of References radical (I) from transient (II) is faster than its [1], Ambroż H.B., Kornacka E.M., Marciniec B., Ogrodowczyk M., Przybytniak G.K.: Radiât. Phys. Chem., in press. decay. However, after first a few days, population of [2J. Kasai P.H., Hedaya E., Whipple E.B.: J. Am. Chem. Soc., 91, a aryl radical is becoming low and more molecules 4364-4368 (1969). RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES PL0001988 21 THE ROLE OF Cu(I) AND Cu(II) IN DNA DAMAGES Hanna B. Ambroz, Ewa Kornacka, Grazyna Przybytniak The presence of copper ions in the vicinity of DNA bound to DNA are necessary to react with hydrogen is important, as they are able to create site-specific peroxide as relationship between Cu(II) concentra- damages. Relatively long ago it was established that tion and strand breaks has been observed. Never- a favourite position for copper binding is guanine 70-, . 0 mM H2O2 base. On the other hand it was confirmed that the . 10mMH O reduction of the square planar Cu(II)-DNA com- 60- 2 2 plex to the tetrahedral Cu(I)-DNA complex strong- • 100 mM H2O2 ly influences on DNA strands conformation [1]. 50- In DNA radiolysis several effects resulting from the presence of Cu(I)/Cu(II) ions are expected: 40- » ^ 1. Cu(II) efficiently scavenges electrons that protect 30- DNA against reductive damages [2]. This process is * especially important in a direct effect of ionising radiation as in this case half (or more) damages is 20- caused by electrons. However, at higher concentra- • tions of Cu(II), binuclear complexes are formed 10- •— rm—-——~~"~" that modify copper influence. n —i— 1—1—1—1—1—1—1—: > 1 • 2. Cu(I) induces DNA cleavage if in the system is 0.0 0.2 0.4 0,6 0,8 1,0 present hydrogen peroxide originated either from a purposely-added reagent or from recombination of Cu(ll)/mM hydroxyl radicals generated upon water radiolysis. Fig.2. Ssb as a function of Cu(II) and H2O2 concentrations for The Cu(I) specific chelating agents might complete- air-saturated solutions of DNA plasmid. ly inhibit such a process [3]. H2O2 molecules, fol- theless the process is slow and needs an excess of lowing spontaneous decomposition, cause scissions H2O2. UV radiation significantly prompts the reac- of DNA strands, even without participation of tran- tion, which eventually to generation of dsb, sient metal ions. However an admixture of Cu(I) Fig.3. considerably intensify damages, as seen in Fig.l. Copper ions on the lower state of oxidation The results indicate that stoichiometric amount of bound to DNA could lead to the site-specific da- hydrogen peroxide is not enough for distinct en- mages in combination with cleavages resulting from hancement of damages and the bulk of H2O2 is irradiation. The Cu(I) and Cu(II) ions might ini- needed to shift the equilibrium towards formation tiate reactions leading to continuous and danger- 100 -, • 0 mM Cu(ll), ssb OmMCu(l) • 0 mM Cu(ll), dsb A 0.24 mM Cu(ll), ssb 80- 0.24 mM Cu(l) 10Q 0.24 mM Cu(il), dsb

60- 80-

J CA V) 60- 40- o 40- 20- W 20-

0 12 3 4 5 0-

H r mM 1 1 r —1—> 2°2 2 3 Fig.l.Ssb as a function of H2O2 and Cu(I) concentrations for air-saturated solutions of DNA plasmid. H2O2 mM of the hydroperoxo-copper (or dicopper) complex Fig.3. The influence of H2O2 and Cu(II) on strand breaks of that is probably responsible for DNA breaks. DNA upon 3 min UV radiation. 3. Cu(II) also might increase the yield of OH' (or ous, for DNA, formation of oxidising agents due to other oxidising agent) due to initiation of catalytic the reproduction of Cu(I) ions from Cu(II) until decomposition of H2O2 [4]. In order to determine the exhaustion of hydrogen peroxide in the system. efficiency of this process the influence of Cu(II) and H2O2 concentrations on the level of plasmid ssb References was studied (Fig.2). Probably two copper ions [1 ]. Stoewe R., Prutz W.A: Free Radical Biol. Med., 2,97-105 (1987). 22 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES

[2]. Ambroz H.B., Kemp T.J., Komacka E.M., Przybytniak O.K.: 14]. Yamamoto K., Kawanishi S.: J. Biol. Chem., 264 15435-15440 Radiat. Phys. Chem., 5J, 491-499 (1998). (1989). [3]. Spear N., Aust S.D.: Arch. Biochem. Biophys., 312, 142-148 (1995).

TEMPERATURE COEFFICIENT OF THE RADIATION YIELD OF THE RADICAL CH3 CH CO2 IN CRYSTALLINE ALANINE is Zbigniew P. Zagorski A popular chemical solid state dosimeter, based on application. The temperature of irradiation is intro- is the formation of the CH3CH CO2 radical anion by duced as a correction factor to the value of radical o radiation induced deamination of alanine, has been concentration measured by electron paramagnetic investigated in hundreds of projects. The deamination resonance or by spectrophotometry in UV. The of alanine has been investigated not only from the temperature of irradiation is sometimes difficult to point of view of dosimetry but also as a basic inves- measure and therefore the dependability of the tigation of paramagnetic (EPR) and optical (UV-Viz alanine dosimeter is lowered. The situation is espe- absorption spectrum) properties of the radical. cially difficult in the case of a high dose rate irradia- The present project deals with one specific feature tion in electron beam processing where the energy of the alanine deamination i.e. the role of the tempe- is deposited adiabatically without the possibility of rature at irradiation on the yield. One of the feature cooling [2]. The starting temperature is often un- of the alanine dosimetric system, in any form (L en- stable and the estimate of the temperature increase, antiomere or DL racemate, crystals alone, or in a by calculation from the assumed dose and the speci- matrix of a polymer) is a comparatively high tempe- fic heat is not of much help. On the other hand, rature coefficient of the radical yield, stated in the irradiation in gamma radiation installations pro- standard for alanine dosimetry as +0.24% K"1 at ceeds with the heat exchange between the sample room temperature. and the environment, allowing more constant (sta- The high temperature coefficient of alanine de- ble) equilibrium. amination, generally accepted as above is constant The influence of temperature during irradiation in a wide range of temperatures of irradiation oc- has nothing to do with the role of the temperature curring in the routine dosimetric practice in radia- at which the concentration of the radical anion is tion processing. It is introduced as a correction in measured. The measurement is usually performed the dose calculation and therefore the temperature at the so called room temperature without precise at which dosimeter has been irradiated must be specification, because the difference in the result known. The value of the temperature coefficient is between, e.g. temperature of 20 and 28°C in the not influenced by the physical form of alanine, size case of the EPR and UV-Viz is negligible. Non-do- of crystals and whether it is pure (alone) or present simetric investigations of the alanine system, di- in the shape of a composite with polymers like poly- rected towards much lower and much higher tem- styrene or polyethylene, convenient for a particular peratures, than the range of usual dosimetry have dosimetric application. The temperature coefficient shown a similar change of response, i.e. much lower is the same for the L-alanine and DL-alanine race- yields at lower temperatures, reaching dramatically mate, indicating that mutual arrangement of neigh- low level at cryogenic temperatures. bouring molecules does not influence the tempe- As the programme for the present investigation rature coefficient, which represents the intramole- was concentrating on untypical conditions of irra- cular property. diation, special approaches have been chosen for The temperature coefficient of alanine deamina- irradiations in conditions far from room tempe- tion i.e. the alanine dosimeter differs in comparison rature irradiations. All samples were sealed in glass to temperature coefficients of other dosimeters of ampoules, excellent for both cryogenic and high wide application. The classic reference dosimeter, the temperature irradiations in any thermostating me- Fricke dosimeter, shows reported values between nil dia, by 7 and 10 MeV electron beam. and +0.09%/K [1]. In the conclusion, in the case of Thermostating media were chosen from the the Fricke dosimeter, the irradiation temperature point of view of similar density to minimize the cor- from +10 to +50°C is considered to be without prac- rection for dose determination: tical importance. The same refers to the Fricke sys- - liquid nitrogen, at 77 K, methanol at 295 K (due tem containing copper, to eerie dosimeter (no correc- to similar density to liquid nitrogen, used for si- tion needed between +7 and +35°C), benzene-water mulation in gamma fields); dosimeter and other aqueous systems. However, non- - acetone/CO2, 223 K, silicone oil at 253, 295, 373, aqueous and solid dosimeters were not investigated 423 K. for temperature dependence as carefully as the ala- As there is no need to investigate alanine radia- nine dosimeter and therefore comparisons are diffi- tion chemistry at room temperature, sufficiently ex- cult. plored for dosimetric purposes, experiments were The necessity of measuring the temperature at concentrated on conditions of irradiation far from which the dosimeter is irradiated complicates the dosimetric routine. They were performed, as deep RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 23 as possible, at low and high temperatures of irra- increased yield of D,L alanine reconstructed during diations and extreme dose rates reachable with deamination and back-amination processes. Experi- electron beam. A new analytical approach has been mental results did not confirm that. The racemiza- tried, using the study of racemization of irradiated tion at liquid nitrogen temperature and at high alanine discovered by Professor Tilquin and Dr. temperatures is similar to the racemization at room Pronce at the University of Louvain. They have temperature. Apparently the temperature coeffi- found that during the irradiation to the sterilisation cient of turning of the molecule is low, and the re- dose, part of the deaminated alanine molecules is construction of alanine molecule runs independent- reconstructed back to the alanine, as the D,L race- ly of temperature. mate. A dramatic drop of radical yields at low tem- The project was started during the period of col- peratures of irradiation has suggested, that such a laboration with the IAEA under the Contract No. phenomenon may be partly explained by increasing 8533/RB, closed in the year 1999. reconstruction of alanine molecules. This would be proved by the increased yield of D-alanine, provid- References ing that the radical can accept an ammonia mole- [l].Sehested K.: The Fricke Dosimeter. In: Mannual on Ra- cule after some resting period. Unpaired electron diation Dosimetry. Eds. Holm, Berry. Marcel Dekker, New on the asymmetric carbon atom may attach the re- York 1970. [2]. Zagorski Z.P.: Thermal and electrostatic aspects of radiation agent statistically 50:50 D or L positions. The work- processing of polymers. In: Radiation Processing of Poly- ing hypothesis was that the lower yield of the mers. Chapter 13. Eds. J. Silverman, A. Sigh. Hanser Verlag, radical after deamination could be accompanied by New York, Munich 1992.

COMPETITION BETWEEN INTRAMOLECULAR TWO-CENTERED gp THREE-ELECTRON BONDED (S. .S)+ AND (S. .N)+ FORMATION s DURING PHOTOOXIDATION OF METHIONINE-CONTAINING PEPTIDES BY THE 4-CARBOXYBENZOPHENONE TRIPLET STATE !§ IN AQUEOUS SOLUTION li x/ 2/ 27 Krzysztof Bobrowski, Gordon L. Hug , Halina Kozubek , Bronislaw Marciniak i o 1/1 Radiation Laboratory, University of Notre Dame, USA 21 Adam Mickiewicz University, Poznari, Poland The one-electron oxidation of methionine to the lated to function as a "last chance" antioxidant in the methionine radical cation, Met(>S +), plays defense system of proteins [4,5]. an important role in protein oxidation under condi- The present work is a continuation of our pre- tions of oxidative stress and biological aging [1]. In vious interests relating to one-electron photooxida- recent years, considerable data have been accumu- tion of methionine derivatives by the 4-carboxy- lated indicating that the brain in Alzheimer's disease benzophenone triplet [6-9]. In this work we report is under increased oxidative stress, and this may play on the mechanism of photooxidation of small a role in the pathogenesis of neuron degeneration N-methionyl oligopeptides (Chart) as a function of and death in Alzheimer's patients [2]. Moreover, it pH, peptide concentration and sequence, as well as was shown that oxidation of methionine might be the number and position of the methionine residues crucial for the aggregation and neurotoxicity of amy- with respect to the terminal functions. It is also of loid /3-peptide which is a major component in the interest whether the presence of various optical core of senile plaques associated with Alzheimer's isomers (L- and D-) of methionine residues might disease [3]. Because of their high susceptibility to oxi- affect the primary reaction pathways following pho- dation, methionine residues have also been postu- tooxidation. The quenching rate constants were of the order o 1 1 H)NH^ of 2xl(r M' s" . There were small, but significant, j differences in the triplet-quenching rate constants, R, R2 R3 and these trends indicate the existence of multiple sulfur targets in the peptides. The absorption of the n = 0-2 transient products was followed in detail by using spectral-resolution analysis (Fig.). From the ab- sorption data, quantum yields were estimated for PEPTIDE R, n the formation of the various transients: ketyl ra- Met-Met -CH2-CH2-S-CHj -CHj-CHa-S-CHj 0 dicals (CBH), ketyl radical anions (CB'~), and Met-Met-Ala -CHrCHrS-CH, -CHrCHj-S-CHj CH, 1 + + Met-Gly-Met -CHi-CHz-S-CHi H •CHj-CH2-S-CH3 1 various sulfur radical cations (S.-.S) and (S.-.N) Met-Mot-Met •CHj-CHi-S-CHj •CHrCHrS-CHa •CH,-CHrS-CH, 1 H (Table). The presence of these intermediates indi- Met-Gly-Mat-Mat -CHj-CHa-S-CHj and •CHJ-CH,-S-CHJ 2 cated that the triplet-quenching mechanism can be •CHj-CHa-S-CHj characterized as being mainly electron-transfer in Chart. nature. There were differences found in the yields 24 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES

1 0.04 • . 1 • r—'1 i r • 1 ' 1 o.oa -Fit • Data ° 0.05 0.03 - o C9" " ] A C8H 0.04 A, ffl (SS)1 0.02 0.03 (SN)* 0.02 °' 0.01 o 0.01

AA 0.00 0.00 1 1 . 1 . 1 300 400 500 600 700 800 300 400 500 600 700 800 Wavelength (nm) Wavelength (nm) Fig. Resolution of the spectral components in the transient absorption spectra following the quenching of the CB triplet by L-Met-Gly-L-Met-L-Met (0.5 mM) in aqueous solutions taken at 2^s after the flash: a - at pH 5.6, and b - at pH 9.8. of the transients products between the experiments Systematic variations were observed, and these where the quenchers were the "mixed" stereoiso- patterns were discussed in terms of competitive mers of methionyl-methionine (L,D and D,L) and donation of protons to the CB~ within the charge- experiments where the quenchers were L,L and -transfer complex. The competition was between D,D, stereoisomers. Triplet-quenching data from protons on adjacent to the sulfur-radical several other methionine-containing small oligo- center and protons on the protonated amino groups peptides were analyzed in an analogous manner. of the radical cation (Scheme). In addition, there Table. Quantum yields of transients and CO2 for CB-sensilized photooxidation of methionine-containing peptides in aqueous solution ([CB]=2mM, [peptide]=0.5 mM).

a a +b +b Peptide pH *CB'~ *CBH *S.-.S OS.-.N *CO2C L-Met-L-Met 5.7 - - - <0.01 5.85 0.15 0.23 0.07 0.19 - 5.85e O.!7 0.29 0.10 0.23 - 9.99 0.41 0.13 0.01 0.43 11.0 - - - £0.01 D-Met-D-Met 5.85e 0.16 0.34 0.10 0.30d - 6.07 0.18 0.24 0.06 0.27 - 9.85 0.40 0.09 0.02 0.41 L-Met-D-Met 5.85e 0.25 0.24d 0.18 0.23d - 6.07 0.23 0.17 0.15 0.18 - 9.8 0.37 0.08 0.06 0.34 - D-Met-L-Met 5.81e 0.24 0.26 0.21 0.16 - 5.9 - - - <0.01 6.01 0.25 0.15 0.16 0.15 9.8 - - - - <0.01 9.9 0.38 0.10 0.06 0.36 - c-(L-Met-L-Met) 5.45 0.12 0.23 0.10 0 - 6.91 0.19 0.17 0.14 0 - L-Met-L-Met-L-Ala 5.65 0.09 0.32 0.02 0.25 - 5.9 - - - <0.01 9.6 0.37 0.15 0 0.39 - 11.2 - - - - 0.016 L-Met-Gly-L-Met 5.75 0.18 0.13 0.16 0.04 - 5.8 - - - 0.01 9.87 0.43 0.17 0.02 0.22 - 11.5 - - 0.015 L-Met-L-Met-L-Met 5.5 - - 0.01 5.65* 0.22 0.17 0.08 0.21 - 9.76* 0.32 0.13 0.03 0.32 - 11.3 - - - 0.02 L-Met-Gly-L-Met-L-Met 5.63 0.18 0.16 0.16 0.09 5.9 - - - - <0.01 9.8 0.41 0.13 0.02 0.25 0.01 Estimated errors: a ±10%, b ±20%, c±50%, d±30%, e [peptide] = 10 mM,f [peptide]=0.25 mM. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 25 was a competition between the two intramolecular of the primary processes, which lead to the conversion two-centered, three-electron bonded species of peptide-bound Met(>S~) into Met-(S.-.S)+ and low pH

H N CO," CBH'... 2 CB'"... co2- s H c / / \ r \ kc" CBH'+ a—S CBH'+ a—S

(S.'.Nf

Scheme. (S.-.S)+ and (S.-.N)+ that play roles in the se- Met-(S.-.N)+ radical intermediates is of relevance to condary kinetics. There are significant yields of the oxidation of recombinant protein Pharmaceuticals (S. • .N)+-bonded species at low pH where there are since most of them contain an N-terminal methionine no electron pairs immediately available on the ami- residue. no groups to form intramolecular three-electron S-N bonds. This observation confirms a previous References + report [6] that the (S.-.N) is formed at low pH [l].Vogt W.: Free Radical Biology&Medicine, IS, 93-105 following a proton transfer (within the CT comp- (1995). lex) from the protonated amino group of the radical [2].Markesbery W.R.: Free Radical Biology&Medicine, 22, cation to the CB ketyl radical anion (Scheme). The 134-147(1997). + [3]. Watson A.W., Fairlie D.P., Craik D.J.: Biochemistry, 22, relatively high primary quantum yields of (S.-.N) 12700-12706(1998). both at low and high pH (Table) show that [4].Levine R.L., Berlett B.S., Moskovitz J., Mosoni L., Stadt- (S. • .N)+ formation can be a competitive process to man E.L.: Mechanisms of Ageing and Development, 107, + 323-332 (1999). intramolecular formation of (S. • .S) . [5].Levine R.L., Mosoni L., Belett B.S., Stadtman E.L.: Proc. The results of this work are relevant to the work Natl. Acad. Sci. USA, 22, 15036-15040 (1996). [10], where one-electron photooxidation of N-methio- [6]. Hug G.L., Bobrowski K., Kozubek H., Marciniak B.: Photo- nyl peptides yields competitively sulfoxide (MetSO) chem. Photobiol., 6JL 785-796 (1998). and azasulfonium (AS) derivatives through the re- [7]. Hug G.L., Marciniak B., Bobrowski K.: J. Photochem. + Photobiol. A, 25., 81-88 (1996). action of superoxide (C>2~) with Met-(S.-.S) and [8]. Hug G.L., Marciniak B., Bobrowski K.: J. Phys. Chem., 1DQ, Met-(S.-.Ny radical intermediates, respectively, in 14914-14921 (1996). that it provides quantitative primary yields. The work [9]. Marciniak B., Hug G.L. Bobrowski K., Kozubek H.: J. Phys. can also form a basis for modelling analogous systems Chem., 22,13560-13568 (1995). [10]. Miller B.L., Kuczera K., Schoneich C: J. Am. Chem. Soc, of oxidants. In addition, a mechanistic understanding 12Q, 3345-3356 (1998).

Trp[NH +] -* Tyr[O ] RADICAL TRANSFORMATION IN H-Trp-(Pro)n-Tyr-OH, n=3-5, SERIES OF PEPTIDES Krzysztof Bobrowski, Jarostaw Poznanski1', Jerzy Holcman2/, Kazimierz L. Wierzchowski17 v Institute of Biochemistry and Biophysics, Polish Academy of Sciences, Warszawa, Poland 2/ Ristf National Laboratory, Denmark Is Intramolecular one-electron oxidation of tyrosine, indolyl radical, Trp[N], involving long-range elec- Tyr[OH], to phenoxyl radical Tyr[O ], by tryptophan tron transfer (LRET), has been intensively studied by 26 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES pulse radiolysis in model peptides [1-7] and proteins phan indolyl radical cation Trp[NH+], remaining [8-11] because of the importance of the mechanism in equilibrium with its neutral Trp[N] form, and of free-radical damage to proteins for understanding tyrosine in aqueous H-Trp-(Pro)n-Tyr-OH, n=3-5, of free-radical-induced cell injury [12] and growing peptides (abbreviated 3, 4, and 5) has been studied evidence for participation of Trp[N] and Tyr[O] by pulse radiolysis as a function of pH 2-8 at 298 K, radicals in functioning of photosystem II and redox and at pH 4 over the temperature range 288-328 K proteins [13-14]. [15]. LRET has been found to occur down to pH 2 with an intrinsic rate constant 20-60 fold higher Table. Kinetic parameters of LRET in H-Trp-(Pro)n-Tyr-OH peptides. than that characteristic of reaction Trp[N']-* 4 1 Tyr[O ] in corresponding peptides (Table). It is Peptide n ki[s-l) k2[10 s~ ] k2/kl contrary to expectations based on the electro- 3 1500 2.67 18 chemical redox potentials for Trp and Tyr in the 4 510 3.04 59 form of free amino acids and indicates that the 5 300 1.87 61 electrochemical driving potential AG° for this reaction in the systems studied is negative in the The kinetics of intramolecular long-range elec- whole pH range of occurrence of TrpJNH +] radi- tron transfer (LRET) between protonated trypto- cal cation. The first-order rate constants of LRET, 2.0 kobs, varied sigmoidally with pH allowing evalua- tion of pKa's for deprotonation of Trp[NH +]: 3.7, 4.1 and 4.3 for 3, 4, and 5 respectively, as well as the intrinsic rate constants of LRET involving solely Trp[NH +] radical cation (Fig.l). It was argued that variation of pKa and consequently also of AG°, with the length of the -(Pro)n- bridge may result from electrostatic perturbation of the electronic wave function of indolyl radicals by the terminal COO" group of tyrosine. This effect in 3 seems to be particularly enhanced by the postulated occur- rence of the/3-»a transition at the ^(Pro3) dihedral angle during the life time of indolyl radicals, lead- ing to formation of a hydrogen between NH (in- dole) and OC (carboxyl) groups (Fig.2) which could bring these groups into a close contact.

—. 2

time, [ps] Fig.2. Evolution in time of the NH(indole)-CO(carboxyl) distance from the transition-state conformer of H-Trp-(Pro)3-Tyr-OH, obtained by 100 ns MD simulation at 300 K: (solid line) conformers with y(Pro)3 angle in the a region where the NH .... OC bond was broken at 18 ns Fig.l. Dependence of kobs on pH at 298 IC for peptides 3, 4, and and reconstructed at 60 ns; (broken line) conformers with 5. The solid symbols represent values of kobs (from three V(Pro) dihefral in the /? region where the NH OC hy- to five independent decay experiments, individual rate con- drogen bond was broken at 3 ns and the separation dis- stants were obtained by a nonlinear fit of a single-expo- tance between NH (indoie) and CO (carboxyl) fluctuated nential decay function to the experimental A58O (0 data). in a broad range of 0.5-2 nm. The solid lines are theoretical curves obtained by a non- k K linear fit of function kobs=(l-f) 2+fkl where f=10"P a / + K H The observed variation of pKa for Trp[NH' ] (10'P a+10"P ) to mean kobs(pH) data with standard errors as statistical weights. The rate constants kj were dissociation and its interpretation in terms of the taken from our previous work [6] and kept constant during electrostatic field effect should be a subject to fitting. further investigations in view of the expected im- RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 27

portance of electrostatic control over LRET in- Radiation Chemistry. Chapter 9. Eds. J.F. Wishart, D.G. volving Trp indolyl radicals in redox proteins and Nocera. American Chemical Society, Washington, D.C. 1998, pp. 131-143. protein-membrane systems. [8]. Butler J., Land E.J., Priitz W.A., Swallow A.J.: Biochim. References Biophys. Acta, 1Q5., 150-162 (1982). [9]. Bobrowski K., Holcman J., Wierzchowski K.L.: Free Rad. [l].Priitz W.A., Siebert F., Butler X, Land E.J., Menez A., Res. Commns., 6_, 235-241 (1989). Garestier T.M.: Biochim. Biophys. Acta, 7J2S, 139-149 [10], Weinstein M., AJfassi Z.B., DeFelippis M.R., Klapper M.H., (1982). Faraggi M.: Biochim. Biophys. Acta, 1076,173-178 (1991). [2]. Faraggi M., DeFelippis M.R., Klapper M.H.: J. Am. Chem. [11]. Bobrowski K., Holcman J., Poznański J., Wierzchowski K.L.: Soc, ill, 5141-5145 (1989). Biophys. Chem., 63,153-166 (1997). [3].Mishra A.K., Chandrasekar R., Faraggi M., Klapper M.H.: [12]. Faraggi M., Klapper M.H.: Intramolecular electron transfer J. Am. Chem. Soc, 116,1414-1422 (1994). reactions in peptides and proteins. In: Excess Electrons in [4]. Bobrowski K., Wierzchowski K.L., Holcman J., Ciurak M.: Dielectric Media. Chapter 13. Eds. C. Ferradini, J.-P. Jay- Stud. Biophys., 122,23-27 (1987). -Perrin. CRC Press Boca Raton, 1991, pp. 397-423. [5], Bobrowski K., Wierzchowski K.L., Holcman J., Ciurak M.: [13], Prince R.C., George G.N.: Trends Biochem. Sei., 15, 170-175 Int. J. Radiât. Biol., 51,919-932 (1990). (1990). [6]. Bobrowski K., Hotcman J., Poznański J., Ciurak M., Wierz- [14¡.Condrads T., Hermann C, Hille R.: Biochemistry, 21, chowski K.L.: J. Phys. Chem., 26,10036-10043 (1992). 7787-7792(1998). [7]. Bobrowski K., Poznański J., Holcman J., Wierzchowski [15], Bobrowski K, Poznański J., Holcman J., Wierzchowski K.L.: Long-Range Electron Transfer Between Proline- K.L.: J. Phys. Chem. B, M2,10316-10324 (1999). -Bridged Aromatic Amino Acids. In: Photochemistry and

EPR OF METALS NANOPARTICLES IN MCM-41 MOLECULAR SIEVES p| Jacek Michalik, David Brown17, Jong-Sung Yu2/, Marek Danilczuk, Larry Kevan3/ WE J 11 !8 University of Huddersfield, United Kingdom 21 Hannam University, Taejon, Korea ; !§ 3/ University of Houston, USA O Introduction mide (from Aldrich) in a mixture of aqueous The recently developed mesoporous molecular solution of hexadecyltrimethylammonium chloride sieves represent the first thermally stable, highly (HTAC1), aqueous NH3 solution and doubly dis- ordered, truly mesoporous (>20 Â pores) solid tilled water. A clear solution of silicate was available. MCM-41 has hexagonal pores control- prepared by combining aqueous NaOH solution lable variable from about 20 to 100 Ä. There is an with colloidal silica, Ludox HS40 (39.5 wt% SiO2) interest in these materials as catalysts and catalyst 0.4 wt% Na2O and 60.1 wt% H2O, from Aldrich) supports to process larger molecules that cannot and heating the resulting gel mixture with stirring penetrate microporous zeolites. for 2 h at 353 K. Alumina source was a solution of In the last three years several studies of metal sodium alumínate dissolved in doubly distilled and metal oxide catalysts in mesoporous MCM-41 water. materials have been reported and it seems that the The silicate solution was dropwise added to the larger pores of these materials do confer higher surfactant source with vigorous stirring at room activity compared with analogous microporous sup- temperature. Then the resulting surfactant-silicate ports. Platinium catalysts have been generated as gel mixture was stirred for 1 h at room temperature, stable small particles (2 nm) in MCM-41 and the the sodium alumínate solution was dropwise added catalyst has shown higher activities towards ethane with vigorous stirring. The resulting surfactant-alu- hydrogenolysis [1] and CO oxidation [2] than equi- minosilicate gel mixture (A1-M41-40) had a bulk valent catalysts supported in zeolites. molar composition of 6.00 SÍO2: XAI2O3: 1.00

The objective of the proposed work was to study HTAC1: 0.25 DTABr: 0.25 TPABr: 0.16(NH4)2O: the formation of Ag, Pd and Pt metallic particles in 1.50 Na2O: 302 H2O with x ranging from 0.3 to 0.05 MCM-41 matrices and to characterize them in so that theoretical Si/Al ratios (6/2x) become 10 to terms of magnetic resonance of conduction elec- 60. The gel mixture was stirred for 30 min more to trons (CESR) spectroscopy in order to prove ex- form a homogeneous mixture before heating in perimentally a theory of Kawabata [3] according to oven at 373 K for 1 day. The HTA-aluminosilicate which the linewidth of CESR signal depends on mixture was then cooled to room temperature. Sub- particle size. sequently, pH of the reaction mixture was adjusted Experimental Section to 10.2 by dropwise addition of 30 wt% acetic acid Synthesis with vigorous stirring. After the pH adjustment the Mesoporous MCM-41 aluminosilicate materials reaction mixture was heated again to 373 K for 1 with high structural integrity and improved textural day. This procedure for pH adjustment to 10.2 and uniformity have been synthesized according to the subsequent heating for 1 day was repeated twice. modification of synthetic methods of Ryoo et al. The precipitated product, MCM-41 with HTA [1]. A surfactant source was obtained by dissolving template, was filtered, washed with doubly distilled dodecyltrimethylammonium (DTA) bromide (from water, and dried at room temperature. The dried Aldrich) and tetrapropylammonium (TPA) bro- MCM-41 aluminosilicate product was stirred in an 28 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES ethanol-hydrochloric acid mixture (0.1 mol of HC1 a week isotopic singlet at g=2.0033 and Hpp=10.1 G per one dm3 of ethanol) for 1 h under reflux con- is developing. It appears at relatively low temperaure ditions. Subsequently, the product was washed with of 50°C and its intensity does not change much after ethanol at room temperature and dried. Calcination heating at higher temperatures. After dehydratation of the product was carried out in O2 flow while the at 400°C its intensity is higher by a factor of about 8 sample was gradually heated to 813 K over 10 h and than noise level. This signal is stable at room tem- then kept at this temperature for 10 h. Elemental perature for months and does not decay in the pre- analysis for the Si/Al ratios was performed with sence of air. The nature of this signal is unknown but inductively coupled plasma (ICP) emission spectro- it seems resonable to assume that it represents para- scopy. The d(001) spacings of the channels were magnetic centers induced in aluminosilica framework around 3.5-4.0 nm by powder X-ray diffraction. during dehydration. MCM-41 molecular sieves load- Sample Preparations and Measurements ed with Ag+, Pd2+ and Pd2+ show the same type of Three types of MCM-41 molecular sieves with EPR signal on dehydration. Si/Al ratio 10, 30 and 50 were exchanged for 24 h at The effective temperature of hydrogen reduction to 3 RT with 0.1 mol-dirr AgNO3, Pd(NH3)4Cl2 and produce CESR signal depends distinctly on the type Pt(NH3)4Cl2 to obtain Ag-MCM-41, Pd-MCM-41 of exchangeable cation. The lowest temperature is and Pt-MCM-41 samples with different Si/Al ratios. required for Pd-MCM-41. For sample with Si/Al=10 After drying the samples were dehydrated on a the strong CESR singlet at g=2.0029 and Hpp=4.5 G vacuum line gradually increasing temperature to was recorded after hydrogen reduction at 70°C for 12 400°C. The temperature of 100°C was reached after h (Fig.1.1). In Pd-MCM-41 (Si/Al=30) reduced at 6 hours, and 400°C after 3 additional hours. After 7()°C the CESR signal with similar EPR parameters dehydratation the samples were reduced with 300 was also recorded. Its intensity, however was much Torr of hydrogen in the temperature range lower than for sample with Si/Al=10 (Fig.1.2). After 50-600°C depending on transition metal loaded to evacuation of hydrogen the EPR spectra are stable for MCM-41 material. months at room temperature as far as samples are The EPR measurements have been carried out degassed. In the presence of air the signals with with an ESP 300 Bruker X-band spectrometer at Hpp=4.5 G quickly decay and after 30 min from air room temperature. The EPR spectra were mea- admission only the low intensity singlet (Hpp=10 G) sured after dehydratation and in the course of hy- of framework paramagnetic centers is recorded drogen reduction. When the reduction temperature (Fig.lb). The narrow singlet with Hpp=4.5 G is not reached the level at which a CESR signal appeared, observed in Pd-MCM-41 (Si/Al=50) reduced with H2 the sample was kept at this temperature untill neither at 70°C nor at higher temperatures. The EPR signal intensity reached a maximum. Some samples measurements show only the signal of framework after evacuation of hydrogen were exposed to the centers with Hpp=10 G. air or water vapour at room temperature. For effective reduction of Ag-MCM-41 much Results and Discussion higher temperature is required: 480 and 650°C for Hydrated MCM-41 samples in sodium form are samples with Si/Al equal 10 and 30, respectively. EPR silent. However, in the course of dehydratation The CESR signals of silver cluster are narrower

2.

r x2

r x4 x4 / i i 330 335 340 .145 niT 3.1'•'0" •"•335" •"34"0 J345"" tn, T Fig.l. EPR spectra of Pd-MCM-41 with Si/Al = 10 (1) and Si/Al=30 (2) reduced by hydrogen at 70°C: a - after evacuation of hydrogen, b - after exposition to air. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 29 Fig.3. The maximum of CESR signals was obtained after reduction for 1 h at 350°C the temperature much higher than for MCM-41 loaded with Pd2+ but lower than for Ag-MCM-41. For temperatures below 330°C EPR measurements reveal only weak singlet A of framework paramagnetic centers (Fig.3). At 330°C the singlet starts growing and shows some deviations from EPR parameters of framework centers indicating that a new signal is overlapped with singlet A. At 350°C the new singlet B: g=2.0029, Hpp=5.8 G reaches the maximum intensity. For Pt-MCM-41 with Si/Al=30 the spec- tral changes with reduction temperature are similar. The only difference is the intensity of CESR signal, which after reduction at 350°C is smaller by a factor of about 5. This is consistent with the results for Pd-MCM-41 and Ag-MCM-41 molecular sieves. The Pt-MCM-41 (Si/Al=50) sample reduced with hydrogen under similar conditions also does not show CESR signal at all. We assigned singlet B to CESR signal of small metallic clusters showing quantum size 327.5 effects. Increasing reduction temperature leads to decay of signal B. We believe that the decay of Fig.2.EPR spectra of Ag-MCM-41 with Si/Al = 10 (a) and Si/Al=30 (b) reduced by hydrogen at 480°C. CESR signal at temperatures higher than 350°C results from the mobility of metallic clusters to the (Hpp=3 G) and recorded at lower magnetic field surface of crystallites where bigger metallic par- (g=2.0065). The intensity of CESR singlet for ticles are formed. For bigger particles, like for bulk Ag-MCM-41 (Si/Al=10) is nearly twice of that for metals, the spin relaxation mechanism is dominated palladium molecular sieve with the same Si/Al by spin-orbit coupling which is extremely efficient ratio. For samples with Si/Al=30 the parameters of and relaxation times are very short. As a result the CESR signal are the same but again signal intensity spectra are extremely broad at 77 K and even at 4 K is lower about one order of magnitude (Fig.2). In they are observed only occasionally. When the Ag-MCM-41 with Si/Al=50 CESR signal is not metal crystallites are sufficiently small the average

348" ' 350 mx SF 348 350 mT Fig.3. EPR spectra of Pt-MCM-41 with Si/Al = 10 (1) and Si/A) = 30 (2) reduced by hydrogen at various temperatures. observed at all. The EPR spectra for Pt-MCM-41 energy spacing 6 between the adjacent levels be- samples with Si/Al=10 and 30 exposed to hydrogen comes larger than the Zeeman energy fta>z and the reduction at different temperatures are shown in relaxation processes are quenched by these quan- 30 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES turn size effects resulting in the narrowing of reso- ion loading in MCM-41. It strongly suggests that nance line. According to Kawabata's theory the metal clusters are located inside MCM-41 channels linewidth of CESR signal of small metal particles is and their size is limited to channel diameter. If metal given by: agglomeration proceeded on the surfaces of MCM-41 crystallites one would expect that bigger clusters ) tico-, (v would form in MCM-41 materials with higher metal loadings. However, the calculated diameters of silver, where: Vp - the Fermi velocity, Ag«, - the bulk me- palladium and platinum clusters show only small tal conduction electron spin resonance g - shift, rTwz differences. According to our opinion these differ- - the Zeeman energy, & - the mean energy spacing, ences result from the fact that numerical values of g«, Ye - the electron-spin gyromagnetic ratio, d - are not known precisely and various authors publish particle diameter. quite different values. As a result we conclude that the Since <5 is reversely proportional to the volume CESR linewidth can be a measure of the size of small of particles, so it varies as d"3, one finds from metallic particles. equation (1) that linewidth is proportional to the In hydrogen reduced MCM-41 molecular sieves square of particle size. with Si/Al=10 and 30 loaded with Ag+, Pd2+ and Pt2+ the metal particles of the same size, close to the dimension of MCM-41 channels, are formed inde- where: M=Vp-Agco - a factor depending on the pendently of the cation concentration. This indicates type of metal, E - the experimental resonance fre- that metal clusters of the same size are located inside quency. channels and only the cluster density is higher in the Putting to the equation (2) the physical constans samples with Si/Al=10 than with Si/Al=30. The Vp and Ag» for Ag, Pd and Pt metals and experi- cation capacity of MCM-41 (Si/Al=50) is so small mental value of resonance frequency we were able that the clusters characterized by CESR signals are to calculate the metal particle diameters stabilized not formed at all. in the MCM-41 materials. They are 3.1 nm for Ag, 3.3 nm for Pd and 3.4 nm for Pt very close to the References average size of MCM-41 channels. [1], Ryoo R, Ko C.H., Kim J.M., Howe R.: Calal. Lett., 22, 37 Conclusions (1996). [2].Junges U., Jacobs W., Voigt-Martin I., Krutzsch B., Schuth The linewidths of CESR signals for the particles of F.: J. Chem. Soc, Chem. Commun., 1617 (1995). the same metal are exactly the same for different cat- [3]. Kawabata A.: J. Phys. Soc. Jpn., 22, 902 (1970).

POLY(ETHYLENE TEREPHTHALATE) COMPOSITE MATERIALS - RADIATION EFFECTS Jaroslaw Sadio, Jerzy Bojarski, Grazyna Strzelezak, Jacek Michalik lo Irradiation of polymers with electron beam from correlation between the results of Electron Spin iO linear accelerators initiates a complex process Resonance (ESR) studies of radiation-induced ra- : O named the radiolysis, which produces different dicals and the changes of physical properties of types of free radicals. The radiation-induced radical polymer composites, namely the viscosity in melting reactions are responsible for chemical changes in state. polymers. The cross-linking and degradation are Two homopolymers: poly(ethylene terephtha- the two major radiation effects changing the mor- late) - PET with crystallinity 25-60% and polypro- phological structure and properties of polymers. By pylene - PP with crystallinity in the range 35-80% applying modern radiation technologies one can were used. In the composite materials prepared in modify polymeric materials introducing new, speci- the Industrial Chemistry Research Institute in War- fic properties. The radiation modification of poly- szawa PET was a basic component with a 10 and mers is described in details in many books and re- 90 20% admixture of PP: PET/PP ( /10) and PET/PP view articles [1-4]. 80 ( /20)- Although the radiation modification of polymers In ESR studies the polymers in the shape of nowadays is industrial technology still the me- cylinder, 2x30 mm, were irradiated at 77 K by chanism of radical reactions induced by irradiation gamma-rays in a Co-60 source at a dose of 36 kGy is not completely known even for homopolymers. and at room temperature by a 10 MeV electron The major aim of our studies was to compare the beam from a linear accelerator LAE 13/9 with a mechanism of radical reactions in irradiated homo- dose of 50 kGy. polymers and composite polymers. As a model sys- The ESR measurements were carried out at 77 K tem we chose poly(ethylene terephtalate) - compo- and at room temperature with a Bruker ESP-300 site with polypropylene (PET/PP). ESR spectrometer operating at X-band frequency. Because radical processes are supposed to de- The Zwick plastometer has been used to measure termine the properties of radiation modified poly- polymer viscosity in melting state and to determine mers we undertook the studies to check if there is a Melt mass-Flow Rate (MFR) index. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 31 Results and discussion composite material after the 72 hour storage is a The ESR spectra of PET, PP and PET/PP (8O/2o) superposition of aromatic and peroxy radical sig- irradiated at room temperature are shown in Fig.l. nals (Fig.lb). However, the total radical concentra- In PET just after irradiation the multiplet F of al- tion in the composite PET/PP polymer after 72 h is kyl radical is seen besides the broad singlet B of higher than the concentration resulting from the radical with unpaired electron located in the aro- additive relationship. The changes of total radical

PET W\B

340 345 350 355 340 B [mTj B [mT] Fig.l. ESR spectra of the PET and PP homopolymers and of PET/PP (80/20) composite irradiated at RT with 10 MeV electron beam: a - just after irradiation b - 72 h after irradiation. matic ring (Fig.la). Although the spectrum F is not concentration for pure PET, PP and two com- 8o resolved enough for the simulation and radical posites: PET/PP (^°/io) and PET/PP ( /2o) are identification we tentatively assigned it to the presented in Fig.2. The concentration of radicals secondary radical center in the alkyl chain. Two just after radiation in pure PP is about two times types of radicals are stabilized in PP: peroxy radi- higher than in pure PET. This factor increases to six cals ROO" represented by anisotropic singlet: after the 72 hour storage at room temperature indi- g|| =2.034 and g|=2.004 and alkyl radicals showing cating that radicals in PP are much more stable multiplet G (Fig.la). The composite polymer 80 than in PET. Interestingly, the stability of radicals PET/PP ( /20) shows complex ESR spectrum in the composite polymers increases dramatically which reveals all the lines seen in pure PET and PP. and the numbers of radicals recorded after 72 h in The alkyl radicals in PET and PP are not stable at 9O 80 PET/PP ( /io) and PET/PP ( /20) are respectively room temperature and after 72 h the PET sample 4 and 4.5 times higher than in pure PET. The shows only a weak singlet B of aromatic radicals, kinetic results clearly indicates that even small per- whereas in PP a strong signal of peroxy radicals is centage of PP units in PET/PP composite affect observed in Fig.lb. The ESR signal recorded in a substantially the radical processes. In PET the transfer of radical centers along the polymer chain PET leads to radical decay, whereas in PET/PP com- PP posite the migrating radical center can be stabilized PET/PP (90/10) PET/PP (80/20) at PP unit with subsequent peroxy radical forma- tion. Owing to this mechanism total concentration Table. MFR index before and after irradiation. MFR [g/10 min) Polymer/composite OkGy 50kGy PET 3.45 5.40 PP 2.52 17.83

PET/PP (90/10) 4.00 7.86 40 80 80 Time [h] PET/PP ( /20) 4.3 8.16 Fig.2. Changes in the total radical concentration in the irradiated of radicals in composite PET/PP polymers does not PET, PP and PET/PE/T composite at room temperature. show the additive relationship. 32 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES Besides the ESR studies the viscosity of PET if PP units are able to stabilize also the radical cen- composites was measured before and after y-irra- ters primarily formed in PET units and migrating diation at a dose of 50 kGy. The changes of MFR along the polymer chain. index are shown in Table. The MFR index increases The changes of MFR index indicate that ir- 90 substantially after irradiation for PET/PP ( /i0) radiation of PET and PP polymers as well as of proving that in these materials polymer degradation PET/PP composites causes polymer degradation. is a major process. The degree of polymer degradation seems to cor- Conclusions relate with peroxy radicals concentration stabilized The ESR results show that the ability of PET at room temperature. and PP polymers for the stabilization of radicals This work was supported by the Polish State differs very much. At room temperature the radicals Committee for Scientific Research under grant 3 in PET are not stable at all, whereas in PP peroxy T09B104 11. radicals are recorded even few days after irradiation with relatively high concentration. It is postulated References that the PP ability for peroxy radical formation is [1|. CRC Handbook of Radiation Chemistry. Ed. Tabata. CRC Press Inc., Boca Raton, Ann Arbor, Boston 1991, p. 721. associated with the structure and chemical pro- [2]. Dole M.: The Radiation Chemistry of Macromolecules. Vol. perties of polymer. Interestingly, in PET/PP compo- I, II. Academic Press, New York, London 1972,1973. sites even a small amount of PP (10-20%) improves [i\. O'Donnell. I.H., Sangster D.F.: Principles of Radiation the polymer ability for radical stabilization indicat- Chemistry. New York 1970. [4], Hori Y.: Organic Peroxy Radicals in Polymeric Systems. In: ing that the radical processes in PET/PP composites The Chemistry of Free Radicals - Peroxy Radicals. Chapter have no additive character. This can be understood 12. Ed. Z. Alfassi. 1998.

FURTHER STUDIES ON IRRADIATION PRODUCTS AND TOXICITY CHANGES IN RADIOLYTIC DECOMPOSITION OF 2,4-DICHLOROPHENOL Przemyslaw Drzewicz, Przemystaw P. Panta, Wojciech Ghiszewski, Grzegorz Nahjcz-Jawecki1', Sri Wahyuni2', Maria H. O. Sampa3/, Sueli I. Berrely3/, Marek Trojanowicz 11 Department of Environmental Health Sciences, Medical Academy in Warsaw, Poland 1 21 National Nuclear Energy Agency, Jakarta, Indonesia 3/ Institute of Energetic and Nuclear Research IPEN, Sao Paulo, Brazil Although numerous different technologies are be- pollutant in the environment and product of decom- ing developed parallel, a radiation technology in position of numerous organic biocides. environmental cleanup has found already several Irradiation of 100 ml solutions of 2,4-DCP was advantageous practical applications [1, 2]. Econo- carried out with a Russian y-irradiation source mical analysis has been reported for ozone/electron Issledovatel with ^Co, dose rate 4 kGy h"1 and beam process for groundwater remediation, where mean energy 1.25 MeV in glass conical flasks of 150 addition of ozone improves the efficiency by elimi- ml volume. In part of the studies a source nation of the reducing species formed simulta- Gammacell (Canada) at a dose rate 6.85 kGy rf1 neously with the OH free radicals [3]. A practical was employed with irradiation of 50 ml samples in usefulness of several routinely utilized technologies glass vials. Reversed-phase HPLC and ion-chroma- such as air stripping, biological degradation, or ad- tography measurements were carried out in experi- sorption on activated carbon has various limitations mental conditions described earlier [16]. Bioindi- for different organic compounds present, for ins- cative measurements of toxicity based on biolumi- tance, in effluents from petrochemical industry [4]. nescence of bacteria Vibro fisherii [17] were carried Numerous research groups have reported recent- out using a Microtox M500 Toxicity Analyser ly studies on radiation decomposition of organic MICROTOX from Azur Environment (Berkshire, pollutants such as mono-, di-, and trichlorophenols Great Britain). The determination of total organic [5], pentachlorophenol [6], chlorinated benzalde- content (TOC) were performed in the Institute of hydes [7], trichloroethane and perchloroethylene Energy and Nuclear Research IPEN in Sao Paulo, [8], hydroxybenzoate and hydroxybenzoic ethyl Brazil, using Shimadzu TOC-5000 analyzer. ester [9], EDTA [10] and atrazine [11]. New data The reversed-phase chromatographic measure- have been reported on electron beam treatment of ments provided new information about the effec- municipal waste water in the aerosol flow [12], on tiveness and mechanism of radiolytic degradation of irradiation of industrial effluents [13] and waste 2,4-DCP in various experimental conditions. At water from a molasses processing [14], doses not exceeding 1 kGy the yield of decompo- This work is a continuation of our earlier research sition essentially depends on the initial concentra- on the radiolytic degradation of chlorophenols [15] tion of 2,4-DCP. For 50 ppm 2,4-DCP only 40% has and on effect of selected scavengers on the radiolytic been decomposed, and a dose of 10 kGy is needed degradation of 2,4-dichlorophenol (2,4-DCP) [16], for complete decomposition. The efficiency of ra- one of the most frequently occurring chlorophenolic diolytic degradation is additionally decreased in the RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 33 presence of scavengers such as nitrate. The pre- 2,4-DCP and the presence of several carboxylic sence of 20 ppm nitrate at a 1 kGy dose results in a acids was found in this study in ion-chromatography decrease of degradation yield of 20 ppm 2,4-DCP by measurements of irradiated 2,4-DCP solutions. At as much as 60%, and a complete degradation in doses above 0.5 kGy the presence of formic and such conditions requires a 20 kGy dose. acetic acids was observed in irradiated samples. In The results of total organic carbon (TOC) mea- the presence of 50 ppm bicarbonate a 4-fold in- surements indicate, however, that even such a large crease of the concentration of propionate and the dose does not lead to complete mineralization of presence of acetate were found at a dose increase the irradiated 20 ppm solutions of 2,4-DCP (Fig.l). from 1 kGy to 10 kGy (Fig.2). For aqueous solutions of 2,4-DCP without any Several additional processes have been observed addition only about a 20% decrease of TOC was during irradiation of 2,4-DCP solutions containing found. The presence of 50 ppm humic acid prac- tically does not affect the degree of mineralization, while the presence of 20 ppm nitrate decrease this 20 1 - acetate 2 - formate efficiency of complete mineralization to 10%. 3 - chloride 4 - bicarbonate 100 5 - sulphite

—wW»yUcjv«ng«r —o— 20 ppm NO, —A— 50 ppm humic acid

to

0 5 10 Minutes Fig.2. lon-chromatogram obtained for solution containing 20 ppm 2,4-DCP in the presence of 50 ppm bicarbonate at pH 7.0 after irradiation to dose 10 kGy. See text for chromato- graphic conditions. 10 12 14 16 2» nitrate. At its content 10 to 20 ppm and a 1 kGy Dose, kGy dose, about 50% of the nitrate undergoes radiolysis and 0.5 to 1.6 ppm nitrite is formed. At higher Fig.l.Relative changes of total organic carbon content in irra- diated 20 ppm solution of 2,4-DCP at pH 7.0. doses the nitrite is decomposed, however, in the nitrate presence of 50 ppm its radiolysis leads to the The high-performance ion-chromatography mea- formation of about 10 ppm of nitrite even at a 20 surements provide more information about the kGy dose (Fig.3). At this initial level of nitrate mechanism of 2,4-DCP degradation and other side cation-chromatography allows to detect 13 to 16 processes. An example chromatogram shown in ppm ammonium in 2,4-DCP solutions irradiated to Fig.2 was recorded for 20 ppm solution of 2,4-DCP 1-5 kGy doses. in the presence of bicarbonate irradiated to a dose of 10 kGy. The determination of chloride indicates that at doses of 1 kGy only 50% of is released from organic compounds as inorganic chloride ion. At 10 kGy, however, only 10 to 15% chlorine, depending on the initial concentration of 2,4-DCP, is converted into chloride. In the presence of 50 ppm nitrate about 70% of dehalogenation of organic species was observed for 20 ppm 2,4-DCP solution at 10 kGy, while complete degradation has been observed at 20 kGy (Fig.3). The presence of 10 to 50 ppm of humic acid practically does not in- fluence the release of inorganic chloride. It was already shown that even a 20 kGy dose does not cause total mineralization of 2,4-DCP at a 20 ppm level. According to earlier suggestions of Getoff and Solar [18] dehalogenation of 4-chloro- 0 2 * 6 8 1t> 12 14 16 18 20 phenol leads to the formation of di- and trihydro- Dose, kGy xybenzenes, and then to the opening of aromatic Fig.3. Ion-chromatographic determination of chloride, nitrate and ring and formation of various carboxylic acids. A nitrite in 20 ppm solution of 2,4-DCP at pH 7.0 containing similar mechanism can be expected in case of 50 ppm nitrate during irradiation to different doses. 34 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES The fundamental purpose of radiation treatment treatment. Because of side effects of various scaven- of polluted waters or wastes is not only decompo- gers and a different toxicity of various compounds B C

- 20 ppm 2.44JCP+ 10 ppm NO -o- ««te ump* tHW **i M PW" !.4-CCf - 20 ppm 2,4-OCP* 20 ppm NO -4- 20 ppm J.4-DCP • 200 ppncMXMt 50 ppm 2,4-DCP - 20 ppm 2,4-DCP* 50 ppm NO -»-»ppm3.4-OCT>10pp«1 hunt K*l 20 ppm 2,4-DCP

I 10 12 H 1* 1* 20 10 12 14 Dose, kGy Dose, KGy Dose, kGy Fig.4. Changes of toxicity measured with bioluminescence test Microtox for solutions irradiated to various doses: A - solutions of 2,4-DCP in the presence of various compounds, B - solutions of 2,4-DCP, C - 20 ppm solutions of 2,4-DCP in the presence of nitrate. sition of particular species, but first of all a decrease formed during radiolysis, doses estimated for effec- of total toxicity of these solutions. In this stage of tive radiolytic degradation of given pure chemical the study additional investigations were initiated to species usually require a significant increase in examine toxicity using widely used bioluminescence practical applications. Further studies should be test Microtox®, which was already employed for the focused on the determination of doses for complete determination of toxicity of numerous chemical mineralization of wastes, or at least for sufficient compounds [19]. As a function of applied dose up reduction of their toxicity. to 20 kGy, the changes of toxicity of 2,4-DCP solu- tions were examined without and with addition of References other substances or laboratory wastes from this In- [1]. Rippon S.: Nuclear News, March 1999, pp. 29-31. stitute spiked with 20 ppm 2,4-DCP (Fig.4). At a 20 [2].Borrely S.I., Cruz A.C., Del Mastro N.L., Sampa M.H.O., ppm 2,4-DCP level a complete reduction of toxicity Somessari E.S.: Prog. Nucl. Energy, 33,3-21 (1998). (3). Gehringer P., Eschweiler H.: Ozone Sci. Eng., 21, 523-538 has been obtained at 10 kGy dose, while for 50 ppm (1999). 2,4-DCP solution a certain residual level of toxicity [4], Kardasz K,, Ksdzierska E., Konopka M., Majzner M., Kem- was found even at a 20 kGy dose (Fig.4B). The piriski R., Wilkanowicz L.: Przem. Chem., 7g, 216-219 (1999). presence of nitrate decreases the reduction of loxi- [5]. Zona R., Schmid S., Solar S.: Wat. Res., 32,1314-1319 (1999). city with increasing dose (Fig.4C). Both in the ab- [6]. Fang X., He Y., Liu J., Wu J.: Radiat. Phys. Chem., 5_3_, 411-415(1998). sence of nitrate, and especially in its presence at a [7J. Bekbolet M., Geloff N.: Radiat. Phys. Chem., 56., 333-339 low radiation dose up to 1 kGy a certain initial in- (1999). crease of toxicity has been found (at 50 ppm nitrate [8]. Gehringer P., Matschiner H.: Wat. Sci. Technol., 3Z, 195-201 even about 60%). This can be explained by the for- (1998). [9].Swoboda F., Solar S.: Radiat. Phys. Chem., 5.6, 291-301 mation at low doses of polyhydroxybenzenes, much (1999). more toxic against bacteria used in Microtox than [10]. Krapfenbauer K., Getoff N.: Radiat. Phys. Chem., 5_5_, 2,4-DCP. For instance, the toxicity of hydroquinone 385-393(1999). is about two orders of magnitude higher than [11]. Leitner N.K.V., Berger P., Gehringer P.: Radiat. Phys. 2,4-DCP [19]. Also inorganic nitrogen compounds Chem., 55, 317-322(1999). [12]. Podzorova E.A., Pikaev A.K., Belyshev V.A., Lysenko with reducing properties formed in the radiolysis of S.L.L.: Radiat. Phys. Chem., 52, 361-364 (1998). nitrate are also highly toxic. A substantial increase [13]. Sampa M.H.O., Duarte C.L., Rela P.R., Somessari E.S.R., of toxicity at a 1 kGy dose is favoured by the Silverira C.G., Azevedo A.L.: Radiat. Phys. Chem., 52, presence of excess of chloride as well as humic acid 365-369 (1998). [14]. Gehringer P., Fiedler H.: Radiat. Phys. Chem., 52, 345-349 (Fig.4A). Changes of toxicity of non-radioactive (1998). laboratory waste containing 500 ppm chloride and [15].Trojanowicz M., Chudziak A., Bryl-Sandelewska T.: J. 5.0 ppm nitrate and spiked with 20 ppm 2,4-DCP Radioanal. Nucl. Chem., 224,131-136 (1997). were also examined. The irradiation to dose 20 kGy [16]. Drzewicz P., Panta P., Gtuszewski W., Trojanowicz M: J. has reduced its toxicity only by 50% (Fig.4A). Radioanal. Nucl. Chem., 2J2,601-609 (1999). [17]. Nalecz-Jawecki G., Sawicki J.: Gaz, Woda, Techn. Sanit 2 47-51 (1996). The broadening of chromatographic diagnostics [18]. Getoff N., Solar S.: Radiat. Phys. Chem., 28,443-453 (1986). of radiolytic degradation of 2,4-DCP with TOC and [19]. Kaiser K.L.E., Palabrica V.S.: Water Poll. Res. J. Canada toxicity measurements allows to make additional 26, 362-431 (1991). conclusions on this method of water and waste RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 35 RADIATION-INDUCED POLYMERIZATION OF 2-ETHYLHEXYL ACRYLATE FOR MEDICAL APPLICATION

17 Przemyslaw P. Panta, Wojciech Ghiszewski, Grazyna Strzelczak, Elzbieta K. Wojtynska , Zbigniew Zimek ==== in a> 1/ Industry Chemistry Research Institute, Warszawa, Poland o> io Introduction Electron beams (EB) from the accelerators LAE 10 Chemically initiated polymerization of some alkyl 13/9 and UELV-10-10-70-1, used on a large scale : O acrylates is widely used in manufacturing of pressure for sterilization and polymer cross-linking, were ca- sensitives adhesives (sticking plasters), useful for me- librated using graphite and polystyrene calorime- dical and technical applications [1, 2]. Such plasters ters. are usually prepared by deposition of suitable glue Parallel to absolute calorimetric measurement layer on cotton textile subgrades or sometime on also routine evaluations of dose were performed in polyester films. Traditionally manufactured adhesives the range of 10-40 kGy (using polymeric films). employ some vinyl compounds, usually selected alkyl The ESR measurements were performend using acrylates with an addition of acrylic acid (AA) poly- a Bruker ESP-300 spectrometer operating in the X merized by a chemically initiated process. As it is well band (9.56 Hz) equippeed with a variable tempe- known, the quality of adhesives depends on the fol- rature unit. The ESR spectra were recorded over lowing parameters (according to International Stand- temperature range 77-273 K. The samples were ir- ards PSTC): adhesion (PSTC-1), cohesion (PSTC-7) radiated at liquid nitrogen temperature in dose and tack (PSTC-6). range 10-25 kGy. The motivation to the present work on the radi- Results and discussion ation induced copolymerization was a considerable Electron beam (EB) irradiations of water micro- industrial interest in emulsion polymerization sti- emulsions of 2HEA with additions of AA and VA mulated by the high yield of free radicals, from the permitted to obtain good properties of adhesive radiolysis of water, which exhibit strong oxidation samples. The effects of radiation - induced emul- effects. Moreover, ionizing radiation attacks the sion polymerization of the above mentioned vinyl Table 1. Main properties of vinyl adhesive as a function of EB dose, For comparison a non-irradiated, chemically polymerized sample is mentioned.

Viscosity Basis weight Tack Adhesion Cohesion Resistance to water Dose [kGy] 2 [mPs] [g/m ] [cm] [N/2.5 cm] [min] [h] 0 158 - - - - - 5 600 24.5 7.8 0.5-2.3 13 1 15 2 800 37.9 9.5 2.5-3.9 96 2 30 2 600 41.3 10.9 4.0-5.9 >1440 4 non-irradiated, chemically polymerized 550 31.5 14.0 3.4-5.5 300 0.5 surfactants and also reduces residual monomers monomers are shown in Table 1. There are some ensuring chemically cleaner products. further differences between radiation - induced and Experimental chemical initiated polymerization: among others Monomers used in these experiments were as velocities (Table 2). follows: We observe significant differences of relation- - 2-ethylhexyl acrylate, stabilized with 100 ppm hy- ship between adhesive properties vs. their mole- droquinone, monomethyl ether, 98%, 2HEA; cular masses which depend on radiation and chemi- - acrylic acid, inhibited with 200 ppm hydroquino- cally initiated polymerization. ne, monomethyl ether, 99%, AA; It is worth pointing out the importance of mi- - vinyl acetate, inhibited with 0.5% hydroquinone, celles in emulsion which provide the polymeriza- monomethyl ether, 99%, VA. tion centers for both radiation induced and chemi- Two Russian production electron linacs with an cal initiated processes [3]. The liquid monomer (in electron energy of 10 MeV and power of 6-10 kW our case HEA with additives), is emulsified in water Table 2. Approximate time scale for radiation and chemically induced polymerization processes for vinyl adhesives.

Polymerization method Time Remarks Radiation induced, water microemulsion, EB irradiation several seconds chemically initiated oligomerization improve (10 MeV electron) final properties Chemical initiation, water microemulsion heating 8-10h (about 90°C), mixing Chemical initiation, in organic solvents over 30 h traditional technology (benzine or ethyl acetate) were employed for the radiation. For comparing ir- by the use of ionic and non ionic surface active radiation EB vs. gamma rays, two laboratory Co-60 agents. Using additionally mechanical homogeniza- sources at a dose rate of about 4 kGy/h were used. tors it is possible to obtain minute spherical mi- 36 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES celles of diameter of several nanometers. Some aqueous emulsion or in dry solid state exhibit simi- comparative experiments with the application of lar ESR spectra. Pimary radicals generated in acry- ultrasound dispersing without surfactants were not lic acid and the adhesive composite samples have successful, because the obtained in this way radia- disappeared upon warning to 180 K. Only peroxy tion polymerized products exhibits rather poor glue radicals ROO' represented by anisotropic singlet properties. with gn=2.034 and gi=2.004 have been observed Instead, the best results were received when over the temperature range 180-250 K. monomer aqueous microemulsions were chemically Dependence of the intensity of ESR signals in oligomerized and next fully polymerized using elec- adhesive composite on irradiation dose has been tron irradiation at a dose of 25 to 35 kGy. Ra- studied at 77 K (Fig.2). Fortunately, the linear diation induced polymerization of 2HEA without dependence of radiation induced generation of free previous chemical prepolymerization is too a fast process and the obtained products reveal insuffi- cient cohesion and adhesion. Summarising, it seems to be clear that micelles are necessary to ensure more regular polymerization conditions for better properties of adhesives. Radiation induced polymerization of acrylic acid and also of vinyl acetate was investigated as early as in the fifties [4]. However, we do not know avail- able papers devoted to radiation polymerization of 2-ethylhexyl acrylate (2HEA). On the other hand, 2HEA is produced on a large scale in the USA and in Western Europe for industrial applications such i . J as adhesives and lackers. For this reason we investi- 3300 3340 33B0 3420 3460 gate the radiation induced polymerization of aque- [61 ous emulsion of 2HEA and try to interpret its me- chanism. Our work is under progress and we focus Fig.2. Dependence of the intensity of ESR signals in adhesive on elaboration of new generation of adhesives for composite vs. irradiation dose. medical application. radicals is in the range of sterilization dose (25 Primary radical products of irradiated monomers kGy). The attained value of correlation coefficient and adhesive composites were studied by EPR spec- of linear regression equation, R, is equal to 0.99909, troscopy. i.e. very close to its maximum possible level. The EPR spectra recorded after irradiation for the detailed mechanism of radiation induced reactions acrylic glue adhesive composite at 77 K are pre- in adhesive composites is still in progress. sented in Fig. 1. Conclusion From the results it can be concluded that EB radiation processing of 2-ethylhexyl acrylate with 3,5- some additives in the form of aqueous microemul-

3,0- sion enables preparation of new generation of im- proved adhesives for medical applications. 2.5- Radiation induced free radicals are long living at 77 K and disappear on warming both of irradiated 2,0- monomers and adhesive composites at 250 K. Over 1,5- the temperature 250 K only peroxy radicals have been observed in acrylic acid and adhesive com- 1.0- posite. The mechanical properties of adhesive com- s 0.5- posite are optimal in the range of sterilization doses (25-30 kGy). 0,0 This work was supported by the Polish State 10 15 20 25 IrrafltaUon dose, Committee for Scientific Research, under grant No TO9B101 11. Fig.l.EPR spectra recorded at 77 K after irradiation for acrylic glue adhesive composite. References The ESR spectrum of radicals for 2-ethylhexyl [lJ.Chapiro A.: Radiation Chemistry of Polymeric System. acrylate, which are stable at 77 K, seems to be very Interscience, New York 1962. (2J. Krenceski M.A., Johnson J.J., Temin S.C.: Macromol. Chem. similar to that obtained by Kumar and Rao [5]. Physics, C 26(1), (1986). The ESR spectrum for the adhesive composite [3]. Emulsion Polymerization. Ed. Piirma. Academic Press, New represents superposition of ESR spectra assigned York 1982. [4j. Allen P.E.M., Downer J.M., Hastings G.W., Melville H.W., to two various radicals. The main component of Molyneux P., Urwin J.R.: Nature, 177,910 (1956). that spectrum is probably due to the presence of [5j. Kumar M., Rao M.H., Rao K.N.: Radiat. Phys. Chem., 27(8), radicals derived from 2-ethylhexyl acrylate. Samples 219-223 (1986). of the adhesive composite investigated in either RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 37 EXPERIMENTAL SIMULATION OF SPECTRA OF PEROXIDES ON CHAINS OF POLYPROPYLENE Andrzej Rafalski, Zbigniew P. Zagtirski Ionizing radiation causes in polypropylene (PP) primarly single ionized sites situated in random i O places in the polymer chain. In the next stage a O.D. hydrogen atom is detached, not always from the primary ionized site, usually it is the weakest bonded hydrogen atom in the surroundings of the ionized site and the alkyl radical is formed: R-H^R +H (1) Part of the energy of ionising radiation (ca 20% in the case of low linear energy transfer (LET) radiations like y and electron beams) is deposited in large spurs, i.e. more than one ionisation close one 200 240 280 280 300 320 to another. This large spurs cause the break of the X Inm] chain, due to hundreds of eV energy deposited Fig.2. Absorption spectra of t-butylhydroperoxide (1) and t-butyl almost in one place. Debris of the chain are hy- peroxide (2). drogen and hydrocarbons, but two new loose ends 60, 196 and 525 days after irradiation, measured of fragments of the chain contain also new radical always against the unirradiated sample of the poly- sites. propylene powder from the same batch. The spectra If the is dissolved in the polymer, it reacts consist of three absorption bands: the first one with immediately with the radicals creating peroxyl radi- the maximum wavelenght 210 nm, that disappeared cals: totaly in 2 months, the second band with the maxi- R +O2-*ROO (2) These radicals react then by detaching and join- ing hydrogen atoms from another place of the same or another polymer chain, form hydroperoxide and remake alkyl radicals: ROO + Ri-H -* ROOH + Ri (3) The new alkyl radicals react again with oxygen (reaction 2) and with a new place in polymer chain (reaction 3) starting a chain reaction. The chain re- action lasts as long as oxygen is present in the polymer or till the meeting of two radicals (which however is very unlikely) which forms a peroxide: ROO + Ri -»ROORj (4) 200 A better chance for the radical to react is the oxygen which diffuses from the surrounding air. Fig.3. Comparison of spectra of t-butyl peroxide and irradiated The hydroperoxide eventually creates a ketone. polypropylene. Fig.l shows the optical absorption spectrum of ir- mum 230 nm and the third band with the maximum radiated PP obtained by the diffuse reflectance spec- 260-^280 nm. The two last bands rose steadily during the investigations. To identify the absorption bands we have ob- tained absorption spectra of several compounds. They were: t-butyl hydroperoxide, t-butyl peroxide, 625 days di-isopropylketone (DIPK) and di-isobutylketone

196 days

.BO days

350

Fig.l.DRS spectra of polypropylene after indicated times after irradiation. troscopy (DRS) method. The irradiation was done by o.o 10 MeV electrons to the dose of 40 kGy. The picture shows also the spectra of the same PP sample after 1, Fig.4. DRS spectra of di-isopropylketone and di-isobutylketone. 38 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES (DIBK). Spectra of two first compounds were ob- ed in another way. Non-irradiated PP was impreg- tained by classical spectrophotometry of a 1% solu- nated with a 1% solution of DIPK or DIBK in me- tion in water or hexane vs. pure solvent. The spec- thanol. As a reference served PP impregnated with tra are shown in Fig.2. Comparison of spectra of pure methanol. Fig.4 shows the spectra obtained by t-butyl peroxide and irradiated PP shows (Fig.3) the DRS method. In both cases the maximum lies at that the absorption band 210 nm is caused by the 288 nm, which corresponds with the absorption peroxide bond (-O-O-) connected to two carbon band 260-^280 nm in irradiated PP. This agreement atoms. is the evidence that this band is caused by the The spectra of two other compounds mentioned ketone group (>C=O), which is formed during above and suspected of the absorption were obtain- oxidation of PP.

ELECTRON PARAMAGNETIC RESONANCE SPECTROMETRY (EPR) FOR DATING OF PALEOANTHROPOLOGICAL NURAGHI SKELETAL TISSUES Waclaw Stachowicz, Jarosiaw Sadfo, Grazyna Strzelczak, Jacek Michalik In a close co-operation with the University of Sassari, plots, which by extrapolation gave values of the ii Italy and the Medical Academy in Warsaw the dating total cumulated doses in both samples. The dose o of skeletons of Nuraghi population living in Sardinia, cumulated in the Nuraghi remains was found to be Italy, centuries BC, based on the quantitative evalua- equal to 31.0 Gy, while that cumulated in the tion of the concentration of stable paramagnetic spe- Roman skeleton - 16.7 Gy. By a rather simple com- cies produced by ionising radiation in tooth enamel, parative calculation based on the assumption that was performed by quantitative EPR spectrometry [1]. the age of the Roman remains was, as established The nuragic culture was developed from 1600 to 500 by archaeologists equal to 1700 years, the age of BC and is characterised by the appearance of abso- nuragic remains was evaluated as being equal to lutely original megalithic monument, the so called 3200 years (1200 years BC). The total error of the "Nuraghi". The remains of bones and teeth, the object EPR measurements, EPR signal analyses and dose of the study, were found in the "Tombs of the Giants" extrapolation was estimated to be 12-15%. assigned to this culture and discovered in La Testa, St. The crystallinity of the bone mineral in Nuraghi Teresa di Gallura, Sardinia in 1990 after the fire that skeletons evaluated by the EPR technique, the burned the surrounding thicket. method adapted earlier by some of the authors for The purpose of the study was dating of the biomedical studies on mineralised tissues, is only Nuraghi skeletal tissue with the use of electron little changed after centuries of the deposition of paramagnetic resonance technique based on the Nuraghi remains in tombs, as compared with con- phenomenon of the interaction of both cosmic rays temporary bone samples. This is an additional argu- and natural radioactivity of the soil surrounding the ment for the correctness of the EPR method adapt- remains with bone mineral. The interaction results ed for the dating. in the formation of a very stable radical ion COf"1 5 Comparison of the chemical composition of (time constant at 37°C equal to 1.9xlO years) Nuraghi skeletons contaminated through percola- giving a rise in EPR to a very specific asymmetric tion by rain or floods with that of contemporary singlet. The intensity of the signal is proportional to bone shows an increase in the concentration of Fe, the absorbed dose. The advantage of the present SiC>2, Al and Ca. As expected, the contamination is dating procedure was that in the close vicinity of minimal in tooth enamel. More details on the Nuraghi tomb the Roman skeletons of the known subject one can find elsewhere [1]. age were also discovered. Thus, it was possible by applying the additive dose method (successive irra- References diation of samples at the same dose of 60Co gamma [1]. Stachowicz W., Sadto J., Streelczak G., Michalik J., Bandiera P., Mazzarello V., Montella A., Wojtowicz A., Kamirtski A., rays) to Nuraghi and Roman remains to construct Ostrowski K.: It. J. Embryol., 1M, 1, 19-31 (1999).

THE CELLULOSE MEMBRANE - WATER INTERACTION STUDIED BY DIFFERENTIAL SCANNING CALORIMETRY |0O Krystyna Ciesla, Hubert Rahier1', Grazyna Zakrzewska-Trznadel is 1/ Department of Physical Chemistry and Polymer Science, Vrije Universiteit Brussel, Belgium ; O ! O Membrane processes are involved in nuclear tech- At present, the preliminary studies of cellulose nologies and other industries. Separation of various membrane - water interaction were carried out ap- media on cellulose membranes is possible due to an plying differential scanning calorimetry (DSC). The interaction of the material of these dense mem- processes like melting and crystallization of water branes with solvents. as well as melting of the polymer phase containing RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 39 water were examined. The studies were performed One to three thermal effects of water melting were with an initial membrane material tomofan (rege- observed during the first, second and third heating of nerated cellulose, product of Poland). The water various samples, depending on the water content, content, equal to 8.82% (as related to dry polymer treatment time and sample history. These pheno- mass), in the film kept in air was found by thermo- mena occur at lower temperatures than the pure gravimetry. Besides, two parts of the tomofan water melting (Fig.l). This is due to the presence of membrane, used before as a filtration material in various types of water, connected to the films with experiments with water, were examined. These two different forces. Moreover, a large amount of non- samples were cut from the central part of the mem- freezeable water was detected, amounting to 30-50% brane or from its edge. The first sample was ex- of dry mass content. Although an extremely rapid posed to the action of water at a temperature of up swelling was detected by the DMTA method imme- to 90°C and a transmembrane pressure of ca. 0.1 diately after the sample was placed into water, the MPa, while the second one was subjected to the structural changes occurring in membranes as a re- temperature treatment (up to 90°C). Moreover, sult of the prolonged water treatment may be still some DSC measurements of initial tomofan ex- concluded on the basis of both the differences be- posed to D2O were performed. tween water melting occurring in particular samples, Melting-crystallization processes in the tempera- and on the appearance of the endothermal effect of ture range from -40 to +10°C were examined in melting of the crystallised polymer fraction in the heating-cooling-heating cycles at a heating-cooling temperature region 65-135°C. This effect was ob- rate of 1 °C/min (2 or 3 heating cycles were applied) for the moisture containing films closed in standard DSC pans. Moreover, DSC measurements for the hermetically closed samples were carried out in the

m -15 -10 0) temperature.°C

Fig.2. Examples of the DSC curves recorded during first heating of the tomofan sample closed in a DSC pan with the fol- lowing amount of water: 91.78 (curve 1) and 107.43% (curve 2) (ca. 75% and ca. 90% of the initial film mass, respectively). Both measurements were done after 15 h. In the case of the first sample the determined enthalpy of water melting was equal to 136.44 J/g. 45.48 and 46.30% of temperature'C the freezable and nonfreezable water, respectively, was Fig.l. Examples of the DSC curves, obtained during first heating: found on the basis of the above result. pure H2O (as calculated per 0.112 mg, while 0.670 mg was used in experiment) as well as the tomofan film kept in water served for the sample exposed to water for as long as for 1 min (recorded after cooling at a rate of 1 °C/min) and 18 h, while no such effect was noticed after a short for 15 min (recorded after fast cooling at a rate of 100 treatment time of 15 min. °C/min). Both films were dried with a paper before closing in DSC pans. The measurements were done directly after Beside the influence of sample history on the preparation. The values of the enthalpy of water melting, further polymer-water interaction, the differences equal to 32.23 and 44.24 J/g, were found in the case of film may be deduced between the H2O and D2O effect exposed to water for 1 and 15 min, corresponding to ca. on the tomofan membrane on the basis of the pre- 10.74 and 14.76% of freezable water content, respectively. The enthalpy of pure water melting is equal to ca. 300 J/g. liminary data. Examples of the DSC curves are presented in temperature range 10-250°C at a heating rate of 5 Figs. 1 and 2. All the values of enthalpy and water °C/min. A Perkin-Elmer DSC instrument (Pyris) content given in the captions were calculated in the installed in VUB was used. term of dry mass content. 40 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES DIFFERENTIAL SCANNING CALORIMETRY STUDIES OF MELTING AND GLASS TRANSITION PROCESSES IN FOOD 1 1 \O> Krystyna Ciesla, Alberto Sereno ', Wojciech Gluszewski, Carla Barbossa ^ x/ Faculdade de Engenharia Quimica, Universidade do Porto, Portugal A recent trend to explain the behaviour of food ma- heating at a rate of 5 °C/min in the temperature terials during processing and storage is based on an range from -25 to 18°C, with a peak temperature at 12 interpretation which considers food materials as 0.6°C. No glass transition was observed even in the systems of water elasticised natural polymers [1, 2]. wide temperature range starting from -120°C. Glass Differential scanning calorimetry (DSC) became transition of dried onion was observed in the tem- recently widely applied in food testing, in particular perature range from -34.0 to -14.3°C. An attempt in the studies of water interaction with a solid poly- was made to study the crystallization of water during mer matrix. Glass transition temperature is treated cooling at a rate of 2°C/min. as a parameter informing about the possible food Four stages of sunflower oil melting were ob- stability during storage at various temperatures. Be- served in the temperature range from -45.5 to -1.5°C. side, the course of several processes like melting Two endothermal minima at -36.0 and -25.9°C and and thermal decomposition of fats connected to two shoulders at -20.2 and - 9.5°C were detected food quality and freshness, are studied applying the during heating at a rate of 5 °C/min. Glass transition above method. was noticed in the range from -79.6 to -71.2°C. At present, the processes like glass transition and melting occurring in vegetables (onion) and fats (sunflower oil, butter) were examined by dif- ferential scanning calorimetry. Besides, the pre- liminary studies dealing with the influence of the former gamma irradiation at a relatively high dose on the above processes was initiated. Onion, sunflower oil and butter were commer- cial products. The irradiation was carried out in a gamma cell Issledovatel in the Department of Ra- diation Chemistry, INCT at a dose of 30 kGy ap- plying a dose rate of 3.28 kGy/h. Each onion was cut into two pieces. One piece was a reference and the second one was irradiated. One of the irradiated onions was afterwards dried at ambient tempera- temperature, *C ture in vacuum for 24 h simultaneously with an ap- Fig.l. DSC curves recorded at a heating rate of 2 °C/min for the propriate reference sample. initial (curve 1) and irradiated (cuive 2) samples of butter. The measurements were done after deep freezing. A Shimadzu Mod. DSC50 differential scanning calorimeter equipped with a LTC50 cooling unit, Several thermal effects of melting were noticed on enabling cooling of DSC chamber with liquid DSC curves of butter, consisting of a mixture of seve- nitrogen, was used. The instrument is installed in ral fat fractions and water (Fig.l). The effects are pro- the University of Porto. The measurements were bably connected to melting of water (-17.5+5.5°C), of performed in the temperature range from -130 to the emulsion created by fat and water (0.0^-21.5°C) +50°C, applying a heating rate 5 and 2 °C/min. and by fat fractions (21.5-=-43.1oC). When DSC mea- Melting of the bound water in fresh onion was ob- surements were performed after deep freezing to a served at a temperature lower than that of free water temperature as low as -40-^-60°C, a large effect of melting. The endothermal effect was noticed during water melting was observed. It was, however, possible -i.xo

-100.00 -50.00 0.00 30.00 temperature, °c Fig.2. The change in heat capacity connected to glass transition in irradiated onion powder, recorded during heating at a rate of 5 °C/min. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 41 to avoid water crystallization during cooling to a tem- melting temperatures were noticed after irradia- perature ca. -6 to -8°C. In such cases, water melting tion. The beginning of exothermal crystallization of was not observed during heating. water in the irradiated onion was noticed, however, Comparison of the results obtained for the non- at a temperature lower (-14.2°C) than in the case of irradiated reference and irradiated samples of the initial sample (-13.5°C). Glass transition of the butter, remaining a solid at ambient temperature, powdered irradiated onion was detected also at have shown significant differences between melting lower temperatures (from -37.2 to -14.0°C; Fig.2) as of fat and emulsion fractions in the initial and the compared with the initial reference sample. irradiated samples. These melting processes were References observed after irradiation at a higher temperature. [1]. Sa M.M., Sereno A.: Thermochim. Acta, 246,285-297 (1994). The effect is caused by a change in the fat structure. [2].Sa M.M., Sereno A.: Rev. Esp. Cienc. Tecnol. Aliment., 34 In the case of sunflower oil and water contained in (2), 203-209 (1994). onion and in butter only a small decrease in the PL0002000 EFFECT OF ANNEALING AND IRRADIATION ON THE OPTICAL PROPERTIES OF OXIDE CRYSTAL Slawomir M. Kaczmarek1^ Marek Berkowski2/, Zbigniew Moroz3/, Stanislaw Warchol 11 Institute of Optoelectronics, Military University of Technology, Warszawa, Poland 21 Institute of Physics, Polish Academy of Sciences, Warszawa, Poland 3/ Soltan Institute for Nuclear Studies, Swierk, Poland Optical characteristics of the optoelectronic ele- of the samples using LAMBDA-2 Perkin-Elmer, ments and devices based on oxide crystals changes ACTA VII Beckman and FTIR 1725 Perkin-Elmer during their staying inside radiation field. Common spectrophotometers. methods of characterization of oxide crystals may The level of crystal defecting after irradiation not give a precise answer to the question what is the depends strongly on its initial quality and also on performance of devices under a strong external ra- the concentration of active dopant. The quantity of diation field. point defects, which may be recharged due to ioniz- The aim of this paper is to determine the ability of ing irradiation, is for the investigated crystals of the the method of ionizing radiation treatment of opto- order of 1017 cm"3 [1]. Also annealing at too low electronic materials to characterize the compounds temperatures can create new defects. and, may be, to change their optical properties. For y-rays with energies =1.25 MeV recharging The following crystals were investigated: Y3AI5O12, processes, due to the Compton effect and ioniza- YAIO3, SrLaGa3O7, LiNbO3, Gd3Ga5Oi2, LaGaO3, tion of active ions, were mainly observed. ZnSe and LiF. For electrons with energies <1 MeV (doses Using various 60Co sources the crystals were 1014-1016 cm'2) ionizing processes of active ions irradiated by y-rays in this Institute and in the were dominant. Institute of Atomic Energy at Swierk. For electron For dose of protons < 1014 cm"2 mainly recombi- irradiation 300 keV or 1 MeV beams from a Van de nation with delta electrons takes place, while for Graaf accelerator of this Institute were used, while doses of protons >1014 cm'2 Frenkel defects also for irradiation with 21 MeV protons a beam from a arise (whose quantity increases linearly with dose compact isochronous proton cyclotron installed in [2]. The latter effect is caused by nuclear scattering the Soltan Institute of Nuclear Studies, Swierk, was of protons. applied. Changes in luminescence spectrum after gamma 2 The dose of y-irradiation was varied from 10 to irradiation were observed in LiF, Co:LaGaO3, and 107 Gy; the fluency of electrons was varied from 1014 Mn:ZnSe single crystals. Such a behavior indicates to 5xlO16 particles/cm2, and the protons fluences that y-irradiation can dramatically change emission from 5xlO12 to 1016 particles/cm2 were applied. An- properties of the crystals. Thus, irradiation and an- nealing was performed in the three regimes: nealing treatments appear to be the effective tools (i) thermal relaxation by annealing in air at 400°C for characterization and alteration of properties of for Y3A15O12 and at 800°C for LiNbO3, for 3 h in oxide single crystals [3]. order to remove radiation defects; References (ii) annealing at 1400°C (or 1100°C) for 3 h in air [1]. Matkovskii A.O., Sugak D.J., Durygin A.N., Kaczmarek S.M., (an oxidizing atmosphere) in order to change the Kopczyfiski K., Mierczyk Z., Frukacz Z., Lukasiewicz T., Sha- defect structure of a crystal; khov A.P.: Opt. Mater, 6,353 (1996). (iii) annealing in a mixture of hydrogen and nitro- [2], Kaczmarek S.M., Jabtoriski R., Pracka I., Boulon G., Luka- gen (a reducing atmosphere) at 1200°C for 0.5 h. siewicz T., Moroz Z., Warchot S.: Nucl. Instr. Meth. Phys. Res., B 142, 515 (1998). Optical transmission spectra were recorded be- [3]. Kaczmarek S.M., Berkowski M., Moroz Z., Warcho} S.: Acta fore and after each irradiation or thermal treatment Phys. Pol. A, 26, 3-4, 418-427 (1999). 42 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES CHANGES IN LUMINESCENCE OF Ce: YAG CRYSTALS UNDER IONIZING RADIATION TREATMENT Stawomir M. Kaczmarek1', Zbigniew Moroz2/, Mirostaw Kwasny1/, Jarostaw Kisielewski3/, IS Tadeusz Lukasiewicz3'4', Jolanta Wojtkowska2, Henryk Rzewuski IS v Institute of Optoelectronics, Military University of Technology, Warszawa, Poland !§ 21 Soltan Institute for Nuclear Studies, Swierk, Poland 3/ Institute of Electronic Materials Technology, Warszawa, Poland 4/ Institute of Applied Physics, Military University of Technology, Warszawa, Poland Ce3+: YAG crystals have some features highly de- radiation (=50%), due to the Ce4+-*Ce3+ recharg- sirable for an active material of the tuned solid state ing reaction. For highly doped Ce: YAG crystals lasers [1] as well as for scintillator materials (e.g. in (0.1 and 0.2 at.%) also an increase, but much medical imaging, tomography, gamma cameras) [2]. smaller (4%), for the Mg codoped crystals (0.1 Parameters of the Ce: YAG crystals as scintilla- at.%) was observed. After 1 MeV electron irradia- tors depend, to a large extent, on its optical pro- tion in the over-threshold type interaction a de- perties as well as on the kind of structural and ra- crease in luminescence is observed due to the do- diation defects [3]. mination of the Ce3+-*Ce4+ ionization process. In The main goal of this work was a study of such the case of proton irradiation, for small fluencies defects in doped YAG crystals which in- (=1013 particles/cm2) an increase in luminescence

b) protons |.10tW.*S*101W

, 2-1o"prolonsAJm? -10Mprc

300 400 500 600 700 800 500 1000 1100 Wavelength [nm] Fig. Additional absorption bands for S4 sample (a) after y, electron and proton (relative fluencies) and (b) after proton (absolute fluencies) irradiations. fluence the crystal properties qualifying them as is observed due to the domination of the recharging scintillators or active laser materials. processes of Ce4+ ions. For larger fluencies (MO1" Radiation induced changes in the luminescence particles/cm2) a decrease takes place due to a high spectrum under influence of UV light, y-rays, elec- level of radiation defects. trons and protons for several concentrations of As an example, in Fig. the influence of all applied Ce3+ ions as well as Mg3+ ions in -alumi- kinds of radiation on Ce: YAG crystals is shown. num garnet crystals were investigated. To irradiate with y and electrons grown crystals were used while References for proton irradiations the crystals were thermally [l].Tomiki T., Akainine H., Gusitikeit M., Kinjoh Y., Miyazato annealed. For small concentrations of cerium ions M., Miyazato I"., Toyokawa N., Hiraoka M., Hirata N., (=0.01 at.%) an increase in the luminescence Ganaha Y., Futemma T.: J. Phys. Soc. Jpn., 60, 2437 (1991). (about 100%) was observed after gamma irradia- [2]. Kaminskii A.A.: Laser Crystals. Nauka, Moskva 1975, p. 215. tion with a dose of 105 Gy. This increase was due to [3]. Kaczmarek S.M., Moroz Z., KwaSny M., Kisielewski X, 3+ Lukasiewicz T., Wojtkowska J., Rzewuski H.: Acta Phys. Pol. the growth in Ce ions concentration after y-ir- A, 91, 6, 953-964 (1999).

LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES - Is STATE-OF-THE-ART iO IO Zofia Stuglik : O Metrological Laboratory for Measurements of Tech- ber 1998 to develope accurate high dose dosimetry nological Doses (LMTD) was appointed in Septem- methods, consistent with international standards. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 43 The main stress has been laid on a high dose According the electron beam dosimetry we have at electron beam dosimetry, however dosimeters for our disposal 6 polystyrene and 3 graphite calorime- other kind of radiation were also within the scope ters produced at the High Dose Reference Labora- of LMTD interest. tory, Risqr, Denmark and dedicated to the measure- Two radiation sources were used in our experi- ments of mean doses delivered by 10 MeV electron ments: accelerators. Polystyrene calorimeters can be used in - a 60Co y-source Issledovatel with dose rates at six the range 3-J-40 kGy and graphite ones -1.5^-15 kGy. standard positions ~50 Gy/min (December According to the certificates, all calorimeters are 1999) and reproducibility of consecutive mea- traceable to NPL primary dosimetry standards and surements better than ±0.5%; their accuracy for Ris0 conditions are: 2.9% for poly- - a 10 MeV linear electron accelerator LAE 13/9 styrene dosimeters at doses higher than 10 kGy and with electron beam stability from 0.3 to 2% and 4.3% - for a graphite calorimeter. stability of the conveyer speed from 2 to 5%. In the near future we plan to verify the calibra- Both ionizing radiation sources operate in the De- tion for the LAE 13/9 conditions. Following the partment of Radiation Chemistry and Technology producer recommendation, the calibration should of this Institute. be carried out annually or after accumulated doses At the moment we offer two liquid y-ray dosi- of 2000 kGy. meters consistent with international standards: The foil dosimeters for electron beams: PVC and Fricke dosimeter (40-400 Gy) [1]; low dose dichro- Sunna are still under investigation. mate dosimeter (2-10 kGy) [2], high dose dichro- In the next year we plan to concentrate our mate dosimeter (5-50 kGy) [2]. attention on foil dosimeters and the so called EPR A foil dosimeter produced by Sunna Company dosimeters. (LiF in polyethylene, foil thickness - 0.25 mm, range - 5-^-50 kGy, a UV spectrophotometer as ana- References lytical device) - is still under investigation. Until [1]. ASTM Standard Practice for Using the Fricke Reference Standard Dosimetry System: E 1026 - 95. now there are no standards dealing with Sunna do- [2]. ASTM Standard Practice for Use of a Chromate Dosimetry simeters. However, on the basis of the experiments System: E 1401 -91. done so far [3] we suppose that they can be suitable [3]. Stuglik Z,., Sharpe P.: prepared to publication. for routine use.

DOSIMETRIC RESPONSES OF SUNNA AND PVC FOIL DOSIMETERS IS IRRADIATED WITH 10 MeV ELECTRON BEAMS - TIME DEPENDENCE !88 Zofia Stuglik !§ Foil dosimeters, only slightly disturbing the radia- an absorption scale up to 4 or more are recom- tion field, are very useful for energy and dose con- mended for signal measurements. All measure- trol at the electron beam radiation processing. In ments presented here were done on a CINTRA 40 this Insitute we traditionally use non-plasticized UV/VIS spectrophotometer (GBC, Australia, ab- polyvinyl chloride foils (PVC, producer Staufen, sorbance scale from 0 to 4.5) obtained as technical Germany) with good signal-to-dose characteristics assistance of the IAEA. in the range 5-60 kGy [1]. Visual information about Five pieces of the PVC foil and five Sunna dosi- dose distribution given just after the irradiation is meters (batch Fll) were irradiated with 10 MeV one of the advantages of PVC films. A colour deve- electrons from linear accelerator LAE 13/9. Doses lops and becomes more stable after heating to were measured by means of polystyrene (Riser, Den- about 70°C. Optical absorbance at 398-396 nm is mark) calorimeters. The PVC foil was heated after commonly used as dosimetric signal. The main the irradiation at 70°C (30 min) and then measured shortcoming is a substantial decay of the signal after irradiation. Its kinetics depends on the batch SUNNA dosimeters irradiated with 10 MeV electrons of the foil and also on irradiation and heating D= 10,2 kGy conditions. Because of that, the PVC dosimeter is 0,40 frequently considered as unreliable. Recently we started to re-investigate dosimetric properties of PVC and also to investigate a new foil 0.20 dosimeter offered by Sunna Systems Corporation, USA. Sunna dosimeters consist of LiF microcrys- tals incorporated into a polymer. The thickness of the foil (0.25 mm) is nearly the same as the thick- 0,00 ness of PVC foils, used by us (0.26 mm). The con- centration of F centers generated in LiF by ionizing Fig.l. A dosimetric response of Sunna foil dosimeter (mean value for 5 foils, batch Fll) during the 4 months after the irra- radiation can be used for dose determination and diation with 10 MeV electron beam from LAE 13/9 linear the high quality UV/VIS spectrophotometers with accelerator. 44 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES at 398 nm. The Sunna dosimeters were measured at tion for 5 samples in the range 1.6-3% seems to 240 nm without any post-irradiation treatment. The be acceptable for both the routine dose measure- measurements started about 1 hour after the irra- ments during the radiation processing and also diation and lasted 4 months. The results (mean for the documentation purposes. values for five samples) are presented in Figs. 1 and - We cannot recommend the use of PVC foil as 2. On the Y axis there are the differences between routine dosimeter during the first day after irra- PVC foils irradiated with 10 MeV electrons, diation. D=9.6 kGy - PVC foils can be used for dose documentation

0,150 0,143 starting from the next day after irradiation (4-months signal fluctuation - ±4%, standard 0,101 °'104 0,103 deviation for 5 samples - 4-7%). However with 0,100 one reservation: our previous investigation [2] showed a much more complicated PVC signal

0.050 • decay than observed in this experiment. We sup- pose that the more positive results presented here, which emerged from a little different post- 0,000 -irradiation treatment, improved the characteris- Fig.2. A dosimetric response of PVC foil (Staufen, Germany, tics of PVC signal decay. Study in this direction mean value for 5 foils) during the 4 months after (he irra- will be continued. diation with 10 MeV electron beam from LAE 13/9 linear We appreciate technical support of the IAEA accelerator. (Project POL/8/016) which enable us to perform the optical absorbance of irradiated and non-irra- this work. diated samples and on the X axis - consecutive References numbers of measurements. Preliminary conclusions [l].ButhakZ.: Dissertation, INR, 1978. from the experiments are as follows: [2].StugIik Z.: INCT Annual Report 1998. INCT, Warszawa - The Sunna dosimeter with 4-month signal fluc- 1999, p. 51. tuations at a level of ±6% and standard devia-

INFLUENCE OF BUTADIENE/STYRENE COPOLYMERS S ON THE STABILISATION OF POLYPROPYLENE IN ELECTRON BEAM IRRADIATION ISo ;o 1 !O Danuta Zuchowska ', Zbigniew P. Zagorski, Grazyna Przybytniak, Andrzej Rafalski Institute of Organic and Polymer Technology, Wroclaw University of Technology, Poland The basic radiation induced reaction in polymers, radiation yield of hydrogen. In our previous pa- originating in single- and multi-ionization spurs is pers, effects of radiation on PE-linear SBS [1] have dehydrogenation (abstraction of hydrogen), causing been described. In another investigation, the elon- the formation of unsaturated moieties in the poly- gation at break of PE-SBS blend (50-50) increased mer, but with very different secondary consequen- twice after the dose of 100 kGy as a result of cross- ces, from crosslinking to degradation. Both reac- linking (gel content in the blend after irradiation tions run parallel, but in polyethylene the final was 73%). The conclusion was supported by the crosslinking dominates, being the basis of produc- results of EPR experiments. Processes in PE-SBS tion of heat-shrinkable polymers, whereas in poly- blends with 25, 50 and 75% of SBS were not the propylene radiation leads to degradation. The latter simple sum of processes observed in neat PE and phenomenon spoils the application of polypropy- neat SBS polymer, which indicates the interactions lene (PP), undergoing radiation processing, if proper between two components of the blend. additives are not applied. Ethylene-polypropylene The aim of the present study was an investigation copolymers have a comparatively good radiation of the absorption of ionising energy in thermo- resistance because negative effects of polypropylene plastic elastomer-PP blends in a full range of pro- degradation are counterbalanced by crosslinking of portions, helping to propose the mechanisms of en- polyethylene. ergy transfer. The investigation on microscopic and Aromatic compounds are more resistant towards mechanical properties will be described in next ionising radiation because of mechanisms direct- papers. ing the dissipation of energy straightforward into Polymers used were styrene-butadiene-styrene heat. This property of aromatics, also of polymers triblock copolymer, SBS of linear structure (Cariflex with aromatic moieties, partially protects aliphatic 1102), styrene content 29%; styrene-butadiene-sty- blocks present in the material from radiolysis. rene triblock copolymer (SB)X, of radial structure Therefore butadiene-styrene elastomer (SBS) is (Cariflex 1184), styrene content 30%; hydrogenated more resistant towards the ionising radiation than SBS triblock copolymer-styrene-ethylene/butylene- polybutadiene rubber what can be expressed e.g. by -styrene block copolymer, SEBS (Kraton G1652), RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 45 styrene content 30%; isotactic polypropylene, iPP for PB, the paramagnetic product decays slowly, with- injection moulding (Malen J400). out conversion to peroxide radical, visible in the Polypropylene-SBS copolymer blends (0-100%) EPR spectrum. The presence of SBS in the mixture were obtained by double melt mixing in a single- with PP creates conditions which allow an easier -screw extruder. Samples for mechanical tests, as access of oxidising agent to alkyl radicals in poly- well as for diffuse reflectance spectrophotometry propylene. The relative participation of peroxide (DRS) and electron paramagnetic resonance (EPR) radicals in mixtures irradiated to 30 kGy is higher, were prepared by compression moulding at 180°C. which indicates the increasing effect of interaction Irradiation was made with the scanned beam of 10 of elastomer on the radiolysis of PP with the dimi- MeV (high monochromacity) electrons from a linac nishing dose of radiation. LAE 13/9 in this Institute. Samples were irradiated Oxidation of PP in the mixture with SEBS (hy- with doses of 30, 60 and 100 kGy, whereas only the drogenated copolymer SBS) is observed after irra- 30 kGy dose was applied in one irradiation act, re- diation to the dose of 30 kGy, with the 15% parti- sulting in a tolerable adiabatic increase of tempera- cipation of peroxide radicals. One can conclude, ture [2]. Higher doses were applied by a split dose that copolymers SBS and SEBS modify radiation technique, with the separation of irradiations by induced changes in PP in different degree. The in- cooling periods, at room temperature. fluence of copolymer SBS (unsaturated) on oxida- Gel content was determined by the extraction tion is much higher than originated from copolymer with boiling xylene, melt flow index was determine SEBS. In the SEBS copolymer the central chain is in Zwick Plastometer; crystallinity of polypropylene composed from meres of ethylene and butylene was determined by a differential scanning calori- (poly[ethylene-co-butylene]), which causes a better meter (DSC), from Polymer Laboratories, in a ni- miscibility with polypropylene and formation of a trogen atmosphere, at a warming rate of 10 structure of smaller inhomogeneity in comparison deg/min, assuming the enthalpy of the fully crys- to the copolymer SBS. That phenomenon may in- talline polymer AH&=290 J/g; EPR spectra were fluence the rate of oxygen diffusion and creation of measured on a Bruker ESP-300-Spectrometer for radicals which fate is the same as in the case of parameters indicated at diagrams; spectra were homopolypropylene. recorded 3 hours after irradiation and those irra- The concentration of radicals in all investigated diated with a dose of 60 kGy were investigated addi- polymers and their mixtures, after 7 months of sto- tionally 3 days and 3 weeks after the irradiation, as rage at room temperature is on the limits of detec- well as 7 months after. Diffuse reflectance absorp- tion by EPR: their concentration is not higher than tion spectra (DRS) were recorded on a Perkin-El- 1-2% of the initial concentration. In this case for mer Lambda 9 spectrophotometer with the light in- the samples in which PP is present (PP, PP-SBS, tegration sphere. PP-SEBS), the shape of the signal indicates the SBS copolymers, both linear and radial, show trace amount of peroxide radical, but signal of pa- identical EPR spectra after doses of 30 and 60 kGy. ramagnetic products in copolymers SBS and SEBS As it was proved earlier, the EPR signals can be preserve the character of spectra recorded imme- ascribed to one type of paramagnetic product. Spec- diately after the irradiation. tra recorded at a wide range of microwave power Changes of peroxide radicals concentrations ob- (0.02-20 mW) as well as those taken after few weeks served by EPR correspond with changes in the from irradiation do not change the shape. It seems crystalline structure in the investigated mixtures. that this type of signal can origin from anisotropic The presence of 50% of copolymer SBS causes the interactions of two equivalent protons of hyperfine increase of concentration of the crystalline phase in splitting equal Aiso=1.10 mT and gy =2.0006 and the PP matrix, which may suggest, that the presence g£=2.0065. In hydrogenated SEBS, the number of of copolymer increases the concentration of crystal- radicals decreases sharply in comparison to the SBS line nucleation. That view is supported by the fact polymer containing double bonds. Although the of lower melting temperature of crystallites, both in hyperfine splitting in that case is also ca. 1.10 mT, the case of homo-polypropylene as in polypropy- the number of lines is reduced to two. lene mixed with elastomer. After the dose of 60 The EPR spectrum of polypropylene is com- kGy, the concentration of crystalline phase in the posed in 7% from the peroxide radical signal and in PP as in the PP matrix in the mixtures PP-SBS is 93% from the spectrum of alkyl radical. The con- similar to that before irradiation - there is no version of alkyl radicals into peroxide radicals is reason to assume otherwise. explained by easiness, with which oxygen molecules Fig.la,b,c shows the EPR spectra of PP-SBS penetrate intermolecular spaces in polypropylene. blends in the function of time elapsed after 60 kGy In the PP-SBS mixtures, this process fastens drama- irradiation at room temperature and the same tem- tically, because, as it is seen from the analysis of perature storage time. All spectra are shown with- EPR spectra, 80% of primary products after the out deconvolution and separation of particular sig- dose of 30 kGy and 61% after the dose of 60 kGy is nals. Fig.2 shows the decay of radicals in the same oxidised to peroxide radicals; the rest of the signal, but expressed as concentration of spins, composed spectra are alkyl radicals from PP and which is important for the hypothetical explana- 6% of SBS radicals. It is remarkable that in irra- tion of the mechanism of phenomena. Discussion of diated copolymers composed of chains of PS and EPR results in comparison with investigations on 46 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES

100%PP/0%SBS 1OO%PP/O%SBS

3400 3490 3500 3SS0 3800 J3S0 J400 3450 3500 3550 3600 3350 3400 3450 3500 3550 t°l 10! PI Fig.l. EPR spectra of PP and PP-SBS blends after 60 kGy dose of 10 MeV electron beam irradiation, in the function of time elapsed after irradiation: a - immediately after irradiation, b - 3 hours after irradiation, c - 3 days after irradiation. crystallinity of blends and results of mechanical in- effect is exhibited by the aromatic participant. The vestigation on irradiated material will be described phenomenon is explained by energy transfer of in the next paper. single-ionisation spurs to the energy dissipating The spectroscopic investigations (diffuse reflec- constituent. The same PP-SBS systems show op- tance spectrophotometry, DRS, [3]) were perform- posite picture in the EPR investigation. In Fig.2, ed on samples of the same composition. The me- which shows the yield of spins in irradiated thod allows to record optical absorption spectra in samples, there is no diminishment of radical con- polymer blends of poor transparency. Fig.3 shows centration in the blend containing 10% of SBS but the spectra of products absorbing in UV, in irra- even a slight increase, immediately after irradiation, diated blends of polypropylene containing no SBS, 3 hours after irradiation and 3 days after! This 10, 25 and 75% of SBS and the SBS alone. The strange difference can be explained by a different products exhibit absorption band at 312 nm and are hypothesis, but the most probable is in terms of the more stable than free radical products (except per- different role of single- and multi-ionisation spurs. oxides) observed by the EPR method. Although a As it is of importance in all irradiated materials, precise identification of these semi-stable products including polymers, it will be discussed in a sep- is not possible at the time being, the most probable arate paper. explanation of the UV absorption is that it is due to unsaturated moieties (UM) in the polypropylene 0.4 1 - 0% SBS chain. However, there is a striking difference be- F(R) tween the dependence of the concentration of unsa- 2 -10% SBS turated species on the composition of aliphatic-aro- 0,3 • 3 • 25% SBS matic composition. In our case, the fact of dramatic 4 - 75% SBS 5 • 100% SBS reduction of formation of UM already by 10% ad- 0,2 dition of SBS is a remainder of the classic concave curve of radiolysis of a aliphatic-aromatic mixture in radiation chemistry. The radiolysis of aromatic 0,1 component is not only less extensive in comparison with the aliphatic participant, but also a protection 0,0 250 300 350 X [nml

1-100% PP Fig.3. Diffuse reflectance absorption spectra of PP, PP-SBS 2 -90%PPM0%SBS blends and SBS after the 60 kGy dose of 10 MeV electrons. 3 -75%PP/25%SBS All spectra are measured against unirradiated sample, * - 50% PP 150% SBS therefore they show only species formed in the result of 5 - 25% PP 175% SBS radiolysis. This project was supported by the Polish State Committee for Scientific Research, under grant No 1197/T08/97/12. References [1]. Przybytniak G.K., Zag6rski Z.P., Zuchowska D.: Radiat. 12 3 4 5 12 3 4 5 12 3 4 5 Phys. Chem., 5_5_,655-658 (1999). 3h 3d [2]. Zag6rski Z.P.: Thermal and electrostatic aspects of radiation Fig.2. Concentration of spins in PP and PP-SBS blends, after 60 processing of polymers. In: Radiation Processing of Poly- kGy dose of 10 MeV electrons in the function of elapsed mers. Chapter 13. Eds. A. Singh, J. Silverman. Hanser Ver- time. lag, Munich 1992. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 47

[3], Zag6rski Z.P.: Diffuse reflection spectrophotometry (DRS) for recognition of products of radiolysis in polymers. Macro- molec. Symposia (2000). PL0002005 RADIATION INDUCED DEFECTS IN MONOCRYSTALS AND GLASSES OF L12B4O7 Slawomir M. Kaczmarek1/, Andrzej Majchrowski1^ Jaroslaw Kisielewski2/, Mirosiaw KwaSny1/, Teresa Wroriska 1/f Military University of Technical, Warszawa, Poland 21 Institute of Technology of Electronic Materials, Warszawa, Poland The subject of the work is a study on the influence of optical absorption were estimated according to of irradiation on defect level of U2B4O7 obtained the equation: in the form of single crystals and glasses. In order to obtain U2B4O7 monocrystals the Czochralski me- thod was adapted. The substrates were H3BO3 and U2CO3 both of high level of purity (4N). L12B4O7 where: K - coefficient of absorption; Ti, T2 - trans- was synthesised according to the following equa- mission of plate before and after irradiation; d - tion: thickness of the plate. 4H3BO3+Li2CO3 -* U2B4O7+6H2O+CO2 (1) The defect level related to the changes of ab- From bigger monocrystals and pieces of glasses sorption in 026407 single crystals and glasses were small plates were cut out of the shapes appropriate determined before and after the irradiation at the to conduct further measurements. The plates were doses from 10 to 1000 kGy. polished and then investigated by microscope and On the basis of the obtained results it can be conescope observations. Optical transmission of concluded that in the case of monocrystals the irra- plates at room temperature has been measured as diation at highest doses of 1000 kGy seems very ad- well with a Lambda-2 Perkin Elmer spectrophoto- vantageous from the point of view of their optical meter within the range 200-1100 nm, while with a quality. It is because monocrystals after the irradia- FTIR Perkin Elmer apparatus within the range tion at high doses become more transparent within 1400-25000 nm. Optical transmission of monocrys- the range 190-1100 nm. In other words their optical tals was measured also after radiation treatment quality becomes much better. 60 ( Co gamma source Issledovatel, doses from 10 to On the contrary, in the case of glasses the effect 1000 kGy) at room temperature and after warming of better transparency is achieved by warming them of plates at 450°C. Numerical values of the changes in air at a temperature of 450°C.

ANALYTICAL METHODS FOR THE DETECTION OF IRRADIATION IN FOOD COMMODITIES ACCREDITED IN THE INCT LABORATORY 0 O FOR DETECTION OF IRRADIATED FOODS M ^= o Waclaw Stachowicz, Kazimiera Malec-Czechowska, Antoni M. Dancewicz, Zbigniew Szot = O During the past two years the Laboratory for De- 3) the thermoluminescence method for the detec- tection of Irradiated Foods of this Institute was in- tion of irradiation in food from which silicate mine- volved in the implementation of the quality assur- rals can be isolated (related to BS-EN 1788). ance system according to the PN-EN 45001 standard Upon completion of required actions and pro- and the ISO/IEC 25 guide for the methods applied in cedures (organisation, methodology, documenta- testing foodstuffs for irradiation. The following docu- tion) and their preliminary approval, the Labora- mentation of the Quality Assurance System imple- tory was subjected to the audit executed by the mented in the Laboratory has been prepared: Gene- experts from the Polish Centre for Testing and Cer- ral Book of Quality Assurance, General Procedures tification. After introducing all the suggested cor- for Quality Assurance and the set of appropriate rections accepted by the decisive body of the Centre executive instructions. the Certificate of Testing, Laboratory Accreditation For detection of irradiation in foods the fol- for the above mentioned methods has been issued lowing analytical procedures have been adapted and on 25th October 1999. tested for their consistence with appropriate CEN The scope of accreditation compiles the follow- European Standards: ing categories of foods in which earlier irradiation 1) the EPR method of detection of irradiated foods treatment can be detected: containing bone (related to BS-EN 1786), - food containing bones (poultry, pork, beef, fish, 2) the EPR method of detection of irradiated foods eggs): Qualitative analysis for the presence of the containing cellulose (related to BS-EN 1787), specific radiation induced paramagnetic sub- 48 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES stances by the EPR spectroscopy method (Docu- be detected by measuring the intensity of lumi- mented testing procedure PB SLINZ 01 edition nescence of isolated minerals subjected to heating i); (thermoluminescence-TL). Irradiation produces - food containing cellulose (nuts, spices, fruits): free electrons which are trapped in the crystalline Qualitative analysis for the presence of the spe- lattice of minerals. During heating electrons absorb cific radiation induced paramagnetic substances thermal energy and pass from the excited to basic by the EPR spectroscopy method (Documented state emitting photons. The intensity of lumines- testing procedure PB SLINZ 02 edition 1); cence at a chosen temperature interval is compared - food containing silicate minerals (spices, herbs, with the luminescence of the same sample subject- fruits, vegetables): Qualitative analysis of silicate ed to reirradiation with a standard dose of gamma minerals for the presence of radiation induced radiation (usually 1 kGy). The value obtained from centres detected by the thermoluminescence relation of these two TL measurements is taken as measurement method (Documented testing pro- indication of irradiation, when it is higher than 0.5. cedure PB SLINZ 03 edition 1). When this value is lower than 0.1 the foodstuff has The accredited methods as well as other methods not been irradiated. When the intermediate values for the detection of irradiated food presently adapt- are obtained an additional evaluation, taking into ed in our Laboratory have been described in earlier consideration the shape of luminescence curve is to publications [1]. Here, we would like to point out to be made. Glow curves for unirradiated samples the highlights of the methods which have been ac- have peaks at higher temperature interval while credited. Food, containing paramagnetic species, that for irradiated ones have their peaks around characterised by the presence of unpaired electrons is 150-200°C. Before accreditation a comprehensive detected by electron paramagnetic resonance spec- investigation of thermoluminescence of irradiated trometry (EPR/ESR). Many years of investigations various herbs and spices has been made in this Lab- have shown that unpaired electrons are present in oratory [2). many stable components of irradiated foodstuffs such In the course of certification procedure the test- as bones, stones, dried fruits, spices etc. The high ing analyses of unirradiated and irradiated food- sensitivity of the method allowing the detection of stuffs have been performed according to the pro- 10"12 mol/sample and its reproducibility enables to cedures indicated above. The results obtained fully detect efficaciously a small concentration of para- confirmed the reliability of these methods and their magnetic centres in irradiated foodstuffs, being in the applicability for detecting whether a given food has 8 order of 10" mol per sample isolated for mea- been irradiated or not. surement. Detection of irradiation by EPR in all Recently in the Laboratory a new EPR spectro- kinds of meat containing bones, eggshells, fishbones meter MINI-10 has been installed addressed ex- and scales is based on finding in the analysed sample clusively to the accredited methods of the detection a characteristic singlet ga=2.003, g2=1.997 and of irradiated foods based on the EPR spectroscopy. AhpP=0.85 mT. In food containing cellulose, in turn, The purchase of the instrument was financed by the as, for example, nuts (husks), strawberries and some Foundation for Polish Science under the Agree- spices, detection of irradiation is based on finding in ment "SUBIN" No 13/99. the EPR signal a symmetrical triplet which has its centre at about gb=2.004-2.006 and the distance be- References tween the outer satellite peaks (g =2.020, gc=1.983) a [lJ.Stachowicz W., Burliriska G., Michalik J., Dziedzic-Goclaw- of 6.0 mT. The presence of these outer peaks in an ska A., Ostrowski K.: EPR spectroscopy for the detection of EPR signal is taken as evidence that food has been foods treated with ionising radiation. In: Detection Methods irradiated. Such peaks have never been found in for Irradiated Foods. The Royal Society of Chemistry, Spe- non-irradiated samples. cial Publication No.171,1996, pp. 23-32. [2]. Malec-Czechowska K., Dancewicz A.M., Szot Z.: Nukleo- In foodstuffs containing silicate minerals (as in- nika, 41,67-76 (1996). herent components or admixtures) irradiation can

DETECTION OF IRRADIATED FOODS WITH THE USE OF GAS CHROMATOGRAPHY - EXPERIMENTS WITH POULTRY CARCASSES ^= IgI Katarzyna Lehner, Wadaw Stachowicz, Kazimiera Malec-Czechowska, Antoni M. Dancewicz, Zbigniew Szot i o The treatment of foodstuffs, which contain fats, with ! O detected in fairly large quantities: hydrocarbons ionising radiation induces a series of chemical chan- which have one C atom less than the original fatty ges. These changes cannot be classified as radiation- acid (Cp.i) and those which have two C atoms less -specific since they also appear in oxidation pro- and an additional double bond in 1-position (C,,.2:i). cesses. There is, however, a preferential cleavage of The main fatty acids of chicken carcasses, pork and certain chemical bonds in triglycerides when treated beef are palmitic acid, stearic acid, oleic acid and li- with ionising radiation. Among others two types of noleic acid. After the treatment, the following radia- volatile hydrocarbons produced in this matter can be tion induced hydrocarbons appear in abundance (a) RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 49 Cn.i: 15:0,17:0,8-17:1, 6,9-17:2 and (b) 0,-2:1:1-14:1, lution, while as exterior one the solution of 11 1-16:1, 1,7-16:2, 1,7,10-16:3. The presence in abun- adequately selected hydrocarbons in hexane were dance of these hydrocarbons in the examined sample applied. The gas chromatography examination was is a proof of its irradiation. The best method of the done with a capillary column PE-5 installed in a detection of hydrocarbons is gas chromatography. Perkin Elmer Model 8700 apparatus equipped with However, to be detected the volatile hydrocarbons a flame-ionisation detector. have to be separated beforehand from the sample. The results obtained show conclusively that in Firstly, it is necessary to separate fat from the sample the chicken carcasses irradiated with the doses of 3 and then to extract hydrocarbons in pentane or and 7 kGy the irradiation treatment has been hexane with a Florosil column. proved with a high level of certainty while in the In the present study, the experiments were done samples irradiated with 0.5 kGy the detection of with chicken carcasses purchased in the market. irradiation was not satisfactory. All the separation Each carcass was cut into four pieces. Three pieces and GC examination were proceeded in agreement were irradiated with doses of 0.5, 3 and 7 kGy, with the procedures recommended in BC EN 1784 respectively, while the fourth one remained nonir- standard. radiated. All the samples were examined in parallel. The aim of this study was to adapt the chemical Fats were separated at 50°C from the homogenised method of detection of irradiation in foods which samples, centrifuged for 10 minutes with 900 g contain fats, based on gas chromatography as a (1400 rot/min). A hydrocarbon fraction was sepa- routine analytical method for the use in the Labo- rated from the fat with hexane and then with the ratory for Detection of Irradiated Foods. The adap- Florosil column. 100 ml of each eluant was concen- tation will be proceeded by the accreditation of this trated to 0.25 ml and examined by gas chromato- method within the frames of existing Quality Assur- graphy. As interior standard haxane eikosan so- ance System.

DSC STUDIES OF GELATINIZATION AND AMYLOSE-LIPID COMPLEX DECOMPOSITION OCCURRING IN INITIAL AND GAMMA IRRADIATED WHEAT AND CORN STARCHES !§ Krystyna Ciesla, Ann-Charlotte Eliasson1/ II v Center of Chemistry and Chemical Engineering, University of Lund, Sweden ; o The course of gelatinization and amylose-lipid com- thermal effect, DSC studies were carried out during plex transition, occurring during heating of starch heating-cooling-heating cycles (up to 3 heating pro- and flour suspensions depends on the structure of cesses). DSC measurements were carried out in the starch granules. Therefore, decrease in order of temperature range 10-150°C at a heating and cooling starch granules [1, 2] and the possible changes in rates 10 and 2.5 °C/min for the suspensions at con- lipids surrounding, brought about by degradation centration of 20-25% (10 °/min) and 45-50% (10 and resulting from gamma irradiation was expected to 2.5 °C/min) closed hermetically in Al pans. A Seiko influence these processes. Our preliminary DSC DSC 6200 calorimeter with a cooling system installed studies of the processes occurring during the first in the University of Lund was used. heating of potato starch and wheat flour suspen- In the case of 20-25% concentrated starch sus- sions [3] showed the essential differences between pensions a single effect of gelatinization is ob- gelatinization occurring in the irradiated and non- served, while in the case of the suspensions at con- irradiated potato starch samples and of the ge- centration of 45-50% two gelatinization processes latinization and amylose-lipid complex transition occur (Fig.l, curves 1, 3). The phenomenon is con- taking place in the irradiated and nonirradiated nected with the existence of two types of ordered wheat flour. Significant differences between the regions in starch granules. Smaller values of en- maximum viscosities were also detected during thalpy were determined for gelatinization taking heating of water suspensions of nonirradiated and place in the irradiated samples in comparison with irradiated wheat and rye flour. The influence on the the process occurring in the nonirradiated sample results of the conditions applied in DSC experi- under the same condition, like in the case of potato ments (concentration of suspensions, heating rate) starch. Differences in the irradiation influence on appeared to be essential the gelatinization occurring in corn, wheat and po- At present, DSC studies were continued for pure tato starch were observed, caused by the differences samples of wheat and corn starches. Wheat and corn in granules ordering. starches (both Sigma products) were irradiated with Only gelatinization was observed during the first Co60 radiation applying a dose of 30 kGy with a dose heating of corn starch. It was stated that gelatiniza- rate of 3.62 kGy/Ti in a gamma cell Issledovatel in the tion occurs always at lower temperature in the case Department of Radiation Chemistry, INCT. With of the irradiated sample than in the nonirradiated the purpose of examination of the reversible amy- one under the same experimental conditions, con- lose-lipid complex transition, characterised by a weak trary to the results obtained for potato starch. For 50 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES example, in the case of the suspensions at a con- the case of the irradiated sample (Fig.2). Thermal centration of 20-25% heated at a rate of 10 °C/min, effects were broad and had diffuse limits, while the peak temperature was detected at 70.8 and narrow, sharp effects were recorded for the initial sample. Differences between the initial and the ir- radiated samples were better visible on cooling than

150 87.2° - 200 3v

«. 1/

0.0 ,.« \ r IE 79.2° i -200 r - r « Vy -400 1.40 20.0 40.0 60.0 80.0 100.0 120.C temperature, °C

100.0 Fig.l.The examples of DSC curves recorded for wheat starch 0.0 80.0 suspensions during the first heating of the suspensions temperature, °C having concentration 20-25% (curves 1, 2) at a rate of 10 °C/min and 45-50% at a rate of 2.5 °C/min (curves 3, 4) Fig.2. Comparison of the amylose-lipid transition exothermal ef- for the initial sample (1, 3) and the irradiated samples (2, fect, observed during the third cooling at a rate of 10 4). With the purpose of the clear data presentation, the °C/min of wheat starch suspensions: initial (21.84% of dry normalised heat flow values in curves 3 and 4 were multiply matter content, curve 1), irradiated (20.40% of dry matter by a factor of 5.5. The gelatinization enthalpies, equal to content, curve 2) (curves 3 and 4 present DDSC signal for 13.7, 10.7, 13.5 and J0.1 J/g, were determined on the basis the initial and the irradiated samples). The peak tem- of endothermal effects presented in curves 1, 2, 3 and 4, perature equal to 87.2 and to 79.2°C and the enthalpy value respectively. equal to -3.2 and -1.2 J/g were determined for the initial and irradiated wheat starch, respectively. 68.2°C in the case of the initial and irradiated sam- ples, respectively. The appropriate values of gelati- during heating and bigger in the case of suspensions nization enthalpy were equal to 18.0 and 16.6 J/g. at concentration of 20-25% than in the case of Amylose-lipid complex transition was noticed dense suspensions. These differences were also a during the first heating and subsequent heating and little larger during the subsequent than the first cooling cycles of wheat starch (Figs. 1 and 2), while cooling, due to the resulting, from thermal treat- the gelatinization process was observed only during ment decrease of temperature of transition occur- the first heating (Fig.l). Decrease of gelatinization ring in the irradiated starch and an increase of temperature after irradiation was stated in the case transition temperature in the initial starch. of the 20-25% of suspensions heated at a rate of 10 It was stated that retrogradation occurs in the °C/min, while similarly to potato starch, an increase case of the gelatinised irradiated wheat starch of gelatinization temperature was observed in the sample after 5 days. The process was not observed case of dense (45-50%) suspensions, both heated at in the case of reference sample of the initial wheat 10 and 2.5 °C/min (Fig.l). However, in contrary to starch, exposed to the same temperature treatment. potato starch, the increase of the height of thermal effect of the first gelatinization stage accompanied References by a decrease in the second, was noticed. [lJ.CieS'la K., Gwardys E., Zoltowski T.: Starch/Starke, 42, 251 The significant changes in amylose-lipid complex (1991). [2]. Cies"la K., ZoHowski T., Diduszko R.: Food Structure, 12,175 structure resulting from irradiation may be con- (1993). cluded on the basis of the present data. Amylose- [3], CieSla K., Svensson E., Eliasson A.-C: J. Thermal. Anal. -lipid complex transition accompanied by a smaller Calorim., 56,1197-1202 (1999). enthalpy was observed at a lower temperature in RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 51 DECONTAMINATION OF NATURAL HONEY BY IONIZING RADIATION Hanna B. Owczarczyk, Wqjciech Migdat, Bogdan Kedzia11//, Elzbieta Holderna-Kedzia1^ Danuta Madajczyk ' a/ Research Institute of Medicinal Plants, Poznan, Poland !S 21 Society of Apiculture, Poznan, Poland i sO Bee honey is usually contaminated with numerous The effects of irradiation on antibiotic activity !§ microorganisms. Among them predominate osmo- and 5-HMF content in the decontaminated honey phylic yeast, mainly the strains of Saccharomycetes, are given in Table 2. Schizosaccharomyces and Torula. Bacillus and anae- It has been observed that the antibiotic value in- robic Clostridium spores and small fragments of creased from 1.8 to 2.6 on an average and the con- mould fungi may also appear in honey. tent of 5-HMF decrease from 1.34 to 0.96 mg/100 g. Table 1. Effect of irradiation at a dose of 10 kGy on the number of microorganisms in honeys. Total number of aerobic bacteria Total number of yeast and moulds Total number of Clostridium spores No before irradiation after irradiation before irradiation after irradiation before irradiation after irradiation 1 11000 10 900 20 10 10 2 460 000 <10 <10 <10 10 000 1000 3 500 <10 <10 <10 100 000 10 4 50 10 10 <10 100 10 5 800 40 <10 <10 100 <10 6 60 <10 10 <10 100 <10 7 10 <10 10 <10 100 <10

The effect of radiatiation on microbiological de- Radiation at the dose of about 10 kGy decreases contamination of honeys is shown in Table 1. effectively the number of microorganisms and their Table 2. The effect of irradiation on antibiotic activity and 5-HMF content in the tested honey samples. Antibiotic activity Honey samples honey dilution inhibiting growth of standard strain S. aureus FDA 209 P inhibine value in units 5-HMF content [mg/lOOg] Before irradiation 1 1:4 1 1.15 2 1:8 2 1.15 3 1:8 2 0.96 After irradiation 1 1:16 3 1.15 2 1:16 3 0.86 3 1:8 2 0.86

The experiments have shown that the irradia- antibiotic activity and stability (5-HMF), while does tion process decreases the number of aerobic bac- not influence the organoleptic value of honeys. This teria and fungi (yeast and moulds) and anaerobic means that radiation treatment could be adapted in spores of Clostridium in honeys by 98.1% on an practice for the production of honey characterized average. by a high level of microbial purity.

DECONTAMINATION OF MEDICAL HERBS BY IONIZING RADIATION Wojciech Migdat, Hanna B. Owczarczyk A good quality of medical herbs, according to the The results show that the applied radiation me- 1° pharmaceutical requirements, may be achieved by thod to microbiological decontamination allows to !O applying suitable methods of decontamination. In achieve medical herbs of high purity. •S the communication, results of decontamination by Some of the pharmacological activities of medi- i O irradiating medical herbs are presented. Table 1 is cal herbs were investigated after irradiation (Table ! O presenting the effect of irradiation on a number of 2). microorganisms occurring in the medical herbs The diuretic action of Urogran and Betagran did tested. not change after irradiation. The spasmolytic action 52 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES

Table 1. Microbiological decontamination of medical herbs by irradiation at a dose of 10 kGy.

Aerobic bacteria Yeast and moulds Bacillus spores Materials OkGy 10 kGy OkGy 10 kGy OkGy 10 kGy Urogran 500 10 20 <10 50 <10 Reumogran 8 500 30 40 <10 4 400 <10 Normogran 102 000 40 <10 <10 47 000 <10 Cholegran 150 000 50 3 100 <10 76 000 <10 Betagran 70 000 70 30 <10 <10 <10

of Urogran, Normogran and Cholegran was the The tests carried out throughout this study have same in nonirradiated and irradiated medical herbs. indicated that the medical herbs show, after the ex- Irradiation of Normogran and Cholegran has no posure to ionizing radiation, identical therapeuti- negative effect on the cholagogic action of these cally action as nonirradiated preparations. Table 2. Pharmacological tests adapted to qualify medical herbs.

Pharmacological activity Medical herbs digestion diuretic spasmolythic cholagogic antibacterial anti inflammatory improvement Urogran + + + Reumogran + Normogran + + Cholegran + + + + Betagran +

fitopreparations. Urogran and Cholegran are cha- The dose of 10 kGy assured a proper purity of racterized, after irradiation, by a slightly higher an- the investigated medical herbs. tibacterial activity as compared with nonirradiated ones.

APPLICATION OF RADIATION TO THE PRODUCTION OF BAITS TO CONTROL CRAWLING INSECTS IN THE URBAN AREA Wojciech Migdai, Ilanna B. Owczarczyk, Janusz Swif tostawski , Jacek Swi^toslawski 18 11 Best-Pest Co., Jaworzno, Poland ;o A bait is any substance used to entice or to allure trations to preserve bait from formulating period animals with a view to catching them. A bait formu- until radiation treatment (Table 2). lation typically consist of an active ingredient that is Materials and Method mixed with food which acts as an attractant. Pests The baits decontamination by radiation was are killed by ingesting a lethal dose of the toxicant carried out in this Institute. (addulticide and/or insect growth regulator). The baits were irradiated by an electron beam The use of baits to control the pest of vertebrates accelerator Elektronika (10 MeV, 10 kW) in the (rodents, birds) and insects (cockroaches, ants, dose range 3 to 15 kGy. termites, etc.) is a technique that is thousands of Dosimetry of the irradiation process was used to years old. The Romans used bulbs of red squill commissioning of the facility, validation of the plant mixed with foodstuffs to control rodents. A treatment procedures and process control. The ab- phosphorous paste bait was used to control co- sorbed dose was measured by a primary standard ckroaches in London as early as 1858. dosimeter, a water calorimeter, and by routine dosi- Baits are the fastest-growing product category in meters. the pest control industry, particularly baits for the The experiments were done with German cock- control of German cockroaches and Pharaoh's ants roaches (Blattella germanica) and Pharaoh's ants - the most ubiquitous urban pest insects. Examples (Monomorium Pharaonis L.). of bait formulations in the USA are shown in Table The quantity of German cockroaches in each 1. group (control and experimental) was 30 insects, Usage of food ingredients in baits requires precau- put into an aquarium without and with baits. The tions. Application of chemical substances as pre- experiments lasted for 34 hours, and deadliness of servatives is very often risky because of decreasing insects was observed. bait palatability for insects, especially Pharaoh's ants. The quantity of ants in each group was: 70 worker In Poland only sorbic acid is used at small concen- ants, 2 apterous females and 30 chrysalides. The RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 53 Table 1. Commercial baits for Pharaoh's ants and German cockroaches control. Trade name Active ingredient Manufacturer Propoxur 2% Bait Propoxur AgrEvo. Health Arthitrol Chloropyrifos Avitrol Coporation Amdro Fire Ant Bait Hydramethylnon American Cynamid Siege Gel Insecticide Hydramethylnon American Cynamid Siege Fire Ant Bait Hydramethylnon American Cynamid Baygon 2% Bait Propoxur Bayer Corporation Magnetic Roach Food 2000 Boric Acid Blue Diamond Manuf. Award Fenoxycarb Ciba Speciality Prod. Maxforce Small Roah Killer Bait Station Hydramethylnon The Clorox Company Maxforce Large Roach Killer bBit Station Hydramethylnon The Clorox Company Maxforce Roach Killer Bait Gel Hydramethylnon The Clorox Company Maxforce Ant Killer Bait Station Hydramethylnon The Clorox Company Maxforce Ant Killer Granular Bait Hydramethylnon The Clorox Company Maxforce FC Fipronil The Clorox Company Musca-Cide Bait Methomyl Farman Companies Fluoro Guard Ant Control Bait Sulfluramid FMC Corporation Alstar Roach Control Baits Sulfluramid FMC Corporation Niban-FG Boric Acid Nisus Corporation Niban Granular Bait Boric Acid Nisus Corporation Prentox Diazinon 5G Diazinon Prentiss INC. Prentoz Larva-Lur Trichlorofron Prentiss INC. PT 300 Avert Abamectin Whitmire Micro-Gen PT 310 Avert Abamectin Whitmire Micro-Gen PT 370 Ascent Abamectin Whitmire Micro-Gen Pro-Control dual Choice Ant Bait Sulfluramid Whitmire Micro-Gen

Faratox-B was applied to the experimental group of palatability of Cockroach Kill Gel was excellent ants instead of feed. The deadliness of the ants in after irradiation at a dose of 12 kGy. This means Table 2. Insecticidal baits manufactured in Poland. Preservation Trade name Active ingredient [%] Manufacturer chemical radiation FARATOX-B methoprene (0.5) Insect Control Baits yes yes COCKROACH KILL GEL Chlorpyrifos microenc. (0.4) Best Pest yes yes both the control and experimental groups was being that the radiation method allows to have substances observed every 7 days. of high purity and palatability and this method does Table 3. Palatability of the controlled insects in baits depending on the radiation dose.

Trade name _ Controlled insect Dose [kGy] Palatability grade after 1 week 1 year FARATOX-B Pharaoh's ant 0 good poor 3 excellent excellent 15 good good COCKROACH KILL German cockroach 0 excellent good GEL 12 excellent excellent 15 good good

Results not change properties of the investigated insecti- In Table 3 the effect of irradiation on the palata- cides. bility of baits is shown. References In conclusion, the present studies indicate that [l].Rust M.K., Owens J.M., Reierson D.A.: Understanding and the radiation method is excellent for the pre- Controlling the German Cockroach. Oxford University servation of insecticidal baits. The palatability of Press, 1995. Faratox-B improved at a dose of 3 kGy. The [2]. Pest Control Technology, May 1996, Part 2 of 2, pp. 36-39. 54 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES [3]. Pest Control Technology, January 1998, pp. 7-13. [4]. Boase C.J., Rupers V.: Proceedings of the 2nd International Conference on Insect Pests in the Urban Environment, July 1996, pp. 153-162. PL0002012

RADUTION EFFECTS IN PVC AND PVC COMPOSITIONS Barbara Swierz-Motysia1^ Zbigniew Zimek, Jerzy Bojarski, Grazyna Przybytniak, Jaroslaw Sadto Xl Industrial Chemistry Research Institute, Warszawa, Poland Exposure of plasticized PVC to ionizing radiation, Formulation I: e.g. gamma rays or electron beam, causes changes in - PVC, Polanvil S-70MS -100 wt. parts, physicochemical and biological properties of ma- - DEHP plus high molecular weight aromatic terial, as it is described in the literature [1-4]. The esters - 54 wt. parts, distinctly discoloration of PVC occurs at a typical - Stabilizer Ca/Zn - 2.5 wt. parts. sterilization dose of 25 kGy, the material tends to Formulation II: darken or to turn yellow. This process is autocataly- - PVC, Polanvil S-70MS -100 wt. parts, tic and continues after sterilization. During irradia- - DEHP - 54 wt. parts, tion of PVC the conjugated double bonds as well as - Stabilizer Ca/Zn plus costabilizer - 3.0 wt. parts. the significant quantities of hydrogen chloride are Sample preparation formed due to the oxidation of PVC resins. The A Stephan mixer was used to homogenize the polyene structure is responsible for discoloration of PVC powder with a plasticizer, a stabilizer and PVC compositions. Moreover, the cross-linking and other ingredients. The blends were heated up to chain scission reactions, that lead to changes in 100°C. The resulting compositions were granulated molecular weight and mechanical properties, are using a one-screw extruder at a temperature of possible [5]. 150/155/160°C and then the product was extruded Plasticized PVC requires several additives that into films of 0.5 mm thickness. can greatly influence the material behaviour during Irradiation of samples irradiation. All these ingredients, e.g. plasticizer, The stripes of film samples made of plasticized stabilizer, lubricant can be decomposed and may PVC were irradiated for evaluation of mechanical contaminate medical formulation with decreasing and physical properties and for Melt Flow Rate the biocompatibility of material [6, 7]. Several dif- examination. Irradiated samples in the form of ferent approaches have been made to improve ra- small rods were applied in EPR measurements. diation resistance of PVC compositions [8-12]. A Four samples of pure PVC powder were irradiated key idea is the creation of protective effect using as well. The irradiation was performed at room compounds which act as an energy transfer agent temperature using an electron beam from a linear without changing polymer properties such as orga- accelerator LAE 13/9 at a dose of 25 kGy and notin mercaptoacid esters, aromatic compounds gamma rays from a 60Co source Issledovatel with a with poly-membered rings, some fillers, dose of 30 kGy at 77 K. and compounds. Unfortunately, the Testing methods above mentioned compounds are toxic and cannot All tests were made simultaneously for samples be used for medical formulations. before irradiation, after irradiation, after irradia- Experimental tion and incubation for 120 h at 50°C. Suspension PVC The Melt Flow Rate test (MFR) was performed The PVC samples were industrial grade product using a Zwick plastometer model 4105 at 190°C powders with an average molecular weight, deter- with a 5 kg load. mined as K-70 and K-61, produced by "ANWIL" The PVC samples were investigated using a band S.A. Polanvil S-70SM medical grade, Polanvil S-70 EPR spectrometer. The measurements were per- general purpose, Polanvil S-61 general purpose and formed using the following parameters: scanned Vinnol H-70DF, were produced by Wacker GmbH. magnetic field - 20 mT, frequency of modulation - The radiation stability of PVC powders was coupl- 100 kHz and modulation amplitude - 0.2 mT for ed with thermal stability according to the Polish three different level of microwave power 0.02,1 and Standard PN-88/C-8929/13. The following PVC for- 100 m W. The measurements were performed at 77 mulation was used: PVC - 100 wt. parts, di-butyltin K. The measurements were repeated after 30 and 90 maleate - 3 wt. parts, stearic acid - 0.5 wt. parts. s from the removal of the samples from liquid nitro- Plasticized PVC gen and after reaching room temperature by the Commercial medical grade plasticized PVC for- samples. mulation contains a plasticizer - di(2-ethylhexyl Results and discussion phthalate) (DEHP), and and stabi- Suspension PVC lizers. Two series of PVC compositions containing Results of the EPR study of the y-irradiated a modified plasticizing system (Formulation I) and PVC suspension samples are collected in Figs.l and a modified stabilizing system (Formulation II) were 2 and Table 1. The EPR spectra of the irradiated prepared. PVC samples have shown the presence of alkyl and RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 55

Fig.l.EPR spectra of peroxy radical: a - Polanvil S-70SM; b Fig.2. EPR spectra of PVC Polanvil S-70SM: a - 1 hour; b - 24 Polanvii S-70; c - Polanvil S-61; d - Vinnol H-70DF. hours; c -148 hours after irradiation, respectively. allyl radicals. These radicals arc not stable and, at almost the same. The better earlier colour resis- room temperature in the presence of atmospheric tance is observed in the case of composition formu- oxygen, oxidation processes occur and two types of lation F-2. Table 2 shows the values of MFR index peroxy radicals A and B are formed. The EPR spec- composition vs. the dose of irradiation. It can be tra of peroxy radicals type A for all PVC samples seen from this Table that the melt viscosity of PVC Table 1. Peroxy radical concentration in the samples irradiated at room temperature. Relative radical concentration after irradiation [%] PVC samples 148 hours after 1 hour after irradiation 24 hours after irradiation irradiation Peroxy radical A Peroxy radical B Peroxy radical B Polanvil S-70MS 79 21 9.1 4.6 Polanvil S-70 74 26 9.6 4.8 Polanvil S-61 88 12 7.05 3.5 Vinnol H-70DF 78 29 8.8 5.5 are shown in Fig.l. The changes of peroxy radical composition does not change after the irradiation concentration in the irradiated PVC samples after dose of 25 kGy. The MFR index distinctly de- storage during 1, 24 and 148 hours, respectively are creased when the dose of irradiation increased to 50 listed in Table 1. As can be seen from this Table, Table 2. MFR index of plasticized composition F-l before and the peroxy radicals disappear in a short time. The after irradiation. EPR spectra of PVC - Polanvil S-70SM (Fig.2) MFR 190°C/5 kg Storage time Dose [kGy] after the same time of storage, also show a very [g/lOmin] [h] weak signal due to peroxy radicals. Moreover, it is 0 10.8 evident from these data that the type and intensity 2.5 10.1 of the degradation of all evaluated PVC samples are 25 9.33 24 comparable. 25 9.50 120 Plasticized PVC 50 4.24 24 The investigation of mechanical properties of 75 0.18 24 PVC compositions shows that an irradiation dose kGy. It is evident in this case that irradiation caused of 25 kGy does not affect the tensile strength and polymer degradation. elongation of both types of PVC compositions. The The obtained results indicate that the addition of determined values before and after irradiation are costabilizer leads to a better radiation resistance of 56 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES plasticized PVC composition than the modification References of the plasticizer system using DEHP together with [l].Zag6rski Z.P.: Melody sterylizacji polimerowych wyrobow a higher molecular weight plasticizer. medycznych. Materiaty Konferencyjne, Ustrort 09.1997. Conclusion [2], Minsker K.S., Kolesov S.V., Zaikov G.E.: Degradation and - The data obtained suggest that it is possible to Stabilization of Vinyl Chloride - Based Polymers. Pergamon Press, Oxford 1988. improve the ionizing radiation resistance of plas- [3]. Yagoui N. el a!.: J. Appl. Polym. Sci., 5_4,1043 (1994). ticized PVC meeting fundamental requirements [4].Naimian F., Katbab A.A., Nazokdast H.: Rad. Phys. Chem., for medical material via the change of the com- 44, 6, 567 (1994). position formulation. [5]. Varshney L. et a!.: Radiat. Phys. Chem., 42,649 (1996). [6]. Hong K.Z.: Poly(vinyl chloride) in medical and packaging - The additional costabilizer imparted a more sig- applications, ANTEC'95. nificantly improved radiation resistance of PVC [7], Chengyun Qi et al.: Radiat. Phys. Chem., 42, 591 (1993). composition than did the modified plasticizer [8j. Luther D.W.: Improvement of gamma radiation resistance. system. ANTEC'95. [9]. Patent USA 4 839 233,1989. - No changes occur in the mechanical properties [10]. Patent EU 0 281 649,1988. and melt viscosity of the plasticised PVC samples [11). Patent PE 111 829,1983. irradiated at a dose of 25 kGy [12]. Patent Jap. 3110-241.1988. This work was supported within the Polish State Committee for Scientific Research, grant 3 T09B 00815. RADIOCHEMISTRY

STABLE ISOTOPES NUCLEAR ANALYTICAL METHODS

CHEMISTRY IN GENERAL RAD1OCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 59 COMPARISON OF SAMARIUM AND YTTERBIUM ISOTOPE EFFECTS IN ACETATE/AMALGAM SEPARATION SYSTEM Wojciech Dembiriski, Marek Poninski, Rudolf Fiedler1' 11 International Atomic Energy Agency, Safeguards Analytical Laboratory, Seibersdorf, Austria i o Continuing our studies on the relation between the sumably for the same reason the even-odd and even- IS isotope effect and the isotope mass, we have frac- -even effects in a series of samarium are not so ex- ^8 tionated the samarium isotopes by means of the posed as in the ytterbium series; however a signifi- exchange reactions between acetate complexes of cant asymmetry in the position of 152Sm and 149Sm Sm(III) in the solution and Sm(0) in the amalgam: can be announced. H L L H Sm(Ac)3 + Sm(Hg) ** Sm(Ac)3 + Sm(Hg) Of interest is the difference in the behavior of the where H and L - heavier and lighter isotopes. lightest isotopes of both the elements: 168Yb and The chemical procedure of the fractionation was Sm. The value of separation gain of 168Yb was similar to those applied in our studies on the sepa- found to be unexpectedly high (18xlO'4) in respect to ration of the isotopes of ytterbium [1]. the separation gains of the heavier isotopes (Fig.2) The isotopic analysis was performed using a mass while the value of separation gain of 144Sm is close to spectrometer with a multicollector system (Finnigam MAT262). In order to eliminate the mass fractiona- 1.00 tion effect the method of total evaporation of the o.ao sample was applied [2]. The precision of the mea- I sured isotopic ratio was 0.07%(lSD) or better. 0.60 It was found that the light isotope of samarium, likewise the light isotopes of ytterbium, are frac- § Q4°- — — — tionated into the amalgam phase. The measured values of unit separation gains as <£ 0.20- a function of the isotope mass number are shown in < Fig.l. The unit separation gain is here defined as 0.00 4 *-> e= q-l«ln(q) m 149 m(l) 149 •0.20- — where q=( (')Sm/ Sm)Hg)/( Sm/ Sm)Ac and - — m(i) - the mass numbers: 144, 146, 147, 148, 150, 152,154. -0.40 167 168 169 170 171 172 173 174 175 176 177 Fig.2. Unit separation gains of Yb isotopes, sd is standard devia- tion of the mean. the mean of the series (Fig.l). It is to be noticed that the unexpectedly high value of separation gain was recently also revealed for the lightest stable isotope of gadolinium 152Gd. It was discovered in the course of isotope separation in the extraction system with dicyclohexano-18-crown-6 [4]. The unit mass separa- tion factor of 152Gd was found to be three times greater (3.15xlO3) than the mean for the heavier iso- 3 topes 154,156,158Gd ^ i.QxiO" ). This behavior arises probably from the unstable configuration of the neutron deficit nuclei 152Gd -015 and r68Yb. This is not the case for the lightest 143 144 145 146 147 148 149 160 151 152 153 154 155 isotope of samarium 144Sm because the shape and Fig.l.Unit separation gains of Sm isotopes, sd is standard devia- charge distribution of this nucleus is stabilized by tion of the mean. the magic number of neutrons equal to 82. The values of separation gain of samarium count- References ed per unit mass difference is, in general, lower than Sm [1], Dembiriski W., Poniriski M., Fidler R.: Sep. Sci. Techn., those of ytterbium: eu.m. was found to be in the 33(11), 1693(1998). A Yb range (Z.2-h3.8)xlO while the values of eu.m. for [2]. Fiedler R., Donohue D., Grabmueller G., Kurosawa A.: Int. the six isotopes from 170Yb to 176Yb was found to be J. Mass Spectrom. Ion Processes, 122, 207-205 (1994). in the range (4.9^-6.6)xlO"4 [3]. The difference may [3]. Dembiriski W., Poniriski M., Fidler R.: INCT Annual Raport 1998. INCT, Warszawa 1999, pp. 70-71. be taken as evidence for a strong screening effect [4]. Fuji T., Yamamoto T., Inagawa J., Gunji K., Watanabe K., arising from 4f-orbital electrons of samarium. Pre- Nishisawa K.: Sol. Extr. Ion Exch., H, 1219-1229 (1999). RADIOCHEM1STRY, STABLE ISOTOPES, 60 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL a-CRYSTALLINE POLYANTIMONIC ACID AS AN ADSORBENT FOR RADIOSTRONTIUM AND ACTINIDES(IH), AND AS A PRIMARY BARRIER IN WASTE REPOSITORIES Aleksander Bilewicz, Jadwiga Krejzler, Jerzy Narbutt !O CM Engineered barriers filled with inorganic ion ex- We measured the radioactivities of the original and io changers which strongly adsorb radioactive metal equilibrated solutions obtained in batch processes io 3+ : O ions are common components of multibarrier sys- [4]. Eu ions of somewhat lower affinity to CAA tems preventing migration of long-lived radionuc- than that of Am3+ [4j were used as an appropriate lides from nuclear waste repositories to the envi- model for the latter. ronment [1]. 137Cs, 90Sr and long-lived actinides The Kd values of both Sr2"1" and Eu3+ ions de- belong to the most troublesome radionuclides often crease with increasing concentrations of Na+ and met in nuclear wastes. The waste managment tech- Ca2+ ions and with increasing acidity of the solu- nology used in Poland consits in the precipitation tion [3,4]. In the presence of Ca2+ ions, adsorption of radionuclides from liquid waste prior to cemen- of Sr is much worse than that of Eu3+ (Fig.l), tation: radiocaesium with copper hexaferrocyanate and radiostrontium with sulphate [2]. The -loaded precipitates, after being immo- bilized in the matrices of Portland cement, act as a primary barrier in nuclear waste repositories. The aim of this work was to study the possibility cn of applying other potential backfill materials in this o primary barrier. Particularly required are still more effective sorbents of radiostrontium and trivalent actinides from liquid waste which is commonly a neutral aqueous solution containing various inorga- nic salts and chelating agents. A number of multi- -3 -2.5 -2 -1.5 -1 -0.5 valent metal antimonates and a-crystalline poly- antimonic acid (CAA) were synthesized and studied log [H2C2O4] as adsorbents of these radionuclides; the CAA Fig.2. Adsorption of radionuclides of Sr2+ and Eu3+ on CAA being selected as the most promising [3], CAA is an from 0.01 mol dm CaCl2 solutions after precipitating 2+ ion exchanger highly effective towards metal cations Ca ions with oxalic acid (H2C2O4) of a given concen- which have radii in the range of about 95 to 120 pm, tration. + 2+ 2+ 3+ i.e. Na , Ca , Sr , Am , etc. [4]. However, and begining from about 10"2 mol dm"3 CaCl2 con- + CAA is a poor adsorbent for the Cs ions [3, 4]. centration it is too low to use CAA for practical Adsorption and leaching properties of CAA purposes. Fig.2 shows that precipitation of calcium towards microamounts of and oxalate with an excess of oxalic acid from 0.01 mol were investigated at room temperature, using dm"3 CaCh solution, followed by filtering off the standard grains of 0.1-0.3 mm size. The distribution precipitate, significantly enhances adsorption of ratios (Kd, cm3 g"1) of 85Sr and 152'154Eu radiotracers Sr2+ ions, as well as that of Eu3+ which copreci- were calculated as the ratio of specific radioactivity of pitate with CaC2C>4. In the absence of Ca2+ ions, the solid sorbent to that of solution at equilibrium. oxalate ions at moderate concentrations only slight- ly affect adsorption of Sr2+ and Eu3+ ions on CAA [3]. Adsorption of 85Sr2+ on CAA (0.1-0.3 mm grains) was also studied in the column process. Be- cause the column bed (0=4 mm, h=35 mm) clogged in the course of normal run, we used a reverse run with the solution passing the column from the bottom to the top. The composition of the solution resembled that of most common liquid radioactive waste treated at the Department of Radioactive Waste Management (DRWM) of the Institute of Atomic Energy at 6wierk. The dilute aqueous solu- tion contained the following components: EDTA (45 ppm), oxalic acid (50 ppm), citric acid (50 ppm), 3 3 CaCl2 (0.1 g dm" ), Na2SO4 (1 g dm" ), KOH (1 g 3 -4 -3 -2 -1 dm" ) [5]. Under these conditions calcium sulphate and oxalate precipitated and were filtered off. EDTA and citric acid at the above concentrations exert log [CaCI2] 2+ Fig.l.The effect of CaCl2 concentration on the adsorption of rather a small effect on the adsorption of Sr and Sr2+ and Eu3+ ions on CAA. Eu3+ ions on CAA, except for the system Eu3+ - RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 61 EDTA [3]. The column process was studied at two CAA was by nine times smaller than that leached different flow rates: 4 and 2 m h'J, i.e. 114 and 57 bed from encapsulated barium sulphate (this tech- volumes (BV) per hour. The decontamination factor nology is used in the DRWM [2]), and by 35 times (DF) of the effluent varied between 20 and 50 until smaller than that leached from the encapsulated the breakthrough of the column (DF>10%) was mixture of the used inorganic salts and chelating reached. That was observed at more than 2000 and agents without any sorbent. An admixture of calc- 4800 BV for the two flow rates, respectively. With a ium oxalate to CAA increases the leachability of longer column (h=70 mm) the DF value incresed to radiostrontium from the cement matrix. 85 about 170 (99.4% Sr removed). Further increase in In summary, a-crystalline polyantimonic acid ap- the column length and a decrease in the flow rate pears to be a very effective adsorbent for radio- should enhance both the decontamination and the strontium and trivalent actinides from common amount of the purified effluent. This is particularly 3+ 3+ liquid radioactive wastes. After encapsulation in the important in the case of Eu (Am ) ions whose matrix of Portland cement it can serve as an ef- sorption kinetics on CAA is much slower than that of 2+ fective primary barrier in waste repositories. Sr [3], The work was financed from the Polish Govern- To study leachability of radiostrontium from ment Programme SPR 4-4b. CAA as the primary barrier in waste repositories, the CAA samples loaded with 85Sr were encapsu- References lated in the matrix of Portland cement (30% CAA, [l].Jedinakova-Kfizov;S V.: J. Radioanai. Nucl. Chem., 222, 13 (1998). 70% cement) according to the technology used in [2].Tomczak W., Cholerzyriski W.: Bezpieczeristwo Jadrowe i the DRWM [5] and leached for a total of 112 days Ochrona Radiologiczna, 22, 3 (1995). with distilled water changed at increasing time [3], Satyanarayana J., Bilewicz A., Narbutt J.: Nukleonika, 42, intervals. The leaching rate and the total activity 531 (1998). [4]. Bilewicz A.: Radiochim. Acta, £9_, 137 (1995). leached from the CAA samples appeared much [5]. Tomczak W. (Institute of Atomic Energy, Swierk): personal lower than those found for the other system information. studied. In particular, the 85Sr activity leached from PL0002015 ADSORPTION OF RADIOSTRONTIUM AND ACTINIDE(HI) IONS ON A NOVEL ADSORBENT APATITE II Jadwiga Krejzler, Jerzy Narbutt Multibarrier systems which prevent migration of neered barriers in nuclear waste repositories. Ad- long-lived radionuclides from nuclear waste reposi- sorption and leaching properties of Apatite II tories to the environment usually include various towards microamounts of radionuclides of , inorganic ion exchangers which strongly adsorb ions strontium, europium(III) and (HI) were of radioactive metals [1]. The most troublesome investigated at room temperature, using the apatite radionuclides often met in nuclear wastes are 137Cs, grains of size 0.1-0.3 mm. The distribution ratios 90Sr and very long-lived isotopes of transplutonium (K

ELECTRON CONFIGURATION AND RELATIVISTIC EFFECTS IN d ELECTRON ELEMENTS [CO Jo Slawomir Siekierski •CM iO i O Unique properties of such as its yellow colour, [1-6]. The unique properties of gold are commonly !O noble character and high electron affinity attract attributed to stabilisation of its 6s shell, but dif- since a long time attention of many workers and ferent views have been presented as to the origin of have been discussed in a number of papers, e.g. in this stabilisation. Taking into account all presented RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 63 arguments one can presume that stabilisation of 6s electrons in the third transition series is a result of three factors. The first may be the direct relativistic effect, the second the shell-structure effect, and the third the relativistic expansion of 4/ and 5d shells. However, Desclaux calculations [7] show that the maximum in the ratio of relativistic to non-relativis- tic orbital energies at gold is not merely a culmina- tion in a steady increase of £(rel)/£(n-rel) across the 5d series but that gold and platinum behave excep- tionally. This strongly suggests that an additional factor, not taken into account till now, is respon- sible for the abrupt increase in £(rel)/£(n-rel) at Au and Pt. Therefore, the objective of this paper was to look for other examples of a local maximum in the e(rel)/e(n-rel) ratio for valence s electrons and to Ln HI Ti W Re Of Ir Pt correlate its appearance with the number of elec- Fig.2. Relativistic and non-relativistic 6s orbital energies in 5d trons in the s and d shells. The relativistic orbital elements. energies and the ratio £(rel)/£(n-rel) used in this less negative than the interpolated values for the work were taken from the Desclaux Tables [7]. hypothetical Sd8^2 and 5d96s2 configurations. The Fig.l shows the £(rel)/£(n-rel) ratio for 6s elec- increase in the 6s orbital energy in Pt and Au is the trons in 5d elements. In Fig.l one can see smooth, effect of two opposite tendencies. On the one hand almost a linear increase in f(rel)/£(n-rel) from Lu the lack of repulsion between electrons in the 6s to Ir and an abrupt increase at Pt and Au, the only shell makes the orbital energy more negative, on elements in the third transition series with the s the other the increased number of d electrons re- sults in increased shielding of the nucleus, which makes the orbital energy of the 6s electron less ne- gative. Apparently, the second factor predominates. We can also see from Fig.2 that the energy dif- ference between the 5dn+W and the hypothetical 5dn6s2 configuration for Pt and Au is smaller in the relativistic than in the non-relativistic case. This is because relativistic expansion reduces the screen- ing ability of 5d electrons, increasing thereby the effective nuclear charge experienced by the 6s valence electron. It is evident that the distinctly smaller relativistic than non-relativistic difference between the 5dn+16sl and the hypothetical 5dn6s2 configuration and the relative position of the two plots in Fig.2 must result in a greater £(rel)/e(n-rel) ratio for Pt and Au. Inspection of the relativistic Fig.l. Changes in f(rel)/£(n-rel) for 6s electrons in 5d elements. and non-relativistic energies of s orbitals in 3d and n+ 1 configuration. Similar plot for 3d elements shows a Ad elements with the d h configuration shows local maximum in £(rel)/£(n-rel) at Cr and at Cu the same pattern as that found for 5d elements, but which also have the s1 configuration. In the second with a much smaller difference between the two transition series Ag shares the high £(rel)/£(n-rel) energies. It is interesting to notice that according to ratio with Nb, Mo, Ru and Rh which all have the s* Desclaux data [7] the maximum at Pt and Au in the configuration. These results could suggest that the e(rel)/e(n-rel) ratio for the 6s electron propagates £(rel)/fi(n-rel) ratio may directly depend on the down the atom core, and can be found in 5p, 5d, 4/ number of electrons in the s shell. However, a more orbitals (for both j values) and even in the deeply plausible explanations is that the £(rel)/£(n-rel) lying 4s orbital. ratio is greater for the dn+1s1 than for the dns2 configuration, i.e. when the nuclear attraction, as References seen by the s electron, is more efficiently screened [lj.Bagus P.S, Lee Y.S., Pitzer K.S.: Chem. Phys. Lett., 22, 408 by the inner d electron than by the second s elec- (1975). [2]. Pyykko P.: Adv. Quantum Chem., 11, 353 (1978). tron. This view is supported by changes in the [3]. Pyykko P., Desclaux J.P.: Ace. Chem. Res., 12, 276 (1979). configuration of relativistic and non-relativistic 6s [4]. Pyykko P.: Chem. Rev., fig, 563 (1988). orbital energies for 5d elements (Fig.2). We can see [5]. Seth M., Dolg M., Fulde P., Schwerdtfeger P.: J. Am. Chem. in Fig.2 that both relativistic and non-relativistic Soc., 112, 6597 (1995). [6]. Kaltsoyannis N.: J. Chem. Soc., Trans., 1 (1997). energies of the 6s electron in Pt and Au are much [7J. Desclaux J.P.: At. Data Nucl. Data Tables, 12, 311 (1973). RADIOCHEMISTRY, STABLE ISOTOPES, 64 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL THE NEW VALUES OF IONIC RADII OF Rf4+, Db5+ AND Sg6+ Aleksander Bilewicz The knowledge of accurate values of ionic radii O (IR) is necessary to determine such important ther- modynamic functions of ions as enthalpy and en- !8 tropy of hydration, standard electrode potentials, etc. Ionic radii are usually obtained from X-ray dif- fraction data for oxides or fluorides. Unfortunately, elements heavier than are produced in non-weighable amounts, so that the experimental structural data for these elements are not available. Until now, experimental ionic radii of transacti- nides have not been reported. In order to plan experiments with transactinides and to interpret the results, accurate thermodynamic functions based on ionic radii have to be known. Some procedures make it possible to predict ionic radii of ions in cases where experimental measurements are diffi- Fig. The ionic radius as a function of the 2j + l weighted expecta- cult or impossible. Commonly used calculations of 4 + 2 . ionic radii based on the correlation between IR and tion radius for group 4 elements. Because the IR values density in the outermost p orbitals due to the of Rf*+ and Db5+ calculated in this work are significant splitting olp orbitals into p\n and/>3/2. almost the same as those of their congeners in rows Electrons in the p\fr orbital are more strongly 5 and 6, one can also expect the properties of ionic bonded than in the ^3/2 orbital and therefore Rmax compounds e.g. oxides or fluorides to be very si- forpi/2 is smaller than Rmax for/73/2. As a result the milar. However, there are experimental and calcula- cloud of the p electrons is more diffuse and is shift- tion data [1,2] showing that in some cases Rf4"1" and ed toward the nucleus. In particular, the electron Db5+ behave more like much larger pseudohomo- charge density at RmaxP3/2 becomes smaller than at logous Th4+ and Pa5+ than their congeners in rows Rmax P in the absence of splitting, so that ligands 5 and 6. This indicates that not only ionic radius is can penetrate deeper into the outermost shell of responsible for complexation and hydrolysis of the cation. As a result the metal-ligand distance de- transactinides. The promotion energy may also be creases and the IR/Rmax ratio for heavy cations an important factor. becomes smaller than for their lighter analogs. Using a linear extrapolation procedure with 2j + l References weighted expectation radii, [lJ.Strub E., Bruchle, Eichlcr R., Gaggeler H.W., Glatz J.P., Grund A., Gartner M., Jager E., Jost D., Kirbach U., Kratz 4 2 J.V., Kronenberg A., Li Z., Nahler A., Nagane Y., Schadel = M., Schausten B., Schimpf E., Schumann D., Thorle P., instead of Rmaxn,P3/2> new values of IR for Rf4"1", Tsukada K., Tiirler A., Zauner S.: Fluoride complcxation of 5+ + . Proceedings of the 1st International Con- Db and Sg° were calculated. These IR values ference on the Chemistry and Physics of the Transactinide are 75 pm instead of 79 pm for Rf4+, 67 pm instead Elements, Seeheim, Germany, 1999. of 74 pm for Db5+ and 64 pm for Sg6+. Fig. [2]. Pershina V.: Radiochim. Acta, 80, 65 (1998).

STEREOCHEMICAL CHARACTER OF s2 LONE PAIR IN Bi3+ AQUA CATION Barbara Wtodzimirska, Aleksander Bilewicz The inert pair effect is characteristic for the p block ciation and hydrolysis. However, Suganuma, Ono elements. Lone electron pair can either be an sz pair and Hataye [3] found only the mononuclear com- + n + or occupy one of the hybrid orbitals. In the case of plexes Bi(H2O)^ and Bi(OH)n(H2O)^Tn ) in Bi3+ the lone pair character depends on the ligand. aqueous solutions with ultratrace concentrations of In fluorides and oxides the lone pair is stereoche- Bi3+. Radioisotope methods with 212Bi, which have mically inactive but in other complexes e.g. chlori- been applied in our studies, permit to study ex- des, bromides or tropolonates, the s2 pair occupies tremely diluted Bi3+ aqueous solutions at concen- the hybrid orbital [1]. According to Cotton and trations down to 10"15-1046 mol dm"3. Under these Wilkinson [2] there is no evidence for the existence conditions, the probability of collisions between 3+ 3+ of simple [Bi(H2O)n] ion. In aqueous perchlorate Bi ions is negligible, therefore, no polynuclear solutions, such species as Bi6Og+, [Bi6(OH)i2]6+ (III) ions are formed. The aim of our and [Bi6O6(OH)3]3+ are formed as a result of asso- studies was to explain the character of 6s2 lone pair RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 65 in the mononuclear aqua complexes of Bi3+ using mically inactive (6s-2 outermost shell) or when it the radiotracer technique. The^T2Bi (Ti/2=60 min) occupies the hybrid orbital and is stereochemically was obtained from 232U as one of the decay active (5d10 outermost shell). For a comparison, the products. Separation of 212Bi from 232U and other distribution coefficient of Sb3+, a homolog of Bi3+ decay products was performed in a two-step pro- in the Group 15, has been determined. As shown in

0,007 0,009 0,011 0,013 0,015 0,017 0,019 1

Fig. The distribution coefficient of 3+ cations on a strong acidic resin Dowex 50x4 as a function of the radius of the outermost shell. In the case of Bi and Sb both ns2 and (n-l)d' outermost orbitals are taken into account. cedure. In the first step 224Ra was eluted by 0.1 mol Fig., the Kd value for Bi3+ fits well to the straight 3 2 dm' HNO3 from an HDEHP-teflon column loaded line drawn for trivalent cations only when the 6s with 232U. In the second step 212Bi was separated shell radius is considered. In the case of Sb3+, K calculated by Desclaux [4J. The nl [2]. Cotton F.A., Wilkinson G., Murillo C.A.. Bochmann M.: Ad- subscript denotes the outermost completely filled vanced Inorganic Chemistry. Sixth Edition. John Wiley & shell in the cation. Two hypothetical cases have been Sons, Inc., 1999, p. 395. 2 3+ [3]. Suganuma R, Ono K, Hataye I.: Radiochim. Acta, 51,5 (1990). considered, when 6s lone pair of Bi is stereoche- [4], Desclaux J.P.: Atom Data Nucl. Data, 12, 311 (1973).

PECULIARITIES OF THE AQUEOUS RARE EARTH FLUORIDE SYSTEMS Tomasz Mioduski The aqueous solubilities of rare earth(III) fluorides, thermic, and the solubility at 1=0 and at pH 5 stead- 6 3 i O reported in 35 source papers, have been compiled ily increases from 9.65xlO" mol • dm" (pK§p=20) for JO 5 3 and critically evaluated [1]. A total disagreement, LaF3xl/2H2O to 2.61xlO" mol •dm" (pK§p=16.9) ;o illustrated in Fig., reaching for LaF3 thirteen pKsp for LuF3Xl/2H2O. units, and concerning even a general trend vs. A quasi- behaviour of Y(III) in the lanthanide atomic number (an increase, decrease, L11F3-H2O system is explained in terms of the ne- constancy or irregular solubility variations reported), phelauxetic effect within the Ln(III) series. This a sign of the dissolution enthalpy, and the actual effect in minutely less pronounced in the fluoride nature of final solid phases, have been overcome. It environment of the crystal lattice than in the aqua has been concluded that for the hemihydrate solid ions for the same coordination number (CN) 8 of phases of the normalized mode of preparation, par- heavy Ln(III) and Y(III) in both phases. ticle size, analogous thermal and equilibration treat- The solubility of fluoride is at least ment, the dissolution of rare earth fluorides is endo- 4 3xlO" moldm-3 (pK§P=12.7). The much higher RADIOCHEMISTRY, STABLE ISOTOPES, 66 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL [5], and sulphates [6-9]. From the practical view- point, these data are of use, e.g., for chemical pro- cessing technology of rare earths, and for treatment of radioactive wastes containing lanthanide and yttrium fission products (the second and first hump of the fission yield curve, respectively), and acti- nides as well. From the theoretical viewpoint, of in- terest is, e.g., the dissolution thermodynamics [8,9], the double-double (tetrad) effect [10, 11], CN in the Lnfcj", An|| [7] and Lnf^j", An|^ aqua ions [10], not to mention the "nomadic behaviour" (a Therald Moeller term) of the lanthanide(III) series, with respect to Y(III) (and Sc(III)) [2, 12]. The latter phenomenon is caused by a minute participation of the 4f-electrons in bonding which depends on li- gand surroundings. In addition, for Sc(III), which does not always stand apart from other rare earths, these are its CN changes vs. those for lantha- La Cs Pr Nd Pm Sm Eu (3d Tb Oy YHo Er Tm Yb LPI nides(III) which are crucial [2,12]. This report on the paper [1] covers the aqueous Fig. Plots of the pKsp values [1] vs. reciprocal ionic radius, 1/r, systems of rare earth trifluorides which are among which was measured in the crystal lattice of L11F3, viz, hexa- the most insoluble salts. The rare earth fluorides, gonal in the La-Nd range (CN 9), and orthorhombic (CN 8) in the Pm-Lu range and Y. except being extensively employed as fluoride-selec- tive electrodes, are investigated for laser, magnetic solubility of SCF3 than that of L11F3 is an indication and optical devices, and in view of an increase in Tc that the scandium aqua ion is [Sc(OH2)6]aq' of CN of the high temperature superconductors. 6, and not 7 [2, 3]. It appears that the CN 7 is cha- racteristic for the dimerized hydrolysis product of References Sclq* even at pH 2-3: [1 j. Mioduski T.: Pecularities of the aqueous rare earth fluoride 2[Sc(OH )6]aq~~ (CN 6) systems. Comments Inorg. Chem., in press. 2 [2]. Mioduski T.: Comments Inorg. Chem., 14,263 (1993). + [(H2O)5Sc^-OH)2Sc(OH2)5]aq (CN 7) 2Ha+ [3j. Cotton S.A.: Comments Inorg. Chem., 21,165 (1999). In the above binuclear cation, scandium(III) [4]. Siekierski S., Mioduski T., Salomon M.: Scandium, Yttrium, must display the d^sp3 hybridization of the empty- Lanthanum and Lanthanide Nitrates. Pergamon Press, Oxford, New York, Toronto etc. 1983. IUPAC SD Series, -acceptor orbitals, related to the pentagonal bipyra- Vol. 13, 490 p. mid arrangement of 7 oxygen donor atoms forming [5]. Mioduski T., Salomon M.: Scandium, Yttrium, Lanthanum la bonds of which 5 are situated in the equatorial and Lanthanide Halides in Nonaqueous Solvents, Pergamon Press, Oxford, New York, Toronto etc. 1985. IUPAC SD plane (Csn). This somewhat exceptional for rare earths hydrolysis of the small and highly charged Series, Vol. 22,390 p. 3+ [6]. Rard J.A.: J. Soln. Chem., 12, 499 (1988). Sc ion, even in weakly acidic solutions, is a pre- [7]. Mioduski T.: Comments Inorg. Chem., 12,231 (1997). sumed reason of some controversies over the Sc|^" [8]. Mioduski T.: Chem. Anal. (Warsaw), 43,457 (1998). aqua ion [1-3]. [9], Mioduski T.: J. Therm. Anal. Calorim., 51,751 (1999). [10]. Mioduski T.: Comments Inorg. Chem., 12, 93 (1997). In a series of publications, concerning the so- [llj.Fidelis I., Mioduski T.: Structure and Bonding, 42. 27 lubility of rare earth salts, framed for the IUPAC (1981). Commission V.8., we elaborated the respective data [12]. Silber H.B., Mioduski T.: Inorg. Chem., 21,1577 (1984). on the nitrates [4], halides in nonaqueous solvents

DETERMINATION OF SOME PRECIOUS METALS IN GEOLOGICAL AND ENVIRONMENTAL SAMPLES BY RADIOCHEMICAL NEUTRON ACTIVATION ANALYSIS USING CHELEX 100 ION EXCHANGE RESIN

; CM Zbigniew Samczynski, Bozena Danko, Rajmund Dybczynski •o io ! O Palladium, platinum and gold together with other few methods can assure reliable determination of precious metals belong to the group of the most dif- noble metals at trace and ultratrace concentrations, ficult elements in analytical chemistry [1-7]. The namely AAS, ICP-AES [1, 2, 4], NAA [1-4, 8-12] reason for this is complexity of their chemistry, pos- and recently ICP-MS [12-15]. Most of these me- sibility of existing in solution in two oxidation thods require preconcentration and isolation of the states, great ability of forming complexes with many analyzed elements. In the case of NAA the presence ligands, susceptibility to hydrolysis, sorption, copre- of other elements, both macro- and microcon- cipitation etc. [5-7]. Despite of great progress in the stituents in analyzed material strongly interferes field of modern analytical techniques, still only a with the quantitative determination of palladium RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 67 and platinum by the instrumental version of NAA. radioactive tracers) in the systems: hydrochloric Radiochemical separation of Pd and Pt after acid solutions (0.01-10 mol I"1), pH buffer solutions irradiation is difficult due to radiation hazards, so (pH 3-9) and ammonia solutions (0.01-10 mol I"1) in many cases the only possibility is the isolation of and Chellex 100 resin (18]. The above investiga- Pd and Pt from the sample before neutron irradia- tions revealed that it should be possible to separate tion. Gold, because of much higher neutron activa- palladium, platinum and gold from many accom- tion cross section, as well as longer half-life and panying elements and then from each other. Series higher y energy of its radioisotope 198Au, can be of column experiments were performed and their determined by INAA. However, when performing results fully confirmed the above expectations. This pre-irradiation isolation the detection limit of this enabled devising a two ion exchange separation element can be distinctly improved. For this reason procedure, based on stepwise elution. The first step the elaborated separation procedure, apart from Pd (Fig.l) is intended for the pre-irradiation isolation and Pt, was also intended for Au. of palladium, platinum and gold from the sample of Ion exchange is one the most often used separa- analyzed material. The second step (Fig.2) is rea- tion methods in analytical chemistry [1, 3, 16-19] lized after neutron activation and its aim is to sepa- and play a very important role in radiochemical rate both Pd and Pt from some accompanying trace NAA [1, 3,19]. elements (including 199Au, a daughter of short Preliminary studies on the possibility of use of lived platinum isotope - 199Pt) and from each other Chelex 100, a commercially available ion exchange as well. resin, for the separation of palladium, platinum and The final shape of the whole analytical method gold from the elements typical for environmental for the determination of Pd, Pt and Au, in which matrices were carried out in 1998. In this year, the the separation process is an essential component, is effort has been made to modify the ion exchange presented in Fig.3. The microwave technique used

3

O Cu, Co. Cd. ZD Cr. Fe. In. fla.

Ni. Pb. Mn. Br 0.0 100 200 330 400 990 1000 volume of effluent, drops (drop volume = 0.031' ml) Fig.l. Isolation of Pd, Pt and Au using Chelex 100 ion exchanger resin before neutron activation. Column: 5.0 cm x 0.0707 cm2 Chelex 100 (200-400 mesh); flow rate: 1.5-2.0 cm min"1; temperature 25°C. procedure to be viable for the determination of Pd, for sample digestion assured effective decomposi- Pt and Au in geological and environmental ma- tion of the analyzed materials. The conversion into terials by radiochemical NAA. Chelex 100 is an a fully soluble form - a very difficult analytical task - organic ion exchanger containing weakly acidic was successfully achieved. iminodiacetic functional groups of strong chelating The use of Chelex 100 results in a very selective properties, forming chelate complexes with numer- isolation of gold, hence the radiochemical separa- ous metal cations. In acidic solutions, these groups tion is not necessary and direct measurement of (due to protonation) become weakly basic ammo- 198Au, by gamma-ray spectrometry is possible. The nium groups capable of retaining anions. Hence, chemical yields of the separation procedure for Pd, Chelex 100 has an amphoteric character and its ion Pt and Au, assigned on the basis of many tracer exchange function is affected by acidity of the ex- experiments, amounted to: Pd: 99.0% ±1.0% for ternal solution. Pd, 95.3% ±2.2% for Pt and 94.5% ±3.1% for Au. In order to investigate the potential separation Analytical results were accordingly corrected for possibilities, ion exchange behaviour of palladium, the chemical yield. platinum and gold together with other elements The accuracy of the elaborated method was test- was studied (batch equilibration technique using ed by determining palladium, platinum and gold in RADIOCHBMISTRY, STABLE ISOTOPES, 68 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL

acetote t>j

traces of: Ir, Mo. 2.0- Sb. Ag. W. Cr C iracet of: Ir. Jte. 3 Sb. Ag. Br

(races of: , ar b I.9- Na. Fe. Cr Mo Yf, Br lv r +j o a

o.o 930 1000 volume of effluent, drops (drop volume = 0.037 ml) Fig.2. Separation of Pd, Pt and Au using Chelex 100 ion exchanger resin before neutron activation. Column: 5.0 cm x 0.0707 cm* Chelex 100 (200-400 mesh); flow rate: 1.5-2.0 cm min"1; temperature 25°C. two available reference materials: SARM-7 of geo- certified for noble metals content. The results of logical and PTC-1 of industrial origin, which are quantitative determinations (Table) show good

dfgaatton of Minpla with equa r~jla (HNO, + 3 HCI) + HF uniafl micrawov* technique

removing of SIOj with HF, •vaporoUon with cone. HCI, diiaoMlon In O-5M HCI

Column: Q.12B cm> K 15.0 cm; Chain WQ[H'] (2aO-+OO m«h)

0.BU HCI HC1 0.1M NH4C1 J. Pd, Pt Cu, Mi, MB., Cr, Fe, Pb, •voparatran to dry Co, Al, CB, concentration, tranvfcrlng dlaaolutlon In O.5M HCI Kg, KB, K into o quartz ampoule. evapor«tlan to drynen Column: 0.071am* x A anx Chalan 100 [H *] (200-400 m—h)

rwutron activation drying Df ion exchanger with lorbed traces of Au, iran*1mr\nq Into PE vllMl

rln«tng of th» ompoula nautron actuation w!th HNO, + 3 HCI, (»-1O*nom-'«-', t-Jh) •vaporatlon wfth oonc. HCI, I diatoMion in 0^M HCI

Column: 0.128 cm" x 15.0 cm; Cholsx 1TJ0(H*] <2O0-4O0 meih)

D.5K aoattt* BH HCI O.eU(MH|)|C6 HCI baffar + ZU HCI J,

NB, Fe. Pd Cr. Mo, ¥, Br Pt

Fig.3. Flow sheet of the analytical procedure for determination of I'd, Pt and Au in geological and industrial materials by NAA. RAD10CHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 69 Table. Results of Pd, Pt and Au determination in the certified reference materials. Certified value and its Results of individual Arithmetic mean* and Relative standard Certified Reference Element confidence limits determinations its confidence limits deviation Material 1 1 1 (rag kg" ] [mgkg- ] [mgkg- ] [%] Pd SARM-7 1.530+0.032 1.50 1.49+0.09 4.0 (1.498-1.562) 1.43 1.47 1.57 PTC-1 12.7 12.2 11.9+0.6 3.2 (12.0-13.0) 12.2 11.9 11.4 Pt SARM-7 3.740±0.045 3.40 3.74+0.49** 8.3 (3.695-3.785) 3.57 3.93 4.07 3.55 3.74±0.60"» 10.1 3.48 3.63 4.30 PTC-1 3.0±0.2 2.96 2.86+0.43** 9.4 (2.8-3.2) 3.18 2.58 2.70

2.95 3.00±0.31»" 6.5 3.28 2.94 2.83 Au SARM-7 0.310±0.015 0.293 0.300±0.058 12.2 (0.295-0.325) 0.342 0.254 0.310 PTC-1 0.65+0.10 0.790 0.649 ±0.188 18.2 (0.55-0.75) 0.504 0.670 0.630 * Results are presented as: x+to 05 "7—. where: x - arithmetic mean, s - standard deviation, to 05 - parameter of t for significance level a=0.05. Vn *• results obtained on the basis of1 'Pt radionuclide. *** results obtained on the basis of ^"AU radionuclide. agreement with the certified values, which indicates [5] Balcerzak M.: Analyst, 122,67R-74R (1997). the absence of systematic errors. The standard de- [6]. Livigstone S.E.: The Chemistry of , . Palladium, , , and Platinum. Pergamon Press, viations values reflect both complexity of chemical Oxford 1973. properties of the analytes and the analyzed matrix. [7]. Puddephatt R.J.: The Chemistry of Gold. Elsevier, Amster- The obtained detection limits (calculated according dam 1978. to Rogers [20] were as follows: 0.5 fig kg"1 for Au, 9 [8].Dybczynski R., Majchrzak J., Stokowska H., Szyszko H.: fig kg'* for Pd, 41 fig kg"1 (via 197Pt) and 19 jug kg"1 Chem. Anal. (Warsaw), 3,5,609-625 (1990). l99 [9].Zmijewska W., Polkowska-Motrenko H.: Chem. Anal. (via Au). Gamma ray spectra of palladium and (Warsaw), 3J&, 211-219 (1993). platinum fractions show a good radiochemical puri- [10]. Parry S., Asif M., Sinclair I.: J. Radioanal. Nucl. Chem.,122, ty. Only minutes activities of , , 2,593-606(1988). , and were observed. [ll].Lahiri S., Nayak D. Naddy M., Das N.R.: Radiochim. Acta, 7J, 35-37 (1996). Gold fraction was of high radiochemical purity. [12]. Li C, Chai C, Mao X., Ouyang H.: Fresenius J. Anal. Chem., 363, 602-605 (1999). References [13]. Chen Z., Fryer B., Longerich H., Jackson S.: J. Anal. Atom. [1]. Lobirtski R., Marczenko Z.: Spectrochemical Trace Analysis Spectrom., 11,805-809 (1996). for Metals and Metalloids. In: Wilson & Wilson's Compre- [14].Coedo A., Dorado M., Padila I., Alguacil F.: Anal. Chim. hensive Analytical Chemistry. Ed. S.G. Weber. Elsevier, Acta, 24Q,31-40(1997). Amsterdam 1997. [15]..Tarvis J.,Totland M., JarvisK.: Analyst, 122,19-26(1997). [2]. Beamish F.E., Van Loon J.C.: Analysis of Noble Metals. [16]. Marhol M.: Ion Exchangers in Analytical Chemistry'. Academic Press, New York 1977. Academia Prague 1982. [3]. Minczewski J., Chwastowska X, Dybczyrtski R.: Separation [17], Ion Exchangers. Ed. K. Dorfner. W. de Gruyter, New York and Preconcentration Methods in Inorganic Trace Ana- 1991. lysis. E. Horwood, Chichester 1982. [18].Samczyrtski Z., Dybczyrtski R.: J. Chromatogr. A, 789 [4].Ginzburg S.I., Ezerskaya N.A., Prokof'eva I.V., Fedorenko 157-167(1997). N.F., Shlenskaya V.I., Belskii N.K.: Analytical Chemistry of [19]. Dybczynski R.: J. Chromatogr., 6_0_0_, 17-36 (1992). Platinum Metals. Nauka, Moscow 1972. [20]. Rogers V.C.: Anal. Chem., 42, 837 (1970). RADIOCHEMISTRY, STABLE ISOTOPES, 70 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL MODIFICATION OF ARSENIC, ANTIMONY AND BISMUTH BY PALLADIUM AND MAGNESIUM IN ELECTROTHERMAL ATOMIC ABSORPTION SPECTROMETRY Leon Pszonicki, Jakub Dudek

Palladium became popular as a very versatile modi- tion of palladium chloride to elemental palladium fier. It was applied to the determination of arsenic and free chlorine (about 500°C). This suggests that [1], antimony [2] and bismuth [3]. Welz and co- the evolved chlorine forms with arsenic the volatile -workers [4-6] suggested improving activity of the chloride, which is lost during the pyrolysis stage. palladium modifier by using a mixture with magnes- The observed losses of arsenic can be removed by ium nitrate. Qiao and Jackson [7] showed that addi- the use of the mixed palladium-magnesium modi- tion of magnesium nitrate causes a homogeneous fier or only a magnesium nitrate modifier. The fact distribution of palladium and the analyte in the that magnesium alone is an equally good modifier as form of small droplets in the centre of the platform. the palladium-magnesium mixture indicates that it These results suggest the physical nature of the acti- works by itself. The suggestion of some workers that vity of magnesium used in a mixed modifier. On the its role is limited to supporting the palladium activity other hand, the application of magnesium nitrate [7] seems to be only marginally correct. The protec- individually as modifier for the determination of tion of arsenic against its losses during the evapora- many elements in sea-water [8] and a comparison of tion of the sample solution containing a large excess its activity with that of palladium and palladium- of hydrochloric acid indicates that magnesium forms -magnesium mixture suggests that its chemical acti- with arsenic a compound (probably magnesium ar- vity should be also taken into account and its modi- senite) already in the solution. This compound is fying properties should be considered. resistant to hydrochloric acid and later, during the In general, one still observes many inconsistencies pyrolysis stage, it is transformed into a more re- in the description of modifier effects. The mechanism fractory form (probably mixed magnesium arsenic of their action is usually unknown and seldom dis- oxide) that is resistant to chlorine gas evolved in the cussed. Most observations have a purely empirical decomposition of palladium chloride. character and concern a given element, a given type The behaviour of antimony is similar to that of of sample or given atomisation conditions. There- arsenic, with one exception. Without modifiers it is fore, they are hardly transferable to other analytical stable at a low temperature in hydrochloric acid systems. The aim of these studies was to test syste- medium. This suggests that antimony exists in both matically the behaviour of arsenic, antimony and media in the form of antimonous acid. In nitric acid bismuth during atomisation in a graphite tube with a the addition of palladium stabilises it up to 1000°C. platform in the presence of palladium, magnesium Addition of palladium to hydrochloric acid solution and mixed palladium-magnesium modifiers. The ef- causes significant losses of antimony at tempera- fect of nitric, hydrochloric and perchloric acid and tures above 400°C. The observed interferences may their mixtures was also tested. Although the inves- be removed by the use of either magnesium nitrate tigated analyte elements belong to the same group of or mixed palladium-magnesium modifier. the periodic system it was found that their behaviour The effect of the investigated modifiers on in the presence of modifiers is differentiated. bismuth is radically different from their effects on Palladium is a very good modifier for arsenic arsenic and antimony. Bismuth without modifiers is only in nitric acid solution. In hydrochloric acid so- stable during pyrolysis up to 600°C. Palladium add- lution arsenic is present in the form of chloride and ed to the nitric acid solution stabilises it up to is lost almost completely already during the drying above 1100°C. Addition of palladium to hydrochlo- stage below 200°C. Addition of the palladium mo- ric acid solution causes losses of bismuth in the difier (in the chloride form) does not improve the range between 400 and 600°C, similarly as it was situation, indicating that palladium in hydrochloric observed for antimony. For bismuth, however, the acid is not able to form any stable compound with atomisation peaks are very badly shaped and irre- arsenic at low temperatures. The situation becomes producible. Exactly the same phenomenon is ob- much more complex when arsenic is in a mixed served for mixed nitric-hydrochloric acid solution. solution of nitric and hydrochloric acid. In this Unlike arsenic and antimony, the application of the solution arsenic is partially transformed into the mixed palladium-magnesium modifier or magnes- chloride and lost during the evaporation and drying ium nitrate alone for bismuth does not improve the of the sample below 200°C. The residue is in the situation. This indicates that magnesium, present in form of arsenic acid and the thermal stability of the system,, does not work as a trap for free chlorine arsenic is typical for this compound. An unexpected atoms. It is able to protect against chlorinating only phenomenon occurs when the palladium modifier is these elements with which it forms the chemical added to the mixed solution. Instead of stabilisation compounds resistant to chlorine. of the measured arsenic signals at higher tempera- The effect of perchloric acid on the investigated tures, one observes their significant suppression. system is ithe same as that of hydrochloric acid. This effect is particularly large above 400°C what More exact information on the presented investi- corresponds to the temperature of the decomposi- gation maybe found in our publication [9]. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 71

References [6]. Welz B., Schlemmer G., Mudakavi J.R.: J. Anal. At. Spec- trom., 2, 1257 (1992). [lJ.Shan X.-Q., Ni Z.-M, Zhang L.: Anal. Chim. Acta, 151, 179 [7]. Qiao H., Jakson K.W.: Spectrochim. Acta, Part B, 46, 1841 (1983). (1991). [2], Shan X.-Q., Ni Z.-M.: Acta Chim. Sin., 22, 575 (1981). [8]. Bermejo-Barrera P., Moreda-Pineiro J., Moreda-Pineiro A., [3]. Jin L.-Z., Ni Z.-M.: Can. J. Spectrosc, 26, 219 (1981). Bermejo-Barrera A.,: J. Anal. At. Spectrom., 13, 777 (1998). [4], Welz B., Schlemmer G., Mudakavi J.R.: J. Anal. At. Spec- [9]. Pszonicki L., Dudek J.: J. Anal. At. Spectrom., 14,1755 (1999). trom., 2,93 (1988). [5], Welz B., Schlemmer G., Mudakavi J.R.: J. Anal. At. Spec- trom., 2,695 (1988).

BEHAVIOUR OF SELENIUM AND TELLURIUM IN THE PRESENCE OF MODIFIERS IN ELECTROTHERMAL ATOMIC ABSORPTION SPECTROMETRY Leon Pszonicki, Witold Skwara Selenium and tellurium are volatile and, therefore, transformed selenium-palladium compounds are their thermal stabilisation by suitable modifiers also resistant to chlorine gas which is evolved during the pyrolysis stage of the atomization pro- during the decomposition of palladium chloride at cess is neccessary. Among the proposed modifiers about 450°C. palladium and its mixture with magnesium belong An identical effect to that of palladium is ob- to those used most frequently [1-7]. Subsequent served in the presence of mixed palladium-magne- investigations indicated, however, that palladium sium modifier or magnesium nitrate. There is only applied individually may accelerate, under some one reservation for magnesium added alone as mo- conditions, the loss of analyte during the pyrolysis difier to hydrochloric acid solution. It must be used stage [8, 9]. It was also found that the effect of the in the nitrate form, and preferably, an additional application of the mixed palladium-magnesium mo- amount of nitrate ion should be present in the solu- difier was identical with that of magnesium alone, tion. It works correctly only as the nitrate and this at least for arsenic and antimony [9]. requires the presence of a sufficient, but relatively The above-mentioned information indicates small in comparison with other anions, quantity of that, although palladium and palladium-magnesium nitrate ions. A similar observation was made re- are very versatile modifiers, the mechanism of their cently for arsenic and antimony [9]. activity may be very different in various media and A much more complex situation occurs when in relation to various analytes, even if they belong palladium modifier is used for selenium in the to the same group of the periodic table. All these mixed nitric-hydrochloric acid solution. Losses of facts should always be taken into account, otherwise almost all the selenium are already observed during a serious analytical error may result. Since very evaporation of the sample solution below 100°C. complex effects of palladium, magnesium and their Since selenium forms with palladium thermally sta- mixture on arsenic, antimony and bismuth dissolved ble compounds in nitric and hydrochloric acids, the in various media have been reported [9], we con- observed losses of selenium must be caused by sidered it important to investigate the behaviour of reactions occurring only in the mixture of both selenium and tellurium in the presence of these acids. The explanation of this phenomenon is that modifiers. Nitric, hydrochloric and perchloric acids in the last phase of sample evaporation the two and their mixtures were chosen as the tested media acids form a concentrated mixture, similar in com- because they are mainly used for dissolution or position to aqua regia. This mixture evolves free mineralization of analytical samples. chlorine atoms, which attack either selenious acid We found that in acid solutions, similarly as in or its compound with palladium forming very vola- neutral aqueous solutions, selenium without modi- tile selenium chloride. It should be emphasized that fiers is already volatile during the evaporation of even a small amount of hydrochloric acid added to the sample and during the drying stage of the ato- the selenium solution in nitric acid containing mization process. At a temperature of 300°C it is palladium modifier, and vice versa, causes very lost completely. Addition of palladium modifier, in large losses of selenium. An effect, similar to that in the form of nitrate into nitric acid solution and in mixed nitric-hydrochloric acid medium, occurs the form, of chloride into hydrochloric acid solu- when selenium is dissolved in perchloric acid or in tion, stabilizes selenium up to 1200°C. This indi- its mixture with nitric acid. In both cases the losses cates that selenium in the solution of both acids is of selenium can be completely eliminated by the in the form of selenious acid which forms with application of magnesium or a magnesium-pallad- palladium non-volatile palladium selenite. With an ium mixture. increase of temperature it is transformed into a The behaviour of tellurium is significantly differ- more refractory form, probably mixed palladium- ent from that of selenium and results from the -selenium oxides or PdxSey compounds. The fact lower volatility of tellurium compounds. Tellurium that selenium is stable during pyrolysis in the dissolved in nitric acid solution or in the mixed presence of palladium chloride indicates that these nitric-hydrochloric acid medium is thermally stable RADIOCHEMISTRY, STABLE ISOTOPES, 72 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERA!.. without modifiers up to 700°C. In hydrochloric acid haviour of magnesium nitrate applied individually solution, however, about 40% of tellurium is al- is different. It stabilizes tellurium in nitric acid as ready lost at low temperature and the residue is well as in all the other media mentioned only up to stable only up to 500°C. This results, probably, 800°C and it must be considered, as a modifier for from the fact that tellurous acid decomposes at tellurium determination, much worse than pallad- 40°C and the formed hydrated oxide is transformed ium. It seems also that when the mixed modifier is in the hydrochloric acid medium into volatile used, magnesium does not play any role in the sta- chlorides or oxychlorides. When nitric acid is added bilization of tellurium. to this solution, tellurium is kept in the form of a More exact information on the presented inves- hydrated oxide and, therefore, its thermal stability tigation may be found in our publication [10], is the same as in nitric acid. References Addition of palladium (nitrate or chloride) sta- bilizes tellurium, dissolved nol only in nitric acid [1]. Garcia-Olalla C, Alter AX: Anal. Chim. Acta,25_2,295 (1992). (2].Torgov V.G., Demidova M.G., Kosolapov A.D.: Zh. Anal. but also in hydrochloric and perchloric acids and in Khim.,5J, 846(1988). the mixtures of these acids with nitric acid, up to [3]. Radziuk B., Thomassen Y.: J. Anal. At. Spectrom., 7, 397 1200°C. The experiments carried out do not allow (1992). to give a reason for the stability of tellurium in the [4]. Fox G.: At. Spectrosc, 11,13 (1990). |5]. Ursinyova M., Hladikova M.: Chem., Listy, 22, 495 (1998). presence of palladium when it is evaporated from [6], Welz B., Schlemmer G., Mudakavi J.R.: J. Anal. At. the mixed nitric-hydrochloric acid solution. The Spectrom., 2, 1257 (1992). answer to this question, however, is not important [7], Shine M.Y., Chan Y.C., Mierzwa J., Yang, M.H.: J. Anal. from the point of view of the application of pallad- At. Spectrom., 14,69 (1999). [8]. Pszonicki L., Essed A.M.: Chem. Anal., 3£, 759 (1993). ium as a modifier. [9], Pszonicki L., Dudek J.: J. Anal. At. Spectrom., 14, 1755 The mixed palladium-magnesium nitrate modi- (1999). fier is effective in exactly the same way as palladium {10]. Pszonicki L., Skwara W.: J. Anal. At. Spectrom., 14, 1925 alone in all the media discussed above. The be- (1999).

APPLICATION OF A CHELATING 2-MERCAPTOBENZOTHIAZOLE LOADED RESIN TO THE SEPARATION OF INORGANIC AND ALKYLMERCURY SPECIES IN NATURAL WATERS Jadwiga Chwastowska, Adrianna Rogowska, Elzbieta Sterliriska belongs to the toxic, dangerous for human spectrometry in the conditions thoroughly de- health elements, whose toxicity depends to a high scribed previously [1,2]. degree on its chemical form. Inorganic compounds The accuracy of the method was checked on the of mercury(II) and its methyl derivatives are ad- basis of the artificially prepared test water samples mitted as particularly dangerous. The admissible containing main components present in natural concentrations of individual forms of mercury in waters and known amounts of inorganic, methyl and natural waters are usually below the determination ethylmercury. The accuracy of the method was found limit of the most commonly used analytical tech- to be correct (recovery 98.0-99.0%) and the precision niqes. Therefore mercury is usually separated from may be considered as satisfactory (Sr=7.0-8.0%). the analysed sample and preconcentrated before The lower limit of determination for the ela- determination. borated method was estimated as 10 ng I"1 for the In the present work for the preliminary separa- water sample volume equal to 11. tion and concentration of inorganic and aikylmer- Table. Determination of mercury in natural waters. cury species a new chelating sorbent: 2-mercapto- 1 benzothiazol immobilized on the acrylic resin Sample n Hg^tngr ] Sr[%l Bio-Beads SM-7 (MBT-BB) was applied. The in- River water 9 35.7 8.2 vestigation of Hg retention on the MBT-BB sor- bent by the batch method as a function of the Ground water 4 <10 acidity of solution show that in the range of pH Examples of the determination of mercury in values 1 to 4 the efficiency of sorption is equal to river and ground waters are presented in Table. Tne 98%. The value of pH 3 was considered as optimal. examples are limited to the determination of in- In these conditions methyl and ethylcompounds of organic mercury only, since we could not find the mercury were also adsorbed with a similar effi- natural samples of water containing detectable ciency. amounts of alkylmercury. Desorption was carried out using a 5% thiourea solution in 0.05M hydrochloric acid. Both the forms References of preconcentrated inorganic mercury and alkyl- [1]. Magos L.: Analyst, 26,847-853 (1971). mercury, were determined sequentially from the [2]. Chwastowska J., Skwara W., Sterlinska E., Dudek J., Pszo- same solution by cold vapour atomic absorption nicki L.: Chem. Anal. (Warsaw), 43, 995-1002 (1998). RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 73 SORPTION OF HEAVY METALS ON HYDROXYAPATITES. PART 2 Jadwiga Chwastowska Monika Sadowska-Bratek Elzbieta Sterlinska In the previous year the sorption of Cu, Cd, Ni, Pb calculated from the difference in the amounts of and Zn on hydroxyapatite obtained by the sol-gel metal in the solution before and after the sorption. method [1] was investigated [2]. In the last year the The results are shown in Fig., as the depedence of investigations of sorption were continued. We want- percentage of sorption on the pH of solution before ed to test the possibility of sorption of the three- sorption. The pH of the solution after sorption in- -valuable elements and also anionic forms of ele- creases probably owing to the partial solubility of ments. Then the sorption of the following metals hydroxyapatite. It can be seen that the retention of was investigated: Bi(III), Fe(III), Al(III), Mn(II), the most elements studied is about 94-100% in the Mn(VII), Cr(III), Cr(VI), Sb(III), Sb(V), As(III), most suitable acidity range. Ions MnC>4~ show low As(V) and Mo(VI). retention - a maximum about 47% from 1M H2SO4 The influence of pH on the sorption of these solution. Some difficulties occurred in the tests of elements were studied by the batch method in the sorption. It appeared that some amounts following conditions: 0.5 g of the hydroxyapatite of aluminium occur in the composition of hydroxy-

ull Fig. Retention of elements from solution of various initial pH values. and 100-200 ng of each element in 20 ml of solu- apatite and in the acid solution (pH<3) this alu- tion, adjusted to a suitable acidity, was shaken for minium is soluble. For this reason the sorption of 30 min in a separatory funnel on a mechanical aluminium could be investigated in the pH>3 range. shaker. Then the solution was filtred off and the The results obtained confirm cation- and anion- element studied was determined in the solution by -exchange properties of hydroxyapatite. The sorp- atomic absorption spectromelry or by the spectro- tion of Cr(VI), which is present in the solution as photometry method. The retention of metal was anions and Sb(V), As(V) and Mo(VI), which have RADIOCHEMISTRY, STABLE ISOTOPES, 74 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL amphoteric character with predominance of acidic ditions established (pH 5, flow rate 2 ml min"1, properties, can exhibit the anion-exchange mecha- sample volume 100 ml, 1 g hydroxyapatite) all the nism of sorption process. metals studied were separated quantitatively. The cation sorption mechanism was investigated In conclusion it can be stated that: by determining calcium released in the sorption - Synthetic hydroxyapatite obtained by the sol-gel process of copper and . In the most published method offers the possibility of separation of works on the hydroxyapatite sorption the molar various cations and anions. ratios of calcium released lo divalent cation sorbed - In contrast to the previously reported hydroxy- is close to 1, suggesting the cation-exchange mecha- apatites the kinetic sorption is very good (the nism [3]. Our results confirm rather a mixed mecha- equilibrium of sorption is obtained in a few mi- nism: cation-exchange with the predominance of nutes). surface adsorption and, may be, solid diffusion, - The retention capacity is rather not high (3 mg which is suggested in some literature data [4-6]. Cu/1 g) from the viewpoint of possible applica- The fraction of hydroxyapatite (~200 mesh) tion of hydroxyapatite, for instance, to sewage separated by sedimentation was used to establish the treatment and as a filter material. sorption conditions by the kinetic method. Copper was selected as an example of metals studied and the References influence of flow rate and sample volume on the [l].Deptula A., Lada W., Olczak T., Borello A., Alvani C, Di sorption efficiency was determined. The process of Bartolomeo A.: J. Noncryst. Solids, 147-148, 537-541 (1992). [2], Chwastowska J., Sterlinska E., Sadowska-Bralek M.: INCT sorption was realized under pressure in a glass Annual Report 1998. INCT, Warszawa 1999, p. 96. column (0.5 mm i.d.) filled with 0.5-1 g of hydroxy- [3]. Suzuki T., Hatsushika T., Hayakawa Y.: J. Chem. Soc. apatite. It was found that a flow rate up to 2.5 ml Faraday Trans., 22,1059-1062 (1981). min1 and a sample volume up to 200 ml do not [4], Reichert J., Binner J.G.P.: J. Mat. Sci., 21,1231-1241 (1996). deteriorate the efficiency of copper sorption. [5], Jeanjean J., Fedoroff M., Faverjon F., Vincent U., Corset J.: J. Mat. Sci., 21, 6156-6160 (1996). The sorption of group metals (Cu, Cd, Pb, Ni, [6]. Xu Y., Schwartz F.W., Trains S.J.: Environ. Sci. Techno]., 2£, Co, Mn) from the artificially prepared test water by 1472-1476(1994). the dynamic method was also studied. In the con-

DETERMINATION OF TRANSITION METALS BY ION CHROMATOGRAPHY Krzysztof Kulisa, Ilalina Polkowska-Motrenko, Rajmund Dybczynski Ion chromatography is a modern analytical tech- suited for separation of Cu2+, Ni2+, Zn2+, Co2+, nique for the fast determination of trace quantities Mn2+, Fe3+ and also allows speciation and quanti- of ionic species (anions and cations) in aqueous tation of Fe3+ and Fe2+. Since the ferrous cation is samples, in particular in those of environmental easily oxidized to the ferric one, oxygen must be origin [1-6]. The ability to analyze transition metals removed from the eluant by degassing. The second by ion chromatography is a unique tool utilizing one is an oxalic acid based eluant which is a mode- ion-exchange resins, a post-column reactor with rate strength complexing agent and separates the PAR as a post-column complexing reagent and metals by a mixed mode mechanism, both as cat- UV/VIS detection. The following discussion will ionic and anionic complexes. The oxalate eluant focus on procedures involved in setting up the separates Pb2+, Cd2+, Cu2+, Ni2+, Zn2+ and series of Dionex 2000i ion chromatograph for tran- Co2+. and coelute with this sition metals analysis and selection of parameters to eluant. achieve the best chromatographic results. The possibility of transition metal cations deter- The Ion Pac CS5 analytical column is designed mination has been tested using the Dionex 2000i/SP specifically for rapid and sensitive determination of system with an Ion Pac CS5 analytical column, an transition metals in a wide variety of matrices. Se- Ion Pac CG5 guard column and a post-column Ion parations are accomplished by interaction of the Pac Membrane Reactor. The following transition resin with pellicular cation and/or anion-exchange metal cations have been examined: Fe3+, Cu2+, functional groups and complexing eluents via cat- Ni2+, Zn2+, Co2+, Mn2+, Fe2+, Pb2+and Cd2+. ion and/or anion-exchange mechanisms. The ion- The cations were separated as anionic complexes -exchange capacity of Ion Pac CS5 is ISO/ieq/col of with the PDCA (2,6-pyridinedicarboxylic acid) che- sulfonic acid functional groups for cation-exchange lating agent. The composition of the eluent solu- and 70 ,ueq/col of alkanol quaternary ammonium tion used was: 6 mM PDCA+50 mM CH3COOH+ functional groups for anion-exchange. The versati- 50 mM CHsCOONa. Composition of the second lity of the Ion Pac CS5 analytical column makes it eluent used was: 50 mM oxalic acic+95 mM LiOH. possible to obtain two different separations simply The eluate has been introduced to the post-column by changing the eluant. The first one is a 2,6-pyri- reaction system with Ion Pac Membrane Reactor dinedicarboxylic acid (PDCA) eluant which is a where took place the converting to colour com- strong complexing agent and separates the metal plexes with PAR (4-(2-pyridylazo)resorcinoI) as a anionic complexes by anion exchange. PDCA is post-column complexing reagent in the following RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 75

004

003

0.02 AU 0.1 AU

0.0't

0.0 0.00

-001 • 1 «T I 1 r 1 1 10 20 5 15 Time, min Time, min Fig. 1. Separation of transition metals. Column Ion Pac CS5, Fig.3. Separation of lanthanides. Column Ion Pac CS5, eluent: 80 eluent: 50 mM oxalic acic + 95 mM LiOH. Peaks: 1 - mM oxalic acid + 150 mM LiOH. Peaks: 1 - La3 + (10 Pb2+(20 ppm), 2 - Cu2+(0.5 ppm), 3 - Cd2+(4 ppm), 4 - ppm), 2 - Ce3 + (10 ppm), 3 - Pr3+(10 ppm), 4 - Nd3+(10 Co2+(2 ppm), 5 - Zn2+(2 ppm), 6 - Ni2+(4 ppm). ppm). solution: 0.2 mM PAR + 1 M CH3COOH + 3 M the detection limits. All the eluent and standard NH4OH. Flow rate of the eluents was 1 ml min"1 solutions were prepared with the use of superpure and the post-column reagent flow rate was 0.7 ml water (18 M£2 • cm) which was obtained by a Milli - Q min"1. As a result of post-column reactions the RG ultra-pure water system (Millipore Co.) and de- coloured complexes of determined transition metal gassed with . cations were obtained and then detected by mea- Examples of chromatograms of the separated suring the absorbance at 520 nm applying a Dionex transition metal cations are presented in Figs.l and UV/VIS variable wavelength detector VDM II. 2. As one can see, the isocratic analytical separa- To obtain the desired detection limits, it is import- tions of the transition metals requires about twenty ant that the system blank, resulting from reagents, minutes using both the PDCA or oxalic acid based air, water etc. is very low (below 1 ppb). Generally, eluents. Detection limits and precision of determi- and zinc are the most common transition metal nations of transition metals were established. De- contaminants, while a small amount of copper may tection limits estimated, using the Small definition also be observed. Care must be taken to minimize [2], for the separated and determined transition reagent and sample contamination during prepara- tion and handling. Reagent purity will often dictate

003

OO2 AU

AU O.O1

0.00 0.0

• •Iflfllf r 0 5 10 T 20 Time, min Fig.4. Determination of transition metals in tap water sample. Time, min Column Ion Pac CS5, eluent: 6 mM PDCA + 50 mM Fig.2. Separation of transition metals. Column Ion Pac CS5, CH3COOH + 50 mM CH3COONa. Peaks: 1 - Fe3+, 2 - eluent: 6 mM PDCA + 50 mM CH3COOH + 50 mM Ni2+,3-Zn2+,4-Fe2+. CHiCOONa. Peaks: 1- Fe3+(5 ppm), 2 - Cu2+(1 ppm), 3 - Nj2^ ppm), 4 - Zn2+(4 ppm), 5 - Co2+(2 ppm), 6 - metals in standard solutions were as follows (in Mn2+(10 ppm), 7 - Fe2+ (5 ppm). ppm): Fe3+ - 0.01, Cu2+ - 0.008, Cd2+ - 0.04, Co2+ RADIOCHEMISTRY, STABLE ISOTOPES, 76 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL - 0.007, Zn2+ - 0.03, Ni2+ - 0.02, Mn2+- 0.04, Pb2+ and Zn2+ were determined with the precision (rela- - 0.08, Fe2+ - 0.02. tive standard deviation) better than 3% (Table). Some rare earths (La3+, Ce3+, Pr3+ and Nd3+) On the basis of obtained results it can be con- were separated and determined with the use of an cluded that the ion chromatograph Dionex 2000i/SP oxalic acid based eluent (80 mM oxalic acid + 150 equipped with Ion Pac CS5 analytical column and the mM LiOH), an Ion Pac CS5 column and the same post-column reaction system allows the separation as Table. Precision of chromatographic analysis of some transition cations in tap water sample. Results of single determinations, xj Arithmetic mean.x Standard deviation, s Relative standard deviation, Sr Cation 1 1 [mg-r ] [mg-r ] [mg-1-1] [%] 0.125 0.127 Fe3+ 0.121 0.126 0.006 2.38 0.126 0.129 0.321 0.331 Ni2+ 0.320 0.319 0.014 2.66 0.311 0.314 1.19 1.21 Zn2+ 1.16 1.196 0.023 1.92 1.22 1.20 0.064 0.061 Fe2+ 0.059 0.060 0.002 2.50 0.058 0.062 chromatographic system as for the transition me- well as accurate and precise determination of tran- tals. In aqueous solution, lanthanide metals are pre- sition and lanthanide metals with low detection sent as trivalent cations. The use of strong complex- limits in aqueous samples. ing agents such as oxalate results in the formation of anionic complexes of the lanthanide metals. References Under these conditions, the lanthanide series may [1]. Haddad P.R., Jackson P.E.: Ion Chromatography, Principles be separated by anion exchange mode. The chroma- and Applications. Elsevier, Amsterdam 1990. 3+ 3+ 3 3+ (2). Small H.: Ion Chromatography. Plenum Press, New York togram of separated La , Ce , Pr "*" and Nd is 1989. presented in Fig.3. Estimated detection limits for [3]. Weiss J.: Ion Chromatography. 2nd ed. VCH, Weinheim the lanthanides were as follows fin ppm): La3+ - 1995. 0.18, Ce3+ - 0.16, Pr3+ - 0.34, Nd3^ - 0.07. [4]. Small H., Stevens T.S., Bauman W.C.: Anal. Chem., £7, 1801 (1975). Analysis of the sample of tap water was per- [5]. Fortier E, Fritz J.S.: Talanta, 34,415 (1987). formed and the obtained chromatogram is pre- [6]. Rey M.A., Pohl C.A.: J. Chromatogr. A, 222,87 (1996). sented in Fig.4. The cations of Fe3+, Fe2+, Ni2+

EFFECT OF THE SAMPLE MINERALIZATION METHOD ON THE ACCURACY OF Co DETERMINATION IN PLANT MATERIALS IS Halina Polkowska-Motrenko, Bozena Danko, Rajmund Dybczynski 18 Many analytical methods for trace element deter- plete mineralization and may have an effect on both O mination, e.g. ICP/AES, GFAAS and electrochemi- preconcentration and measurement steps. As an cal methods, require decomposition of the material example the effect of mineralization prottdnre on to be analyzed. Great progress, which has been analytical result was investigated during the de- made in analytical instrumentation in the last two termination of cobalt in plant materials. Cobalt is decades, has been not accompanied by the develop- considered to be one of the so-called analytically ment of sample preparation methods. Hence, the difficult elements [1, 2]. Its content in biological sample preparation, when involved, has become the materials is generally lower than 1 pg g'1 [3-5]. step of analysis, which may strongly affect the un- The following methods of mineralization were certainty of the final result. This is especially im- investigated: portant in the determination of trace elements in - classical open wet digestion procedures with plant materials, because plant materials are, as a nitric, perchloric and hydrofluoric acids; rule, not homogeneous and usually contain various - closed-vessel microwave digestion with nitric mineral fractions. The commonly used sample de- acid followed by open-vessel decomposition with composition procedures do not always ensure com- perchloric and hydrofluoric acids; RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 77 - closed-vessel microwave digestion with nitric, hy- were found. Hence, they can be considered equi- drofluoric acids and hydrogen peroxide. valent. Good agreement of the results obtained by The studies were carried out using certified refe- the RNAA method with the microwave digestion rence materials (CRMs) of plant origin, most of step and the non-destructive INAA results was them certified for Co content. The cobalt content found. was determined using instrumental neutron acti- Losses of Co in the case of an incomplete vation analysis (INAA) and radiochemical neutron decomposition are due to a failure in converting the activation analysis (RNAA), because the nuclear analyte originally present in several chemical forms properties of Co enable its determination by both into a single form required for the applied pro- INAA and RNAA methods with excellent detection cedure. In the case of a plant material two kinds of limits (4 ng g"1 and 0.04 ng g"1 for INAA and compounds, mineral and organic, must be taken RNAA, respectively). Previously elaborated in our into account. The mineral fraction originates main- Laboratory the "definitive" method for the deter- ly from soil and is characterized by a high Si mination of Co traces in biological materials was content. This fraction is, as a rule, difficult to applied [6-9]. The combination of ion exchange and dissolve. For decomposition of mineral fraction and Table. Results of Co determination by RNAA and INAA procedures. RNAA results* Certified or information value Material INAA results* [ngg'1] open wet microwave plus open microwave only digestion** digestion digestion Virginia Tobacco Leaves 429 ±26 391 + 15 425 ±38 424+6 420+19 CTA-VTL-2 n = 15 n=4 n=4 n=5 Tomato Leaves 1573a N1ST 570±20 490+19 571±32 570±16 577 ±23 n = 18 n=7 n=4 n=4 Oriental Tobacco Leaves 879+39 906+47 - 964±17 967±19 CTA-OTL-1 n=5 n=14 n=9 Bowen's Kale 63.2±10.7 70.5±8.9 - 71 + 12 n = 9 n=3 Spinach Leaves 1570a NIST 390±50 363+21 - - n = 14 Hay Powder IAEA V-10 130 136+5 - - 141 ±4 [110-140] n=9 n = 3 Orchard Leaves 1571 NBS (200)*;;.. 137 + 7 - 148±6 150 ±22 160±37 n = 10 n=5 n-4 Apple Leaves 1515 NIST (90)*" 81±6 89±13 92±7 91 + 11 n=8 n=2 n=6 n=6 *x+tfj.05-s-n 1V. ** 10 ml of HNO3+2 ml of HCIO4+IO ml of HF; sample mass 100-200 mg. *** information value. ***• consensus value by Gladney et al. [10]. extraction chromatography used in this procedure volatilization of silica HF treatment has been in- assured a very selective and quantitative separation cluded into the wet digestion procedures. The effec- of ionic cobalt from all accompanying radionuclides tiveness of the decomposition depending on the present in acidic digest solution. In the case of in- amount of HF added has been examined in case of complete decomposition of the sample, Co retained open wet digestion. The results are summarized in on the top of the first column could be detected Fig. Taking into account the amount of HF ne- using gamma ray spectrometry. cessary for complete mineralization the analyzed The results of Co determination are presented in materials can be grouped into three categories: A - Table. The results obtained by RNAA were com- materials decomposed when 10 ml of HF were pared with certified (or information) values and the added (for 150 mg sample), B - required 15 ml of results obtained by the -INAA method by means of HF and C - materials for which even 15 ml of HF the Student's t-test. For some materials a distinct were not sufficiently effective. As follows from the effect of the mineralization method on the results above results (Fig.) the open wet decomposition can be observed, i.e. statistically significant differ- with HNO3, HCIO4 and HF can be applied for ences at 95% confidence level have been found some materials. However, for some plant materials between mean results. The materials affected are (CTA-OTL-1, 1515 NIST) it is not sufficiently Virginia Tobacco Leaves CTA-VTL-2, Tomato effective. The content of Si in the above CRMs was Leaves NIST 1573a, Oriental Tobacco Leaves lower than 1%. So, in all the cases the amount of CTA-OTL-1, Apple Leaves NIST 1515 and also HF used significantly exceeded the stoichiometri- Orchard Leaves NBS 1571. The results obtained for cally equivalent value. An increase in the HF open wet digestion are lower than those for two amount up to 15 ml resulted in better recoveries of microwave decomposition methods. For the results Co. However, the increase in the amount of HF obtained by the latter two methods no statistically requires also a longer time of decomposition, which significant differences at the 95% confidence level might affect the Co recovery. It seems that the ne- RADIOCHEMISTRY, STABLE ISOTOPES, 78 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 100 with the open wet decomposition. It takes much iiiiiimimiiimmi i less time (1 h comparing with 8-16 h) and requires DA less reagents. It is easy to control and almost does > 60 HB not require supervision. Taking the above into o 40 account the use of the closed-vessel microwave de- IC 20 composition should be recommended as a standard o approach for plant materials. o 0 I 1 0 10 15 References [l].Parr R.M.: In: Trace Elements Metabolism in Man and HF volume, ml Animals - 3. Proc. 3rd Intern. Symposium, Freising-Weihen- Fig. Co recovery as a function of HF amount used during open stephan, 1977. Technical University, Munich 1978, p. 622. wet decomposition, sample mass -150 mg, uncertainty of [2]. Advisory Group of the IAEA. Anal. Chim. Acta, 165, 1 the results ±5%. A - Bowen's Kale, Hay Powder IAEA V-10, (1984). Spinach Leaves NIST 1570a; B - Tomato Leaves NIST [3], Kabata-Pendias A., Pendias H.: Trace Elements in Soils and 1573a, Virginia Tobacco Leaves CTA-VTL-2, Orchard Plants. CRC Press, Boca Raton 1992. Leaves NBS 1571; C - Oriental Tobacco Leaves [4]. Metals and Their Compounds in Environment. Ed. E. CTA-OTL-1, Apple Leaves NIST 1515. Merian. VCH Verlagsgesellschaft, Weinheim 1991. [5]. Metals Ions in Biological Systems. Vol. 5. Reactivity of Co- gative systematic error could be also connected with ordination Compounds. Ed. H. Sigel. Marcel Dekker INC., the incomplete decomposition of organic com- New York and Basel 1976. pounds. It should be mentioned that the observed [6].Dybczy(iski R., Danko B., Maleszewska H.: J. Anal. Chem. (Moscow), 49,31 (1994). losses of Co depend on the gamma-radiation dose [7].Dybczynski R., Danko B.: J. Radioanal. Chem., 181, 43 and temperature during irradiation. A higher dose (1994). and temperature result in more significant changes [8].Dybczyriski R., Danko B.: Biol. Trace Element Research, of organic matrix due to polymerization and dehy- 43-45, 615 (1994). [9]. Polkowska-Motrenko H., Dybczyriski R., Danko B., Becker dration and irradiated material is much more dif- D.A.: J. Radioanal. Nucl. Chem., Articles, 207, 401 (1996). ficult for mineralization. [10[. Gladney E.S., O'Malley B.T., Roelandts I., Gills T.E.: It follows from our results that the complete Standard Reference Materials: Compilation of Elemental Concentration. Data for NBS Clinical, Biological, Geo- decomposition of all the investigated materials was logical and Environmental Standard Reference Materials. reached when the closed-vessel microwave diges- NBS Special Publication 260-111, US Government Printing tion with HNO3, H2O2 and HF was applied. This Office, Washington D.C. 1987. method reveals a number of advantages comparing

SOL-GEL PROCESS FOR SYNTHESIS iS OF Ndi.o5Bai.95Cu30x SUPERCONDUCTORS i O FROM Nd, Ba AND Cu ACETATES/AMMONIA/ASCORBIC ACID SYSTEMS Andrzej Deptuta, Wieslawa Lada, Tadeusz Olczak, Kenneth C. Goretta1/ 1/ Argonne National Laboratory, USA

The irreversibility line of NdBa2Cu3Ox (Nd-123) superconductors is substantially above that of Variant I. Variant II ( CSGP) YBa2Cu3Ox (Y-123) and much effort has been Nd.Bo.Cu aq. owlates (pH 4.5) _ . Ascorbic acid (ASC) to expended on fabricating Nd-123 materials [1-7]. In EMeO.36M, Bltadlng molar ralio ASC: IMe=0.« previous papers [8] we have described a new variant I2MNH,OHaq. .... UMNH.OHaq of sol-gel process to synthesize YBa2Cu4Os having NJ,Ba,Cu AC sol, pH 6.0 ( i Nd.Ba.Cu AC ACS sol, pH S.8

satisfactory superconducting properties. This va- Evaporation (M'C) riant, Complex Sol-Gel Process (CSGP), utilizes wndervAcnam 2-3 tines ascorbic acid as a very strong complexing agent with in volume strong reducing properties promoting formation of AC sol, vi jcosily 3.2 cSl ! ASC sol viscosity 6.2 cSt high phase purity in powders synthesized by sol-gel methods (INCT and ANL-USA teams patent [9]). Drying Itt'C, (2»h),~ MO'C solidification. The goal of this work was to synthesize a phase- AC gel i ASC gd

-pure nominal composition Ndi.05Bai.95Cu3Ox Final thermal treatment: powder by the sol-gel method. We expect that this RT-450'C heating rate 2'C/min, making tine lh 450-900 °C keatlng rate S'C/rain, soaldng time 2h process can in the future be adapted to production with flail grinding of coated conductors. A further goal of this work was to compare Nd-123 powders made with and without ascorbic acid additions. A schematic diag- Irregularly shaped powders O/NO1J5B», ^CujO, ram of the preparation of acetate (AC) and acetate- -ascorbate (ASC) derived Nd-Ba cuprates is shown Fig.l.Flow chart for preparation of irregularly shaped powders in Fig.l. The thermal analyses of AC and ASC dried Ndi.05Bai.95Cti3Ox (derived from AC gel) and Ndi.05Bai.95Cu3Ox (derived from ASC gel). R/YDIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL. 79 at 250°C gels are shown in Fig.2. In the AC gels, the It is known that Tc values of Nd-123 are strongly thermal transformations are more distinct. The first affected by annealing [5, 6]. To optimize Tc, the synthesized Nd-123 powders were first annealed for 12 h at 950°C in flowing Ar that contained ~10 ppm O2. They were then heated in flowing O2 by the following schedule: 150°C/h to 600°C, holding y eozo —«— /h DTA V endo I I TG % Am •——. 10

\ m — __ 20

30 100 300 500 700 1000 temperature Fig.2. Thermal analysis of AC and ASC gels dried at 250°C for 19 h 100°C. Ndi.05Bai.95Cu3 ASC, Ndi.05Bai.95Cu3 AC. exotherm at approximately 400°C, is accompanied by a drastic mass loss connected with the decompo- sition of acetates. After this, a maximum stabi- lization of weight is observed till 1000°C. Similarly, as for YBCO 124 ASC gels, the exotherm is shifted toward higher temperatures and accompanied by a continuous weight loss till 800°C. The small endo- thermic deeps at 830°C, without weight losses, indicate of the presence of residual BaCC>3, which at this temperature is transformed from rhombic to hexagonal phase. Each powder that was heated to 900°C consisted primarily of Nd-123, BaCO3, and CuO (Fig.3a, XRD patterns). These three phases were in general distributed on a submicrometer scale within particles that were as large as =50 /um (Fig.4a). There were no obvious differences be- tween powders derived from AC or ASC sols. Heating the partially synthesized powders in air at Fig.4.SEM micrographs of (a) Ndi.05Bai.95Cu3 precursor 960°C for 6 to 12 h produced a powder that (AC and ASC) healed at 900°C and (b) pure phase appeared to be phase pure by X-ray diffraction Ndi.05Bai.95Cu3 superconductor obtained at 960°C. (Fig.3b), and SEM (Fig.4b). Its onset of melting in for 12 h; then 150°C/h to 500°C, holding for 24 h; air was =1050°C. Lower heat-treatment tempera- tures did not induce complete reaction. and finally 150°C/h to 350°C, holding for 60 h. The resulting powder were essentially phase pure and 1 1 1 1 | 1 1 ll|l i I ! i I I . | iv vi-p-i v ri-r-i-rrv-i-rrr exhibited a sharp Tc at 94 K. (b). The AC and ASC variants of sol-gel processing produced equally pure Nd-123 powders. However, we found that the ASC sols maintained stability at lower viscosities. This property may allow for one to use ASC sols to produce high-quality Nd-123 films. We have begun spin coating Nd-123 ASC sols & on substrates such as Y2C>3-stabilized ZrC>2 and .. il .,,A , . ft" MgO. Preliminary results suggest that our heat- 1 - 1,2 -treatment schedule must be modified to promote well-textured films of good phase purity.

13 2 1 2 23 1 922 ' 3 l" References

20 25 30 35 40 45 50 55 60 [1]. Murakami M., Sakai N., Higuchi T, Yoo S.I.: Supercond. Sci. Technol., 9,1015 (1996). 23 O [2]. Goodilin E., Kambara M., Umeda T., Shiohara Y.: Physica C. Fig.3.XRD patterns of (a) Ndi.05Bai.95Cu3 precursor (AC and 289, 37 (1997). ASC) heated at 900°C and (b) pure phase Ndi.05Bai.95Cu3 [3]. Wu H, Kramer M.J., Dennis K.W., McCallum R.W.: Appl. superconductor obtained at 960°C. Phys. Lett., 21, 3572 (1997). RADIOCHEMISTRY, STABLE ISOTOPES, 80 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL

[4], Hu A., Schätzte P., Bieger W., Verges P., Fuchs G., Krabbes [8]. Deptuła A., Lada W., Olczak T., Goretta K.C., Di Bartolomeo G.: Appl. Phys. Lett., 25., 259 (1999). A., Casadio S.: Mat. Res. Bull., 32, (3) 319 (1997). [5]. Yu R., Sandiumenge F., Martnez B., Vilalta N., Obradors X.: [9]. Deptuia A., Lada W., Olczak T., Lanagan M., Dorris S.E., Appl. Phys. Lett., 21,413 (1997). Goretta K.C., Poepel R.: Method for preparing of high tem- [6].Salama K., Parikh A.S., Woolf L.: Appl. Phys. Lett., êS, 1993 perature superconductors. Polish Patent No 172618, June 2 (1996). 1997, valid since 1993. [7]. Hari Babu N., Lo W., Cardwell D.A., Campbell A.M.: Appl. Phys. Lett., 25,2981 (1999).

SYNTHESIS OF LiNii-yCoyO2 POWDERS BY COMPLEX SOL-GEL PROCESS (CSGP) AND THEIR ELECTROCHEMICAL ! CM CHARACTERIZATION IS Andrzej Deptuła, Wiesława Lada, Fausto Croce1', Fabio Rond1', Angelo Di Bartolomeo2'', !CM Aldo Brignocchi2/ !§ 11 University "La Sapienza" Department of Chemistry, Rome, Italy 2/ ENEA, C.R.E. Casaccia, Italy The layered oxides, among the wide family of inter- ii) route B, according to which the starting Li, Ni calation compounds, have received considerable at- and Co acetate solutions were first alkalied by tention as positive electrode materials in high- ammonia and then ASC was added. The detailed -energy density and lithium ion batteries. experimental procedure is shown in Fig.l. Some Within this frame LÍNÍO2 and LÍC002 oxides and properties of the intermediate and final products their solid solutions have been extensively studied as are illustrated in Table. they (and the LiMn2Û4 spinels) are the only known Li Ac (5.03)-> Blending materials able to intercalate reversibly lithium at Ni Acj (0 69M)-H

high cell voltage (3.5-4 V). Recently, solid solutions CoAc2(1.02M)- such as LiNii-xC0xO2 have attracted the attention as alternative cathodes to the state of art LÍCOO2 in ASCSMeMR- commercial rechargeable Li-ion batteries. These ma- Molar ratio=0.2 terials are comparable in performances to LÍC0O2, however their cost is radically considerably lower. Alkalizing to pH=9 The solid state reaction routes commonly utilized to synthesize this kind of materials have the drawback complex of the necessity of high temperature synthesis (HT). solution 1 Dissolving and alkalizing to Alkalizing However Tarascón et al. [1] and Barboux et al. [2] ASC pH=9 with topH=9 demonstrated that the low temperature (LT) me- lo MR=0.2 ammonia thods, such as the Sol-Gel process, produced finer particles with higher cell capacity. In a previously complex sols published work [3] we reported on the preparation Evaporation under vacuum and the electrochemical characterization of the com- concentrated >2M ZMe sols pound LiNio.5Coo.5O2 synthesized by the Complex I viscosity >1000 cSt Sol-Gel Process (CSGP). As a continuation of this work we have extended the study to the entire family Gelation and drying 60"C-12 days, 80°C -3 days.lOCC -11 days, 160"C* -1 of the mixed oxides LiNixCoi_xO2, in which x ranges day, 170°C - 3 days_». solidification from 1 to 0. In this work we describe the results obtained on the preparation of some members of this ,, dried gel, shard family of compounds. Grinding in agate mortar It is well known [3] that during the hydrolysis gel powders step in the Sol-Gel process there is the formation 3+ Preliminarily heating (I °C/min) till selfignition of polymeric cationic species such as Me2(OH) temperature indicated in Table. Foaming observed in + and Me4(OH)^ . It is supposed that this step is temperature range 220-250 °C. Grinding. strongly influenced by the formation of complex species between the cations and ASC before hydrolysis. To verify this hypothesis and in order to Final temperature treatment at temperatures 750-900°C evaluate the influence on the properties of the final for various times (see Table) material of the extent of cations polymerization in the gel we have prepared the starting sols from Grinding in agate mortar Li+-(l-x)Ni2+-xCo2+ acetate aqueous solution by T T two different routes. Namely: LiNi,Coi.,O2 i) route A, according to which aqueous ammonia Type A Type B *- foaming („balloon" formation 2-4 times increasing in volume) was added to Li, Ni and Co acetates starting solu- Fig.l. Experimental procedure for preparation of LiNixCoi-xO2 tion containing ascorbic acid; by Complex Sol-Gel Process. RADIOCHEM1STRY, STABLE 1SOTOPBS, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 81 We observed that the compounds with a higher No clear correlation was found between the Ni content showed higher quantities of carbonates cations polymerization in the gels and some macro- impurities. Some low level of carbonates impurities scopic property of the samples. However all the Table. Characterization of samples calcined at different conditions.

Densities g/cm , product characterization: Shard - yery hard (sintered), Shard - hard Sample no and SIT*, (partially sintered), Pwd - powder. Structure classification: yery good, good; % CO3 in () compound type °C of xerogel 170°C, xerogel 750°C, 24 h 800°C, 8 h 800°C, 18 h 900°C, 18 h lALiNiO2 380 1.67 4.55 g 4.00 Sh.v.h. 4.82 (1.2) (11) 2B LiNiO2 400 4.00 Sh.h. 4.81 (15) 7A LiNioo.75Coo.25O2 390 1.62 4.97 v.g. 4.19 Sh.h. (1.3) (4) (?) 5A LiNioo.5Coo.5O2 390 1.62 4.97 g. 4.46 Sh.h. (0) (1.7) (3.5) 6B LiNioo.5Coo.5O2 440 1.64 4.70 Sh.h. (2.5) (°) 8A LiNioo.25Coo.75O2 460 1.61 5.26 v.g. Sh.h. (0) (0) (0.9) 3A LiCoO2 420 1.63 5.17 V.g. 4.99 Pwd (0) (0) 4B LiCoO2 440 1.63 4.91 Pwd (1) * SIT - self-ignition temperature. is not surprising in samples prepared by organic samples prepared, following the route A, show precursors. It has been previously reported in the higher densities and well defined XRD patterns, literature that they can hinder the spinels phase implying the possibility of more homogeneous pre- formation and retard the formation of High Tem- cursors. perature Superconductors [4, 5]. The XRD pattern, showed in Fig.2a, confirms that All the xerogels show similar densities. Further- the final structure of LiNio.75Coo.25O2 is obtained more, the samples with higher Co content and lower even after the relatively mild heat treatment for 24 level of carbonates impurities have higher densities. hours at 750°C. The pattern shows the formation of a

iiiii (a) 0188

36BB

Z5BB

16BB

988

488

iae **1^M«W * a

(b)

Fig.2. XRD patterns (a) and SEM (b) micrograph of LiNio.75Coo.25O2. RADIOCHEMISTRY, STABLE ISOTOPES, 82 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL unique phase having the expected layered (R3m) tuned to optimise both the purity and, even more structure. No XRD detectable trace impurities seem important, the morphology of the powders. With to be present and, in particular, no carbonates peaks regards to this latter point, in fact, powders having have been found. The SEM image reported in Fig.2b higher surface area and smaller grain size are reveals a very fine grained morphology. The powders expected to lead to improved cell performances in consist of small agglomerates, having a mean dia- terms of better capacity, electrode polarisation and meter ranging from 1 micron to 5 microns, which in periodicity. The Sol-Gel process, as a member of the turn are formed by sub-micrometer grains. wide family of Homogeneous-Precursors Low-Tem- The electrochemical properties of the compound perature Synthesis processes, is well suited for the LiNio.75Coo.25O2 prepared by route A were eva- production of very fine sub-micrometer powders. luated by: galvanostatic measurements, cyclic vol- tammetry measurements and galvanostatic cycling. References This material has shown an interesting high reversi- (l).Tarascon J.M., McKinnon W.R., Coowar F., Bowmer T.N., bility for the electrochemical Li+ intercalation/de- Amatucci G., Guyomard D.: J. Electrochera. Soc, 141, 421 -intercalation process and a good periodicity even if (1994). [2].Barboux P., Tarascon J.M., Shokooh F.K.: J. Solid State the anodic potential is extended up to 4.4 V, where Chem., 24,185(1991). degradation processes usually occur. Furthermore, [3]. Deptuia A, Lada W., Olczak T., Croce F., Ronci E, Ciancia A, the material has shown a quite interesting value of Giorgi L, Brignocchi A, Di Bartolomeo A.: Synthesis and Pre- charge retention upon cycling. In fact the specific liminaiy Electrochemical Characterization of LiNio.5Coo.5O2 Powders Obtained by the Complex Sol Ge! Process (CSGP). In: capacity remains in the range of 2/3 (= 120 rnAh/g) of Materials for Electrochemical Energy Storage and Conversion II the theoretical value after more than 100 cycles. The - Batteries, Capacitors and Fuel Cells. Eds. D.S. Ginley, D.H. results here obtained confirm the satisfactory Doughty, T. Takamura, Z. Zhang, B. Scrosati. Mater. Res. Soc. electrochemical response of our material when ope- Proc. 4%, Pittsburg 1998, pp. 237-242. [4]. Deptuia A., Olczak T., Lada W., Goretta K.C., Di Bartolo- rating as cathode in Li-ion systems. Besides, it can be meo A., Brignocchi A.: J. Mat. Res., 11,1 (1996). regarded as a starting point considering that still [5], Deptuia A., Olczak T., Lada W., Di Bartolomeo A., Brig- many variables in the Sol-Gel synthesis can be fine nocchi A.: Applied Superconductivity, 2, 613 (1995).

FABRICATION OF Li2TiO3 SPHERICAL MICROPARTICLES CO BY A CLASSICAL SOL-GEL ROUTE o Andrzej Deptuia, Tadeusz Olczak, Wiestawa Lada, Bozena Sartowska, Andrzej G. Chmielewski, O Carlo Alvani1', Sergio Casadio17 8 17 ENEA, C.R.E. Casaccia, Italy

In this most recent review paper Johnson [1] under- processes of a just prepared Li2TiO3 powder. Lith- lines that tritium, the principal fuel for future fu- ium titanate powders are prepared by a solid-state sion power reactors, can be produced only through reaction of titania with L12CO3. transformation of lithium. According to Johnson, The objective of the present work was the pre- Li-based ceramics, especially Li2TiC>3, can be re- paration of lithium titanate microspheres (diame- cognized as the most promising tritium-breeding ters <100 /urn) by this process which has been materials for fusion reactor blankets due to its in- developed till the level of a pilot plan scale (1 kg/h). herent thermal stability and chemical inertness. Trit- We expect that spherical powders of this diameter ium formation and release from a blanket is a very can be used in a mixture with larger pebbles in complex process and according to [2] consists of 18 order to increase blanket density. In the so called steps. Some of them are strictly connected with the gel-sphere-process, spheres of nuclear ceramic ma- microstructure and morphology of a ceramic blan- terials [5], preferably of three sizes with a diameter ket. Generally, blankets are formed in the shape of ratio of about 40:10:1 were loaded directly into rods solid ceramics made from ceramic powders. and packed to achieve a smear density of 88% TD The ENEA team was the first who proposed in only by low energy vibration. Also compaction of 1982 the application of microspheres for their polydispersed spherical particles results in higher production. Proposed LiAlC>2 spherical powders compacts density than monosized [6]. (diameters < 100 fim) were produced by the IChTJ We prepared Li-Ti sols directly by neutralization sol-gel process described in [3], The authors expect- a TiCl4 aqueous solution with 4.5M LiOH. The re- ed strong improvement of tritium release from sulting sol concentration of ~ lMTi has a relatively pellets prepared from microspheres. It seems ob- low viscosity 2 cSt, too low for the next step, being vious that open interconnected pores formed in a the gelation to microspheres [3]. Consequently, the blanket can improve tritium release from it. For sols were concentrated under vacuum approximate- this reason, the recently proposed [4] applications ly 4 times to a volume of viscosity lOcSt. The sols of ceramic pebbles for tritium breeding ceramic were then gelled to spherical particles (Fig.l). blanket, are generally of 1 mm diameter. Generally, Unfortunately, after the process, the molar ratio of they are prepared by various routine agglomeration Li:Ti decreased to a value of - 0.3, presumably due RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANA1.YTIC.AL METHODS, CHEMISTRY IN GENERAL 83 Gel, 50°C

Gel after impregnation, 50°C

750°C, 24 h

1200°C, 2 h

Fig.l. SEM micrographs of spherical particles of Li2TiO3 obtained in various steps from T1CI4 solution. RADIOCHEMISTRY, STABLE ISOTOPES, 84 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL to the extraction of Li chloride, together with water product. Evidently, chlorides content in a final by EH. In order to prepare a stoichiometric gel, we ceramic blanket is not allowed. Further experi- applied an impregnation process used for spherical ments confirmed that the removing of chlorides by powders. The desired quantity of LiOH solution thermal treatment of Li-Ti-OH-Cl gels is a rela- tively serious problem. Further thermal analysis of this material, shown in Fig.3, confirmed this conclusion. Final weight t stabilization with an endothermic effect is observed at 1200°C with a weight loss corresponding with 1 losses of chlorides. This temperature is significantly egzo lower than the temperature of sublimation of LiCl DTA endo (1383°C). X-ray diffraction results confirmed that | 1 at 1200°C lithium titanate is present and the chlo- 4. rides content is very low (<0.03%) comparable TG with the quantities (0.02%) introduced to the syn- '/oAm 10 \\ thesis with LiOH (Fluka p.a. 0.01% Cl) applied in our work. 70 u In order to lower the temperature of formation 30 we carried out the following experiments to remove \ V chlorides in various stages of the process: 40 - (I) A gel precursor fired at 750°C with aq. am- — - monia and slurry were evaporated to a solid. After 50 — .. •1 thermal treatment at 750 C only small quantities too 300 500 700 900 of Cl (~1%) were found. This confirmed that temperature, °c during heating NH4CI sublimes (T.s. 338°C). gel before impregnation, 50°C, 22h Thermal analysis (Fig.3) of dechlorinated material gel after impregnation, 50°C, 2h (vacuum) is similar as in the ENEA product prepared in Fig.2. Thermal decomposition of Li-Ti gel before and after im- absence of Cl. A particularly strong weight loss in pregnation. the temperature range 900-1200 C is not ob- was introduced into gel microsphers located in a Rotavapor. It was observed (Fig.l) that after water evaporation the shape of microspheres remained unchanged. The thermal decomposition of both gels is shown in Fig.2. It can be seen that the weight loss is lower for the impregnated gel. After a similar exothermic effect also the weight stabilization after 700°C is more effective for the impregnated gels. Unfortu- nately, after calcination at 750°C considerable quantities (~20%) of chlorides remained in the

1100 """" 1300 temperature, °c

T,i!TiO, (Cl) precursor, 750°C, lh LijTiOj ENEA production • • > Li2Ti03 precursor treated with NH4OH, 750°C, 24h . Li2Ti03 precursor treated with HNO3, 75O°C, 24h LijTiO] precursor from HNO stabilized titania sol, 75O°C, 24h 3 Fig.4. SEM micrographs of Li2TiO3 spherical particles prepared Fig.3. Thermal decomposition of various Li2TiO3 precursors. from Li-Ti-NO3 sol in various steps of production. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS. CHEMISTRY IN GENERAL 85 served. X-ray diffraction data confirmed a lithium - (Ill) Starting aqueous solution of TiCU was treat- titanates structure. ed with concentrated HNO3 in a similar way as - (II) A gel precursor fired at 750°C was treated in described above in (II). A concentrated solution of the Rotavapor with concentrated HNO3 and eva- TiO nitrate (- 200 g Ti/1), white in color, was pre- porated under vacuum. The process was repeated pared. To this solution LiOH can be introduced several times (generally 4) until chlorides were easily to MR Li:Ti=3, pH=0.4. At higher pH, not observed in the evaporated solution. Chemi- precipitation takes place. A stoichiometric 2Li-Ti

1M of TiCU. joiwion in HCI nq. nitrate sol, after concentration in the Rotavapor, or TiO-NOj solution (~200g Ti/1rV-) 1 «-*« I 2M LiOH. aq. solution, the concentrated sol (230 g/1, viscosity 15 cSt) was (concentration ~4. 5M) Li-Ti-CI (01 MOj) sol, viscosity - 2 cSt gelled to microspheres and then supplied routine-

Conceatraden ander vacuum ly to impregnation. Thermal analysis of the fired at I (Appro*. 4 tinea in volume) 750°C precursor (Fig.3), as well as the content of j Viscous sol, viscosity? 10 c chloride are similar as for the former material.

I FoniuHra of «ol I Micrographs of microspheres in various stages of 2-ctyiohexiirol 1 + SPAN 80 (EH)_J emuUon in EH I fabrication are shown in Fig.4. Emulsion of sol in EH The elaborated processes of fabrication of Li2TiC>3 of medium size microspheres (with dia- meters below 100 fxm) are shown in Fig.5. These

Suspension of gel microsplieres in EH results indicate that the effective possibility of che- mical, low temperature removal of chlorides from Ti-Li-Cl systems is feasible. All the described pro- Gelled mktospheres, Li:Ti motor ratio cedures do not change the spherical shape of parti- , p.3-0.4 cles. It is necessary to underline that the formation M Impregnation I and evaporation of medium sized microspheres is practically not I «nler vacuwn* possible by powder agglomeration processes routi- Gelled micraspheres, Li:Ti molar ratio 2:1 nely used for the fabrication of pebbles. References [1]. Johnson C.E.: J. Nuclear Mat., 22Q, 212 (1999). [2], Nishikawa M., Baba A.: J. Nuclear Mat., 2i2, 213 (1998). llWClh foreMoride precursors [3], Deptuta A., Rebandel J,, Drozda W., Lada W., Olczak T., «0"CMhJM nitrate Chmielewski A.G.: Production of Spherical Powders of prcetmon Inorganic Compounds by Water Extraction Variant of Sol-gel Process. In: Better Ceramic Through Chemistry V. Eds. M..I. Hampden-Smith, W.G. Klemperer, C.J. Brinker. Spherical particles ofLi2TiO3 (4>=10-100fim) Mat. Res. Soc. Symp. Proc. 270, Pittsburgh 1992, p. 277. Fig.5. Flow-chart for preparation of spherical powders of Li2TiO3 [4].Tsuchiya K., Kawamura H., Fuchinoue' K., Sawada H., by the sol-gel process. Watarumi K.: J. Nuclear Mat., 258-263.1985 (1998). [5]. Report ORNL-5469. Nov. 1979. Compiled by R.L. Beaty, cal analysis (Cl<0.04) as well as thermal analysis R.E. Norman, K.J. Katz. (Fig.3) indicated that this procedure is more [6], He D., Ekere N.N.: J. Mater. Sci. Lett., 11,1723 (1998). effective than (I).

PROTON NUCLEAR MAGNETIC RESONANSE STUDIES OF HYDRATION OF OXAALKANES IN BENZENE SOLUTION Ewa Gniazdowska, Piotr DobroWolski1^ Jerzy Narbutt i O 11 Pharmaceutical Research Institute, Warszawa, Poland Thermodynamic studies on hydration of oxaalkanes mol dm"3 water and a varying excess concentration in aqueous solution fl] put two questions: 1) whether of some oxaalkanes (given in Table) either com- hydrophilic properties of the oxygen atom in mono- mercial or synthesized according to Williamson ether molecules depend on the inductive effect of al- reaction [3]. A Varian Gemini 2000-200 MHz spec- kyl groups; and 2) how does the second oxygen atom trometer was used to collect XH-NMR data at 25°C in dioxaalkane molecules affect the hydrophilic pro- (thermostated), using TMS as an internal standard. perties of the first oxygen atom. Because the effects At the low water concentration used in this study it of hydrophilic hydration of amphiphilic solutes in can be safely assumed that the proton chemical aqueous solution are obscured by those of hydropho- shift of about 0.4 ppm downfield of TMS is due to bic hydration, the answer could be obtained when water monomers [4]. Upon progressively adding a studying hydration of oxaalkanes in non-aqueous so- large excess of oxaalkanes (up to 2 mol dm 3) to lution. rH-NMR is a proper method for such a study. such a solution, the water resonance shifts down- We studied the formation of hydrogen bonds be- field, to be eventually obscured by a large signal tween water molecules and ethereal oxygen atoms from the methyl protons of the oxaalkanes. Given [2] in a [2H]6-benzene solution containing ca 0.01 the low water concentrations throughout the study RADIOCHEMISTRY, STABLE ISOTOPES, 86 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL and low values of the stability constants of the oxa- two hydrophilic in each diether molecule alkane hydrates, we asumed that only 1:1 hydrates instead of one in the monoethers. Thus, the hydro- are formed under the experimental conditions and philicity of each ethereal oxygen is nearly the same, the formation of 2:1 species is less probable [5]. The irrespectively of its parent molecule - either mono- data in Fig. are indicative of hydration of oxaal- or diether. 5 2 Table. Stability constants (molar concentration scale) of 1:1 hy- drates of some oxaalkanes in [ H]6-benzene solution at US' 25°C. Oxaalkane Kl Monoethers CH3OC4H9 0.38 ± 0.02 C3H7OC3H7 0.43 ± 0.03 0,4 Acetals CH3O(CH2)OCH3 0.54 ± 0.02

C2H5O(CH2)OC2H5 0.52 ± 0.08 Diethers CH3O(CH )2OCH3 0.96 ± 0.06 0 0,2 0,4 0,6 0,8 1 1,2 1,4 1,6 2 Fig. Plots of the water (0.01 mol dm"-') proton chemical shifts in CH3O(CH2)4OCH3 0.83 ±0.18 [ H]6-benzene solution containing increasing concentrations (c) of two oxaalkanes: a - 1,2-dimetoxyethane, b - dimetoxy- C2H5O(CH2)2OC2H5 1.07 + 0.17 methane; at 25°C. C2H5O(CH2)4OC2H5 1.10 ± 0.05 kanes by hydrogen bonding, and were analyzed The number of oxygen atoms in the molecules of according to the following equilibrium: diethers and acetals is the same (two), therefore (1) much lower Ki values obtained for the acetals indi- R'RO + H2O -^i-> R'RO- • -HOH cate for much lower hydrophilicity of acetal oxygens Ki = [R'RO- • HOH]/([R'RO][H2O]) than that of ethereal ones. This observation can be where: R'RO - an oxaalkane molecule, explained by assuming a strong mutual inductive ef- R'RO- • HOH - its 1:1 hydrate, [x] - molar concen- fect of the two oxygen atoms [7] separated by only tration of x, Ki - the stability constant of the 1:1 one CH2 group in acetal molecules. This is also in hydrate. The data in Fig. were analysed using equa- line with our earlier experimental results showing tion (2) which assumes that the observed shift (<5) is much lower values of standard enthalpy and Gibbs a weighted average of the coordinated-water free energy of water-heptane partition of acetals, and free-water ((5W) positions [6]: compared to those of diethers [1,8]. This well cor- responds with our earlier conclusion that two oxy- gen atoms in diether molecules interact with water where - under the conditions of the experiment - the nearly independently of each other, and form hy- equilibrium concentration of oxaalkane (co) can be drogen bonds of strength comparable to that in mo- approximated by its initial molar concentration (c). noethers and much greater than that in acetals [8]. Table presents the values of stability constants calculated using equation (2). Three groups of oxa- References alkanes of similar Ki values can be distinguished: [lj.Gniazdowska E., Narbutt J.: INCT Annual Report 1996. INCT, Warszawa 1997, p. 51. the values for monoethers and acetals are close to [2]. Cabani S., Gianni P., Molica V., Lepori L.: J. Sol. Chcm., 10. one another, while those for diethers arc about 563(1981). twice as large as those for acetals. [3]. Shaefer G.: J. Org. Chem., 42., 567 (1975). The similar Ki values obtained for two different [4]. Moore P., Narbutt J.: 3. Sol. Chem., 2Q, 1227 (,iwi;. [5].Kinart W.J., Kinart CM, Skulski L.: Pol. J. Chem., 61, 581 monoethers, one of them with the terminal methyl (1989). group, show that the inductive effect of alkyl groups [6]. Hartley F.R., Burgess C, Alcock R.M.: Solution Equilibria. has small (if any) influence on the hydrophilic pro- Ellis Horwood, New York 1980, p. 152. perties of the ethereal oxygen atom. On the other [7}.Wolfendcn R: Affinites of organic compounds for solvent water: hydrophilic and hydrophobic character. In: Topics in hand, nearly twice as large Ki values obtained for Molecular Interactions. Eds. W.J. Orville-Thomas, H. Rataj- diethers (practically the same for each) seem to czak, C.N.R. Rao. Elsevier, Amsterdam 1985, p. 121. indicate that the difference is due to the presence of [8], Gniazdowska E., Narbutt J.: J. Mol. Liquids, 81, 273 (2000).

X-RAY MOLECULAR AND CRYSTAL STRUCTURE OFBIS(PENTANE-2,4-DIONATO)LEAD(II) Jerzy Narbutt, Beata Paluchowska1/, Jan K. Mauriny 11 Institute of Atomic Energy, Swierk, Poland Recent interest in the lead(II) chemistry [1] results soning [2]. Volatile lead(II) compounds, including not only from the role of the metal as an environ- /3-diketonate complexes, are used for metaloorganic mental contaminant and from the need to design vapour deposition of lead-containing thin ferro- drugs which could counteract the effects of lead poi- electric films for microelectronics [2]. Amphiphilic RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS. CHEMISTRY IN GENERAL 87 lead (212Pb) chelates are also studied as radiophar- 2.363(4) and 2.370(3) A and the OO edges of maceuticals - precursors of therapeutic 212Bi [3]. 2.969(6) (two bite distances), 2.850(6) and 3.033(6) The diversity of co-ordination chemistry of the A. The bite angles in the ligands are equal to ion results from the presence of the lone electron 78.56(15)° and 77.74(13)°. The diagonals of the pair 6s2 on the Pb ion [4]. A great variety of square base are close to each other [4.160(6) and co-ordination numbers (CN) of Pb and structures 4.198(6) A]. All the oxygen atoms lie in one plane. of its complexes have been reported [5], depending on the character of the 6s2 pair. The large ionic Pbfl! radius of Pb11 is due to the lone electron pair occupying 6s orbital, but the radius decreases to a 0(2'! value comparable with that of PbIV when the pair enters a hybrid orbital and becomes stereochemi- cally active [6]. However, scarce information is available on the C!5'l structure of lead(II) /?-diketonates and on the cha- racter of 6s electrons in these compounds [1, 5, 7], Only recently X-ray crystal structures of two such compunds have been reported, indicating of stereo- chemically active lone 6s2 pair [2], but there are no data in the literature on the structure of the simp- Fig. Molecular structure of the title compound. The heavy atoms lest /J-diketonate, bis(pentane-2,4-dionato)lead(II), are shown as the 30% probably ellipsoids. Pb(acac)2. In the recent paper we studied solvent extraction of this species from aqueous solution, Such short PbO distances and the structure of and attributed its good extraction to the assumed square pyramid are characteristic for the stereoche- stereochemically active lone electron pair [8]. The mically active lone electron pair 6s2 at the axial aim of the present work was to determine the mole- position on the lead ion in the title compound, cular and crystal structure of bis(pentane-2,4-diona- similarly to that found in its homologue, bis(2,2,6,6- to)Iead(II) in order to confirm the above assum- -tetramethylheptane-3,5-dionato)lead(II) [2]. How- ption. ever, on the contrary to the monomeric structure of Well-defined colourless single crystals of that chelate, the title compound crystallizes in the bis(pentane-2,4-dionato)lead(II) were obtained by monoclinic space group P2i/c, and its polymeric refluxing pentane-2,4-dione solution in dry toluene structure consists of zigzag chains, passing along over a lead foil [9], followed by overnight contact- the monoclinic b-axis, formed by the molecules si- ing the solution with dry hexane through the gas tuated around the twofold screw axis. One can for- phase in a desiccator over CaCl2- Structure of the mally consider the co-ordination sphere of the lead compound was determined by the single crystal atom to be completed by three additional bridging X-ray diffraction method, using a Kuma KM-4 oxygen atoms from the symmetry related ligands of K-axis diffractometer. The single crystal of dimen- two neighbour Pb(acac)2 molecules. The additional sions 0.4x0.2x0.2 mm sealed in a glass capillary was PbO contacts are much longer [from 2.917(4) to studied. Semiempirical absorption correction based 3.243(4) A], in the range of the sum of van der on the t/j-scan method [10] was applied. The struc- Waals radii, thus indicating weak interactions. ture was solved by the heavy atom method from the These additional interactions result in some in- SHELXS-90 package [11] and then refined aniso- crease in the short PbO distances as compared to tropically by a full matrix least-squares method on those in bis^^Ae-tetramethylheptane-s.s diona- F2 using a SHELXL-97 program [12]. All hydrogen to)lead(II) [2]. The described crystal packing sig- atoms were used, during the refinement procedure, nificantly differs from those described for both as fixed contributors in their calculated positions bis(2,2,6,6-tetramethylheptane-3,5-dionato)lead(II) with their isotropic displacement coefficients being and bis(2,2-dimethyl-6,6,7,7,8,8,8-heptafluoroocta- 1.2 (for methylene group hydrogen atoms) and 1.5 ne-3,5-dionato)lead(II) [2]. In the first referred (for methyl ) times of isotropic equi- structure the chelated lead atoms are more distant valents of the corresponding carbon atoms. The from one another, and they are four co-ordinate. In prevalence of the high electron density of the metal the second structure, the molecules form dimeric atom in the structure resulted in not very stable arrangements where each lead atom may be con- refinement of the ligand atoms positions. We con- sidered as seven co-ordinate [2]. A similar picture sider, therefore, reasonable to constrain their geo- has been observed in the case of bis(pentane-2,4- metries to be symmetrical and similar to one -dionato)lead(II) with the difference that polymer another with the deviations of 0.01 A in the res- chains of chelate molecules are formed instead of pective interatomic distances. dimers. Nevertheless, the main structural feature, which is the square pyramid, looks almost the same The molecular structure of bis(pentane-2,4-dio- in all the structures of lead(II) ^-diketonates. The nato)lead(II) consists of a Pb atom chelated by two additional interactions leading to the formal in- pentane-2,4-dione molecules (Fig.). The Pb atom crease in the co-ordination number of lead atom in and four oxygens form a distorted square pyramid the title compound and in bis(2,2-dimethyl-6,6,7, with the PbO distances equal to 2.339(4), 2.351(4), RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 7,8,8,8-heptafluorooctane-3,5-dionato)lead(II) [2] [4J. Kepert D.L.: Inorganic Stereochemistry. Springer Verlag, are possible because of lack of two bulky ?-butyl Berlin 1982. [5]. Harrison P.G.: , , and lead. In: Compre- substituents in the ligands, which sterically hinder hensive Coordination Chemistry. Vol.3. Eds. G. Wilkinson, the access to the oxygen atoms in the chelate as is R.D. Gillard, J.A McCleverty. Pergamon Press, Oxford 1987, the case of bis(2,2,6,6-tetramethylheptane-3,5-dio- p. 183. nato)lead(II). [6]. Hancock R.D., Shaikjee M.S., Dobson S.M., Boeyens J.C.: Inorg. Chim. Acta, 154, 229 (1988). [7j. Holloway C.E., Melnik M.: Main Group Met. Chem., 2Q, References 399 (1997). [1]. Shimoni-Livny L., Glusker J.P., Bock C.W.: Inorg. Chem., [8], Narbutt J.: Solv. Extr. Ion Exch., 17, 1271 (1999). 27,1853 (1998). [9]. Menzies R.C.: J. Chem. Soc., 1755 (1934). [2). Malik M.A., O'Brien P., Motevalli M., Jones A.C., Leedham [10]. North ACT., Phillips D.C., Mathews F.S.: Acta Cryst., T.: Polyhedron, IS, 1641 (1999); Khan L.A., Malik M.A., A42, 351 (1968). Motevalli M., O'Brien P.: J. Chem. Soc. Chem. Commun., [11]. Sheldrick G.M.: Acta Cryst., A46, 467 (1990). 1257 (1992). [12]. Sheldrick G.M.: Program for Crystal Structure Refinement. [3], Mirzadeh S., Kumar K., Gansow O.A.: Radiochim. Acta, 6H, University of Gottingen, Germany 1997. 1 (1993).

SMALL AGGREGATES FORMED IN POLYURETHANE-MEMBRANE STRUCTURE DURING SWELLING IN ETHANOL iS Helena Grigoriew, Aleksandra Woliriska-Grabczyk1', Andrzej G. Chmielewski, Heinz Amenitsch2/, IS Sigrid Bernstorfl37 !§ 11 Institute of Coal Chemistry, Polish Academy of Sciences, Gliwice, Poland 21 Institute of Biophysics and X-ray Structure Research, Austrian Academy of Sciences, Graz, Austria 3/ Synchrotrone ELETTRA, Trieste, Italy Studies of the permeant state in a membrane and compositions of the polymers under study and their the membrane microstructure are of prime impor- characteristics are given in Table 1. tance to understand membrane transport pheno- The X-ray measurements were carried out using mena. a SAXS Austrian beamline of the synchrotron Segmental polyurethanes foils are used as mem- ELETTRA in Trieste, Italy. At the beamline a high branes for the separation of liquids. They are re- power wiggler is used as the beamline source. Two garded as multiblock copolymers of (AB)n type, in one-dimensional gas-filled detectors make it pos- Table 1. Sample characteristics.

Hard segment content Mass density Molecular weight* Sorption constant Polymer Molar composition 3 M /M [g/cm ] [g/mol] w n [g/lOOg] [wt.%] [vol.%] . PU-3 PTMOATDI/HQE 1/4/3 39 28.5 1.1148 71 900 2.1 98.5 PUU-3 PTMO/TDI/PP 1/4/3 39 29.9 1.098 49 500 2.7 76.1 PUU-1 PTMO/TDI/PP 1/2/1 22 16.8 1.053 44 000 1.7 137.3 * GPC, polystyrene standard which A arid B are the hard- and soft-segments sible simultaneous SAXS and WAX measurements. repeat units. In this typeof materials often was ob- Because of primary beam collimation system ap- served a microphase separation due to thermody- plied, no desmearing correction was needed. The namical incompatibility between segments of vari- measurements were performed at room tempera- ous types and forming impermeable hard-segment ture. All prepared materials were measured in dry domains dispersed in the rubbery soft-segment ma- and saturated with ethanol states. trix. The treatment of measured data was done using Synthesis of the segmented polyurethanes (PU) an OTOKO program. SAXS curves of the dry poly- and poly(urea-urethane)s (PUU) was carried out by urethane samples show a broadening of the primary a two-step method in DMF solution involving beam which is evidence of the microphase separa- endcapping hydroxy-terminated poly(tetramethyle- tion. ne oxide) with a molecular weight of 2000 (PTMO) This course of the SAXS curve is characteristic for with 2,4-tolylene diisocyanate (TDI) followed by a "gas-like" structure that is also conformable with not chain extention with hydroquinone bis(2-hydroxy- great volume fractions of the hard segments (Table ethyl)ether (HQE) or 4,4'-diaminodiphenylmetha- 1) and no endothermal high-temperature peaks in ne (PP). Three polymers were investigated differing DSC. It enabled us to use the Guinier method in their hard segment structure due to the different present in the OTOKO program to estimate the size chain extenders used and in the hard segment of the domain. The method determines a radius of length resulting from the different initial ratio of gyration of the domain, Rg, without any assumption diisocyanate to the chain extender. The overall of its shape. To find Rg, the program forms a plot: RADIO CHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 89 2 In I vs. s , In I(j) arb.ua. where: I - intensity of X-ray, s=2sin 6>U, 6 - half of the scattering angle, A - wavelength of X-ray, and then fits a straight line to experimental points. 10 The radii of gyration of dry polyurethanes are given Rg=5.1 in Table 2. Their values are in the range 15-17 nm that is typical for polyurethanes. Rg for the sample of shorter hard segment, PUU-1, is the same as for the samples of longer segments (PUU-3). Table 2. Domain radius of gyration,. PU-3 Radius of gyration, Rg [nm] Material dry swollen in ethanol PU-3 15.3 13.3 5.1 10

PUU-3 17.2 15.2 3.5 Rg =3.4 PUU-1 16.7 11.8 3.8 SAXS curves generated by the samples saturated with ethanol show, besides the first down-turn, i.e. broadening of the primary beam, as for dry samples, a part of greater intensity, then for the dry samples PUU-3 a gradual decrease with s. So, each curve has a shape of two sectors of various declination to the axis. Radii of gyration found from the first down- 10 -turn of the curves (Table 2) are in the range 13-15 nm, i.e. they are slightly lower than those for the dry samples. This can be caused by some re-arrange- ment in the outer parts of the domains as a result of a real increase of mobility of the segments in the matrix, ethanol being also involved. Radii of gyration obtained from the second sector of the SAXS curves for the saturated samples PUU-1 are much smaller, they are in the range 3.5-5 nm (Table 2), for all the materials studied. There is no dispersion in Rg, because all the measured points are located strictly on a straight line for each curve Fig. Plots I vs. s* of second sectors SAXS curves of polyure- (Fig.). It occurred that swelling in ethanol results in thanes saturated with ethanol. the creation of new aggregates of much smaller size, and are built from hard-segments, which would be a than previously mentioned. The small aggegates can result of co-operation of a greater mobility of the be additional ones and/or can be a result of medium in the presence of ethanol and the in- partition of the large domains. A specific feature of fluence of a polar group of the solvent. The hard- the aggregates is their very small dispersity in -segments may come from the outer parts of big dimensions. Only one size of the aggregats is pro- domains and from those existing in the medium. bably a result of thermodynamic equilibrium condi- The second explanation of the phenomen of tions. small domains is the existence of ethanol aggre- Previously, breaking of aggregates (micelles) was gations (droplets) of small size, but there is a ques- related into smaller particles of higher polydis- tion of no dispersion in their size. persity, as the solvent density increased. This was The nature and way of creation of the small related to a PS - PFOA copolymer swollen with aggregats are under further investigation. supercritical CO2 that was interpreted as an The change in polyurethane microstructure increase in the solubility of the copolymer, pointing should be taken into account during consideration the existence of a critical micelle density. of the processes of permeation through polyure- In our case this interpretation seems to be im- thane membranes. probable because of impossible increase in the The work will be printed in the "Journal of solubility as well as the lack of polydispersity of the Membrane Sciences". aggregates that excludes their breaking. The work was financially supported by the State Lack of the dispersity suggests that the aggre- Committee for Scientific Research, Poland under gates have the size of thermodynamical equilibrium Contract No 1297/T09/99/16. RADIOCHEMISTRY, STABLE ISOTOPES, 90 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL NEW VIEW ON STRUCTURE OF THE SYSTEM: CELLULOSE-WATER FROM TEMPERATURE TIME-RESOLVED SAXS Helena Grigoriew, Andrzej G. Chmielewski, Heinz Amenitsch1/ 11 Institute for Biophysic and X-ray Structure Research, Austrian Academy of Sciences, Graz, Austria This work is a continuation of our previous lab- set of very small peaks, close to the peak maximum. oratory studies on the system: cellulose-water [1,2]. Positions of the small peaks are the same for both The main goal of the work was to examine struc- systems. Their successive d-values follow the pro- tural changes induced by water in a dense cellulose portions: 1 : 2l!2 : 31/2 : 41/2, which are characteristic film. A membrane of cellulose film Tomophan I, for cubic crystal structure. It is the first indication dry and swollen in H2O or D2O to saturation (e.g. that the domains order to the cubic structure. The to 2.5 times its volume) was studied. lattice constant of the structure is about 30 nm. The measurements were performed using a Because cubic structure can be formed by spherical home made temperature chamber. In the center of centers only, the domains must be of spherical a heated concave cylinder is placed a sample shape. Similar structural effects in SAXS were container 2.5 mm long having small openings on its observed and explained earlier for copolymers cylindrical wall, joined with a pipe for vapor, which saturated with water. In the case of copolymers the assures the vapor flow across the container. Hot effect is due to self-association as a consequence of water vapor produced in a heated kettle is blown increased hydrophobicity of the copolymer at through the sample container by means of nitrogen. higher temperatures. For copolymer segments of The flow of vapor is started by opening of the elec- the first kind self-associate to form thermodynami- tro-magnetic valve. The temperature of vapor in the cally stable aggregates of reduced hydration. Seg- kettle, conducting tubing and sample, are con- ments of the second kind form a common medium trolled. The chamber makes it possible to conti- with water. The aggregates are commonly micelles nuously supply the sample with wet vapor as well as and can order themselves to crystal structure at to increase its temperature. high temperature. The mutual incompatibility of The SAXS and WAX measurements were various segments is considered to be essential to carried out using an Austrian SAXS Beamline at an the structural changes. Identical behaviour of such ELLETRA synchrotron. The line is mainly dedi- a polymer as cellulose is surprising. cated to time-resolved studies of fast structural The question is which parts of homogeneous transitions in non-crystalline systems. A high power polymer play a role of hard segments and which wiggler is used as bcamline source. Two one-dimen- ones - soft-segments, and what for? Now, one can sional gas-filled detectors [3] enabled us to simul- taneously perform fast, time-resolved SAXS and 1 WAX measurements. The first mreasurements were performed at room temperature starting with dry cellulose and saturating it with wet water vapor during the measurement cycle. This enabled us to determine the time period of the structural transition: dry cellulose-cellulose swollen in H2O or D2O. It occurred that the range was less than 1 sec, for both kinds of water. SAXS curves obtained at room temperature for dry cellulose and after saturating it in water revealed the effect of primary beam broadening. The radii of gyration obtained for the samples according to Guinier are the same (5.4 and 5.45 nm, respectively). It means that in the materials micro- regions inaccessible to water exist, which is evi- cC/J dence for their hydrophobicity. 1) Time-resolved temperature SAXS and WAX measurements were performed for the systems: cellulose-H20 and cellulose-D20 in the tempera- ture range 25-85°C at a rate of about 15 °C/min. They revealed emergence and growth of broad peak in SAXS of d-value 28 nm. The critical temperature of the effect, Tc, occurred of about 60 and 55°C, for D2O and H2O, respectively [4, 5]. In Fig. there is shown a SAXS peak for both systems at a maximum temperature (85°C). A specific feature of the peak 0.004 0.006 is the presence of its modulation in the form of a Fig. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 91 expect that this behaviour is characteristic also for [3]. Amenitsch H., Bernstorff S., Kriechbaum M., Lombardo D., simple polymers. To understand such a behaviour Mio D., Rappolt M., l^ggner P.: J. Appl. Cryst., 30, 872-876 (1997). of cellulose, further studies are needed. [4]. Grigoriew H., Chmielewski AG., Amenitsch H., Bernstorff S., Domagala J.: Time-resolved measurements of the system: Reference cellulose membrane-water. EPDIC-6, Budapest, August 1998. [1). Grigoriew H., Chmielewski A.G.: J. Mat. Sci. Lett., 16, Abstact book, PO9-18. 1945-1947 (1997). [5]. Grigoriew H., Chmielewski A.G., Amenitsch H.: sent for pu- [2]. Grigoriew H., Chmielewski A.G.: J. Membr. Sci., 142, 87-95 blication. (1998).

NEUTRON SPECTROSCOPY AND AB INITIO STUDY OF HYDROGEN BOND DYNAMICS IN L-SERINE Andrzej Pawlukojc, Janusz Leciejewicz PL0002027 Serine (2-amino-3-hydroxypropanoic acid) is one of diffraction experiments. Vibrational frequencies the aliphatic amino acids which constitute the build- were calculated using these data. All computations ing elements of protein systems. Crystallograhic data were performed on an HP-SPP computer in the indicate that in the solid state L-serine occurs in the Joint Institute of Nuclear Research in Dubna dipolar (zwitterionic) form and both, the amino and (Russian Federation).The results of optimized geo- hydroxyl groups participate in the network of hydro- metry calculations show that the molecule in the gen bonds. Neutron inelastic and incoherent scatter- zwitterion form is in the exited state due to the ing (IINS) spectra were collected for the normal and hydrogen bonds because large deformation of tors-

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0.50 -

0.00 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 Energy transfer (cnv1) Fig. Phonon density of states vs. energy transfer curve at 10 K for normal and deuterized L-serine. deuterized samples of the title compound at the ISIS ion angles appears only at the atoms taking part in Pulsed Neutron Facility in Rutherford-Appleton the hydrogen bond system. Vibrational frequencies Laboratory, Chilton, United Kingdom using a were calculated using the HF/6-31G* and TFXA spectrometer. The spectra were recorded at HF/6-311G** models for the free molecule in the 10 K. Fig. shows the phonon density of states against dipolar form. The analysis of the spectra obtained energy transfer curves for both samples. Gaussian 98 for both samples jointly with the results of ab initio program package was used for optimalization of the calculations made it possible to identify uniquely the molecular structure in the zwitterionic form adopt- modes due to the vibrations of hydrogen bonds ope- ing the data obtained in earlier X-ray and neutron rating in the crystals of L-serine. RADIOCHEMISTRY, STABLE ISOTOPES, 92 NUCLEAR ANALYTICAL. METHODS, CHEMISTRY IN GENERAL NEUTRON DIFFRACTION STUDY OF INCOMMENSURATE MAGNETIC ORDER IN TbOs2Si2 AND HoOs2Si2 1 2/ 1 1 |00 Malgorzata Kolenda ^ Michael Hofmann , Janusz Leciejewicz, Bogustaw Penc ', Andrzej Szytula ' iS v Institute of Physics, Jagellonian University, Krakow, Poland 21 IS Hahn-Meitner Institute, Berlin, Germany The title compounds exhibit the well known tetra- gonal crystal structure of ThCr2Si2 type which shows the c/a ratios of ca. 2.5. Therefore, the magnetic properties of these compounds are influenced by frustration of magnetic interactions associated with large magnetocrystalline anisotropy which in some compounds results in appearence of complex mag- netic ordering schemes at low temperatures. Neutron diffraction data collected at low temperatures using an E6 instrument at the BER II reactor in the Hahn-Meitner Institute in Berlin have shown that in TbOs2Os2 the magnetic moments of 11.3(1) Bohr magnetons at 1.5 K, localized on Tb+3 ions form an 15 T(K) 2° incommensurate sine modulated magnetic structure Fig. The temperature variation of magnetic moment values in described by the wave vector k= [0.313, 0, 0]. The HoOs2Si2- moments are aligned along the tetragonal axis. The first by ki = [3/10, 0, 0], the second by k2=[0.22, 0, 0]. Neel point is at 45 K. Two groups of magnetic The temperature variation of magnetic moments reflections were identified at 1.5 K on the neutron associated with each structure, shown in Fig., reveals diffraction pattern of HoOs2Si2 as belonging to two that the k2 structure vanishes at 8.6 K, while the kj magnetic ordering schemes. Both were found to be structure is stable up to 15.8 K - the Neel point of sine modulated described by the wave vectors; the

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART XXVIII: THE CRYSTAL STRUCTURE OF A FURAN-2-CARBOXYLATE 2+ POLYANIONIC COMPLEX n[Zn(H2O)6] [Zn8Na2(C5H3O5)i8(OH)2]n~ Beata Paluchowska1/, Jan K. Maurin1/, Janusz Leciejewicz 11 Institute of Atomic Energy, Swierk, Poland The crystals of the title compound contain octa- the [010] in the crystal (Fig.). In the polyanion tri- hedral cations [Zn(H2O)6]2+ and polyanions with meric moieties composed of Zn(II) ions forming the composition [Zn8Na2(C5H3O5)is(OH)2] 2- in rings with a hydroxy group inside can be dis- the form of molecular ribbons propagating along tiguished. These hydroxy groups are situated in the centers of the rings and aretriply bridged to the zinc(II) ions which make apices of nearly equi- lateral triangles. Each zinc(II) ion in this trimeric moiety is coordinated by furan-2-carboxylate li- gands and exhibits different coordination: Zn5-te- trahedral (mean Zn-O bond distance 1.949 A), Zn3-pentagonal (mean Zn-O bond distance 2.040 A) and Zn2-octahedral (mean Zn-O bond distance 2.109 A). The coordination polyhedra are distorted in each case. Furan-2-carboxylate ligands act either as bidentate bridges or are monodentally bonded both via the carboxylate oxygen atoms and furan heteroring oxygen atoms. Na(I) ions which are located in the symmetry centers coordinate either ten (Nal) or eight (Na2) oxygen atoms with mean Na-Ocarboxyiate and Na-Oheteroring bond lengths of 2.714 and 2.928 A, respectively. The cations are Fig. Simplified packing diagram of n[Zn(H2O)6] located in the cavities formed by adjacent anions. [Zn8Na2(C5H3O5)i8(OH)2]i~. Only one polyanion is The coordinated water molecules around the displayed. The cations in this picture are located between two adjacent polyanions which are not shown for clarity. Zn(II) ion, which is located in the center of symme- RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 93 tryform - a slightly deformed octahedron with the zine-2,3-dicarboxy!ic and 3-aminopyrazine-2-carboxylic acids. Zn-0 bond distances ranging from 2.059 to 2.121 Polish J. Chem., 12, 715-725 (1999). [2]. Part XXIV: Ptasiewicz-Bak R, Leciejewicz J.: Molecular A. Each of the water molecules interacts via hydro- ribbons in the crystals of a new Cu(II) complex with pyra- gen bonds with carboxylate oxygen atoms and the zine-2,3-dicarboxylate ligand. Polish J. Chem., 73, 853-858 oxygen atoms situated in the centers of the triangles (1999). composed by the zinc(II) ions. X-ray diffraction [3]. Part XXV: Ptasiewicz-Bqk H., Leciejewicz J.: The crystal and molecular structure of a Zn(II) complex with pyrazine-2,3-di- measurements were carried out using a KUMA carboxylate ligand. Polish J. Chem., 22,1887-1894 (1999). KM4 four circle diffractomer at this Institute. Data [4]. Part XXVI: Ptasiewicz-Bqk H., Leciejewicz J.: Molecular rib- processing and structure refinement was performed bons composed of calcium(II) ions bridged by carboxylate and using the SHELXL 97 programme package. water oxygen atoms in the crystals of Ca(II) complex with 5-me- thylpyrazine-2-carboxylate ligands. J. Coord. Chern., in press. [5], Part XXVII: Paluchowska B., Maurin J.K., Leciejewicz J.: References X-ray diffraction study on manganese(II) complexes with [lJ.Part XXIII. Ptasiewicz-Bgk H., Leciejewicz J.: Crystal and thiophene-2-carboxylate and furan-3-carboxylate ligands. J. molecular structures of nickcl(II) complexes with pyra- Coord. Chem., in press.

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART XXIX: THE CRYSTAL STRUCTURE OF MONOAQUABIS(TRANS-5-METHYLPYRAZINE-2-CARBOXYLATO N,O) COPPER(II) TRIHYDRATE Halina Ptasiewicz-Bqk, Janusz Leciejewicz Molecular chains consisting of Cu(II) ions coordi- hedral with distinct elongation along the axis which nated by two ligand molecules via their N,O bond- is perpendicular to the plane formed by the two ing moieties, bridged by carboxylate oxygen atoms pyrazine-2-carboxylate molecules. Since we have donated by the adjacent ligand molecules were observed in calcium(II) complexes with pyrazine detected in the crystals of copper(II) complex with carboxylate ligands that their molecular patterns pyrazine-2-carboxylate ligand [1]. This compound depend on the size of the ligand molecules, we have exhibits a second modification with a different mo- undertaken a study of molecular structure of lecular pattern consisting of monomeric molecules copper(II) complex with 5-methylpyrazine-2-carbo- in which the Cu(II) ion is coordinated by two py- xylate (MPZA) ligand in order to check if this effect razine-2-carboxylate ligands in trans configuration is present in the complexes with other than calc- and two water molecules [2]. In both modifications ium (II) ions. The title complex was obtained by re- the coordination around the Cu(II) ion is octa- acting hot aqueous solutions of MPZA and copper H7"'

012IV

Hll

H23 H21

Fig. Two molecules of Cu(MPZA)2(H2O) • 3H2O. Broken line indicates the Cu-O distance of 3.253 A. RADIOCHEMISTRY, STABLE ISOTOPES, 94 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL nitrate. Dark-blue plate-like single crystals depo- molecule is situated above this plane at a distance sited after standing over a couple of days. X-ray of 2.250 A resulting in a coordination polyhedron data collection was done using a KUMA KM4 four in the form of a square pyramid. Another oxygen circle diffractometer at this Institute. Data pro- atom belonging the the carboxylate group of an cessing and refinement was performed using the adjacent ligand molecule has been found at a SHELXL 97 programme package. The crystals of distance of 3.253 A. Two molecules of the title the title compound contain monomeric molecules complex are displayed in Fig. in which the Cu(II) ion is coordinated by two ligand References molecules via their N,O bonding moieties forming a [1]. Klein C.L., Majeste R.J., Trefonas L.M., O'Connor C.J.: planar square around the metal ion with mean Inorg. Chem., 21, 1891(1981). Cu-O and Cu-N bond distances of 1.951 and 1.992 [2]. Ptasiewicz-Ba.k H., Leciejewicz J., Zachara J.: J. Coord. A, respectively. An oxygen atom donated by a water Chem., 26, 317(1995).

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART XXX: THE CRYSTAL STRUCTURE OF A Ca(II) COMPLEX WITH PYRIDINE-3,4-DICARBOXYLATE LIGAND Wojciech Starosta, Halina Ptasiewicz-Bqk, Janusz Leciejewicz Calcium(II) ion in its complexes with carboxylate pyridine-3,4-dicarboxylate (cinchomerate) ligand ligands is known for its bonding flexibility and coor- was determined. The crystals of the title compound dinates from 5 to 9 donor ligands showing irregular contain molecular ribbons in which two adjacent geometry with Ca-O bond distances ranging from Ca(II) ions are bridged via oxygen atoms donated 2.2 to 2.8 A. In the Ca(II) complexes with pyridine by the carboxylate group attached to the carbon and pyrazine carboxylate ligands heteroring nitro- atom in position "3" in the pyridine ring. Both car- gen atoms are often participating in coordination of boxylate oxygen atoms act in bidentate mode, each the central ion forming N,O bonding moiety with being coordinated to two Ca(II) ions with Ca-O nearest carboxylate oxygen atom. It has been ob- bond distances of 2.423 and 2.779 A. In addition, served that Ca(II) coordination modes are affected every second pair of Ca(II) ions is bridged by an by the size of the ligand. We have therefore under- oxygen atom donated by a water molecule with taken a systematic study of calcium(II) coordination Ca-O bond distance of 2.572 A. The coordination modes in the crystals of its complexes with pyridine polyhedron is a pentagonal bipyramid: its equa- dicarboxylate ligands. As the first step the crystal torial plane is composed of two bridging oxygen and molecular structure of a Ca(II) complex with a atoms each belonging to the carboxylate group of

Fig. A fragment of the molecular ribbon in the structure of Ca(3,4-PDDC)(H2O)4 with numbering of atoms. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 95 the neighbouring ligands, the bridging water oxygen metal ion. Both oxygen atoms of the carboxylate atom and two oxygen atoms from the coordinated group attached to the carbon atom in the position water molecules with Ca-O bond distances of 2.433 "4" in the pyridine ring are not directly coordinated and 2.395 A. Another oxygen atom of a coordinated to the Ca(II) ion and act as acceptors in the water molecule constitutes the apex of the pyramid hydrogen bond system. Fig. shows a fragment of the on one side of the equatorial pentagon, while two molecular ribbon with numbering of atoms. X-ray bridging oxygen atoms donated by the same car- diffraction data were collected using a KUMA KM4 boxylate group form two apices on the other side of four circle diffractomer at this Institute. Data pro- the pentagon. The pyridine heteroring nitrogen cessing and structure refinement was carried out atom does not participate in coordination of the using the SHELXL 97 program package.

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLATE LIGANDS. PART XXXI: THE CRYSTAL STRUCTURE OF A Ca(II) COMPLEX WITH PYRIDINE-3,5-DICARBOXYLATE LIGAND Wojciech Starosta, Halina Ptasiewicz-Bqk, Janusz Leciejewicz As a consecutive step in our ongoing research on five oxygen atoms with Ca-O bond distances rang- the crystal chemistry of calcium(II) complexes with ing from 2.397 to 2.429 A. The coordination poly- pyridine dicarboxylate ligands we have determined hedron is represented by a strongly distorted pen- the crystal and molecular structure of a calcium tagonal bipyramid. The molecule of each ligand is complex with pyridine-3,5-dicarboxylatc (dinicoti- planar. Its second carboxylate group does not coor- nate) ligand. This complex contains in its crystals dinate the metal ion but is involved in an extensive centrosymmetric dimeric molecules in which two network of hydrogen bonds. X-ray diffraction data

O3

C6

N

Fig. The dimeric molecule of Ca2(3,5-PDDC)2(H2O)i0 dihydrate with numbering of atoms. Ca(II) ions are bridged by carboxylate oxygen atoms were collected using a KUMA KM4 four circle acting in monodentate mode. This molecule is diffractomer at this Institute. Data processing and shown in Fig. with numbering of atoms. The Ca-Ol structure refinement was carried out using the bond length is 2.443 A, Ca-O2 - 2.340 A. The coor- SHELXL 97 program package. dination around each Ca(II) ion is completed by RADIOBIOLOGY RADIOBIOLOGY 99 DIFFERENTIAL INACTIVATION OF DNA-DEPENDENT PROTEIN KINASE IN H2O2-TREATED L5178Y-R AND L5178Y-S CELLS Barbara Sochanowicz, Marcin Kruszewski, Irena Szumiel DNA-dependent protein kinase (DNA-PK), a 3 cells to X-rays is related to the impairment of DSB subunit complex of high molecular weight, is ac- rejoining [2], whereas hypersensitivity of LY-R tivated by DNA double strand breaks (DSB) [1]. cells to H2O2 is due to a high iron content in the The enzyme is a part of the DSB repair system, nuclei of these cells [3]. OK-1035, an inhibitor of called NHEJ (non-homologous end-joining). It is DNA-PK, inhibits DNA repair in LY-R cells (Gl and S phase) but not in LY-S cells [4]. On the other LY-R hydrogen ptrontt 1 h. 37 oC hand, we found (unpublished data) that in the presence of excess fragmented DNA, that is, under standard assay conditions [5], there is a comparable activity of DNA-PK in both LY sublines. There is, however, a difference between LY sublines in DNA-PK activity levels after y-irradiation. Upon post-irradiation incubation there is a marked de- crease in activity in LY-R cells and a delayed but relatively more pronounced one, in LY-S cells. After H2O2 treatment the pattern of relation- 0 oi O3S os© 10 20 ship between H2O2 concentration and DNA-PK ac- HYDROGEN PEROXIDE (MILIMOLES) tivity differs between the LY sublines, when mea- sured 1 h after the end of treatment. As shown in Fig., the marked decrease in activity in LY-R cells LY-S is in proportion to the expected extent of damage in hydrogen p«rcrkS« 1 h. 3TeC the H2O2 concentration range from 0.1 to 1 mM; in LY-S cells the decrease starts only at 0.5 mM H2O2. FFi This result is in agreement with that after X-irradi- ation, where early inactivation of DNA-PK has been observed in LY-R, in contrast with LY-S cells. - This work was supported by the Polish State Committee for Scientific Research, a statutory grant for the INCT. Q — oLi L_i 1 References 0 01 025 090 10 20 HYDROGEN PEROXIDE (MILIM3LES) [1]. Anderson C.W., Lees-Miller S.P.: Crit. Rev. Eukaryot. Gene Fig. Alterations in DNA-PK activity after treatment of LY cells Express., 2, 283-314 (1992). with hydrogen peroxide (1 h, 37°C) and subsequent 1 h incu- [2].Wtodek D., Hittelman W.N.: Radiat. Res., 112, 146-155 bation. (1987). [3]. Kruszewski M., Green M.H.L., Lowe J.E., Szumiel I.; Mutat. active in Gl and S phases of the cell cycle. We Res., 226, 55-163(1994). undertook examination of DNA-PK activity in a [4], Kruszewski M., Wojew6dzka M., Iwaneriko T., Szumiel I.: Mutat. Res., 409, 31-36 (1998). pair of L5178Y (LY) sublines, LY-R (radiation re- [5]. Finnie N.J., Gottlieb T.H., Blunt T, Jeggo P.A., Jackson 5.P.. sistant, H2O2-sensitive) and LY-S (radiation sensi- Proc. Nat. Acad. Sci. USA, 22, 320-324 (1995). tive, HkCVresistant). The high sensitivity of LY-S

ERBSTATIN-INDUCED INCREASE IN APOPTOSIS DOES NOT RADIOSENSITIZE L5178Y CELLS Iwona Buraczewska, Anna Gasihska1', Iwona Gr^dzka, Nella Jarocewicz, Barbara Sochanowicz, IS Irena Szumiel IS 1/ Radiotherapy Clinic, Oncology Center, Krak6w, Poland ! O Tyrosine protein kinase (TPK) activity is essential lignant cells. In this report we examine the effect of in the cell cycle control, cell-cell communication, ERB treatment in combination with X-irradiation generation of lipid-linked second messengers, etc. on a pair of L5178Y (LY) sublines. The sublines TPK signalling is an important target for anticancer are: LY-R (parental) and LY-S (radiation-sensitive drug development [1]. One of such anticancer drugs variant). Mean lethal doses of X rays are about 1 is erbstatin (ERB). Gy and about 0.5 Gy for LY-R and LY-S cells, No reports have been published so far on the respectively [2]. The difference is due to the defect possible interaction of ERB with radiation in ma- in DSB rejoining [3-6]. 100 RADIOBIOLOGY There was a difference in the extent of the irradiation. However, apoptosis was markedly en- ERB-induced apoptosis in the LY sublines. Apop- hanced by combined treatment, as shown in Fig.: tosis was measured cytometrically as the percentage LY-R cells were much more susceptible to this treatment than LY-S cells. These results were essentially confirmed by the electrophoretic DNA pattern (Fig.). Fragmentation was not seen clearly enough in ERB-treated LY-R cells, in spite of a large sub Gl fraction. In clonogenic survival determinations the effects of the drug and radiation were additive. The mean lethal doses (±SE) were 1.56 ±0.330 Gy and 1.52 ±0.163 Gy for LY-R cells, irradiated without or with ERB pre-treatment, respectively. For LY-S cells the respective values were 0.576 ±0.060 Gy CTRL ERB 4OyX ERB*X CTRL ERB 2QyX ERB«X and 0.573 ±0.125 Gy (mean results from 3-4 experi- LY-R LY-S ments; survival of cells subjected to combined ERB plus X-ray treatment was normalised to that of the ERB-treated cells). LY-R The ERB-induced increase in apoptosis in the X-irradiated cell population affects post-treatment growth (not shown). Nevertheless, it does not affect LV-S the X-ray cell killing: the results of cloning reveal no difference between ERB untreated and pre-treated cells. Factors that induce apoptosis are often con- sidered as potentially sensitising [7]. This report shows that this is not always the case. It strongly Fig. Top panel: Induction of apoptosis in LY sublines by ERB (5 supports the numerous warnings that short-term ,ug/ml) alone and in combination with X-rays (4 Gy (LY-R) and 2 Gy (LY-S)). The measure of apoptosis was sub Gl assays do not reliably estimate the level of cell kill- fraction determined by flow cytometry. Mean values from 2 ing, which is the ultimate measure of the therapeutic measurements ± range are shown. Bottom panel: Electro- efficiency. phoretic DNA pattern in LY cells treated with ERB (5 jUg/ml) alone and in combination with X-rays, 4 Gy (LY-R) References and 2 Gy (LY-S). The "ladder" pattern seen e.g. in lane 1 (standard) indicates advanced internucleosomal fragmenta- [1 j. Powis G., Kozikowski A.: Clin. Biochem., 24, 385-397 (1991). tion. [2], Beer 3.7.., Budzicka E., Niepokojczycka E., Rosiek O., Szu- miel I., Walicka M.: Cancer Res., 42, 4736-4742 (1983). [3].Wiodek D., Hittelman W.N.: Radiat. Res., 112, 146-155 of cells with less than Gl amount of DNA; the loss (1987). is due to DNA fragmentation that is a hallmark of [4j.Wtodek D., Hittelman W.N.: Radiat. Res., Hi, 550-565 apoptotic death. Fig. (top panel) shows that the (1988). used ERB concentration caused apoptotic death in [5]. Wtodek D., Hittelman W.N.: Radiat. Res., Ill, 566-575 a relatively low fraction of the cell population. The (1988). [6]. Evans H.H., Ricanati M., Horng M.F.: Proc. Natl. Acad. Sci. effect was significantly more pronounced in LY-R USA, 8.4, 7562-7566 (1987). than in LY-S cells (Student's t test, p<0.05). X-rays [7]. Schmitt C.A., Lowe S.W.: J. Pathol., 181,127-137 (1999). alone did not induce much apoptosis 24 h after

ERBSTATIN-INDUCED ALTERATIONS IN CELL CYCLE DISTRIBUTION IN THE X-IRRADIATED L5178Y CELLS 1 I O Iwona Buraczewska, Anna Gasinska ', Irena Szumiel ! CM 11 i§ Radiotherapy Clinic, Oncology Center, Krakow, Poland ! O A potential anticancer drug, erbstatin (ERB) in- ERB treatment (5 ^g/ml) affected cell cycle hibits tyrosine protein kinase (TPK.) activity be- distribution of both LY sublines. Untreated cells longing to receptor kinases (e.g. epidermal growth showed a similar distribution among the three cell factor receptor, EGFR) and non-receptor kinases cycle phases analysed (Figs. 1A and 2A), but the (among them many proto-oncogenes). Information pattern was changed 24 h after ERB treatment in on its effects in X-irradiated cells is scarce. We used LY-R cells. There was a considerable increase in cell flow cytometry to estimate ERB effects on cell cycle percentage in the Gl phase compartment accom- progression of X-irradiated L5178Y (LY) cells of panied by a decrease in S phase compartment two sublines, LY-R and LY-S; their mean lethal (Fig.IB). In LY-S cells, these changes were much doses of X rays are about 1 Gy and about 0.5 Gy, less marked (Fig.2B). The size of the S phase com- respectively [1]. The procedure of cell staining was partment alone does not tell about the course of according to [2]. DNA replication. Therefore, the labelling index (LI) RADIOBIOLOGY 101

A. LY-R CONTROL B. LY-R ERB 80 as in ERB-treated LY cells it decreased. This shows that DNA replication was disturbed by ERB treat- 70 ment. The effect was pronounced in LY-R cells in 60 rh (LI/S ratio equal to 0.51) and much less marked in o 50 LY-S cells (LI/S ratio equal to 0.89). Further, we examined the effects of combined s ERB+X-radiation treatment The same concentra- tion of ERB was applied (5 jug/ml) but the X-ray dose was adjusted to be approximately equitoxic for LY-R and LY-S cells (4 and 2 Gy, respectively). Radiation alone emptied the Gl compartment due

G1 G2 C2/W to the G2 arrest. LY-R cells traversed the S phase relatively undisturbed, as judged from the compari- son of S phase cells and the labelling index (LI/S C. LY-R 4 Qy X D. LY-R ERB+X ratio equal to 0.87; Fig.3A). On the contrary, a low percentage of LY-S cells incorporated BrUrd (LI/S ratio equal to 0.26; Fig.3B). ERB treatment considerably increased the G2 I compartment in LY-S cells; since the LI/S ratio A. LY-R i mm I i

G1 S G2/M G1 S G2/M Fig.l.Cell cycle distributions of LY-R cells: A - control; B - treated with 5 ,ug/ml ERB alone; C - X-irradiated (4 Gy); D - ERB-treated and X-irradiated. Mean values from 2 measurements ± range are shown.

CONTROL ERB X 4Oy ERB*X was estimated and compared with the percentage of X

A. LY-S CONTROL B. LY-S ERB SO1 — B. LY-S

70 70 w 60 dEq _j "J 60 of O 50 XI O 50 O JL (3 2 « i i

LL) a io —1 1*1 CONTROL ER9 X 2G» 6RB-X G.I. S G2/M G2/M X2Gy ERB'X CONTROL 6RB % IN S PHASE % LABELLING INDEX Fig.3. Comparison of the percentage of cells in S phase and C. LY-S Z Oy X 0. LY-S ERB»X percent labelling index (bromodeoxyuridine incorporation 80 so into DNA); A - LY-R cells; B - LY-S cells. X-ray doses: 4 Gy (LY-R) and 2 Gy (LY-S); 5 fig/ml ERB for single or 70 70 combined treatment. Mean values from 2 measurements 3 60 i 80 are shown.

50 u. after combined treatment was equal to 0.41. Appa- O + g 40 rently, ERB counteracted the post-radiation inhibi- tion of DNA replication and thus, the cells were SO able to progress through the S phase and pass to 2D 20 the G2/M phase (compare Fig.2C and D). On the 10 contrary, the Gl compartment of LY-R cell popu- lation was not emptied and the G2/M compartment 1-*-, n en G- S G2/M Gl S G2/M did not differ from that after irradiation alone Fig.2.Cell cycle distributions of LY-S cells: A - control; B - (Fig.lC,D). treated with 5 ,ug/ml ERB alone; C - X-irradiated (2 Gy); D - ERB-treated and X-irradiated. Mean values from 2 In spite of these differences in ERB effects on measurements ± range are shown. progression through the cell cycle of the X-irradi- 102 RADIOBIOLOGY ated LY cells, we found no difference in the drug's [2]. Wilson G.D., McNally N.J., Dunphy E., Kracher H, Pfagner effect on the post-irradiation cell kill. R.: Cytometry, 6, 641-647 (1985). References [1]. Beer J.Z., Budzicka E., Niepokojczycka E., Rosiek O., Szu- miel I., Walicka M.: Cancer Res., 42, 4736-4742 (1983). PL0002053

TOTAL TYROSINE PROTEIN KINASE ACTIVITY IN X-IRRADIATED L5178Y CELLS Barbara Sochanowicz, Irena Szumiel Tyrosine protein kinase (TPK) activity is manifest- ed by 2 classes of enzymes: receptor kinases (e.g. epidermal growth factor receptor, EGFR) and non- -receptor kinases (among them many proto-onco- genes). Both transfer a phosphate residue from a nucleotide, usually ATP, to a substrate protein. This results in an alteration of the protein's biologi- cal activity; the consequence is the modulation of the relevant cellular process (review in [1, 2]); TPK activity is essential in the cell cycle control, cell-cell communication, generation of lipid-linked second messengers etc. Its importance for the cellular res- ponse to ionising radiation has been studied for the last few years. Ł CONTROL 1 3 CONTROL 1 TIME AFTER IRRADIATION (HOURS) TPK activation is a mandatory proximal step in radiation-induced signalling through protein kinase C-dependent pathway [3]; some further steps down- stream there are such important tyrosine-phospho- rylated kinases as RAF1 and MAPK (mitogen acti- vated protein kinase). Also the c-Abl TPK becomes activated in irradiated cells and plays an important role in the cellular response, both in cell cycle prog- ression and radiation-induced apoptosis (review in W)- For determination of TPK approximately 4x10 LY-R or LY-S cells were X-irradiated (1 Gy) and the whole cell extracts were prepared according to Finnie et al. [5] after time intervals indicated in Fig.l. Total TPK activity was determined in cellular 5. CONTROL 1 3 CONTROL 1 3 extracts with the use of Boehringer-Mannheim TIME AFTER IRRADIATION (HOURS) (GFR) ELISA kit, according to the manufacturer's Fig.l.Stimulation of tyrosine protein kinase activity by X-ir- procedure. radiation in LY-R and LY-S cells. A) PKS1 - protein kinase TPK activity in the control and X-irradiated LY substrate 1 (Biotin-KVEKIGEGiTGVVK-amide) cor- cells was estimated with the use of two protein responds to amino acids 6-20 of the cell division kinase p34cdc2 g) PKS2 - protein kinase substrate (Biotm- kinase substrates, PKS1 and PKS2 (Fig.l legend). -EGPWLEEEEEAYGWMDF-amide) corresponds to the Figs.lA and B show the results obtained with PKS1 amino acid sequence 1-17 of gastrin. Cells were X-ir- and PKS2, respectively. In the control LY-R cells, radiated (1 Gy); after 1 or 3 h incubation whole cell extracts were prepared according to Finnie et al. [5], Data the activity was the same with both substrates and shown are mean results of 2 determinations ± range. the course of TPK activity increase and decrease - almost identical. In the control LY-S cells, the ac- close relation of the LY sublines and many simi- tivity was lower than that in LY-R cells with PKS1 larities in the basic characteristic features [6], the but higher - with PKS2. The differential substrate pattern of TPK activation in the X-irradiated LY specificity of TPK in the LY sublines also was seen sublines differs; this observation warrants further after irradiation: with PKS1 stimulation, it was investigation of PTK in these sublines. delayed in LY-S, as compared to LY-R cells, but was of similar magnitude; with PKS2 stimulation, it References was seen 1 h after irradiation, but again, the highest [l].Glenney J.R., Jr: Biochim. Biophys. Acta, 1134, 113-127 activity in LY-S cells was revealed 3 h after irra- (1992). diation, when it exceeded that in LY-R cells. At [2], Kaplan D.R., Perkins A., Morrison D.K..: Signal transduction by receptor tyrosine kinases. In: Oncogenes and Tumor Sup- that time point, the TPK activity in LY-R cells pressor Genes in Human Malignancies. Eds. C.C. Benz, ET. returned to the control level. So, in spite of the Liu. ICluwer Academic Publishers, Boston 1993, pp. 265-279. RADIOBIOLOGY 103

[3]. Uckun F.M., Schieven G.L., Tuel-Ahlgren L.M., Dibirdik I., [5]. Finnic N.J., Gotlieb T.M., Blunt T., Jeggo P., Jackson S.P.: Myers D.E., Ledbetter J.A., Song C.W.: Proc. Nat. Acad. Sei. Proc. Nati. Acad. Sei. USA, 92,320-324 (1995). USA, 20,252-256(1993). [6], Beer J.Z., Budzicka E., Niepokojczycka E., Rosiek O., Szu- [4]. van Etten R.A.: Trends Cell Biol., 2,179-186 (1999). iniel I., Walicka M.: Cancer Res., á2, 4736-4742 (1983).

APOPTOSIS IN MAMMALIAN CELL LINES PL0002054 WITH DIFFERENT RADIATION SENSITIVITY: COMPARISON AFTER LOW DOSE X-IRRADIATION Alicja Jaworska1'', Paula De Angelis1', Irena Szumie!, GoriI Olsen1'', Jon Reitan1' 11 Norwegian Radiation Protection Authority, Oslo, Norway In the past few years the interest for using apoptosis In this work we have measured apoptosis in 5 re- as a possible measure of radiosensitivity has been latively radiation sensitive cell lines following X-ray substantially increased both with regard to the irradiation with doses from 0.1 to 2 Gy. These were possibilities of using the extent of apoptosis as a two lymphoid AT cell lines, one homozygous and biological dosimeter [1] and for estimating the one heterozygous for the ATM gene, the human radiosensitivity of cancer cells prior to radiotherapy pre-B cell line, Reh, and two murine L5178Y lym- [2-4]. phoma cell lines, LY-R and LY-S.

L5178Y-R G00736A

0,5 1.0 1/ 2.0 0.5 1,0 1,5 Dose(Gy) Dose(Gy)

L5178Y-S „G00717C

0.S 1.0 ij svo Doae(Gy) Oose(Gy)

Reh

0.0 05 1,0 1,5 2.0 Dose(Gy) Fig. X-ray-induced apoptosis in human and murine lymphoid cell lines, estimated by the TUNEL method. 104 RADIOBIOLOGY For detection of apoptotic DNA fragmentation at X-rays (Do=O.7 Gy) was similar to that of LY-S, different time intervals after X-irradiation, cells were deficient in radiation induced apoptosis. In were fixed in 1% paraformaldehyde for 10 min at the homozygous GM00717C cells, levels of apopto- 0°C, spun down, resuspended in ice cold methanol sis were not higher than those seen in LY-R. and stored at -20°C. For fluorescence staining of Timing of apoptosis also varied considerably. For free DNA ends the TUNEL assay of Gorczyca et al. L5178Y and Reh cells, a maximum was detected 48 [5] was used. Fluorescence distribution in the cells h after X-irradiation, whereas for AT cell lines was measured using a FACS Vantage flow cytome- maximal apoptosis was seen at 72 h. Significant in- ter (Becton Dickinson Immunocytometry Systems, duction of apoptosis was found for G00736A only San Jose, CA, USA), equipped with an Enterprise at 2 Gy and 72 h. ion laser (Coherent, Santa Clara, CA, USA) Overall, approximation to linear relationship be- that had an excitation wavelength at 488 nm. tween dose and apoptosis percentage could be ob- Fluoresceine (green) fluorescence from the apopto- served only for the optimal time of apoptosis for tic cells was detected at wavelengths from 500 to 560 those two lines which were relatively proficient in nm, and propidium iodide (red) fluorescence (DNA it, that is, LY-S and Reh. Thus, it seems that apop- content) was detected at 608-652 nm. CellQuest tosis alone has no potential as a radiation sensi- software (Becton Dickinson) was used to estimate tivity marker or as an exposure indicator in these the apoptotic fraction. cell lines. Possibly, it may serve as such in conjunc- The propensity for apoptosis as determined by tion with other markers which have to be identi- the TUNEL (terminal deoxynucleotidyl transfe- fied. rase) assay was very different in the cell lines examined (Fig.) and was not related to radiation References sensitivity, estimated from clonogenic survival. At [1]. Boreham D.R., Dolling J.A., Maves S.R., Miller S., Morrison D.P., Mitchel R.E.: Biochem. Cell Biol., 25., 393-397 (1997). the doses examined, the highest levels of apoptosis [2]. Guo G.Z., Sasai K., Oya N., Shibata T., Shibuya K., Hiraoka were detected in the X-ray sensitive cell line LY-S M.: Int. J. Radiat. Bio!., 71, 857-864 (1999). (Do=O.5 Gy), whereas in the more resistant LY-R [3].Rupnow B.A., Murtha A.D., Alarcon R.M., Giaccia A.J., line (Do=l.O Gy) only a small percentage of apop- Knox S.J.: Cancer Res., 5j£, 1779-1784 (1998). [4]. Kem P., Keilholz L., Forster C, Seegen-Schmiedt M.H., Sauer totic cells was detected. Reh cells, which are the R., Herrmann M.: Int. J. Radiat. Biol., 75_, 995-1003 (1999). second resistant cell line in this study (Do=ca 1.2 [5]. Gorczyca W., Gong H., Darzynkiewicz Z.: Cancer Res., 53., Gy), was relatively proficient in radiation-induced 1945-1951(1993). apoptosis. The AT cell lines whose sensitivity to

CELL CULTURE CONDITIONS AS A CRITICAL FACTOR IN DETERMINATION OF APOPTOSIS: FETAL CALF VERSUS BOVINE SERUM Tomasz Otdak , Martin Kruszewski, Iwona Buraczewska, Iwona Grqdzka 1/ Oncology Center, Warszawa, Poland

It is considered that the cellular machinery pre- LY-R.0O4 pared to eliminate a damaged cell by apoptosis is in OH the state of readiness and can be set to work by selective stimuli. A counterbalance is formed by "survival factors". According to the apoptosis (dual signal) model of Evan et al. [1] these are various growth factors of differential selectivity and specificity, which have an anti-apoptotic effect. In vitro, the source of survival factors is the serum added to the cell culture medium. In order to examine the apoptosis proneness of a pair of L5178Y (LY) sublines we used hyperthermia (HT; 42°C, 30 min) as apoptosis inducer and various cell culture conditions (Fischer's medium with bovine (BS) or fetal calf (FCS) serum, 8 and 10%, respec- tively), before HT; phosphate-buffered saline (PBS) was used for post-HT treatment incubation.

The LY-R subline is relatively more radiore- 102 10" 10"* sistant than the LY-S subline, while being slightly DIOC6 more susceptible to HT, and markedly more sen- Fig. An example of flow cytometric measurement of various states sitive to UV-C radiation and oxidants [2-4]. We of cells in the examined cell population. The upper left quad- rant corresponds to necrotic cells, lower left - to apoptotic used flow cytometry to identify the fraction of cells cells and lower right - to viable cells with high mitochondrial in early apoptosis. Cells were stained according to membrane potential. RADIOBIOLOGY 105 the previously described method [5] with modifi- negligible. These results indicate that pre-HT cul- cations. DiOC6 (3,3 dihexylocarbocyanine , turing in the medium with bovine serum allows the Sigma) was stored as a 1 mM stock in DMSO Table 2. Percentages of viable, apoptotic and necrotic cells in LY (dimethyl sulfoxide; Aldrich). The volume of 2 //I cell populations pre-cultured in BS or FCS-supplement- ethanol diluted stock of DiOC6 (to the concen- ed Fischer's medium and placed in PBS for 3 h. 5 tration of l?0 /uM) was added to 2xlO cells Cells BS -» PBS FCS -» PBS resuspended in 0.5 ml PBS (Gibco). Incubation (15 LY-R min) at 37°C in the dark, was followed by the addition of 10 /J.1 PI (propidium iodine, 500 fig/ml; viable 78.0 99.4 Sigma). Cells were immediately analysed. Two- apoptotic 4.0 0.26 -colour flow cytometric analysis performed on necrotic 18.0 0.6 FACSCalibur instrument (Becton Dickinson) with LY-S the use of CellQUEST™ software (Becton Dickin- viable 89.6 99.0 son) consisted in creating a gate for optimal debris apoptotic 3.3 0.3 exclusion on forward scatter (FSC) versus side necrotic 7.1 0.7 scatter (SSC) dot plot. Then the DiOC6-events were gated on a FL1 histogram plot. A second FL2 development of apoptosis during the subsequent histogram plot showing DiOC6-cells was created to incubation in PBS. In contrast, pre-HT culturing in exclude the Plbright (necrotic) events in the DiOC6- the fetal calf serum-supplemented medium pre- -population. The DiOC6-/PI-events were regarded vents the onset of apoptosis for at least 20 h. The as a apoptotic cells. Fig. shows an example of the latter can be expected to contain survival factors at higher concentrations or some additional survival Table 1. Percentages of viable, apoptotic and necrotic cells in LY cell populations pre-cultured in BS or FCS-supplement- factors, which delay the onset of apoptosis or pre- ed Fischer's medium and HT-treated (42°C, 30 min). vent it completely. The proneness to HT-induced Cells BS- PBS FCS -• PBS apoptosis in LY sublines is similar under all condit- ions; hence, the response to survival factors con- LY-R Oh 3h Oh 2h 20 h tained in FCS is equal in both LY sublines, when viable 80.8 13.7 99.4 92.7 97.0 the end-point considered is the HT-induced apop- apoptotic 3.6 79.9 0.3 6.1 2.3 tosis. necrotic 15.6 6.4 0.4 1.2 0.7 References LY-S Oh 3h Oh 2h 20 h viable 95.5 14.4 99.7 97.2 94.3 (lJ.Evan G., Littlewood T.: Curr. Opin. Genet. Dev., 3_. 44-49 (1993). apoptotic 0.8 71.9 0.1 1.7 5.7 [2]. Beer J.Z., Kapiszewska M.: Natl. Cancer Inst. Monographs, necrotic 3.7 13.7 0.2 1.1 0.01 61,115-117(1981). [3]. Beer J.Z., Budzicka E., Niepokojczycka E., Rosiek O., Szu- above-described cytometric measurement of apop- miel I., Walicka U.: Cancer Res., 42, 4736-4742 (1983). tosis. The percentages of apoptotic cells thus iden- [4]. Kruszewski M., Green M.H., I.owe .T.E., Szumiel I.: Mutat. Res., 3J8_,233-241 (1994). tified are presented in Table 1. Table 2 shows that [5]. Hertveldt K., Philippe J., Thierens H., Cornellisen M., Vra! the effect of incubation of control cells in PBS is A., De Ritter L.: Int. J. Radiat. Bio!., ZL, 429-433 (1997).

X-IRRADIATION OF Gl CHO CELLS INDUCES BOTH TRUE AND FALSE SCE IN BrdU-SUBSTITUTED CELLS BUT ONLY FALSE SCE IN BIOTIN-dUTP-SUBSTITUTED CELLS LO Elisabeth Bruckmann1, Andrzej Wojcik, Giinter Obe1/ IS ^Institute of Genetics, University of Essen, Germany !8 Sister chromatid exchanges (SCE) are regarded as a [3]. DNA lesions leading to SCE in BrdU-sub- result of DNA repair by homologous recombina- stituted DNA could be produced by debromination tion. In linear chromosomes SCE can only be reco- and radical reactions which can give rise to alkali gnised if the two sister chromatids of metaphase labile sites and strand breaks and this is augmented chromosomes are differentially labelled. This was by X-rays [4]. first achieved by incorporation of tritiated thymi- It is generally assumed that SCE are formed dine and later on by substitution of thymidine with from DNA lesions during the S-phase of the cell 5-bromodeoxyuridine (BrdU) [1]. A major disad- cycle [5]. This applies to S-phase dependent agents. vantage of tritium is that it induces SCE through its In contrast, S-phase independend agents which [2]. However, also the radica- directly produce DNA double strand breaks (dsb) lisation of BrdU may lead to SCE [3]. Despite such as restriction endonucleases, bleomycin, neo- numerous studies, the exact contribution of BrdU carcinostatin, DNasel and ionising radiation, can to "spontaneous" and "induced" frequencies of SCE lead to SCE when unifilarily BrdU-labelled cells are in linear chromosomes remains a matter of debate exposed in Gl-phase [6]. The question regarding 106 RADIOBIOLOGY the DNA lesions responsible for SCE formation by inducing SCE. Both nucleotide analogs were de- X-rays and other S-phase independent agents in the tected with the help of monoclonal antibodies Gl phase remains open. conjugated with fluorochromes. The analysis was Because the SCE-test is widely used in genetic performed with the help of a fluorescent micro- toxicology [7] the knowledge of the contribution of scope. BrdU to the formation of spontaneous SCE and The results show that following radiation nearly SCE induced by DNA damaging agents is of great twice as many SCE were found in BrdU- than in importance. The present study was undertaken to biotin-dUTP-labelled cells (Fig.). This clearly points towards radiation damage in BrdU-moieties as the source of DNA lesions leading to SCE. Whether the same mechanism is responsible for SCE induced by other S-phase independent agents is not known. However, our results clearly show that caution must be applied when interpreting Q. results obtained in experiments in which BrdU is LLI O used to visualise SCE. 03 References [lJ.Latt S.A.: Sister chromatid exchange: new methods for detection. In: Sister Chromatid Exchange. Ed. S. Wolff. John Wiley and Sons, New York 1982, pp. 17-40. 0 Gy 4.8 Gy [2]. Gibson D.A., Prescott D.M.: Exp. Cell Res., 74, 397-402 (1972). Fig. Spontaneous SCE and SCE induced by X-rays in Gl cells [3]. Morris S.M.: Mutat. Res., 22S, 161-188 (1991). unifilarly labelled with biotin-dUTP or BrdU. [4]. Zwanenburg T.S.B., van Zeeland A.A., Natarajan AT.: adress this question. Spontaneous and radiation Mutat. Res., 15Q, 283-292 (1985). [5]. Wolff S., Bodycote X, Painter R.B.: Mutat. Res., 21, 73-81 induced SCE frequency was studied in cells pre- (1974). labelled with BrdU or biotin-deoxyuridine triphos- [6].Schunck C, Miura K.F., Obe G.: Mutat. Res., 412, 207-212 phate (dUTP). Biotin-dUTP has been recently suc- (1998). cessfully applied to differentiate sister chromatids [7]. Tucker J.D., Aulette A., Cimino M.C., Dearfield K.L., Jacob- son-Kram D., Tice R.R., Carrano A.V.: Mutat. Res., 297, in CHO cells [8]. Its advantage over BrdU is that it 101-180(1993). does not give rise to radicals. It can thus be assumed [8]. Bruckmann E., Wojcik A., Obe G.: Chromosome Res., I, that it will not interact with ionising radiation in 185-189(1999).

DETERMINATION OF DNA DOUBLE STRAND BREAK REPAIR

CD IN HUMAN LYMPHOCYTES BY THE COMET ASSAY S Maria Wojew6dzka, Iwona Buraczewska, Iwona Grqdzka CM O O Microgel electrophoresis of lysed cells, often called Phytohaemagglutinin-stimulated lymphocytes in O comet assay, usually is applied for DNA damage culture (from full blood taken from 3 different do- examination at alkaline pH. Then the DNA migra- nors in 5 separate experiments) were X-irradiated tion behavior is determined by the presence of 24 h after stimulation. The dose was 10 Gy (at a single (SSB) and double (DSB) breaks directly in- dose rate of 1.1 Gy/min) and irradiation was carried flicted by the tested damaging agent, as well as by out at 37°C. Samples were taken from the cultures nicks introduced by excision repair enzymes. After incubated at 37°C in a CO2 incubator at intervals exposure of isolated human lymphocytes to X-rays indicated in Fig.l. After lysis and electrophoresis, DNA damage inflicted by 0.2 Gy has been suc- cessfully determined in our Laboratory. For quantification of DSB the comet assay is less sensitive. This is due to a lower frequency of DSB induction by X-radiation: 1 Gy generates 1000 SSB per cell and only 40 DSB. Also, the non-denaturing conditions of the assay preserve DNA-protein interactions which affect the DNA migration be- havior. Although the neutral comet assay has been applied by a few authors [1, 2] it seems necessary to On n 30 m n 120m n Control adapt the lysis conditions as well as the electropho- ISntin 60min retic parameters for each cell type. For quantifica- tion of DSB in human lymphocytes we applied lysis Repair time at pH 9.5 (other conditions according to [3]) and Fig.l. Mean tail moment (100 nucleoids scored per data point), a the electrophoresis buffer of pH 8.3 (other condi- measure of DNA damage, decreases with time of post-ir- radiation incubation, reflecting DSB repair in human lym- tions according to [4]). phocytes after X-irradiation with 10 Gy. RADIOBIOLOGY 107 leoids scored per data point), a measure of DNA damage, decreased with time of post-irradiation incubation, reflecting DSB repair (Fig.l). As shown in Fig.2, the residual damage corresponded to about 16% of the initial lesions. These results indicate a satisfactory methodo- logical preparation for estimation of the role of DSB repair in the adaptive response in human lymphocytes. References io M » •« so 60 70 so 'Xi ion i in i:« [1]. Olive P.L.: Radiat. Res., l£fl (Suppl.), S42-S51 (1998). Repair time (min) [2]. Olive P.L.: Int. J. Radiat. Bio!., 71 395-405 (1999). Fig.2. The time course of DSB repair in human lymphocytes [3]. Singh N.P., Stephens R.E.: Mutat. Res., 383,167-175 (1997) (data from Fig.l) presented as decrease in the relative [4).Tronov V.A., Konoplyannikov M.A., Nikolskaya T.A., Kon- damage, that is, as % of the initial damage. stantinov E.M.: Biochemistry (Moscow), 64, 412-420 (1999). [5]. Kruszewski M, Green M.R.L., Lowe J., Szumiel I.: Mutat. the tail moments of the nucleoids were measured, Res., 326, 155-163(1995). as described in [5]. Mean tail moment (100 nuc- PL0002057 ANALYSIS OF INVERSIONS AND SISTER CHROMATID EXCHANGES IN CHROMOSOME 3 OF HUMAN LYMPHOCYTES EXPOSED TO X-RAYS Andrzej Wqjcik, Bertram Opalka1', Giinter Obe2/ 11 Inner Clinics and Policlinics, University Clinics, Essen, Germany 21 Institute of Genetics, University of Essen, Germany The mechanisms of sister chromatid exchange G Mitosis TB T8 T T& (SCE) formation are not known. It is generally identifiable assumed that SCE are a consequence of DNA no as 'true* SCE inversion FISH signal (s) replication on a damaged template [1]. Thus an centromere (c) SCE can only arise when a DNA damage is not c-s distance repaired in an error free way before the cell enters not changed the S-phase. Various models exist which seek to explain SCE as either a result of DNA repair [2] or idanWiaola as false" SCE o •*:•* paracentric damage bypass [3-7]. The results of recent publica- c-s distance £ B inversion tions indicate that SCE induction is not influenced changed by a defect in mismatch repair [8] and SCE occur predominantly within damaged, transcriptionally active regions of the genome [9]. not MtntlflaMe as falsa'SCE S-phase dependent chemicals, especially those paracentric c-s distance capable of alkylating DNA are among the most ef- notcnanjad fective agents that induce SCE [1]. In contrast, the S-phase indpendent agent, ionizing radiation, is a poor inducer of SCE. It is mostly effective when Gi cells with unifilarly BrdU substituted chromosomes MantMabla are irradiated [10-12]. Because ionizing radiation no as nnw* SCE invention induces mainly single and double strand breaks, p/q ratio both of which are expected to be repaired before not changed the cell enters S-phase [13], the nature of radia- I tion-induced SCE is a matter of debate. Wolff et al. [14] were the first to suggest that SCE observed parteantric a* falsa- SCE following exposure to low LET radiation could be Inversion p/q ratio "false" ones resulting from paracentric inversions changed induced in Gi chromosomes. These would be visible as double internal, or inerstitial SCE when cells after one round of replication with BrdU were irradiated. This hypothesis was indirectly supported not identifiable paricantnc as false" SCE by the observation that no SCE were observed in invention p/q ratio human lymphocytes irradiated in the Go stage, not changed prior to the addition of BrdU [10]. Muhlmann-Diaz and Bedford [12] analysed interstitial deletions and Fig. Scheme of the labelling of chromosome 3 and the types of internal double SCE in cells irradiated in Gi, and SCE which would result from inversions. 108 RADIOBIOLOGY found their frequencies to be similar. Based on the a shift of the hybridisation signal in relation to the supposition that ionizing radiation induces equal centromere (Fig.). Similarly, asymmetric pericentric frequencies of interstitial deletions and inversions, SCE resulting from pericentric inversions would they concluded that low LET ionizing radiation modify the p/q arm ratio (Fig.). induces only "false" SCE. In total 21 paracentric SCE were found (cf. Table. Frequencies of inversions and of SCE which could poten- Table) which covered the FISH signal. Only 3 SCE tially result from a detectable inversion in chromosome 3. were accompanied by a modified s-c distance indi- Dose Paracentric Pericentric Cells cative of an inversion. Similarly, out of 21 asymme- [Gy] scored tric, pericentric SCE, only two were found to be SCE inversions SCE inversions pericentric inversions with a modified p/q ratio. 0 1 1 0 0 100 These results clearly indicate that the majority of 1.2 1 0 3 0 100 radiation induced SCE, both para- and pericentric, 2.4 4 0 7 0 100 are not inversions. 3.6 6 1 6 1 200 4.8 9 1 5 1 200 References [I]. Latt S.: Ann. Rev. Genet., 15_, H-55 (1981). Conventional staining of chromosomes with [2]. Ishii Y., Bender M.A.: Mutat. Res., 79,19-32 (1980). Giemsa does not allow scoring inversions. Thus, the [3]. Evans H.J.: Chrom. Today, 6_, 315-326 (1977). assertion of "false" SCE is based on theoretical [4]. Shafer D.A.: Hum. Genet., 22,177-190 (1977). considerations and indirect observations. In the [5]. Painter R.B.: Mutat. Res., 2Q,337-341 (1980). present report we present results of a more direct [6], Cleaver J.E.: Exp. Cell Res., 136,27-30 (1981). [7]. Schubert I.: Biol. Zentrbl., 1Q9_, 7-18 (1990). approach of visualising inversions. Human peri- [8].Afzal V., Feeney L., Thomas G.H., Volpe J.P.G., Cleaver pheral lymphocytes unifilarly labelled with BrdU J.E.: Mutagenesis, 1Q, 457-462 (1995). were irradiated with X-rays and harvested in the [9]. Cleaver J.E., Mitchell D.A., Feeney L., Afzal V.: Mutage- second mitosis. Chromosome preparations were nesis, 11,183-187 (1996). [10]. Littlefield L.G., Colyer S.P., Joiner E.J., DuFrain R.J.: hybridised with an in situ hybridisation probe Radial. Res., 78, 514-521 (1979). specific for the pl4 band of chromosome 3. Simul- [11). Renault G., Gentil A., Chouroulinkov I.: Mutat. Res., 94, taneously SCE were detected with anti-BrdU anti- 359-368 (1982). bodies. Using this protocol, any paracentric SCE [12].Miihlmann-Diaz M.C., Bedford J.S.: Radiat. Res., 143. 175-180(1995). (i.e. double, internal SCE) occurring in the chro- [13]. Szumiel I.: Radiat. Res., 150. (Suppl.), S92-S101 (1998). mosome region covered by the probe which re- [14]. Wolff S., Bodycote J., Painter R.B.: Mutat. Res., 21 73-81 sulted from an inversion would be accompanied by (1974).

RADIATION-INDUCED MALFORMATIONS AFTER EXPOSURE OF MURINE GERM CELLS IN VARIOUS STAGES OF SPERMATOGENESIS s 00 = IO 1 1 u = O Wolfgang-UIrich Miiller ', Christian Streffer ', Andrzej W6jcik, Frauke Niedereichholz ;CM •o 11 io Institute of Medical Radiobiology, University Clinics, Essen, Germany A controversy exists as to what extent radiation exposure. Male mice were exposed in small cages to effects such as cancer and malformations can be 137-Cs gamma rays at a dose rate of 0.28 Gy/h and a transmitted from parents to children [1]. Many ani- total dose of 2.8 Gy to the whole body. Immediately mal experiments indicate that such a transmission is after the iradiation, and throughout the following 8 possible. For humans, the data of Hiroshima and weeks, the exposed and sham-irradiated control Nagasaki still demonstrate only a trend without

reaching a statistical significance. On the other postnMMfc meloBc PremcMk hand, from time to time results of human studies are published that also point to the possibility of a transmission of radiation effects to the offspring. The reaction of male germ cells to radiation ex- posure is of particular interest, because in this case neither indirect radiation effects nor extragenetic effects can play any role. Indirect effects have to be taken into consideration whenever results of ex- posure of female cells are analysed because radia- tion sickness of the mother can affect the outcome of the study. Such indirect effects are impossible after parental exposure. Extragenetic effects can be ruled out because sperms contribute almost ex- waek of conception after txpotui* clusively their genetic material to the zygote. Fig. Pattern of malformation frequencies after radiation exposure of various spermatogenic stages of mice. Asterisks represent We performed analyses of the response of the level of significance between irradiated and control various murine spermatogenic stages to radiation groups («: p < 0.1, "*: p < 0.05, ***: p < 0.01). RADIOBIOLOGY 109 males were caged together with three females and malformation (4.5%). All malformations were gas- the females were checked for vaginal plugs (a sure troschisis, a typical anomaly of the mouse strain sign of copulation) each morning between 8 and 9 studied [3]. It was found that the meiotic stages o'clock. Pregnant mice were collected on a per were particularly sensitive to radiation (Fig.). week basis and replaced in cages by new females. Although these results do not answer the ques- The identification of the developmental stage of tion whether and to what extent humans may be male germ cells at which the radiation exposure affected by a comparable phenomenon, they do took place was based on the record of the time span contribute another piece of evidence that at least in between the exposure and the successful copulation mice malformations can be induced by radiation [2]. On day 19 of gestation pregnant mice were exposure of paternal germ cells. killed by cervical dislocation, and the frequency of malformed fetuses was recorded. References Altogether 53 malformed fetuses were found [1]. Gardner M.J.: J. Natl. Cancer Inst. Monogr., 133-135 (1992). among 2308 living control fetuses (2.3%). Follow- [2]. Oakberg E.F.: Am. J. Anat., 22,391-409 (1956). ing radiation exposure 72 of 1610 fetuses showed a [3]. Pampfer S., Streffer C: Teratology, 22, 599-607 (1988).

HYDROGEN PEROXIDE-INDUCED DNA DAMAGE IN MEL CELLS OVEREXPRESSING A HEAVY SUBUNIT OF THE HUMAN FERRITIN Marcin Kruszewski, Teresa Iwanenko, Teresa Zebrowska, Pawet Lipinski1'', Elzbieta Bouzyk lf Institute of Genetics and Animal Breeding, Polish Academy of Sciences, Jastrze_biec, Poland Formation of DNA damage by hydrogen peroxide H2C>2-induced DNA breakage was also higher in (H2O2) is unambiguously associated with the pre- this cells (Fig.l) as compared to MEL/H-FR0 cells. sence of transition metal ions. Although most of For further decrease in LIP, both lines were forced the transition metals are able to generate the highly to differentiation by the addition of 100 fiM reactive hydroxyl radical from H2O2 in vitro, which N,N'-hexamethylene bisacetamide (HMBA) to the transition metal is of the greatest importance in the culture medium. During differentiation process living cells is still an open question. Previous study MEL cells synthesise hemoglobin, thus further de- [1, 2] and ESR study by Meneghini et al. [2] in- crease in LIP takes place [3]. Addition of HMBA to dicated that a transition metal responsible for DNA the culture medium caused a further decrease in damage in vivo might be the iron. Here we report a DNA damage, marked especially in ferritin produ- preliminary study on the viability and DNA damage cing cells (Fig.2). These data are in good agreement of two closely related mouse erythroleukaemia + (MEL) cell lines treated with H2O2. MEL/H-FR 200 cells posses the vector coding a heavy subunit of the HMEtA-N.N'-hexamsthylene bijacetamitH 0 human ferritin (H-FR). Overexpression of the 160 •I MEL/H-FR H-FR in MEL cells causes depletion of the labile CSS MEL/H-FR0 + HMBA iron pool (LIP) [3]. Untransfected MEL/H-FR0 cells were used as a reference. Both cell lines were 120 EH MEL/H-FR* treated with H2O2 then cell survival and the yield of ESS MEL/H-FR4 + HMBA arising DNA SSB was evaluated by the dye I, exclusion test and the alkaline version of comet assay, respectively. MEL/H-FR+ cells were more resistant to H2O2 treatment than control cells. 180 Control 10

H2O2 [uM] •• MEUH-FR Fig.2. The effect of HMBA-induced differentiation on the hy- CZU MEUH-FR* drogen peroxide dose-dependence of DNA damage esti- mated by the alkaline comet assay in MEL/H-FR0 and MEL/H-FR+ cells. with our previous study on two mouse lymphoma L5178Y cell lines differing in iron/copper content [1,4-6]. Control 0.5 2.5 Taken together, this result supports the thesis that iron is the most important transition metal H2O2 Fig. 1. Hydrogen peroxide dose-dependence of DNA damage involved in H2C>2-induced DNA damage in vivo. estimated by the alkaline comet assay in MEL/H-FR0 and MEL/H-FR+ cells (treated with H2O2 for 5 min at 0°C). References Tail moment is the measure of single strand breaks and [1]. Kruszewski M., Green M.H., Lowe J.E., Szumiel I.: Mutat. alkali-labile lesions. Res., 326_,155-163 (1995). HO RADIOBIOLOGY

[2].Mello-Filho A.C., Hoffmann M.E., Meneghini R.: Biochem. [5].Szumiel I., Kapiszewska M., Kruszewski M., Iwaneńko T., J., 21S, 273-275 (1984). Lange C.S.: Radiât. Environ. Biophys., 24,113-119 (1995). [3]. Picard V., Epsztejn S., Santambrogio P., Cabantchik Z.I., [6]. Zastawny T.H., Kruszewski M., Oliński R.: Free Rad. Biol. Beaumont C.-. J. Biol. Chem., 223.,15382-15386 (1998). Med., 24,1250-1255 (1998). [4].Kruszewski M., Green MR, Lowe JE., Szumie! I.: Mutat. Res., 202,233-241(1994). NUCLEAR TECHNOLOGIES AND METHODS NUCLEAR TECHNOLOGIES AND METHODS 113

PROCESS ENGINEERING PL0002029

CONCENTRATION OF LIQUID LOW- AND MEDIUMACTIVE LEVEL RADIOACTIVE WASTES (LLRW AND MLRW) USING MEMBRANE METHODS Andrzej G. Chmielewski, Marian Harasimowicz, Bogdan Tymiriski, Grazyna Zakrzewska-Trznadel Since the end of 1997 the INCT has been partici- Preliminary experiments were carried out using pating in Strategic Governmental Programme SPR-4 three samples of original radioactive wastes from "Treatment of radioactive wastes and burned nuclear storage tanks at the Institute of Atomic Energy. The fuel". The part of SPR-4 carried out in the INCT has samples contained onlv 6 and y emitters, mostly 51Cr, the aim: investigations of a purification/concentration ^Co, 65Zn, 90Sr, 95Zr 121Te, 124Sb, 125Sb, 131I, process on reverse osmosis (RO) membranes and 133Ba,137Cs, 144Ce, and i55Eu. Decontamination fac- construction of a pilot plant with an efficiency of rege- tors are close to 200, that means that 99.5% of the nerated water (permeate) 1 m3/h. This pilot plant radioactive compounds are retained by RO modules. creates part of the decontamination line of LLRW Pilot plant experiments proved the usefulness of and LMRW in the Institute of Atomic Energy (IEA) reverse osmosis for liquid low- and medium-level ra- at Swierk an will be placed before an evaporator. dioactive wastes processing. To achieve sufficient pu- At the end of 1998 some laboratory membrane rity of permeate the process has to be run as a multi- units have been constructed and various RO modules stage operation. Employing a 3-stage JP3RO reverse with a high value of the retention coefficient for osmosis unit it is possible to clean the wastes of NaCl (>99.5%) were tested for their resistance to /? 300-800 ppm salinity, obtaining a product of specific and y irradiating - the results were published in [1-4]. activity 200-14000 times less than that of initial ac- Using a CAROL program (ROPUR AG, Basel, tivity of the feed, and a retentate of specific activity CH) the NaCl retention coefficients for a 2-stage pu- 7-15 times higher. At very low TDS (total dissolved rification unit with thin-film-composite RO modules salts concentration) the efficiency of RO membrane SU-720R (TORAY, Japan) have been calculated. decreases. An improvement of the efficiency and an Using the same program calculations were carried out increase of radionuclides retention is possible by an

Z1 stage Fig. A scheme of a 3-stage JP3RO plant for liquid radioactive wastes treatment. for 4 various LLRW and main operating parameters additional injection of salt solution. Since the rela- for the pilot plant (1 m3/h) were calculated. On the tion between the retention of radioactive ions and basis of these calculations a technical project of the TDS is not linear, careful control of TDS is necessary. JP3RO pilot-plant (Fig.) was prepared. The wastes are purified on two modules (8-inch, SU-720R), and References the retentate from 1st purification stage is concen- (1). Chmielewski A.G., Harasimowicz ML, Tymiiiski B., Zakrzewska- trated on four modules used for sea-water desalintion -Trznadel G.: 3-stage RO pilot plant for purification and concen- tration of liquid radioactive wastes (LRW). Proc. of XIV Inter- (4-inch, SU-810). In May 1999 the JP3RO unit was national Symposium ARS SEPARATORIA, Gniew, Poland, 5-8 ready for setting in operation. July 1999, pp. 134-137. 114 PROCESS ENGINEERING

[2], Chmielewski A.G., Harasimowicz M., Tymiński B., Zakrze- [3]. Chmielewski A.G., Harasimowicz M., Zakrzewska-Trznadel wska-Trznadel G.: Zastosowanie procesów membranowych G.: Czechoslov. J. Phys., 4J>, Suppl. SI, 979-985 (1999). do przerobu ciekłych odpadów promieniotwórczych. 111 [4], Chmielewski A.G., Harasimowicz M, Tymiński B., Zakrze- Ogólnopolska Konferencja Naukowa "Membrany i procesy wska-Trznadel G.: 1NCT Annual Report 1998. INCT, War- membranowe w ochronie środowiska", Szczyrk, Poland, 21-23 szawa 1999, pp. 122-123. October 1999. Proceedings, p. 127.

RADIOTRACER INVESTIGATIONS ON SELECTED CHEMICAL INSTALLATIONS PL0002030 Edward Hier Tracer investigations of media transport through Particular attention has been paid to dynamics of chemical reactors play a significant role in chemical the liquid phase on the column plate. A dispersion technology. They provide a basis for determination model of liquid flow with hold-up zones has been of some important process parameters, such as flow proposed for description of the liquid phase trans- character of the transported medium, degree of port in the plate - overfall assembly. The model utilisation of the reactor volume during chemical consists of a number of flow and stagnant zones, transitions of substrates or even indicate possible with mass transfer occurring between them. Diffe- mechanisms of chemical reactions. Determination rent cases of model equations have been analysed, of the medium flow characteristics is closely con- depending on the location of the pints of measure- nected with mathematical description of the pro- ment of the tracer concentration distribution. Also cess, the mathematical model of transport. different values of mass transfer coefficients be- In tracer investigations of mass transport, proper tween the zones have been considered. selection of the tracer is of paramount importance Another example of practical application of radio- thus becoming a specific task to be solved at the tracer investigation results is the analysis of phase stage of detailed planning of the experiment. dynamics in installations designed for the process of In the case of radioactive tracers it is necessary to liquefaction of Polish coals by means of their cata- take into account the type and energy of the radia- lytic and non-catalytic hydrogénation. For the ana- tion emitted. Moreover, it is recommended that the lysis of phase transport in a reaction vessel various final assessment of a radiotracer suitability for a mathematical models were applied with the purpose given purpose be made on the grounds of testing its of obtaining the best match of the mathematical properties under actual conditions of the process to description for the actually observed hydrodynamics. be investigated. The method of assessment of radio- The adapted mathematical model of transport of tracers' suitability for investigation of distillation substrates through the reaction vessel was then processes presented in [1] allows to determine, in a combined with the kinetics of the hydrogénation simple manner, the parameters of distillation cha- process to obtain the degree of conversion of the racteristics of the radiotracers, the average distilla- carbon substance contained in the coal [2]. tion temperature, a range of distillation tempera- The investigation techniques and methods of tures, suitable radiochemical purity. These parame- interpretation of the tracer experiments described ters precisely determine the behaviour of tracers to in this paper can be used for the analysis of ope- be expected in a wide range of variable conditions ration of chemical industry apparatus, particularly of the distillation process. Application of radio- in the cases when their operational parameters tracers tested in such a manner to investigations of (high temperature and/or pressure) do not permit hydrodynamics of industrial rectification columns usage of other than radiotracer investigation tech- has resulted in obtaining a dependable evaluation niques. of those columns' performance in a wide range of changes of their operational parameters. References The adopted methodology has been presented on [1]. Graczyk J., Hier E.: J. Radioanal. Chem., 33,175 (1976). [2], Hier E.: Dyspersyjny model transportu mediów w radioznacz- the example of radiotracer investigations of the liquid nikowych badaniach pracy wybranych instalacji przemysło- phase dynamics in a plate rectifying tower under ope- wych. Raporty IChTJ. Seria A nr 1/99. IChTJ. Warszawa ration at the Chemical Works "Oświęcim". 1999,134 p.

DEGRADATION OF VOLATILE ORGANIC COMPOUNDS EMITTED FROM COAL COMBUSTION BY ELECTRON BEAM TREATMENT 18 Andrzej G. Chmielewski, Anna Ostapczuk, Yongxia Sun, Krystyna Kubica1', Janusz Licki2/ 11 !O Institute for Chemical Processing of Coal, Zabrze, Poland 21 Institute of Atomic Energy, Świerk, Poland In Poland energy is produced mostly in coal power known as a main source of gaseous pollutants emitted stations and contemporary fossil fuel combustion is into the atmosphere. The most harmful compounds NUCLEAR TECHNOLOGIES AND METHODS 115 among them are SO2, NOX and VOCs (volatile orga- ranged from 11%, for chrysene, till 98% for fluo- nic compounds), A method of simultaneous desul- rene. The figures for polyaromatic hydrocarbons phurization and denitrifrication of flue gas has been irradiated without NH3 in a combustion gas were elaborated in this Institute, an industrial installation lower, they ranged from 30% for pyrene, till 79% of this type was constructed at the EPS Pomorzany for fenantrene. near Szczecin [1]. Recent regulations and interna- The polyaromatic hydrocarbons in question have tional obligations, concerning emission of harmful several benzene rings in their structure and it seems organic compounds into the atmosphere, have caused that this parameter has some influence on the effi- a necessity to enlarge our investigations by using elec- ciency of compound decomposition, smaller molecu- tron beam treatment as a method of organic com- les are decomposed more easily (acenaphtylene, ace- pounds removal. naphtene, florene) than those having a greater num- Decomposition of many VOCs by electron beam ber of rings, like benzo(a)pyrene, benzo(e)pyrene. treatment is being intensively investigated. Using this Mechanism of degradation process technique, it was found that the decomposition of Organic compounds are oxidised during electron chlorinated aliphatic compounds exeeded 90%, the beam treatment and the final products of this pro- final products being H2O, CO2, HC1 and Cl [2-4]. cess are: H2O, CO, CO2 (HC1 for chlorohydro- Experimental carbons). In a real process the outlet gas contains The compounds chosen for experimental work numerous other organic compounds - indirect pro- belong to the group of polyaromatic hydrocarbons ducts. Results obtained in this experiment show (PAH). These compounds are known to be toxic, that the harmful compounds are degraded by the mutagenic and cancerogenic and are emitted from electron beam treatment. Efficiency of this process the coal combustion process with concentrations ran- is higher when ammonia is added to the gas stream. ging from few ppm/Nm3, like C20H12 (benzo(a)py- This probable mechanism of this process is des- rene) or chrysene (C18H12), till 335 ppm/Nm3 for cribed below: Table. Inlet and outlet PAH concentrations in irradiated gas stream. Dose: D=7kGy, Dose: D=1 kGy NH3 PAH Formula Concentration [ppm/m^] Concentration [ppm/m3] E E inlet outlet inlet outlet

Acenaphlylene Ci0H6(CH2)2 5.36 5 0.067 12.2 0.59 0.96

Acenaphtene CioH6(CH2)2 142.86 64.28 0.55 26.8 0.59 0.95 Fluorene C13H10 221.43 85.72 0.61 41.5 14.63 0.65 Fenantrene C14H10 100 21.43 0.79 21.9 4.87 0.78 Antracene C14H10 242.86 150 0.38 36.59 21.95 0.4 Benzo(a)antracene C18H12 242.86 78.57 0.68 21.95 19.51 0.11 Benzo(b+k)fluorantene C20H12 135.7 100 0.26 60.98 31.7 0.47 pyrene (C16H10). Experimental work has been done After irradiation of combustion gas we obtain a in a pilot plant for electron beam flue gas treatment mixture of ions, active molecules and radicals placed in the EPS Kawczyn, the plant being equipped with 2 electron accelerators (5 kW/700 keV each), N2, O2, H2O, CO2, SO2> NOX, QHX S. OH*, O*f ^ 3 the gas flow being 20 000 Nm /h. The used dose H2O*, N2*, O2*, O*. H*. N2+, O2+, H2O + , CO2+ ranged from 0 to 14 kGy and the process run with Organic compounds are oxidised: added ammonia and without this compound. Con- OH*,O*,H O*... . (2) centrations of investigated compounds were con- 2 trolled before and after the irradiation chamber. The Then hydrocarbons react with nitrogen oxide pre- compounds were collected on the surface of a sor- sent in combustion gas bents XAD-2 and on activated carbon. Then they NO (3) were extracted by a solvent and analysed by gas chro- RO2 0,^02 + NO2 matography combined with a mass spectrometry Reactions (2) and (3) are analogous to photoche- technique. mical reactions taking place in the atmosphere. Results Ammonia added to gas stream neutralise active ni- The obtained results are collected in Table. trogen oxide Efficiencies of the PAH removal from a gas stream NO OH*,O*,HO *,NH ^^ (4) (E) were calculated from the equation: 2 3> E=(C0-Ck)/C0, and hydrocarbons take part in competitive reac- where: Co - PAH concentration in the inlet, C^ - tions causing their oxidation: PAH concentration in the outlet. RO OH*,O*,HO *,R+,R-,I+,I- , (5) In these findings some tendencies are observed. 2 2 Efficiencies of the PAH decomposition are higher ROH, ROOH, CO2, CO, H2O, CxHy in the case when ammonia is added into the gas The elaborated results may be summarised as stream, for this process the removal efficiencies follows: 116 PROCESS ENGINEERING - Polyaromatic hydrocarbons are degraded in the . electron beam as well as on detailed description electron beam process. of this process mechanism. - Efficiency of the electron beam PAHs treatment process is higher when ammonia is added to the References: flue gas stream. [1]. Chmielewski A.G., Iller E., Zimek Z., Romanowski M., Ko- pcrski K.: Radiat. Phys. Chem., 45(4-6), 1063-1066 (1995). - Efficiency of the removal of PAHs is higher for [2J. Hakoda T. et al.: Decomposition of tetrachloroethylene by compounds having a lower number of benzene ionizing radiation. Proceedings of International Symposium rings. on Radiation Technology for Conservation of Environment. - PAHs are decomposed in the gas stream simul- IAEA-TECDOC-1023, IAEA, Vienna 1998. [3j. Vitale S.A. et al.: Decomposing VOCs with an electron beam taneously with denitryfication and desulphuriza- plasma reactor. Chemtech, 1996, pp. 58-63. tion of combustion gas. [4]. Penetrante B.M. et al.: Pure&Appl. Chem., 6_8_, 5, 1083-1087 - Further work should be focused on the opti- (1996). misation of organic compounds degradation by

DECOMPOSITION OF 1,1-DICHLOROETHYLENE IN HUMID AIR UNDER ELECTRON BEAM IRRADIATION !8 Yongxia Sun, Teruyuki Hakoda1'', Andrzej G. Chmielewski, Shoji Hashimoto1', Zbigniew Zimek, O Sylwester Butka, Anna Ostapczuk, Henrieta Nichipor2/ O O 1 Japan Atomic Energy Research Institute, Takasaki Radiation Chemistry Research Establishment, Japan 21 Institute of Radiation Physical and Chemical Problems of the Academy of Science of Belarus, Minsk-Sosny, Belarus Study on Volatile Organic Compounds (VOCs) re- results. The possible reaction mechanism was pro- leased in the atmosphere from various industrial pro- posed in Fig. and Scheme. Furthermore, the relation- cesses is developing due to VOCs hazardous impact ship between 1,1-DCE decomposition efficiency and on the environment and human health. 1,1-dichlo- dose rate was also studied.

HCO, H2O, HO COCl oa

H2O/HC1, CO. HO2 OHJCO2 :HCICC 4 6S Al V * 13V N^45 CHCUCOC1 NO 2, Cl O2,CU H. CO2 COCl

IQO.i

IK66 CO, CCIS

coca,a

Fig. Schematic of reaction pathways of 1,1-DCE decomposition and organic products formation. Products with boldfaces shown here are mainly formed from relevant reactions. Numbers following R with arrows refer to reactions in the text. roethylene(l,l-DCE) removal by ionizing radiation The main results of this study may be sum- has been investigated in JAERI using EB irradiation. marized as follows: Meanwhile, a theoretical study was carried out by the - It has been found that more than 90% 1,1-DCE INCT to explain the experimental results. Computer is decomposed when doses reach 9 kGy, 13 kGy code Kinetic [1] and Gear method were used. 80 at a 2.083 kGy/s dose rate for 903.8 ppm and different species and 309 reactions were considered. 1583 ppm, respectively. CH2CICOCI is the main Calculation results agree well with the experimental organic product (which is over 50% obtained NUCLEAR TECHNOLOGIES AND METHODS 117

from experimental work and is proved by calcula- ducts predicted by modelling simulation. HCHO tion results) as well as COCb, HCHO, CH2CI2, is decomposed with dose increase. Formation of CHCI2COCI and HCOC1 as minor organic pro- inorganic carbon products is below 25%. CI2, 1 electron beam HC1, 03, HNO4, NO2 and N2O are the other possible inorganic products. These organic pro- N2,02, H2O, CH2CCI2 ducts (except for CH2CI2, HCHO) as well as sec. ~ 1.0 inorganic products could be removed from the

e + CH2CCI2 gas phase by adding alkaline solution. N2+, O2+, O+, N+ + CH CC1 - Cl' dissociative electron attachment as well as ra- 2 2 pid charge transfer reactions of carrier gas positive ions predominate in the initial stage of 1,1-DCE decomposition while Cl radicals become signifi- .0 x 10"6 sec. -l.Ox 10"^ sec. 4. cant after milli-seconds' irradiation. Water cluster + + e + CH2CC12 positive ions (O2(H2O) , H3O(OH) ), OH H, O 1 + OH, H, Cl, 0 + CH2CC12 H3CXOH)" ". O2(H2O) + and Cl become active after microseconds irradia- tion. CH2CC12 - OH radicals involve in the 1,1-DCE as well as or- O + +CH CC1 2 2 2 ganic products decomposition reactions and H3O(OH)+ ions' formation reactions. H3O(OH)+ ions take part into 1,1-DCE decomposition and -i-1.0 x 10*3 sec.~ 6.3sec. water formation reactions. - Irradiation at lower dose rate (<200 kGy/s) is Cl + CH2CCI2 more efficient for 1,1-DCE removal in humid air. e + CH2CC12 + OH + CH2CCI2 H3O(OH) + CH2CCi2 References [1]. Bugaenko W.L., Grichkin W.L.: Program for modelling of Scheme. Three stage of 1,1-DCE decomposition. chemical kinetics. Report ITEP 50.1980, pp. 1-19.

ACTIVITIES OF THE LABORATORY OF ISOTOPE RATIO MASS SPECTROMETRY (IRMS) PL0002033 Ryszard Wierzchnicki, Matgorzata Derda, Agnieszka Mikotajczuk, Andrzej Owczarczyk In the year 1999 the planned process of collecting tion parameters on a (specially prepared) equipment necessary for sample preparation and effi- surface are entirely controlled by a computer. cient measurement of isotope ratios D/H, 18O/16O, Measurement of 5 samples/per hour is possible 13C/12C and ^S/^S has been completed. with a guaranteed accuracy of <5(D)<0.5%. An The following devices have been designed, built additional advantage of the method is a very small and purchased at that time: volume of water sample needed (1/<1). 1. Equipment for water reduction on metallic Zn 3. Gasbench II Finnigan Mat The method consits in the reduction of water on This device is devoted to automatically on-line con- the surface of hot (T= 500°C) Zn specially prepared trolled mass spectrometric measurement of 18O/16O for that purpose. The reaction runs in oxygenless and 13C/12C isotope ratios. The method consists in conditions assured by sample preparation in one of the isotope exchange reaction between a sample of the terminals of a vacuum line. After preparation the investigated water and CO2 in isothermic condi- (degassing of Zn and water in proper proportions), tions at 25°C. Then CO2 is transferred by the helium the reaction is carried out in a specially designed (as carrier) to a gas chromatography part. oven. Then the released hydrogen is transferred to Impulses of CO2 from a chromotographic column IRML. are analysed with mass spectrometry and (18O) of the A series of calibration preparations and measure- analysed gas is periodically compared with gas im- ments have been done up to now. The reproducti- pulses of a CO2 standard, which is dosed auto- bility with a good accuracy of obtained results matically. Control of procedures connected with gas confirmed the usefullness of the proposed analytical flow reaction conditions and samples is assured by an procedure. However, only 4 samples per day can be on-line computer by means of an ISODAE code. prepared by means of that method. The whole analytical procedure for 96 samples 2. H/Device Finnigan Mat (capacity of samples) needs about 20 h. For the acceleration of preparation procedure The guaranteeed accuracy of <5(18O) and (5(:3C) and elevate analytical efficiency, an automated line measurements is <0.08 %o- for IRMS measurement of D/H have been pur- 4. Vacuum line terminal for sulfides and sulfates chased from Finnigan Mat. convertion into SO2- The H/D device is permanently connected on-line Most common chemical forms, being the pro- to a Delta Plus mass spectrometer. The water reduc- ducts of earlier sample preparation for mass spec- 118 PROCESS ENGINEERING trometric measurement of sulfur isotope ratio, are factors influencing the value of isotope partition co- AgS, CdS or BaSO,). efficient, which is a result of isotope fractionation in A vacuum line terminal enabling the convertion many physical and chemical processes. So, the first of the above compounds to SO2 was built based on part of planned experimental work will be the deter- the Halas concept [1,2]. mination of portition coefficient for sulfur isotopes About 10 samples for mass spectrometric mea- fractionating in the reaction: 34 32 surement can be prepared in this terminal per day. H2 S(gas)+ SOi~(aq) -* The equipment gathered in this Laboratory will H 32S(gas) + 34SO?T(aq) be a good basis for present and future scientific re- 2 search in the field. The theoretically calculated value of portition The three topics that have already started and coefficient in the above reaction is 1.074 at 25°C will be continued are: [9]. The reaction will be conducted in the closed system for about 20 h. Then the products will be - Isotope effects of chemical reaction of sulfur converted into CdS and BaSC>4 and further to SO2 compounds by means of the Halas method in the vacuum line The purpose of the work are investigations of sul- terminal. fur isotope fractionation during combustion of fuel - H/D and 18O/16O isotope ratios as a tracer of materials, especially different kind of cools. Sulfur can be present in coal in different chemical forms e.g. surface and ground water pollution in industrial areas sulfides, sulfates, elementar sulfur and sulfur organic 18 16 compounds. All of them should be determined sepa- A application of the D/H and O/ O isotope rately. The method of Westgate and Anderson [3] ratio as a tracer for water pollution based on the has been proposed for coal samples preparation. The assumption that water taken from a river and used in method consists in HC1 addition to a milled sample industrial processing changes its isotope ratios being of coal. The formed H2S is precipated in the form of characteristic for the river in the intake point. So the CdS in a cadmium acetate solution. The conversion waste water discharged back to the river would have of CdS into SO2. another isotope ratios and can be identified as a mixture with other water bodies e.g. river down the The sulfates present in primary solution are then outfall point and ground water if any leakages exist of determined after precipitation in the form of BaSO4 a sewer system. The first measurements confirms the and also converted into SO2 in the vaccum line. above assumption. The <5(D) were measured for In the primary coal sediment, after washing, industrial water taken from the Vistula river by the pyrite can be determined as H2S released after reac- Ptock Petrochemistry Ltd. at Plock and for waste tion with lithium aluminium hydride tetrahydrofu- water discharged back to this river, after passing ran. Then H2S is precipitated as AgS and converted industrial processing and purification treatment, was to SO2 in the vacuum line. The Eschka mixture <5(D)VISTULA=-5O.O, <5(D)P RO=-64.0, respectively. (MgO+NaCO3) will be used for organic sulfur de- ET termination. Obtained Na2SC>4, as a reaction pro- Similar differences are expected concerning 18 duct, can be precipitated as AgS after sulfate reduc- c5( O). The sample preparation line for these mea- tion in a mixture of HJ, H3PO4 and HC1. AgS is surements will be ready soon. then converted into SO2 in the same vacuum pro- The purchase of H/Device and Gasbench II from cess as described before. Finnigan Mat was in part sponsored by the Polish In portions of SO2 obtained during all steps of State Committee for Scientific Research (KBN). sample preparation the isotope ratio 3 S/32S will be determined. References A procedure for isotope separation coefficient in [1J. Halas S., Wolacewicz W.D.: Anal. Chem., 53, 686 (1981). a combustion process will be elaborated later. [2]. Halas S., Szaran X: Anal. Chem., 71, 3254 (1999). [3]. Westgate L.M., Anderson T.F.: Anal Chem., 54, 2136 (1982). - Determination of sulfur isotope ratio in fuel [4], Bigeleisen J.: Proc. Naft. Acad. Sci. USA, 95, 4808 (1998). materials [5]. Mioduski T.: Comments Inorg. Chem., 00,1-22 (1999). It is well known now that isotope effects depend [6].Dembirtski W., Poniriski M., Fiedler R.: Sep. Sci. Tech., not only on mass defferences of nuclides taken into 33(11), 1693 (1998). [7]. Dembiriski W.: Wiadomofci Chem., in press. consideration. Departure from the classic Bigeleisen [8], Nishiwara K. et al.: Sep. Sci. Techn., 3115,643 (1996). theory [4, 5] has been experimentally confirmed for [9].Tudge A.P., Thode H.G.: Can. J. Res., B28, 567 (1950) (sec. some elements [6-8]. It will be interesting to define B).

HYDROCHEMICAL AND ISOTOPE STUDY OF GROUND AND SURFACE WATERS IN THE REGION INFLUENCED IS BY THE LIGNITE MINE "BELCHATOW" iS Wojciech Soltyk, Jolanta Walendziak, Andrzej Owczarczyk A strip lignite exploitation is only possible with very The Lignite Mine "Belchat6w" maintains about efficient drainage systems protecting the exacava- 550 large diameter wells pumping water perma- tion against flood. nently with a total efficiency of about 5.8 m3/s. NUCLEAR TECHNOLOGIES AND METHODS 119 The pumped water is dicharged into the small the excavation site - 500 m from its north edge. rivers Widawka and Kras6wka localized in the vici- Since 1994 all wastes have been deposited in an old, nity of the exploited lignite deposit. already exploited eastern part of the "Belchat6w" After 25 years of the drainage, the depression has Lignite Mine. arised with an effective radius around the excava- Both localizations have strongly been affected by tion estimated as 13 km and a surface of about 500 the drainage depression, causing pollution of the km2 (the surface of the excavation Belchat6w itself pumped ground water. is only about 20 km2). Taking this into account, monitoring of pumped The pumping water quality is influenced not only waters quality is very important and required by the by the natural geological factors but also by the de- Environmental Protection Site Authorities. gradation antropogenic factors such as the presence Annually repeated water quality control included of ash and slag respositories gathering wasters from the following measurements: the Electric Power Plant "Beichat6w". - determination of basic chemical composition as During the first 14 years of exploitation period well as Chemical and Biochemical Oxygen De- the ashes and slag were stored inside a 400 ha mand (COD, BOD) and eutrophic component respository area without any sealing of its bottom. concentrations in samples taken from waters on The respository has been located in the vicinity of the borders of the monitored surface; Table. Results of hydrochemical and isotope ratio determination in waters from the region of Lignite Mine "Betchat6w".

Element (ion) Widawka River Salt dome region Ash repository region Isotope unit up-stream down-stream water water collecting repository repository mine mine fresh saline channel wet dry Soluble mg/dm3 402.3 408.7 439.9 4004.3 520.3 448.0 652.0 substances Suspensions mg/dm3 31.3 24.7 21.5 pH 7.6 7.5 7.3 7.4 7.7 7.3 7.7 Ca mg/dm3 72.7 80.2 79.2 340.6 80.6 81.8 131.5 Mg mg/dm3 7.8 9.3 14.2 43.1 15.4 12.4 27.2 Na trig/dm-* 9.3 16.1 27.6 490.0 37.7 20.5 6.0 K mg/dm-' 2.15 2.54 1.00 2.34 1.25 1.64

HCO3 mg/dm-' 172.9 201.4 270.7 196.3 245.6 140.4 323.4 •2 Cl mg/dm-> 25.8 38.4 32.8 2009.6 62.7 88.3 25.2 SO4 mg/dm3 55.7 63.0 22.9 973.3 55.2 91.0 117.0 PO4 mg/dm-' 0.65 1.60 HN4 mg/dm-' 0.22 2.13 0.09 COD mgO2/dm3 10.1 7.5 3.8 BOD mgO2/dm3 3.2 4.5 1.9 Ba ^g/dm3 64.6 70.8 30.0 23.0 46.0 91.8 143.9 Br ,ug/dm3 170.0 610.0 130.0 140.0 140.0 1270.0 180.0 Cr ,«g/dm3 2.1 2.6 3.0 1.5 1.9 1.3 1.8 J ^g/dm3 24.0 34.8 Zn ftg/dm 15.2 22.6 28.0 22.7 13.8 7.0 11.2 Cd jMg/dm3 0.06 0.41 0.21 2.10 0.06 Cu ,ug/dm3 21.0 14.4 52.0 17.0 24.1 10.9 8.3 Ni /jg/dm 3.3 3.4 3.6 6.0 2.3 2.1 3.9 Pb fig/dm 2.9 3.0 3.6 56.0 3.4 2.8 1.6 Hg /ig/dm3 0.11 0.09 <0.03 0.48 0.33 Rb jMg/dm 3.5 5.9 5.8 5.5 Ag ,«g/dm3 0.3 0.2 0.4 0.5 0.3 Sr ^g/dm3 275.5 538.6 432.8 1591.4 675.5 434.5 777.5 V fig/dmr 1.7 1.4 4.1 0.1 1.0 H-3 [TU] 0.1 9.8 11.9 9.3 Rn-222 Bq/dm3 6.1 9.0 Ra-226 Bq/dm3 <3.0 3.1 <5S~34 °/00CDT 6.69 10.57 3.86 -2.68 (50-18 °/(X)SMOW 2.99 10.62 3.82 -3.14 120 PROCESS ENGINEERING - determination of microcomponents, including Based on the obtained results, range of the de- heavy metals in 61 water samples collected in the grading influence of salt dome "De.bina" on the pum- examined area; ping water quality in the depression area has been - determination of trace amounts of tritium in 30 determined. A forecast for surface water desalination water samples and 34S/32S and 18O/16O isotope in the year 2000 has been worked out. ratios, determination of (Ra-226) and ra- A hydrochemical analysis of the disadvantageous don (Ru-222) radioactivity in 12 water samples changes of macro- and microcomposition of ground taken from the region of salt dome localization. water in the probable affected region of the existed The results are presented in Table. ash and slag rcspositories has been also performed.

DIOMETRIC STUDY OF GROUND WATER MOTION IN THE ELBLAG ZUtAWY AQUIFER PL0002035 Wojciech Soltyk, Jolanta Walendziak, Andrzej Owczarczyk Fresh water delivery for Elbl^g municipality and centration of the tracer [imp/min], N - final concen- Zulawy inhabitants needs detailed studies of ground tration of the tracer [imp/min], Nt - background water capacity and motion in the local aquifers con- [imp/min], q - hydrodynamic field deformation co- sidered for actual and future exploitation. efficient. The location of some mesurement piezometric The local flow direction was measured by means wells in the vicinity of actually existing water deli- of a colimeted probe localizing the direction of a very points and other wells lying out of its inter- radioactive cloud maximum concentration around action range in the Zulawy aquifer region, allow to the piezometric well. compare the ground water flow parameters, con- The four localizations were chosen for ground cluding the water circulation mechanism and plan- water flow parameters measurements. They were as Table. Results of the velocity and direction of ground water [low measurements in the Elblag Zulawy Region.

Measurement depth Flow velocity No localization Azimuth of measurements of flow direction M E-7[m/s] [m/y] 1 Szopy P-1B 25.8 -0.6 -1.9 256° ±13° 6.6 20.8 +0.8 + 2.4 2 Zwier/.noP-2A 21.6 -1.0 -3.3 245° ±4° 7.6 23.9 + 1.0 + 3.3

3 Zwierzno P-2B 43.7 •0.3 -0.8 660 ±60 4.0 12.6 +0.3 + 1.0 4 Kopan6w IIP-4 25.5 -0.6 -2.0 68° ±1° 3.8 12.0 + 0.9 +3.0

ning future development of a Zulawy water sup- follows: the region Szopy Village (6 km from El- plying system. blaj); the Zwierzno Village (4 km from Elbl^g) and A radiometric method with the application of ra- the Kopan(3w Village (4 km from Elblaj). The ob- diotracers gives a unique possibility for measuring tained results of the direction and horizontal velo- the flow direction and velocity in a single well [1-5]. city of the ground water flow in the examined places The 131I nuclide was used as a tracer. are presented in Table. An isotope portion prepared for a single mea- surement, sealed in a flask, was let down and crash- References ed at a chosen depth of the well. [l].Ogilwi Ch.A.: Electronic method for determination of ground The horizontal velocity of water flow can be cal- water velocity. Biuletin nauczno-techniczeskoj informacji, 4, culated as a function of the registered radioactivity Gosgieoltiechizdat, Moskwa 1958 (in Russian). changes in time. [2). Borowczyk M., Jurkiewicz L., Zuber A.: Nukleonika, 7-8 (1964). [3], Borowczyk M., Grabczak X, Zuber A.: Radioisotope mea- -Nt surements of groundwater flow direction by the single well - 4qtD N - Nt method. IBJ, Warszawa 1964. Raport nr 502/VI. [4]. Nuclear well logging in hydrology. IAEA Technical Reports where: V - horizontal water velocity [cm/min], D - Series No. 128, Vienna 1971. well diameter [cm], d - radiometric probe diameter [5], Gwidebook on Nuclear Techniques in Hydrology. IAEA [cm], t - measurement time [min], No - starting con- Technical Reports Series No 91, Vienna 1983. NUCLEAR TECHNOLOGIES AND METHODS 121

PL0002036 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS

NEW SILICA SORBENTS BINDING EFFECTIVELY HEAVY METALS FROM WATER Andrzej Lukasiewicz, Luzja Rowiriska, Lech Walis Introduction are shown in Table 1. 5 cm3 of the working solution Some copper complexes of ethanolamine (EA) was shaken for 2 min with a sorbent (0.2 g). After are investigated in this Institute as wood preserva- sedimentation of the solid, 1 cm3 of the liquid was tives [1]. On investigating the properties of these Table 2. Binding of metals by silica sorbents. complexes it has been found that copper complex 2+ Degree of binding of metal by sorbent [%] [CunEA] (n>4) binds effectively to silica gel and Sorbent that the material SiO2-CunEA formed binds some Sr2+ Cs+ Yb3+ Cr3+ Co2+ Au3+ heavy metals from water. It was found further that SiO2-EA 81 91 94+ 67 96 84 more effective sorbents of heavy metals are formed 83 + + 96* when silica gel is treated with EA alone (SiC>2-EA) 92+ + + 2+ or with the complex [Mg4EA] (SiO2-EA(Mg)). SiO2-EA(Mg) - 77 - 86 - 22 The material SiO2-EA can be further modified by treating with AICI3 aqueous solution. The silica SiO2-EA(Al) 52 92 28 74 50 45 sorbent SiO2-EA binds effectively most heavy + inactive YbCl3 added (400 ppm). metals, also from very dilute solutions (~ 10 ppm), + + SmCl3 added (400 ppm). whereas SiC>2-EA(Mg) and SiC>2-EA(Al) are most + + + A1C13 added (400 ppm). effective for Cr3+ and Cs+. By acidification, the ad- • inactive C0CI2 added (400 ppm). sorbed metal is quickly released from the sorbent. taken for measurement of radioactivity. Radioacti- Preparation of the sorbents vity measurement was performed with an Ortec HP The sorbent SiC>2-EA was prepared by treating detector and a spectrophotometer Canberra - Sys- silica gel (Merck grade 60, 63-200 /u) with a 20% tem 100 with an IBM computer. This measurement aqueous solution of EA, SiC>2-EA(Mg) by treating system allowed to eliminate completely the interfe- silica gel with a 2% MgCl2-4EA solution (in water) rence of other isotopes, which might occur as impu- and SiO2-EA(Al) by treating SiC>2-EA with a 2% Table 3. Binding of two metals by the S1O2-EA sorbent. solution of AICI3 (in water). The sorbents were dried on the air. They contained 4-4.5% of EA. Degree of binding [% Binding by the sorbents of heavy metals from dilute 1 2 3 4 5 6 solutions Cs+Yb Cs+Cr Cs+Co Yb+Cr Yb+Co Co+Cr Cs Yb Cs Cr Cs Co Yb Cr Yb Co Co Cr SrCl3, CsCI, YbCl3, CrCl3, CoCl2 and Au were radioactivated by irradiation with thermal neutrons 78 39 64 44 59 92 76 62 40 94 91 68 in the reactor MARIA (Swierk). Technical parame- rities. Effectiveness of the metal binding to the sor- ters of the activation were: neutron, beam - 8-1013 bent was estimated as % ratio of the radioactivity of ncrrfV1, irradiation time - 24 h. Mass of the ac- the solution after shaking with the sorbent to the 3 tivated metals was: SrCl2 - 0.1 g; CsCI - 1.3-10" g; activity of the standard (solution before shaking 3 2 3 YbCl3 - 1.7 • 10" g; CrCl3 - 1 • 10" g; CoCl2 - 1 • 10" with the sorbent). Effectiveness of the metal bind- g; Au - 4-10'4 g. The radioactive samples were dis- ing to the silica sorbenl (mean value for 5 measure- Table 1. Physical data of radionuciides and concentration of me- Table 4. Binding of Co by the S1O2-EA sorbent in presence of tals investigated. NaCl, NaNO3, Na2SO4 (400 ppm).

2+ Metal used Nuclide y-Energie Concentration of Salt added Degree of Co binding [%] No for activation formed [keV] working solution [g/g] NaCl 91 1 SrCl2 85Sr 514 8E-4 + HC1 96 2 CsCI 134cs 796 1E-5 NaNO3 90 3 YbCl3 197Yb 197 1E-S 4 CrCl3 51Cr 320 8E-6 + HC1 95 5 C0CI2 60Co 1172 8E-6 Na2SO4 90 198 6 Au Au 412 ^ 4E-6 ments) is shown in Table 2. Binding of metals to the solved in water (Au in aqua regia) and diluted to S1O2-EA sorbent from mixtures of two metals is working concentrations. These concentrations as shown in Table 3, and binding of Co2+ in presence well as some physical data of the radionuciides used of some mineral salts (400 ppm) in Table 4. 122 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS Discussion of the results dilute solutions. Sorbents treated additionally with The results showed high affinity of heavy metals for MgCl2 or AICI3 had a high adsorption activity for the SiO2-EA sorbent. The degree of binding to this Cr*+ and Cs+. These new sorbents can be used for sorbent of most metals from dilute solutions (~ 10 effective removal of heavy metals and radionuclides ppm) was >80%. SiO2-EA(Mg) and SiO2-EA(Al) from factory and radioactive wastes. They can also be sorbents bound effectively Cs+ and Cr3+ but, in re- used for the concentration of metal solutions. The gard to other metals, their binding activity was lower. new silica sorbents are being patented [2]. A paper Yterbium was bound to SiC>2-EA the yield being has been prepared for publication. Furher work is in >90% in the presence of AICI3 or SmCl3 as carriers progress. and at a higher concentration of YbCb (400 ppm). The highest degree of binding showed Co2+, also References from mixtures with another metal (Table 3) as well as [1]. Krajewski K.J., Lukasiewicz A., Wazny J.: A wood preser- in the presence of NaCl, NaNO3 and Na2SC>4 (400 vative based on polymerised complexes of arainotriazole with ppm). Slight acidification with HC1 influenced posi- copper acetate. The International Research Group on Wood 2+ Preservation 29th Annual Meeting, Maastricht, the Nether- tively the adsorbion of Co by the SiO2-EA sorbent. lands, 14-19 June 1998. Conclusions [2]. Lukasiewicz A., Rowifiska L., WaliS L.: Polish patent appli- New materials obtained by the treatment of silica cation P3361188. gel with EA showed high affinity for heavy metals in

ION ASSISTED PALLADIUM TREATMENTS

s FOR IMPROVED CORROSION RESISTANCE OF A TITANIUM WINDOW :1 - 18 IN THE ELECTRON BEAM DRY SCRUBBER PROCESS !CVJ Stephen D. Barson17, Peter Skeldon17, George E. Thompson17, Andreas Kolitsch2/, Edgar Richter27, IS Egbert Wieser , Jerzy Piekoszewski, Andrzej G. Chmielewski, Zbigniew Werner ' o 11 Corrosion and Protection Centre, University of Manchester Institute of Science and Technology, United Kingdom 21 Institute of Ion Beam Physics and Materials Research, Forschungszentrum Rossendorf e.V., Dresden, Germany 3/ Soltan Institute for Nuclear Studies, Swierk, Poland Titanium foil windows have been employed in the beam assisted deposition and plasma source assist- dry scrubbing of flue gases by electron beam irradia- ed deposition. The coated foil revealed significantly tion, with a window lifetime limited by corrosion. increased open-circuit potentials compared with As part of the programme aimed at improving the the untreated titanium, which assists protection of lifetime of windows, the corrosion resistance of ti- the titanium foil when the coating is detached local- tanium foil has been assessed, following palladium ly from the substrate. The main results may be con- surface treatments applied by vacuum evaporation, cluded as follows: ion beam mixing, ion beam assisted deposition and 1. Palladium coatings, of up to 415 nm thickness, plasma source ion assisted deposition, with produc- deposited upon a titanium foil by vacuum evapora- tion of palladium layers up to about 400 nm thick. tion, ion beam mixing, ion beam assisted deposition For evaluation of corrosion behaviours, immersion and plasma source ion assisted deposition result in tests and potential-time and potentiodynamic pola- significant improvements in the corrosion resis- rization measurements were carried out, mainly in tance of the foil in 0.1 M H2SO4 and 0.1 M HNO3 0.1 M H2SO4 and 0.1 M HNO3 environments at at 80°C. 80°C which approximate possible conditions in a 2. Corrosion of the coated foil is negligible during plant. The foil surfaces were examined by scanning immersion in 0.1 M H2SO4 and 0.1 M HNO3 at electron microscopy, Rutherford backscattering 80°C for a time up to at least 2000 h. The loss of spectroscopy and a nuclear reaction analysis to palladium, as determined by EDX and RBS ana- determine the nature of surface degradation and lysis, is negligible. changes in surface composition. 3. The adhesion of the coatings to the titanium sub- The results indicated major improvements in the strate is weakened during immersion in 0.1 M H2SO4 corrosion resistance of the titanium foil from all at 80°C, with detachment of the coating occurring in palladium treatments, with surfaces undergoing re- removal of specimens from the acid after a 1000 h latively minor or negligible corrosion, following im- immersion. However, there was no significant corro- mersion testing for up to 2000 h. However, the sion of the titanium substrate at sites where the coat- coatings often suffered a loss of adhesion with ex- ing had detached. tended periods of immersion in H2SC"4 either local- 4. The detachment of the coating proceeds by at- ly or generally, possibly associated with the pre- tack at, or close to the coating/substrate interface, sence of a thin oxide layer at the interface between which may be facilitated by stresses in the coating the coating and the substrate. The optimum perfor- and substrate and the presence of an oxide film at mance was found for coatings produced by ion the interface. NUCLEAR TECHNOLOGIES AND METHODS 123 PL0002038 SURFACE MODIFICATION OF CONSTRUCTIONAL STEELS BY IRRADIATION WITH HIGH INTENSITY PULSED NITROGEN PLASMA BEAMS Jerzy Langner17, Jerzy Piekoszewski, Zbigniew WernerJ/, Vladimir I. Tereshin2/, Volodia V. Chebotarev2/, Igor Garkusha2/, Lech Walis, Bozena Sartowska, Wojciech Starosta, Wladyslaw Szymczyk1^ Michat Kopcewicz3/, Agnieszka Grabias3/ 11 Soltan Institute for Nuclear Studies, Swierk, Poland 21 Institute of Plasma Physics NSC KFTI KHARKOV, Ukraine 3/ Institute of Electronic Meterials, Warszawa, Poland In ref. [1] it was shown that in a high alloy tool steel melted by a CO2 laser, the near surface region ex- hibits phase composition far beyond the equilibrium ! state. Especially, the oversaturated austenite (called "ZLT" structure) of surprisingly high hardness has been identified. The austenite formation has also been observed in our previous work, in which a low carbon alloy steel was irradiated by high intensity I 0-5 pulsed plasma beams (HIPPB) of nitrogen. In view of 10 these facts, in the present work we undertook a more systematic study of the effect of HIPPB on tribologi- o o cal and structural properties of alloy constructional steels 40H and 12HN3A using nitrogen plasma pulses generated in two facilities: an IBIS (Swierk, 20 40 60 Poland) and a PROSVET (Kharkov, Ukraine). Basic yN content [%] parameters of pulses generated by the IBIS and Fig. Wear rate normalised to the initial value as a function of yN PROSVET were (respectively) as follows: energy contrent formed as a result of nitrogen pulsed plasma density - 6 and 10-12 J/cm2, pulse duration -1 and 3-5 treatment; open circles - 12HN3A steel, open triangles - 40H ,MS, mean energy of ions up to 10 and 2 keV. In both steel. cases each sample was irradiated with 10 pulses. The (yN-phase in which an Fe atom has an interstitial processed samples were characterized by sapphire nitrogen atom as the nearest neighbour. In view of ball-on-flat wearing measurements, Mossbauer spec- the present results it appears that the conclusions Table. Phase composition of pulse plasma treated samples of 40H and 12HN3A steels, as derived by numerical fitting of CEMS data. Phase content [%] Sample a-Fe Martensite y (austenite-single line) yN (doublet) Fe3C Fe3N H=33T H=30T H=20.8T H«23T ' 40H (initial) 62 37 1 - - 40H (IBIS) 60 13.5 21.5 5 - 40H (PROSVET) 10 12 25 41 - 12 12HN3A (initial) 88 11.5 0.5 - - 12HN3A(IBIS) 82 12 4.5 1.5 - 0 12HN3A (PROSVET) 25 - 31.5 40.5 4(?) troscopy, XRD and NRA analysis, and microscopic presented in ref. [1] that a wear-resistant austenitic observations. surface layer is formed under the conditions of a It is shown that the irradiation of medium and sufficiently low cooling rate should be questioned. low carbon constructional steel with high intensity pulses of nitrogen plasma leads to the formation of Reference uniform, fine-grain, wear-resistant layers of a thick- [l].Zhu J., Liu J., Chou C, Chen N.: A new structure of laser ness of few microns (Fig.). These layers exhibit the melted Cr-12 tool steel. In: Surface Engineering Practice. austenite structure, although on closer examination Processes, Fundamentals and Applications in Corrosion and Wear. Eds. K.N. Straford, P.K. Datta, J.S. Gray, Ellis Hor- by CEMS spectroscopy (Table), it can be concluded wood. New York, London, Toronto, Sydney, Tokio, Singa- that the improvement of tribological properties pure 1990, p. 168. should be attributed to the presence of austenitic 124 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS A LABORATORY-UNIT FIELD TEST OF A PALLADIUM-TREATED TITANIUM FOIL PL0002039 FOR DRY SCRUBBER APPLICATION Stephen D. Barson17, Peter Skeldon1^ George E. Thompson1^ Jerzy Piekoszewski, Andrzej G. Chmielewski, Jerzy Licki2/, Bozena Sartowska, Zbigniew Werner3'', Edgar Richter4', Egbert Wieser4/ 11 Corrosion and Protection Centre, University of Manchester Institute of Science and Technology, United Kingdom 21 Institute of Atomic Energy, Swierk, Poland 3/ Soltan Institute for Nuclear Studies, Swierk, Poland 4/ Institute of Ion Beam Physics and Materials Research, Forschungszentrum Rossendorf e.V., Dresden, Germany A titanium foil of about 50 ^m thickness was em- PSIAD coating deposited with a high pulse bias ployed for electron transparent windows in the provided the best performance, with an estimated electron beam dry scrubber process. The electron 60% of the surface remaining relatively free of cor- induce reactions in flue gas lead to reduced levels rosion. However, further improvements are necess- of SO2 and NOX. The window suffers corrosion ary to the coating procedures to provide the re- during operation of the process. Previous labora- quired adhesion of the coatings for windows in tory studies demonstrated enhanced corrosion re- commercial plant. sistance of the foil by a palladium coating. Here, the The main results may be concluded as follows: results of examination of a palladium-coated titan- 1. The main factor determining the corrosion beha- ium window, following service in a laboratory viour of the present palladium-coated window, pre- set-up electron beam dry scrubber plant, are re- pared by IBAD and PSIAD, in the electron beam ported. The palladium was deposited on the foil by dry scrubber process is adhesion of the palladium ion beam assisted deposition (IBAD) and plasma coating. The adhesion of the present coatings re- source ion assisted deposition (PSIAD), with de- duces significantly during exposure to the flue gas, position conditions selected to provide five types of with pieces of the coating becoming detached and coating in total. Untreated titanium windows were the flue gas attacking the revealed titanium. also exposed to similar flue gas conditions. The un- 2. Pitting, intergranular and general corrosion occur treated titanium suffered general corrosion and at the locally revealed titanium, the extent and types extensive fine pitting. The performance of the of corrosion being dependent upon the particular coated foil was influenced greatly by the adhesion region of the surface. In places, general corrosion of the coating, which was reduced during exposure and extensive fine pitting are similar to those found to flue gas. In places where the coating remained on untreated titanium exposed to the same compo- attached to the foil, the titanium surface was un- sition of flue gas. At locations where palladium affected by corrosion, confirming the anticipated remains on the surface for the duration of the test, high corrosion resistance provided by the coating. the underlying foil is free of significant corrosion. Elsewhere, loss of palladium at different stages of 3. Of the treatments employed, the plasma source the test allowed corrosion of the foil by the flue gas. ion assisted deposition, with a high pulse bias, pro- In the worst case, the corrosion was similar to that vided the best performance, with about 60% of the of untreated titanium. In other areas, intergranular coated region being free from corrosion at the end corrosion, general corrosion and pitting were in of the test period. evidence, although the surface damage was less. A

EROSION OF ELECTRODES IN THE DPE PROCESS

1/ 1 2/ 2 ' CM Jerzy Piekoszewski, Rainer Grotzschel , Egbert Wieser ^ Jacek Stanislawski , Zbigniew Werner ', :O 2 2 I O Wladystaw Szymczyk '', Jerzy Langner '' !O 11 Institute of Ion Beam Physics and Materials Research, Forschungszentrum Rossendorf e.V., Dresden, Germany 21 Soltan Institute for Nuclear Studies, Swierk, Poland No mixed metal-ceramic layer was ever observed on portion of metal released from electrodes in a dis- the surface of ceramic substrates already after ap- charge arrived to the target after its surface - melted plication of the first pulse of metallic plasma within earlier by high-energy ions of the working gas gene- the Deposition by Pulse Erosion (DPE) process. rated in the discharge - had already solidified. Metal For instance, mixing of Ti in AI2O3 was observed into ceramic mixing may take place within the DPE only after application of the second pulse regardless process only when working gas ions melt the cera- of the used working gas: nitrogen, argon, or heavy mic surface on which some metal atoms have been and slowly-drifting xenon. Microscopic details of already pre-deposited by some earlier discharges. the target surface topography obtained for other Erosion of electrodes in the DPE process was metal-ceramic combinations also suggested that a studied more deeply. It was assumed that two NUCLEAR TECHNOLOGIES AND METHODS 125 mechanisms might account for the observed release stant thermal conductivity was assumed for tem- of metal from electrodes in the form of atoms: sput- peratures above the melting temperature. Energy tering or evaporation. Therefore it was decided to density was taken as 10, 25, and 50 J/cm2. FWHM select for further investigations such metals, for of the Gaussian energy pulses was taken as 1,3, and which sputtering yields are similar but vapor press- 5 [is. The calculated temperature (T) vs. time curves ures (controlling efficiency of evaporation) differ were transformed into the vapor pressure (P) vs. significantly. Loss of mass of electrodes was in both time curves using the best fit to the compiled ex- cases measured by weighing on a micro-scale. To perimental data taken from ref. [2]: verify which set of electrodes - the inner one or the for Ti: log™ (P [Pa])=-23340/T+9.79; outer one - is the main source of metal in the DPE for W: logio (P [Pa])=-44485/T+12.74. process, the measurements were performed sepa- Electrodes erode mainly within their end parts, rately for both sets of electrodes. at a distance of about 3 cm. After several hundred Some numeric simulations of temperature vs. time discharges the originally cylindrical ends of the and vapor pressure vs. time on surfaces of the elec- electrodes take a conical shape. The weighed mass trodes were performed with the help of a MELT losses were re-calculated as losses of atoms per computer program. It was assumed that pulses of electrode per pulse. The results are given in Table. Table. Erosion of electrodes as measured by weight loss and re-calculated into number of atoms per electrode per pulse, and number of atoms deposited on the substrates as determined by the EDX technique. The working gas in the discharge was argon. Erosion of electrodes [xlO atoms/pulse electrode] Gain in substrate Material [xlO1 atoms/pulse cm ) Outer Inner Ti 36 10 6.5 W n 7.8 1.1 3.7

Gaussian shape deliver the energy. According to the Over 5 times more Ti atoms than W atoms have Knudsen-Hertz rule the area under the vapor press- eroded from both inner and outer electrodes ure vs. time curve was taken as the measure of (combined). This figure correlates well with the 4.2 amount of the material evaporated form electrodes. ratio of areas under the P(t) curves calculated for Ti Ratio of these integrals calculated for the various and W for the following set of parameters: energy metals at identical parameters may be compared to density - 25 J/cm2, pulse FWHM - 1 fis. One can the ratio of the experimentally measured losses of conclude that erosion is governed by some thermal mass of the electrodes made of these metals. If it mechanism, including evaporation - although the turns out that metal evaporates (and is not sput- latter mechanism may not be the only one. Other tered), results of the performed calculations might be possible mechanism observed for laser ablation at helpful to estimate conditions prevailing at the elec- large densities of energy is liquid expulsion (recoil trodes during discharges. pressure causes the melted matter to flow outward). Tungsten and titanium have been selected as a The main source of metal is the set of outer elec- pair of metals with similar sputtering yields, and trodes. In case of Ti they are about 3.6 times more with significantly different vapor pressures. Argon efficient than the inner ones, for W - about 7 times. was selected as the working gas. Tungsten vapor pressure is in a broad range of temperatures several References orders of magnitude lower than that of titanium. [1]. Andersen H.H., Bay H.L.: Sputtering data for metals. In: Sputtering yields of both these metals in argon (for Topics in Applied Physics. Vol. 47. Ed. R. Behrish. Springer Verlag, New York, Heidelberg, Berlin 1981, p. 145. argon ion energies in the 5-10 keV range) are prac- [2]. Langley R.A.: J. Plasma Phys. and Thermonuclear Fusion, tically the same. Rich literature data compiled in Special Issue 1984, p. SS. ref. [1] do not extend beyond the 0.5-2 region. Con-

STUDY OF ELECTROCHEMICAL PROCESSES PL0002041 USING TRACK ETCHED MEMBRANES Marek Buczkowski, Danuta Wawszczak, Wojciech Starosta, Bozena Sartowska Track etched membranes (TEMs) produced by including different kinds of microfiltration mem- means of cyclotron heavy ions beams are a product branes in the form of a disc, 25 mm in diameter. The of advanced technology, characterised by unique scheme of such cell is given in Fig.l. As electrolyte, features such as precisely determined pore diameter CUSO4 0.5 N aqueous solution was employed and the and smooth membrane surface [1, 2]. Behaviour of voltage was equal to 2.1 V DC. The electrodes were TEMs in many processes, is different in comparison made of a 5 mm diameter graphite rod. with conventional microfiltration membranes, in- Parameters of TEMs used in the experiments were cluding among other electrochemical processes. the following: pore diameter 0.16, 0.45 and 2.3 fim Introductory experiments have based on the regis- with the porosity of about 12% in each case. For tration of electrolysis current in a cell with a barrier comparison fibrous PALL and Millipore membranes 126 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS

Table.

Membrane parameters Electrolysis current No Type of barrier Thickness Mean value of pore size Permeability* [mA] [um] [urn] [1/min • cm ] 1 - - - - 40 2 TEM 10 0.16 0.7 38 3 TEM 10 0.45 9.5 36 4 TEM 10 2.0 21.7 39 5 TEM 20 0.4 8.3 35 6 Disk of PET film with 8 mm diam. hole** 10 - - 27 7 PALL0.2^m 130 0.34 3.4 26 8 PALL2^tn 300 1.70 138.6 34 9 Milipore0.3^m 120 0.48 8.0 33 10 PP unwoven fabric (pressed) 200 =3 27.2 1.4 *At 0.05 MPa air pressure. ** Surface of the hole -12% of whole active surface. as well as a PP unwoven fabric were taken for experi- close to the current value without any membrane. ments. The important parameters of membranes, i.e. These values are bigger in comparison with the electrolysis current for the disc with the surface hole equal to the value of TEMs porosity. In all cases of the barriers made of fibrous or unwoven membranes the electrolysis currents were lower than in the case of TEMs membranes in spite of the fact that the values of pore size and permeability for these membranes are higher in comparison with TEMs. One can suggest that the above results are con- cerned with the existence of surface charge in the case of TEMs. Such a surface charge can be mea- sured by using zeta potential conception [3, 4]. These measurements for some kinds of TEMs were Fig.l. Scheme of the cell for electrolytic measurements: 1 - elec- made by the present authors [5]. trolyte, 2 - electrodes, 3 - membrane, 4 - barrier with the The change of configuration and type of the membrane holder. cathode gave the possibility of another process mean value of pore size and permeability, were mea- observation. After a close putting of a track etched sured by means of Coulter® Porometer II instru- membrane on a lenticular, polished cathode, made ment. of stainless steel, electrolytic copper was deposited Results of electrolysis current measurements in the membrane pores. As a final result copper after stabilization of the process (about 20 min) are microcylinders were obtained, whose surface de- given in Table. In the case of TEMs, the values of picted mapping of the inside pores structure. SEM electrolysis current are similar to each other and pictures of such structures are given in Fig.2.

Fig.2. Scanning electron microscope pictures of copper microcylinders (diameter about 0.5 ftm) by electrolytic way deposited inside pores of track membranes: a - general view, b - enlarged fragment showing the inside structure of pores. NUCLEAR TECHNOLOGIES AND METHODS 127

References [4]. Berezkin V.V. et al.: Kolłoidnyj Zumal, 5JL, 6,10-15 (1993). [5]. Buczkowski M., Starosta W., Wawszczak D.: Procesy permea- [1]. Spohr R.: Ion Tracks and Microtechnology, Principles and cyjne oraz elektrochemiczne z wykorzystaniem membran treko- Application. Vieweg, Braunschweig 1990. wych. III Ogólnopolska Konferencja Naukowa "Membrany i pro- [2]. Particle track membranes and their applications. Proc. of the cesy membranowe w ochronie środowiska", Szczyrk, Poland, 2nd Meeting, 2-6 December 1991, Szczyrk, Poland. Ed. W. 21-23 October 1999. Proceedings, pp. 25-31. Starosta, M. Buczkowski. INCT, Warszawa 1992, p. 90. [3]. Fridrichsberg D.A: Kurs kolloidnoj chimii. Izd. Chimija, Leningrad 1974, p. 351. PL0002042

APPROACH TO ATTRIBUTION OF A 17th-CENTURY ALABASTER ALTAR FROM THE CLARISTS NUNNERY IN KRAKÓW Ewa Pańczyk, Maria Ligęza1', Lech Waliś 11 Academy of Fine Arts, Kraków, Poland Introduction Alabaster is a massive crypto-crystalline form of A 17th-century alabaster altar in low-relief, ori- gypsum, deposited in inland seas during the last ginating from the Clarists Nunnery in Kraków, period of Palaeozoic era (the Permian period) and depicts Crucifixion of Christ (Fig.l). The entirety of the first period of the Mesozoic era (the Triassic the altar, contained within architectural frames is period). Alabaster is a pure substance with a very restricted by pilasters on both sides. From the top, low content of trace elements [1,2]. Alabaster was used, particularly in the Middle Ages as sculpture material, mainly in Normandy, Westfalen, Northern Netherlands and England. As sculpture material, alabaster has excellent proper- ties: it can be easily shaped, it allows to obtain fine details, it is semi-transparent and can be readily plated with gold or polychromed [3]. Its disadvan- tages are brittleness and sensitivity to atmospheric agents. Table 1. Description of the examined samples. Material examined Sample no. Upper part of the object, final 1 Upper part of the object, phial 2 Lower part of the object, left corner, stuck-on 3 Left side of the object 4 Right side of the object 5 Lower part of the object, base 6 Alabaster deposit "Nowy Ląd" - open cast No. 2 Ik Alabaster deposit "Nowy Ląd" - open cast No. 3, 2k NE wall, level +213 m above sea level Alabaster deposit "Nowy Ląd" - open cast No. 3, 3k SW wall, level +220 m above sea level Alabaster deposit "Nowy Ląd" - open cast No. 3, 4k SW wall, level +220 m above sea level

Fig.l.The alabaster altar - Crucifiction of Christ (17th century). The present investigations have been performed on 6 samples taken from the sculpture of the altar the relief is finished by a finial and two small phials. (Fig.l) and on 4 samples from the gypsum and an- Detailed history of the object is unknown. Un- hydrite deposit "Nowy Ląd" at Niwnice near Żagań. known remain both the author of the piece of art The samples are described in Table 1. and its origin. Two possible places of origin are The samples were analysed by INAA, using being considered: the Netherlands and Lwów. How standards of the elements to be determined. Major the altar got to the Nunnery is also not known. constituents of alabaster (CaSO4*2H2) have low Perhaps it was a dowry of one of the nuns. Or (n,y) reaction cross-sections, which is of advantage perhaps it was presented by nuns from the neigh- for carrying out the analysis. By irradiating alabas- bouring Carmelitess Nunnery at that time the nuns ter with thermal neutrons, its major constituent have relocated their congregation to another place. undergoes the nuclear reaction ^Ca (n,y)47Ca -* Investigations of archival and bibliographic collec- 47Sc. The radioisotope 47Ca has a half-life of 4.53 tions and tests should allow for discovering history days and emits gamma rays of energy 1290 and 800 of the altar and its attribution. keV. On the other hand, 47Sc having a half-life of 128 MATERIAL. ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS 3.4 days, emits gamma rays of energy 160 keV. The samples were taken. This could be attributed to reaction cross-section is 0.250 barn and the natural later conservative actions. Concentration of other abundance of 46Ca is 0.0033%. elements, found in the sajnples taken from the Table 2. Concentration of determined elements in the alabaster samples examined [ppm]. 1 2 3 4 5 6 Ik 2k 3k 4k Na 1090 370 420 320 620 228 47.5 52.5 57 54.5 K 2120 36 000 590 840 1400 350 107 55.5 55 58.5 Ca[%] 23.37 13.8 26.2 23.57 18.77 21.99 23.25 21.57 24.36 25.55 Sc 2 0.7 3.9 0.6 1.5 0.2 0.2 0.1 0.06 0.2 Cr 237 58 110 92 190 41 6.8 11.1 7.7 7.4 Mn 416 14 590 9.2 110 29 9 21.5 10.8 8.7 Fe 3 520 1400 920 2 700 410 82 155 210 95.5 150 Co 7.3 1.8 4.4 3.8 4.4 1.4 0.3 0.3 0.3 0.2 Cu 82 38 49 13 61 23 7 8.6 8.5 4 Zn 22 25 30 55 92 32 3.4 20.8 1 1.3 As 28 12 11 8.2 21 9.6 0.5 0.7 0.9 0.6 Se 1.8 0.3 1.3 0.1 0.7 0.2 0.03 0.1 0.02 0.04 Br 170 32 33 29 45 120 12.6 11 17 21.5 Rb 7.3 11 5.3 - 3.5 2.3 0.5 1.4 0.8 0.7 Sr 320 380 1400 5 000 470 2 600 1050 7150 1325 1785 Zr 44 8.7 14 6.7 - - - - 2.8 - Mo 5.7 1.6 1.1 1.7 7.5 0.3 0.3 0.2 0.5 0.9 Ag 0.04 0.005 0.03 0.007 0.03 0.004 0.003 0.001 0.0004 0.0009 Sn 2300 42 440 110 440 . 41.1 34 61 39 Sb 23 6.4 9.1 5.2 15 1.3 0.2 1 0.5 0.3 Cs 2.4 1.8 1 1 3.1 0.3 0.2 0.2 0.1 0.1 Ba 740 135 270 330 560 490 34.5 39 30 29 La 5.9 0.6 1.4 1 2.8 0.9 0.09 0.6 0.2 0.3 Ce 18 3.9 8.8 5.9 13 4.5 0.6 1.1 0.5 0.8 Sm 0.6 0.09 0.1 0.2 0.3 0.05 0.2 0.3 0.02 0.04 Eu 0.2 0.03 0.3 0.05 0.08 0.01 0.005 0.008 0.004 0.007 Tb 0.2 0.04 0.1 0.07 0,4 0.03 0.007 0.008 0.05 0.04 Yb 2 0.07 0.4 0.07 0.05 0.04 0.02 0.04 0.03 0.07 Hf 0.5 0.07 0.2 - 0.4 0.007 0.02 0.009 0.04 Ta 0.04 0.3 0.008 0.01 0.03 0.006 0.002 . 0.0006 0.02 W 21 1.2 5.6 2.9 8.7 1.7 0.1 0.3 0.2 0.1 Ir 0.02 0.004 0.002 0.0006 0.005 0.002 0.0004 0.0001 0.0008 0.0006 Au 0.3 0.03 0.07 0.04 0.3 0.04 0.003 0.004 0.003 0.004 Hg 3 500 1000 1320 - 4 600 250 114 100 27 91 Th 1.5 0.4 0.6 1.4 1.7 0.3 0.1 0.09 0.05 0.2 2.6 0.7 0.7 2.2 0.7 0.2 0.05 0.05 0.04

Experimental sculpture, differs significantly from that found in 200 g samples of alabaster deposits were ground in the samples taken from the "Nowy La.d" deposit. an agate mortar. Next, approximately 50 mg samples Methods of a multivariate statistic analysis - clus- were taken from the ground material. The samples ter analysis and principal components analysis have were weighed and sealed in quartz ampoules and been applied to elaborate the obtained results using then packed together with standard samples of 40 STATISTICA 5.5 software, supplied by StatSoft. elements. Each packet contained also Sc and Au as Cluster analysis has been performed for all the monitors of the thermal neutron flux. TiMDkgranlsttOCnn Irradiation was carried out in the MARIA reac- VMIIMM tor at Swierk near Warszawa, using a neutron flux of 8xl013 ncm'V1. The samples were irradiated for 24 hours and then cooled for 12 hours. Radioactivity of 100 the samples was measured using an HP-Ge detector M (ORTEC) coupled to a CANBERRA-System S100 spectrometer, controlled by an IBM computer. Ana- K lysis of the gamma-ray spectra of the samples was 40 _— performed using the microSampo software. Discussion of results 30 Total of thirty six elements were identified and determined in the examined samples. Concentra- tion of trace elements in the said samples is pre- Fig.2. Cluster analysis of 10 samples of alabaster described by 36 sented in Table 2. There are significant differences features. between the content of Ca and K in sample No. 2 assayed elements. Results of this analysis for 10 (phial) and other parts of the altar, from which the tested objects and 35 assayed elements are pre- NUCLEAR TECHNOLOGIES AND METHODS 129 dNft, Factor I r& Factnrl The results prove that the altar has not been made of alabaster, originating from the "Nowy La_d" A I e 1 deposit. Further investigations are in progress, with 31 Ik the aim of obtaining more material for comparative 0,8 studies and analysing alabaster deposits of South- 0.4 4-1 o -Eastern Poland and the Lower Silesia region. 07 l_

00 References O -0.2 [1]. Pariczyk E., Rowiriska L., WaliS L., Lige.za M., Nalepa B.:

4 3 Activation Analysis as a Method for Determining Origin of a Sculpture. Proceedings of the Conference on Nuclear Tech- nics in Industry, Medicine, Agriculture and Environment Protection, Krak6w, Poland, 16-18 September 1998. Fig.3. Principal component analysis for 10 alabaster samples. [2]. Beasley S.M.: The Attribution of Alabaster Tomb Carvings to Medieval Schools. Analytical and Typographical Problems. A Further Study. University of Bradford. Post-graduate Thesis, un- sented in Fig.2. The results obtained by principal published, 1978. components are presented in Fig.3. The method is [3]. Cheetman M.: English Medieval Alabaster Catalogue. Vic- very useful in grouping various objects. toria and Albert Museum, Oxfr

PL0002043 INVESTIGATION OF ART OBJECTS WITH THE USE OF TOTAL REFLECTION X-RAY FLUORESCENCE Joachim Kierzek, Jerzy Kunicki-Goldflnger, Bozena Matozewska-Bucko Total reflection X-ray fluorescence (TXRF) is a trace element method of analysis [1]. Trough the use of a total reflection of X-rays the background under the peak of characteristic radiation is reduced by several orders of magnitude. In consequence the very low detection limits, amounting to a few picograms, for about 60 elements are achieved. This corresponds to a concentration below 1 part per billion (ppb). The range of the atomic numbers of analysed elements extends from 16 (sulphur) to 92 (uranium). 10 The TXRF differs from the classical XRF in the following: Fig.l. Spectra of characteristic X-rays excited in an archeological - A beam of exciting radiation strikes a flat and glass. Continuous line - a spectrum from the fracture (bulk, smooth surface of a quartz disc, with an analysed not corrode); pointed line - a spectrum from the leached sample on it, under an angle smaller than the cri- glass surface. tical one. This is a condition for the total reflec- pies were also taken from the glazed surface of the tion. bas-relief (X. Dunikowski, The Annunciation). The - A sample mass can be reduced to about 0.5 ^g or analysis enabled the determination of glaze as a less. In practice it is enough to rub an examined lead-alkali one and a cobalt compound as a colour- surface, for example of a painting, with a soft ing agent. cotton swab similar to one used for cleaning the Analysis of pigments and gilding layers . ears. With this swab a quartz disk is rubbed and In this case the sample taking is less invasive the sample is ready for analysis. The sample can than described above. It is enough to gently rub the be transferred and deposited as a powder or solu- examined surface using the above mentioned cotton tion. swab. Such a procedure is satisfactory in the majo- The method is applied both for the analysis of rity of cases both when we deal with a wall painting pigments in painting layers on different supports [2-4] and for the determination of chemical compo- io5F sition of glassy materials [5-6]. Analysis of glass and glazed objects Part of a glass vessel, transparent, greenish, vi- sibly corroded from the 18th century was investi- gated (property of the Warsaw Castle, inv. number ZK/95/6/98). Two samples were taken by the scratching with a diamond tip of the outer corroded and the fractured surfaces. As can be seen from Fig.l, the concentration of leachable elements such as K, Ca and Sr is significantly lower at the outer Fig.2. A spectrum of characteristic X-rays excited in a blue poly- surface than at the intact part of the glass. The sam- chrome. 130 MATERIAL. ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS and other techniques of painting on various sup- the traces of the original gilding layer are composed ports. Fig.2 shows an X-ray spectrum of the sample of pure gold. taken from the blue area of the 16th-century poly- The described examples show that TXRF is a chrome frieze, located under the chapel dome of very convenient tool for investigation of art treas- the Primate Jakub Uchanski in the cathedral at ures and other valuable objects due to its multi- Lowicz. In this sample Co was identified, which can element capability. The microsize of the analysed be evidence of the use of smalt as a blue pigment. sample makes it practically non-destructive for the The gilding layers are particularly suitable for investigated item. XRF examinations. In the majority of cases it is References 10b [1]. Klockenkamper R.: Total-Reflection X-Ray Fluorescence Analysis. John Wiley & Sons, Inc., New York, Chochester, Brisbane, Toronto, Singapore, Weinheim 1997. [2J.Devos W., Moens L., Von Bohlen A., Klockenkamper R.: Studies in Conserv., 4Q, 3,153-162 (1995). [3].VandenebeeIe P., Wehling B., Moens L., Dekeyzer B., Cardon B., Von Bohlen A., Klockenkamper R.: The Analyst, 124. 169-172(1999). [4]. Hotyriska B., Najman J., Ostachowicz B., Ostachowicz J., Trqbska J., Wqgrzynek D.: J. Trace and Microprobe Tech- niques, 14_(1), 119-130 (1996). [5].Wegstein M., Urban H., Rostam-Khani P., Wittershagen A, Kolbesen B.O.: Spectrochim. Acta, Part B, 52,1057-1061 (1997). Fig.3.A spectrum of characteristic X-rays excited in a sample [6]. Bonizzoni L., Cicardi C, Galli A., Milazzo ML: Mutual inte- from overpainting gilding layer. gration of different XRF techniques in quantitative analysis of stained glasses. The case of Roisan Church (Valle d'Aosta, enough to take a sample using the cotton swab. As XVI cent.). Proceedings of the 6th International Conference can be seen from Fig.3 in the sample taken from an on Non-destructive testing and microanalysis for the diagno- stics and conservation of the cultural and environmental overpainting drapery of the Madonna (attribution heritage, Rome, Italy, 17-20 May 1999. AIPnD, ICR, Rome unknown, wooden support, from private collection) 1999, vol. II, pp. 1379-1384.

DETERMINATION OF URANIUM AND POTASSIUM CONTENT IN A HISTORICAL GLASS VESSEL BY MEASURING ITS NATURAL RADIOACTIVITY Joachim Kierzek, Jerzy Kunicki-Goldfinger, Aleksandra Kasprzak1' !§ [/ National Museum, Warszawa, Poland Natural radioactivity of historical glasses can be decay with a half-life of 2.46xlO5, 7.04xl08 and considered under several aspects. Qualitative detec- 4.47xlO9 years, respectively. During the radioactive tion and quantitative chemical analyses of the ele- decay of uranium isotopes, the alpha and beta par- ments, which show natural radioactivity, as well as ticles as well as gamma and X radiation are emitted. the possibility of dating the artefacts made of uran- The initial part of the 238U decay series and the ium glass, constitute an important chance of appli- 235U decay as well as the energies and intensities of cations of nuclear methods. So, in some cases, ra- the main gamma lines are reported in Table 1. Only dioactivity can be employed as a useful tool for these steps of the decay chains are shown, which technological research of historical objects [1-6]. can be useful for estimating the uranium content in In historical glass objects potassium and uranium historical glass objects. The strong 63.29 and 92.6 radioisotopes can be identified in some circum- keV gamma lines of 234Th appear to be suitable for stances. Radiorubidium may occur in these objects uranium determination in little objects. In the case only in trace concentrations. So, most of historical of larger ones, a significant error may arise as a glasses produced up to the end of the 18th century result of the self-absorption effect. For the objects contain only 40K as the only radioactive nuclide at a of irregular shapes, the determination is very dif- level more than trace concentration. In glasses made ficult to accomplish. The 143.76, 163.36, 185.71 and in the 19th century, it is also possible to detect ra- 205.31 keV gamma lines that are accompanying the diometrically a higher concentration of uranium. 235U decay, as well as the 766.38 and 1001.03 keV 234m The determination of potassium in historical glass gamma lines that are accompanying the Pa decay via beta-particle emission (99.87%), could be objects employing gamma spectrometry has been 238 already discussed [5]. Using an appropriate standard utilised to determine the uranium content. U for calibration, it is possible to measure the uranium decays via alpha-particle emission to its daughter product, 234Th, which, with a half-life of 24.1 days, content in historical glass, in a similar way. If a glass 234m contains both potassium and uranium, it is possible decays in the next step of the chain to Pa. to measure their contents simultaneously. Secular equilibrium for this chain is reached within Natural uranium consists of three isotopes: 234U less than 1 year (about 250 days). So, there is a (0.0058%), 235U (0.714%) and 238U (99.28%). They possibility to measure the uranium content in histo- NUCLEAR TECHNOLOGIES AND METHODS 131

Table 1. Schematic diagram of the 238U and 235U decay series down lo 230Th and 231Th, respectively, energies and intensities of the main gamma lines. Main gamma ray lines Intensity Radionuclide Half life [keV] [%] 4.47xl09y °L—-~-"—" 234Th 24.1 63.29 4.8 92.60 5.58

1.17 m 766.38 0.318 9987% IT(0.13%)f\F( > 1001.03 0.845 6.75 h 234u 2.46xlO5 y

23O Th 7.54xl04y 67.67 0.38 143.87 0.049

8 235U 7.04xl0 y 143.76 10.97 163.36 5.08 185.71 57.25 205.31 5.02

231Th 25.52 h

rical glass pieces (which are certainly older than measurement of a silicon mould with the glass vessel one year) applying gamma spectrometry with a high inside. For the second measurement, the same mould resolution HPGe detector. was filled with powdered material that was used for A Bohemian, fooled, green glass beaker made in calibration. A U3Og and K2SO4 mixture at the rate 1840s was examined using gamma spectrometry. of 22.5 g and 385.4 g, respectively, was used for this The vessel has been made available for examination purpose. The mixture was homogenised in a ball mill by the National Museum in Warszawa (object inv. and contained 4.678 wt% of elemental uranium. No 188645). The weight of the object was 448.8 g. Weight of the standard for calibration, which filled This was done in a non-destructive manner essen- the silicon mould, was equal to 274.7 g. The results tial for objects of historical value. obtained are listed in Table 2. The uranium content Radiometric measurements were performed by a that was computed on the basis of the intensity of the gamma ray spectrometer, containing an HPGe de- individual gamma lines showed good agreement. tector with the resolution of 1.9 keV, and a relative Only a value computed on the basis of the 143.76 detection efficiency of 92.4% for the 1.33 MeV keV gamma line was higher. It was due to an im- gamma line. A 10 cm passive lead shield lined with possibility of separating the 143.76 keV gamma line from the 143.87 keV one accompanying the decay of 0.5 cm cadmium and 0.5 cm copper was applied for 230 4 230 reducing the natural background radiation. The full Th (Ti/2=8.0xl0 y). The Th nuclide consti- block diagram of the gamma spectrometry system tutes a farther part of the ^U decay chain (Table 1). and more detailed experimental information were If we reject this last extreme result (0.36 wt%) as the given in the previous paper [5]. outlier, the mean uranium content in the examined Full examination consisted of two measurements. glass, computed on the basis of intensities of the five The counting time of each measurement amounted remaining lines, amounts to 0.32 wt%. The K2O to 86400 s (a day and night). The first step included content is equal to 16.2 wt%. Table 2. Gamma spectrometry of the glass vessel (National Museum in Warszawa, inv. No 188645).

Isotope Gammma line [keV] Net peak intensity' [counts/day/g] U content [%] K2O content [%]

235U 143.76 418 0.36 163.36 190 0.33 185.71 2114 0.33 205.31 189 0.32

234mPa 766.38 143 0.30 1001.03 338 0.31

40K 1460.75 367 16.2

* Background corrected. 132 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS On the basis of this historical glass object, the for further studies on dating artefacts and in some limits of detection of uranium and potassium were other technological comparisons. estimated. This was evaluated for the gamma lines, which were taken into account for the compula- References tions. The results are as follows: for objects in the 11]. Brill R.H.. Fleischer R.L., Price P.B., Walker R.H.: J. Glass Stud., 6,151-155(1964). range of 200-500 g and a measurement time of 24 h, [2]. Murray S., Haggith J.: J. Glass Stud., 15., 184-186 (1973). the uranium and potassium limits of detection are [3]. Festag J.G., Gentner W., Miiller O.: Search for uranium and equal to about 0.0002% and to about 0.025%, res- chemical constituents in ancient Roman glass mosaics. In: pectively. For the same mass range of the objects, Applications of nuclear methods in the field of works of art. and for the measurement time of 1 h, a limit of International Congress, Rome and Venice 1973. Accademia Nazionale Dei Lincei, Rome 1976, pp. 493-503. uranium detection amounts to 0.0010%, and that of [4]. Hudson A.P., Newton R.: Archaeometry, 18, 2, 229-232 potassium detection to around 0.1%. (1976). In conclusion, high-resolution gamma spectro- [5]. Kunicki-Goldfinger J., Kierzek J.: Glastech. Ber. Glass. Sci. Technol., 21,11, 332-335 (1998). metry enables simultaneous determination of uran- [6]. Kunicki-Goldfinger J., Kierzek J., Sartowska B.: Utilisation ium and potassium content in historical glass objects. of natural radioactivity oC potassium for the determination of This method is especially convenient for a non-des- chemical homogeneity of historical glassware. A case study. tructive uranium determination in historical objects. Proceedings of the 6th International Conference on Non- Destructive Testing and Microanalysis for the Diagnostics Thanks to the low uranium detection limit, it can be and Conservation of the Cultural and Environmental used for determining even trace amounts of uranium. Heritage, Rome, Italy, 17-20 May 1999. AIPnD, ICR, Rome Exact knowledge of uranium content may be useful 1999, vol. II, pp. 1529-1538. NUCLEAR TECHNOLOGIES AND METHODS 133

PL0002045

NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS

A NEW BETA BACK-SCATTERING COATING THICKNESS GAUGE GIL-99 Waldemar Antoniak, Edward Swistowski, Piotr Urbariski Beta back-scattering coating thickness gauges have strument meets requirements of the international been used for many years [1, 2] and hundreds of standards for the beta back-scattering coating thick- instruments constructed as the analogue devices are ness gauges [5] and its design and construction ful- still in use. Some attempts to develop computerised fils demands for the modern measuring devices. The block diagram of the instrument is present- ed in Fig.2. The analogue part of the gauge consists of a G-M counter, H.V. power supply, an amplifier, and pulse shaping circuits. The measuring process is fully controlled by a microprocessor system. The results are presented on a display and all settings performed using a foil keyboard. Operation of the gauge is shown in the form of a flow-chart diagram (Fig.3). There are four modes of the instrument operation: settings, calibration, mea- surement and results handling. In the mode settings, the measurement and calibration, such as measuring time, source, coating and base materials, diameter of the aperture and coefficients of the calibration model can be chosen and entered from the keyboard. Cali- bration mode allows to check response of the instru- Fig.l. Beta back-scattering coating thickness gauge GIL-99. START versions were undertaken about ten years ago [3, 4]. Recently, in this Institute a new, fully computerised X V CHECK *— /pSELrMINARYS gauge GIL-99 has been designed (Fig.l). This in- SETTINGS \. TESTOK. S

PC ft KEYBOARD CXSPLAY

II POWER 1 SUPPLY INTERFACE BATCHY KEYBOARD DISPLAY f INTERFACE INTERFACE RS232 J.5V

BATERY REAL WATCKJOG WCROPROC BACKUP TIME CLOCK

MEMORY MEMORY INTERFACE COUNTER RAM EPROM CENTRONICS THERMAL y PRINTER I

KV. AMPL PULSE VOICE POWER GENERATOR DISCR SHAPING SUPPLY

JL Fig.3. Flow-chart of the GIL-99 gauge. G-M COUNTER ment for the base (substrate) material and coating of the known thickness. The measurement mode can be Fig.2. Block diagram of GIL-99. activated only after calibration has been performed. 134 NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS The results are stored in an internal memory, can be References displayed, printed and/or transmitted to an external [1]. Szepke R.: Report INR, 1272/XVA/1971. computer. An additional software has been develop- [2]. Urbafiski P., Antoniak W.: Zeszyly Naukowe Politechniki Slq- ed for statistical processing of the results transmitted skiej, Seria: Automatyka, 1042,75-82 (1989). to the computer. [3], Urbartski P., Antoniak W., Szepke R.: Nukleonika, 24, 247-256 (1989). It is expected, that the new instrument will re- [4]. ISO Standard No 3643,1980. place the analogue gauges, still exploited by the in- [5]. Szepke R., Urbanski P.: Pomiary, Automatyka i Kontrola, 12 dustrial users. (1966).

RADON PROBE SRDN-2 FOR LONG TERM RADON MEASUREMENTS Jakub Bartak, Jan P. Pienkos IS The SRDN-2 probe (Fig.l) is a new version of the data, and set of time. They are selected from the main probe SRDN-1 developed earlier in the frame of co- menu by pressing an appropriate key on the key- i§ operation with the Central Mining Institute [1-3]. board, corresponding to abbreviated name, of the The probe is designed for long term measurements of mode displayed on LCD. Selection of the mode of radon concentration in air, and variation of radon measurements enables to set parameters of measur- emanation in mining excavation due to variation of

/ \_ air Inlet

air filler

measuring cell

detector

Fig.l. General view of radon probe SRDN-2 with PSR-1 con- troller. preamplifier geological stress in the layer where coal or other minerals are extracted. When developing the probe special attention was to be paid to ensure good tech- nical parameters, especially to enable long term mea- lithium battery surements in the hard mining environment including a methane explosion hazard. microprocessor The probe is constructed in the form of a cylinder system operating with a PSR-1 microprocessor controller. lithium ballery The housing of the probe is made of acid-proof steel. Connecting cable has a zinc plated copper wire con-

volution terminated with a special water- and dust- air pump -proof connector. The probe is equipped with an im- planted silicon semiconductor detector as alpha de- tector, a measuring cell, approx. 35 cm3 in volume, with an exchangeable air filter, a pulse amplifier and discriminator, circuits of galvanic separation, a dc lithium battery voltage converter, a microprocessor system control- ling operation of the probe, an RS232C series com- air pump control munication port, power supply for air pump, and supply batteries (Fig.2). Radon can be measured in two ways: 1) with natural diffusion of radon into the measuring cell, 2) with forced flow through the measuring cell by an air sir outlet pump, to speed up exchange of air in the cell. Access to the measuring results is enabled through the Fig.2. Radon probe SRDN-2. PSR-1 controller. The controller fulfils spark-proof ing cycles and to start the measurements, or to review requirements and can be used in mines. Operation of the measurements stored in the memory of the con- the SRDN-2 probe is programmed from a keyboard. troller. The controller enables three basic modes of opera- In the mode of measurements of radon concen- tion: measurements with the probe, transmission of tration the time of forced flow of the ambient air NUCLEAR TECHNOLOGIES AND METHODS 135 through the measuring cell has to be set (advice 1 supply the semiconductor detector the alkaline min), and the counting time can be set in the range battery is used. Power consumption of the detector, 1 .. 99 min. In case the natural diffusion of air into the microprocessor system and the analog channel is the measuring cell is selected, the pumping time is very low and the batteries are sufficient for 3 years of set to zero. Selection of review of the measuring re- operation. The battery supplying the air pump at a I sults enables to read out up to 8000 measurements min pumping time is sufficient for approx. 4700 stored in the memory. In the mode of transmission measuring cycles, e.g. at a counting interval of 90 min of data, the measuring results stored in the con- is sufficient for 360 days of operation. troller memory are transmitted through the series References port RS232C to an external computer or to a serial [lj.Lebecka J., Skubacz K., Chalupnik S., Michalik B., Skowro- printer. In the mode of setting time the date and nek J.: The methods of control of radiation hazard coal time of measurement are set. mines. National Seminar, Warszawa, Poland, 25-26 February The probe is supplied from three spark-proof, 1993 (in Polish). lithium non-rechargeable, batteries 3.76 V; 13 Ah [2].Gierdalski J., Bartak J., Urbariski P.: Nukleonika, 2S, 27-32 (1993). and one alkaline battery 12 V. Two lithium batteries [3].Fraczak J.: Explosion-proof instrumentation in spark-proof supply the microprocessor system and the analog make. Academic text-book. Slqskie Wydawnictwo Technicz- channel, the third battery supply the air pump. To ne, Katowice 1995 (in Polish).

CONTINUOUS MEASUREMENT OF RADON IN AIR WITH LUCAS CELL Bronislaw Machaj, Piotr Urbanski IS Introduction the Lucas cell, decreases within approx. 3 h due to IS Lucas cell [1, 2] was investigated as an a-radia- decay of the attached radon daughters. A similar tion detector for continuous measurement [3] of effect but of opposite direction takes place when !§ radon concentration in air with air sampling by radon is introduced into the cell. Thus the indi- means of a pump. The investigations indicate that cation of Lucas cell for a step radon concentration all the short lived radon decay products produced variation is loaded with a dynamic error. Simulating inside the Lucas cell 054x74 mm (0.17 L) are computations [4-6] of radon concentration showed attached to the internal walls of the cell and are not by the Lucas cell, expressed in the fraction of radon removed when the cell is flushed with some fresh concentration at radiation equilibrium, in consecu- air. This effect, and the well known effect of tive 15 min measuring intervals is: 0.5902; 0.7178; increase of the a particle concentration when only 0.772; 0.8248; 0.8712; 0.9087; 0.9375; 0.9587; radon is introduced into the cell, result in a dyna- 0.9739; 0.9844; 0.9914; 0.9959, after radon was mic error due to delayed response of the gauge to introduced into the cell. The relation between the variations of the radon concentration. To cope with count number r at radiation equilibrium and the this phenomenon, a way of processing of the signal o radon concentration Co at t=0 is given by the equa- from the Lucas cell is proposed, which decrease the tion: dynamic error. Sensitivity of the Lucas cell for the detection of low radon concentration is limited by random where: v - volume of measuring cell [L], e - counting errors due to statistical fluctuation of the signal. efficiency of a-particles, k=0.97 - coefficient for a Principal Component Analysis (PCA) was applied decrease of the radon activity until radiation equi- to the Lucas cell signal, to see if this kind of pro- librium is achieved. cessing can improve the sensitivity of Lucas cell. Correct indication of the Lucas cell can be ob- Count rates were measured at 1 min intervals in the tained after first reading of the Lucas cell if the period up to 180 min since radon was introduced count rate from the Lucas cell is processed as into the Lucas cell. Achieved in such a manner set shown below, for eight counting intervals, and for of characteristics for different radon concentration kl .. k8=0.5902; 0.7178; 0.772; 0.8248; 0.8712; were then PCA processed. It was found that PCA 0.9087; 0.9375; 0.9587: processing considerably decreases random fluctua- - Mean count rate r is computed from the mea- tions. The PCA method of signal processing can be sured count number R in the first counting in- employed in the case of continuous measurements terval j = 1. Mean count rate corresponding to ra- with a long period of repetitions and flushing the diation equilibrium is computed ro=r/kl [cpm]. cell with clean air after each measurement, or in Mean count rate in successive 8 intervals are standard non-continuous measurements. computed: r(l,2)=ro-kl, r(l,2)=ro-k2 and Dynamic error of the Lucas cell remembered as shown in Table. Radon concen- Measurements carried out showed, that for the tration Co is computed from equation and dis- Lucas cell 0.17 L in volume, all the radon daughters played. Co is remembered as Q (last). produced inside the Lucas cell are attached to the - Mean count rate r is measured in the second time internal walls of the cell and are not removed. In interval j=2. The count rate r is compared with consequence the alpha activity that is registered by the expected count rate Re2=2r(i,2). If r is equal 136 NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS

Table. Expected count rates at successive time intervals. i\i 1 2 3 4 5 6 7 8 1 KM) r(l,2) r(l,3) r(l,4) 1(1.5) r(l,6) r(l,7) i(l,8) 2 i(2,8) r(2,l) i(2,2) r(2,3) r(2,4) r(2,5) r(2,6) r(2,7) 3 i(3,7) r(3,8) r(3,l) r(3,2) r(3,3) r(3,4) r(3,5) r(3,6 4 ...... •... 5 ...... 6 7 r(7,3) r(7,4) r(7,5) r(7,6) r(7,7) «7,8) r(7,l) r(7,2) g r(g,2) r(8,3) r(8,4) r(8,5) K8,6) r(8,7) r(8,8) r(8,l) Sr Rel ^2 Re3 Re4 Re6 Re7 Re8 At start of measurements all count rates are set to r(i,j)=O. j -successive counting time intervals (columns in Table), if j=9 then j = l. i • successive simulated count rates at time intervals (raw in Table), if i=9 then i=l.

Rej = 2r(i,j) expected total count rate in j time interval, i = 1..8. r to Re2 ± o (Re2) (standard deviation), C0=Q is To avoid excessive fluctuations of indication of displayed and count rates in successive 8 time the gauge correction of radon concentration is intervals r(2,l).. r(2,8) are set = 0. If r is higher or made only (in successive counting intervals) if the lower than Re2 ± o-(Re2) then dR=R-Re2, measured count rate r is greater or lower than ro=dR/kl and mean count rate in successive 8 standard deviation of the expected count rate. Pro- time intervals: r(2,l)=rokl, r(2,2)=ro-k2 are cessing up to 12 time intervals can be adopted for a computed and remembered as shown in Table. further decrease of the dynamic error. dCo is computed from equation. Radon concen- PCA processing of Lucas cell signal tration Co=Ci+dCo is displayed. Q> is remem- Measurements of count rate from the Lucas cell bered as Q (last). (0.17 L) at 1 min intervals against time up to 180 min since radon was introduced into the cell, cover- Mean count rate r is measured in the time interval ing the range of radon concentration in air from j=8. The count rate r is compared with the ex- 400 to 300 000 Bq/m3, were carried out. Applying pected count rate Re8=2r(i,8). If r is equal to the Principal Component Analysis to the count Re8 e ± <7(Re8), Co=Ci h displayed and count rates from the Lucas cell measured [5, 7, 8], it was rates in successive 8 time intervals r(8,l) .. r(8,8) found, that the first principal component explains are set = 0. If r is higher or lower than 99.97% of the total variance of measured count rate Re8 ± cr(Re8) then dR=R-Re8, ro=dR/kl and spectra, hence the spectra can be superseded by its mean count rate in successive 8 time intervals: first component. Fig.l shows a set of measured r(8,l)=ro-kl, r(8,2)=ro-k2 are computed and count rates, and in Fig.2 the count rates corres- remembered as shown in Table. dC0 is computed ponding to the first PCA component are presented. As it can be seen the first component contains the

80 100 time [mini B0 100 Fig.l. Measured count rates of the Lucas cell for radon concen- time [min| tration 400 .. 300 000 Bq/m3. Continuous lines present the computed average value using Multi Linear Regression Fig.2. First component PCA processed count rates from Fig.3. (MLR). principal information about the shape and magni- from equation. Radon concentration C0=Ci +dCo tude of the raw data, but it removes a great part of is displayed. Co is remembered as Ci (last). its fluctuations. NUCLEAR TECHNOLOGIES AND METHODS 137

3 3 10 pressed in Bq/m , plotted vs. radon concentration are given. It is seen that the PCA processing con- siderably reduces fluctuations, particularly for low radon concentrations. It may be expected, that an £1 S* + influence of fluctuations for the radon concen- g ***** tration of 100 Bq/m3 can be reduced by a factor of + * + 100. y References sftheor [1]. Lucas H.F.: Rev. Sci Instr., 28,2,680-683 (1957). 0- s< calc 110° [2], George AC: Health Physics, 20,4, 451-463 (1996). sfPCA [3]. Ward D.C., Borak T.B.: Health Physics, 61,6,799-807 (1991). [4]. Nazaroff W.W., Nero A.V.: Radon and its decay products in + indoor air. John Wiley & Sons, 1988. 10' [5]. Ewans R.D.: The Atomic Nucleus. McGraw-Hill Book Com- 102 103 10* 10° 10* pany, 1970, p. 972. radon concetration [Bq/m3] [6], Machaj B., Urbartski P.: Nukleonika, 44, 4, 579-594 (1999). Fig.3. Standard deviation of fluctuations for raw and PCA pro- [7], Martens H., Naes T.: Multivariate Calibration. Wiley & Sons, cessed data against radon concentration. Chichesterl991. [8], Rencher A.C. Multivariate statistical inference and applica- In Fig.3 the computed standard deviations of tion. John Wiley & Sons, New York 1998. fluctuations for raw and processed PCA data, ex-

AN ATTEMPT TO USE WAVELET TRANSFORM FOR DENOISING XRF SPECTRA

1 Antoine L'Eplattenier ', Ewa Kowalska, Piotr Urbariski ! CO l! iS Ecole Nationale Superieure des Techniques et des Mines de Nantes, France IS Wavelet transform is a novel signal - processing from an industrial in - stream XRF analyser design- technique which has been recently used in several ed for measurements of iron, zinc and lead content !8 fields [1-4]. One of the most promising application in the Zn-Pb ore processing products [7]. All calcu- of this technique for radiometric instruments is sig- lations were performed using a software based on nal denoising. There is an important difference be- Wavelet Toolbox for Matlab [8]. tween denoising and smoothing. Whereas smooth- Fig. shows some results of denoising XRF spec- ing removes high frequencies and retains low fre- tra with the Wavelet technique. The used algorithm quencies, denoising attempts to remove whatever was based on smoothing of the entire set of data in noise is present and retain whatever signal is pre- the best-basis for their variance spectrum by killing sent regardless of the frequency content of signal all Wavelet coefficients at scales informed by the [5]. user [4, 9], It can be seen that the denoised spectra Feasibility study of applying Wavelet - based de- are smoother than the original ones and the re- noising techniques for processing data from an moved noise has a mean value close to zero whereas X-ray fluorescence analyser was prepared [6]. The its variance spectrum resembles the shape of the data consisted of 34 experimental spectra collected denoised spectra.

First and lest spectra of the de-notsed 3A-spoctra sot

Fig. Denoising of some XRF spectra using Wavelet transform. 138 NUCLEONIC CONTROL SYSTEMS AND ACCELERATORS In the case of the signal from radiation detectors, [4].Walczak B., Massart D.: Chem. and Int. Lab. Sys., 2£, 81-94 observed fluctuations are caused by the statistical (1997). [5].Taswell C: Computational Toolsmiths, Stanford. CA nature of the registered radiation and their variance 94309-9925. should be equal to the number of accumulated [6].L'Eplattenier A.: Different Wavelet-based de-noising techni- counts. This can explain a similarity of the variance ques applied to some data from radioizotope instruments. spectrum of the removed noise to the spectrum of Internal report of the INCT. Warszawa 1999, unpublished. [7]. Urbanski P., Kowalska E.: Zastosowanie wielowymiarowej registered radiation. analizy statyslycznej do kalibracji fluorescencyjnej sond zanu- rzeniowych. Internal report of the INCT no 10/111/98. References [8J. Buckheit J., Chen S., Cruthfield J., Donoho D., Gao H., John- [l].Xsueguang S., Wensheng C, Peiyan S.: Chem. and Int. Lab. stone I., Kolaczyk E., Scargle J., Young K.-. Wavelab (1996). Sys., 42,147-155 (1998). [9].Coifman R., Wickerhauser M.: IEEE Trans. Inform. Theory, [2]. Depczynski U., Jetter K., Molt K., Niemoller A.: Chem. and 22,712-718 (1992). Int. Lab. Sys., 22, 19-27 (1997). [3]. Alsberg B., Woodward A., Kell D.: Chem. and Int. Lab. Sys., 22,215-239(1997). PL0002049 PERFORMANCES OF LAE10 ACCELERATOR WITH A THREE ELECTRODE ELECTRON GUN WITHOUT MESH GRID Zygmunt Dzwigalski, Zbigniew Zimek The aim of this research was an accelerator with a Fig.2 shows shapes of the electron beam pulses three electrode electron gun without mesh grid. provided by the LAE10 accelerator. The first pulse Construction and design of the gun is described in [1] and [2]. The influence of the electric and mecha- 25 ns, pedestal nical electron gun parameters on the properties of the nanosecond linear LAE10 accelerator was in-

Fig.l. ait' /to.evc* in' TxMmvti uiiom CB1 \ -34.2 V vestigated. The shape of the electron pulses was investigated, in particular. Electron pulse profiles registration circuit dia- Fig.3. gram is presented in Fig.l. The current of the acce- lerator electron beam was collected by a specially has a duration of about 100 ns and the second one - designed Faraday's cup. The pulse shape was mea- about 8 ns. We can distinguish two parts (the pe- sured using a TDS620 Tektronix digital oscillo- destal and main nanosecond pulse) in the second scope. A Casio QV-100 digital camera was used to oscillogram. The shape of the pedestal is shown record the oscillograms. distinctly in Fig.3 (this oscillogram was obtained

Fig.l NUCLEAR TECHNOLOGIES AND METHODS 139

0.4 200 mV for the pedestal oscillogram presented in r L~ 1.2 mm Fig.3. - - ... Fig.4 shows the relation between the pedestal r 0.3 • • - Vg = _2.5kV charge and the total charge of the accelerator - - V g = - 3 kV current pulse ratio and the gun accelerating voltage

..... -• 1 amplitude. The ratio of the charges increases with • voltage amplitude and reaches a value of 0.1 for 47 a 0.2 i . - _ - - • kV for the first curve (for Vg=-2.5 kV) and 54 kV for the second curve (for V =-3 kV). We assume -V • g 0.1 that the accelerator pulse will be suitable for radio- • —1 lytic experiments if the pedestal charge is lower

• than 0.1 multiplied by total charge (Qp<0.1 • Qt).

i 1 40 50 60 70 References

GUN ANODE VOLTAGE - Va ( kV) [1J. DZwigalski Z., Zimek Z.: Electron Technology, 2Q, 4, 331-334 (1997). Fig.4. [2].D<)bek J., D2wigalski Z.: Electron gun design for linear ac- celerator. First Congress Polish Vacuum Society, Krak6w, without nanosecond grid pulse). The scale interval Poland, 25-27 May 1998, pp. 120-125 (in Polish). has 5 V on the second oscillogram of Fig.2 and only 140 THE INCT PUBLICATIONS IN 1999

THE INCT PUBLICATIONS IN 1999

1. Ambroz H.B., Kemp T.J., Kornacka E.M., Przybytniak G.K. Transition metal ions in the y-radiolysis of DNA at cryogenic and room temperatures. 32nd Annual International Meeting: ESR Spectroscopy; Recent Advances and Applications. Abstracts, York, England, 11-15.04.1999, p. PI. 2. Ambroz H.B., Kornacka E.M., Przybytniak G.K. Influence of DTT on radiolysis of DNA as seen by EPR spectroscopy. International Workshop on Reactive Intermediates IWRP99. Book of Abstracts, Szczyrk, Poland, 22-27.08.1999, p. P34. 3. Ambroz H.B., Kornacka E.M., Przybytniak G.K. Influence of metal ions andy-irradiation on DNA. 2nd International Conference of PhD Students. Section Proceedings, Medical Sciences. Miskolc, Hungary, 8-14.08.1999, pp. 41-46. 4. Ambroz H.B., Kornacka E.M., Przybytniak G.K. Modyfikacja radiolizy DNA jonami Cu(II) i Fe(III) (Modification of DNA radiolysis by Cu(II) and Fe(III). II Sympozjum Chemii i Techniki Radiacyjnej. Materiaty. Ladek Zdroj, Poland, 20-23.09.1999, p. P-10. 5. Ambroz H.B., Kornacka E.M., Przybytniak G.K. Single and double strand breaks in plasmid DNA at room and cryogenic temperatures by gel-elec- trophoresis. International Workshop on Reactive Intermediates IWRI'99. Book of Abstracts. Szczyrk, Poland, 22-27.08.1999, p. P14. 6. Baran S., Szytuta A., Leciejewicz J., Stusser N., Yong Fan Ding, Zygmunt A. Commensurate-incommensurate magnetic phase transitions in RAgSn and RCuSn (R=Tb-Er) com- pounds. Proceedings of the International Conference on Aperiodic Crystals "Aperiodic'97". Eds. M. de Boissieu, J.-L. Verger-Gaugry, R. Currat. World Scientific [1999], pp. 599-603. 7. BartoS B., Bilewicz A. A chemical separation scheme of 24Na the of the cluster radioactivity of 233U. Proceedings of the XlVth International Symposium on Physico-Chemical Methods of the Mixtures Separation "Ars Separatoria'99". Gniew, Poland, 5-8.07.1999, p. 47. 8. Bilewicz A. WlasnoSci chemiczne pierwiastk6w transfermowych (Chemical properties of transfermium elements). Wiadomosci Chemiczne, 52, 9-10,631-645 (1999). 9. Bilewicz A., Siekierski S. Influence of relativistic effects on hydration and hydrolysis of rutherfordium, and some 6th row element cations. Nukleonika, 44,4,521-528 (1999). 10. Btasiak J., Kowalik J., Trzeciak A., Wojewodzka M. Cytotoxicity and DNA damage and repair in human lymphocytes exposed to three anticancer plati- num drugs. Comet Assay Workshop. Book of Abstracts. Smolenice, Slovakia, 29.05.-2.06.1999, p. [1]. 11. Btasiak J., Kowalik J., Trzeciak A., Wojewodzka M. DNA damage and repair in human lymphocytes exposed to three anticancer platinum drugs. 7th International Symposium on Molecular Aspects of Chemotherapy. Abstract Book. Gdansk, Poland, 8-11.09.1999, p. 99. THE INCT PUBLICATIONS IN 1999 141 12. Btasiak J., Matecka-Panas E., Trzeciak A., Kowalik J., Drzewoski J., Wojewodzka M. DNA damage in human gastric mucosal cells exposed to chromium and curcumin. Gastroenterology, H6_, 4, Part 2, Abstract p. [G1659].

13. Btasiak J., Trzeciak A., Kowalik J., Matecka-Panas E., Drzewoski J., Wojew6dzka M. In vitro studies on the genotoxicity of chromium and curcumin. The 4th Congress of Toxicology in Developing Countries "Chemical Safety for Every Country". Abstracts. Antalya, Turkey, 6-10.11.1999, p. 92.

14. Btasiak J., Trzeciak A., Malecka-Panas E., Drzewoski J., Iwaneriko T., Szumiel I., Wojew6dzka M. DNA damage and repair in human lymphocytes and gastric mucosa cells exposed to chromium and curcumin. Teratogenesis, Carcinogenesis and Mutagenesis, 19,19-31 (1999). 15. BobrowskiK. Electron migration in peptides and proteins. In: Properties and Reactions of Radiation Induced Transients. Selected Topics. Ed. J. Mayer. PWN, Warszawa 1999, pp. 177-204.

16. Bobrowski K. Zastosowanie radiolizy impulsowej w badaniach reakcji fotochemicznych (Application of pulse radiolysis in investigations of photochemical reactions). In: Metody badania mechanizm6w reakcji fotochemicznych. Wydawnictwo Naukowe PWN, Poznari 1999, pp. 139-153.

17. Bobrowski K., Hug G.L., Marciniak B. Intra-complex proton transfer involving the amino group during photooxidation of methionine derivatives. The Fifth International Conference on Solar Energy and Applied Photochemistry [SOLAR'99] & The 2nd International Training Workshop on Environmental Photochemistry. Book of Abstracts. Cairo, Egypt, 30.03.-4.04.1999, p. 1.

18. Bobrowski K., Hug G.L., Marciniak B., Schoneich C, Wisniowski P. Intramolecular hydrogen transfer during oxidation of jS-hydroxysulfides and a-(methyl)thioacetamide. Pulse radiolysis and flash photolysis studies. Research on Chemical Intermediates, 21, 3, 285-297 (1999). 19. Bobrowski K., Hug G.L., Schoneich C. Intermediates during radiation-induced oxidation of conformationally constrained methionine-con- taining oligopeptides. International Workshop on Reactive Intermediates IWRI'99. Book of Abstracts. Szczyrk, Poland, 22-27.08.1999, p. P6. 20. Bobrowski K., Hug G.L., Schoneich C. Radical processes during radiation-induced oxidation of sulphur-containing model peptides. 21st Miller Conference on Radiation Chemistry. Programme & Abstracts. Doorwerth, The Netherlands, 24-29.04.1999, p. 21. 21. Bobrowski K., Poznariski J., Holcman J., Wierzchowski K.L. Pulse radiolysis studies of intramolecular electron transfer in model peptides and proteins. 8. + Trp[NH ]-*Tyr[O] radical transformation in H-Trp-(Pro)n-Tyr-OH, n = 3-5, series of peptides. Journal of Physical Chemistry B, 102,10316-10324 (1999). 22. Bruckman E., Wojcik A., Obe G. Sister chromatid differentiation with biotin-dUTP. Chromosome Research, 2,185-189 (1999). 23. Bruckman E., Wdjcik A., Obe G. X-irradiation of Gl CHO cells induces SCE which are both true and false in BrdU-substituted cells but only false in biotin-dUTP-substituted cells. Chromosome Research, 7, 277-288 (1999). 142 THE INCT PUBLICATIONS IN 1999

24. Buczkowski M., Starosta W., Żółtowski T., Fiderkiewicz A., Wawszczak D. Odporność radiacyjna folii polimerowych oraz membran mikrofiltracyjnych (Radiation resistance of polymeric films and microfiltration membranes). V Wiosenna Szkoła Sterylizacji Radiacyjnej Sprzętu Medycznego, Przeszczepów, Farmaceutyków i Kosmetyków. Sterylizacja radiacyjna w Polsce w świetle wymogów Unii Europejskiej. Warszawa, Poland, 27-28.05.1999, p. XII.

25. Buraczewska I., Gasińska A., Grądzka 1., Jarocewicz N., Sochanowicz B., Szumiel I. Erbstatin-induced increase in apoptosis does not radiosensitize L5178Y cells. Nukleonika, 44_, 4, 561-578 (1999).

26. Chmielewski A.G. Environmental effects of fossil fuel combustion. Proceedings of the International Conference "The Discovery of and Radium - Its Scientific and Philosophical consequences, Benefits and Threats to Mankind". Polska Akademia Nauk, War- szawa, Poland, 17-20.09.1999, pp. 327-340.

27. Chmielewski A.G. Twórcze elektrony (Creative electrons). V Wiosenna Szkoła Sterylizacji Radiacyjnej Sprzętu Medycznego, Przeszczepów, Farmaceutyków i Kosmetyków. Sterylizacja radiacyjna w Polsce w świetle wymogów Unii Europejskiej. Warszawa, Poland, 27-28.05.1999, p. XIII. 28. Chmieiewski A.G. Zanieczyszczenia powietrza atmosferycznego emitowane w procesie spalania węgla (Emission of air contaminants in process of coal combustion). Energetyka Jądrowa dla Polski. Referaty. Otwock-Świerk, Poland, 25-26.03.1999, pp. 1-6.

29. Chmielewski A.G., Dobrowolski A., Tymiński B. Dose distribution effect on optimal geometry for industrial flue gas treatment system. Radiation Physics and Chemistry, 26,509-518 (1999).

30. Chmielewski A.G., Harasimowicz M., Tymiński B., Zakrzewska-Trznadel G. 3-stage reverse osmosis pilot plant for purification and concentration of radioactive wastes. Proceedings of the XlVth International Symposium on Physico-Chemical Methods of the Mixtures Separation "Ars Separatoria'99". Gniew, Poland, 5-8.07.1999, p. 74. 31. Chmielewski A.G., Harasimowicz M., Tymiński B., Zakrzewska-Trznadel G., Tomczak W., Cholerzyński A. Membrane processes for liquid radioactive waste treatment. Proceedings of the XlVth International Symposium on Physico-Chemical Methods of the Mixtures Separation "Ars Separatoria'99". Gniew, Poland, 5-8.07.1999, p. 20. 32. Chmielewski A.G., Harasimowicz M., Zakrzewska-Trznadel G. Membrane technologies for liquid radioactive waste treatment. Czechoslovak Journal of Physics, 49, Suppl. SI, 979-985 (1999).

33. Chmielewski A.G., Hier E., Tymiński B., Zimek Z., Licki .1. Electron flue gases treatment in Poland. In: The Modern Problems of Electrostatistics with Application in Environment Protection. Eds. I.I. Inculet et al. Kluwer Academic Publishers, Amsterdam 1999, pp. 181-197. 34. Chmielewski A.G., Ostapczuk A., Kubica K., Licki J. Możliwości zastosowania metody radiacyjnej do oczyszczania gazu z wielopierścieniowych węglo- wodorów aromatycznych (WWA) (Possibilities of application of radioactive method for removal of polyaromatic hydrocarbons from flue gases). II Sympozjum Chemii i Techniki Radiacyjnej. Materiały. Lądek Zdrój, Poland, 20-23.09.1999, p. C-2.

35. Chmielewski A.G., Ostapczuk A., Licki J., Kubica K. Emisja zanieczyszczeń organicznych w procesie spalania węgla i możliwość jej redukcji (Emission of organie compounds from coal combustion and possibility to decrease it). IV Konferencja na temat "Problemy Badawcze Energetyki Cieplnej". Materiały. Warszawa, Poland, 1-3.12.1999, pp. 15-22. THE INCT PUBLICATIONS IN 1999 143 36. Chmielewski A.G., Owczarczyk A., Palige J., Dobrowolski A. Application of radiotracers for investigation of wastewater and air pollution control installations. Report of the Second Research Co-ordinating Meeting of the Co-ordinated Research programme on "Radiotracer Technology for Engineering Unit Operation Studies and Unit Process Optimization". International Atomic Energy Agency. Second Research Coordination Meeting, Krakow, Poland, 19-23.07.1999, pp. [1-36]. 37. Chwastowska J., Rogowska A., Sterlinska E., Dudek J. Chelating 2-mercaptobenzothiazole loaded resin. Application to the separation of inorganic alkyl- mercury species for their atomic absorption spectrometry determination in natural waters. Talanta, 49,837-842 (1999). 38. CieslaK. Badania metodami r6znicowej kalorymetrii skaningowej i dyfrakcji rentgenowskiej zmian fizyko- chemicznych zachodzacych w foliach poliestrowych pod wprywem cie_zkich jon6w (DSC and X-ray diffraction studies on the physicochemical changes occuring in polyester films exposed to heavy ion irradiation). Polimery, 44, 2,123-130 (1999). 39. CieSlaK. Badanie metodami rdznicowej kalorymetrii skaningowej i dyfrakcji rentgenowskiej zmian fizyko- chemicznych zachodzacych w foliach poliestrowych pod wpfywem napromieniowania cie.zkimi jonami (Differential scanning calorimetry and X-ray diffraction studies of the physico-chemical transfor- mation occuring in the polyester films under influence of heavy ions irradiation). I Og61nopolskie Seminarium Sprawozdawcze z Realizacji Grant6w KBN w Zakresie Nauk Che- micznych. Rzeszow, 7-8.09.1999. XLII Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowa- rzyszenia Inzynierow i Technik6w Przemyslu Chemicznego. Rzeszow, Poland, 6-10.09.1999, p. 267. 40. CieslaK. The influence of annealing and heavy ion irradiation of multiple melting and crystallization in PBT films. Journal of Thermal Analysis and Calorimetry, 56,1141-1146 (1999). 41. Ciesla K., Svensson E., Eliasson A.-C. Preliminary studies using differential scanning calorimetry of radiation-induced transformations in starch and flour. Journal of Thermal Analysis and Calorimctry, 56,1197-1202 (1999). 42. Croce F., Nobili F., Deptuta A., Lada W., Tossici R., D'Epifanio A., Scrosati B., Marassi R. An electrochemical impedance spectroscopic study of the transport properties of LiNio.75Coo.25O2. Electrochemistry Communications, 1, 605-608 (1999). 43. Danko B., Polkowska-Motrenko H., Dybczyriski R. Wpfyw sposobu mineralizacji pr6bki na wyniki oznaczania kobaltu w materialach ros"linnych metoda_ radiochemicznej neutronowej analizy aktywacyjnej (The influence of mineralization on the results of the determination of cobalt in plant materials by radiochemical neutron activation analysis). Nowoczesne Metody Przygotowania Pr6bek i Oznaczania Sladowych Ilos"ci Pierwiastk6w. Materialy VIII Poznanskiego Konwersatorium Analitycznego. Poznan, Poland, 8-9.04.1999, p. 29. 44. DembinskiW. Udzial pola jadrowego w chemicznych efektach izotopowych (Contribution of the nuclear field to the chemical isotope effects). WiadomoSci Chemiczne, 53., 9-10,725-744 (1999). 45. Deptuta A., Chmielewski A.G., Wood T.E. Sol-gel ceramic beads and bubbles - A historical perspective, modern fabrication and cost analysis. In: Advances in Science and Technology. Vol. 16. Ceramics: Getting into the 2000's. Ed. P. Vincenzini. Techna 1999, pp. 771-791. 46. Deptula A., Olczak T., Lada W., Ciancia A., Giorgi L., Di Bartolomeo A., Brignocchi A., Croce F. Thermal conversion of gels prepared by complex sol-gel process (CSGP) from the Li+ - Mn2+ - CH3COC - ascorbic acid (ASC) - NH4" - OH" - H2O system to LiMn2O4 for electrochemical applica- tions. 144 THE 1NCT PUBLICATIONS IN 1999 In: Advances in Science and Technology. Vol. 24. Ceramics: Getting into the 2000's. Ed. P. Vincenzini. Techna 1999, pp. 149-156.

47. Deptuia A., Zmijewska W., tada W., Olczak T., Di Bartolomeo A., Brignocchi A. Preparation of hydrated antimony pentoxide microspheres (diameter <20 /j.m) by water extraction variant of sol-gel process and its application to sorption of sodium. In: Advances in Science and Technology. Vol. 15. Ceramics: Getting into the 2000's. Ed. P. Vincenzini. Techna 1999, pp. 183-189.

48. Dobrowolski A., Palige J., Chmielewski A.G. Methodology of RTD data interpretation achieved on the base of radiotracer experiments. Report of the Consultant's Meeting on "The preparation of a technical document on intercomparison of available process engineering software in tracer technology". Vienna, Austria, 22-25.11.1999, pp. [1-36].

49. Drzewicz P., Panta P., Gluszewski W., Trojanowicz M. Effect of selected scavangers on radiolytic degradation of 2,4-dichlorophenol for environmental purposes. Journal of Radioanalytical and Nuclear Chemistry, 242,3,601-609 (1999).

50. Dybczyriski R., Danko B., Kulisa K., Polkowska-Motrenko II., Samczyriski Z., Stepniewski M., Szopa Z. Badanie sktadu chemicznego nowego polskiego meteorytu "Baszkowka" za pomoca^ neutronowej analizy aktywacyjnej (First chemical characterization of the new Polish meteorite "Baszk6wka" by neutron activation analysis). Nowoczesne Metody Przygotowania Prbbek i Oznaczania Sladowych IloSci Pierwiastk6w. Materialy VIII Poznanskiego Konwersatorium Analitycznego. Poznan, Poland, 8-9.04.1999, p. 26.

51. Dybczynski R., Danko B., Kulisa K., Polkowska-Motrenko H., Samczyriski Z., Stepniewski M., Szopa Z. First chemical characterization of the new Polish meteorite "Baszk6wka" by neutron activation ana- lysis. Chemia Analityczna, 44_, Special issue 3A, 471-484 (1999). 52. Dzwigalski Z., Zimek Z. Wybrane wyniki badan liniowego akceleratora elektron6w LAE 10 (Selected results of studies on Linear Electron Accelerator LAE 10). V Krajowa Konferencja Techniki Prozni. Materiary konferencyjne. Borki k/Tomaszowa Maz., Poland, 9-11.06.1999, p. 78.

53. Dzwigalski Z., Zimek Z. Wybrane wyniki badan liniowego akceleratora elektronow LAE 10 (Selected results of studies on Linear Electron Accelerator LAE 10). Techniki Pr6zni i Technologic Pr6zniowe. Wybrane Materialy V Krajowej Konferencji Techniki Pr6zni i V Polsko-Biatoruskiego Sympozjum Technologii Prozniowych. Prace Naukowe Politechniki Warszawskiej. Prace Naukowe Elektronika, 123, 215-218 (1999).

54. Gniazdowska E., Narbutt J. The effect of hydrophobic and hydrophilic hydration on partition of alkoxyalkanes between water and heptane. International Solvent Extraction Conference. Solvent Extraction for the 21st Century. ISEC'99.Book of Abstracts. Barcelona, Spain, 11-16.07.1999, p. 405. 55. Grigoriew H., Chmielewski A.G., Amenitsch II., Bernstorff S., Domagala J. Kinetics of structural changes in polymer membranes. In: Australian Small Angle X-ray Scattering (SAXS) Beamline at ELETTRA. Annual Report 1998. ELETTRA. SINCTROTRONE TRIESTE. Trieste, Italy, [1999], pp. 90-91.

56. Kaczmarek S.M., Berkowski M., Moroz Z., Warchol S. Effect of annealing and irradiation on the optical properties of oxide crystals. Acta Physica Polonica A, 26,3-4, 417-427 (1999). 57. Kaczmarek S.M., Jabloriski R., Pracka J., Swtrkowicz M., Wojtkowska J., Warchd S. Radiation defects in LiNbO3 single crystals doped with Cr3+ ions. Crystal Research Technology, 34,5-6, 729-735 (1999). 146 THE INCT PUBLICATIONS IN 1999

69. Kowalik J., Biasiak J., Wojewodzka M. Protective action of vitamin C against genotoxic effect of organophosphorus pesticides. The 4th Congress of Toxicology in Developing Countries "Chemical Safety for Every Country". Abs- tracts. Antalya, Turkey, 6-10.11.1999, p. 259.

70. Kowalik J., Trzeciak A., Wojew6dzka M., Btasiak J. In vitro genotoxic effect of curcumin assessed by the comet assay. Comet Assay Workshop. Book of Abstracts. Smolenice, Slovakia, 29.05.-2.06.1999, p. [1].

71. KowaIskaM.,W6jcikA. Aberracje chromosomowe jako biologiczny dozymetr promieniowania jonizuj^cego (Chromosomal aberrations as a biological dosimeter of ionizing radiation). Poste_py Techniki Jadrowej, 42, 2, 31-36 (1999).

72. Krai J., WaliS L. Kontrola szczelnoSci zbiornikdw metalowych podziemnych i posadowionych na gruncie utwardzonym, przy uzyciu znacznik6w promieniotw6rczych (Control of leakproof of underground metallic boilers founded on a hardered ground by means of radiotracers). Poste.py Techniki Jadrowej, 42, 4, 30-33 (1999).

73. KraS J., Walis L. Lokalizacja nieszczelnos"ci w obiektach technologicznych przy uzyciu metody znacznik6w radioizoto- powych (Leak localization in technological installations using radioactive tracers). PostQpy Techniki Jadrowej, 42, 4, 27-29 (1999).

74. Kras" J., Walis L., Myczkowski S. Zastosowanie metody znacznikow promieniotw6rczych do kontroli szczelnos"ci i lokalizacji nieszczel- nos"ci w rurociqgach podziemnych (Application of isotopic tracers methods for leakproof control and leak localization in underground pipelines). Poste.py Techniki Jadrowej, 42,4, 22-26 (1999).

75. Kruszewski M. Popromienne podwojnoniciowe pe.kni^cia DNA: Zagrozenia i korzySci (Double strand breaks: Threatens and benefits). Poste.py Techniki Jadrowej, 42,1,48-53 (1999).

76. Kruszewski M., Iwanenko T., Bouzyk E., Szumiel I. Chelating of iron and copper alters properties of DNA in L5178Y cells, as revealed by the comet assay. Mutation Research, 424,1, 53-60 (1999).

77. Kruszewski M., Wojewodzka M., Iwanenko T., Okuyama A., Zebrowska T., Jarocewicz N., Szumiel I. Differential inhibitory effect of DNA-PK inhibitor (OK-1035) on DNA repair in L5178Y mouse lym- phoma cell lines. Neoplasma, 46., Suppl., 32-33 (1999).

78. Kruszewski M,, Wojew6dzka M., Iwanenko T., Szumiel I., Okuyama A. Differential inhibitory effect of DNA-PK inhibitor-OK-1035-on DNA repair in L5178Y murine lym- phoma sublines. Comet Assay Workshop. Book of Abstracts. Smolenice, Slovakia, 29.05.-2.06.1999, p. [1].

79. Krynicki J., Puton J., Oieniak J., WarchoJ S., Rzewuski H. High energy ion implantation profiles. Nukleonika, 4_4_, 1,3-14 (1999).

80. Kukielka A., Iller E., Chmielewski A.G., Zimek Z., Stupinska II., Madaj R., Mikotajczyk W. Radiation stimulation reactivity different type of chemical paper-pulp appropriately for production of derivative. Fifth International Conference on Frontiers of Polymers and Advanced Materials. NATO Advanced Research Workshop on Polymers and Composites for Special Applications. Conference & Exhibi- tion. Book of Abstracts. Poznan, Poland, 21-25.06.1999, p. 213. THE INCT PUBLICATIONS IN 1999 145

58. Kaczmarek S.M., Moroz Z., Kwaśny M., Kisielewski J., Łukasiewicz T., Wojtkowska J., Rzewuski H. Changes in luminescence of Ce: YAG crystals under ionizing radiation treatment. Acta Physica Polonica A, 95, 6,953-964 (1999).

59. Kaczmarek S.M., Wojtowicz A.J., Drozdowski W., Koepke C, Wiśniewski K., Kisielewski J., Jabłoński R., Grinberg M., Barzowska .1., Kukliński B., Zimmerer G., Moroz Z., Rzewuski H. Changes in optical properties of YAG: Ce single crystals due to codoping and ionising radiation treat- ment. International Conference on Solid State Crystals '98. Single Crystal Growth, Characterization, and Applications. Proceedings of SPIE. Zakopane, Poland, 12-16.10.1998,1999, vol. 2324, pp. 339-345.

60. Kalicki A., Pańczyk E., Kierzek J,, Wasilewska-Dobkowska J. Analysis of elemental composition of Thai ceramics by X-ray fluorescence and instrumental activation analysis. 6th International Conference on "Non-destructive Testing and Microanalysis for the Diagnostics and Conservation of the Cultural and Environmental Heritage". Proceedings. Volume II. Rome, Italy, 17-20.05.1999, pp. 1513-1528.

61. Katuska I. Normy europejskie dotyczące sterylizacji radiacyjnej (European standards concerning radiation steri- lization). V Wiosenna Szkoła Sterylizacji Radiacyjnej Sprzętu Medycznego, Przeszczepów, Farmaceutyków i Kosmetyków. Sterylizacja radiacyjna w Polsce w świetle wymogów Unii Europejskiej. Warszawa, Poland, 27-28.05.1999, p. VII.

62. Kałuskal. Sterylizacja radiacyjna wyrobów medycznych w IChTJ (Radiation sterilization of medical products at the INCT). V Wiosenna Szkolą Sterylizacji Radiacyjnej Sprzętu Medycznego, Przeszczepów, Farmaceutyków i Kosmetyków. Sterylizacja radiacyjna w Polsce w świetle wymogów Unii Europejskiej. Warszawa, Poland, 27-28.05.1999, p. VIII.

63. Kahiska I., Zimek Z. The impact of European standards concerning radiation sterilization on the quality assurance of medical products in Poland. Proceedings of a Symposium "Techniques for High Dose Dosimetry in Industry, Agriculture and Medicine". Vienna, Austria, 2-5.11.1998. IAEA-TECDOC-1070. IAEA, Vienna 1999, pp. 327-330.

64. Kierzek J., Małożewska-Bućko B., Bukowski P., Parus J.L., Ciurapiński A., Zaraś S., Kunach B.f Wiland K. Assessment of coal and ash environmental impact with the use of gamma- and X-ray spectrometry. Journal of Radioanalytical and Nuclear Chemistry, 24Û, 1,39-45 (1999).

65. Kierzek J., Parus J. Performance of a modified complon suppression spectrometer at the IAEA Safeguards Analytical Laboratory. International Atomic Energy Agency, Vienna 1999, 12+[11] p. IAEA/AL/120.

66. Korzeniowska A., Hug G.L., Bobrowski K. Dwa typy kationorodników generowanych w reakcji rodnika hydroksylowego z tioanizolem (Two types of radical cations formed on reaction of hydroxyl radicals with thioanisole). II Sympozjum Chemii i Techniki Radiacyjnej. Materiały. Lądek Zdrój, Poland, 20-23.09.1999, p. P-14.

67. Korzeniowska A., Hug G.L., Bobrowski K. Two types of radical cations formed on reaction of hydroxyl radicals with thioanisole. International Workshop on Reactive Intermediates IWRI'99. Book of Abstracts. Szczyrk, Poland, 22-27.08.1999, p. P15.

68. Kowalak S., Stuglik Z., Kruszona K., Jankowska A. Application of alaninę adsorbed on the molecular sieves for the dosimetric measurements. Proceedings of the 12th International Zeolite Conference.. Baltimore, Maryland, USA, 5-10.07.1998, 1999 Materials Research Society Conference Proceedings, pp. 277-284. THE INCT PUBLICATIONS IN 1999 147 81. Kukiełka A., Hier E., Chmielewski A.G., Zimek Z., Stupińska H., Madaj R., Mikołajczyk W., Gawryszczak A. Radiacyjna degradacja różnych rodzajów masy celulozowej z przeznaczeniem do wytwarzania pochod- nych (Radiation stimulation of the reactivity of different types of cellulose pulps for production of derivatives). II Sympozjum Chemii i Techniki Radiacyjnej. Materiały. Lądek Zdrój, Poland, 20-23.09.1999, p. P-2. 82. Kulisa K., Dybczyński R., Polkowska-Motrenko H. Effect of column overloading and its influence on the quality of analytical results in the determination of inorganic ions by ion chromatography. Chemia Analityczna, 44, 945-961 (1999). 83. Kunicki-Goldfinger J.J., Kierzek J., Kasprzak A.J., Małożewska-Bućko B. Non-destructive examination of 18th century glass vessels from Central Europe. 6th International Conference on "Non-destructive Testing and Microanalysis for the Diagnostics and Conservation of the Cultural and Environmental Heritage". Proceedings. Volume II. Rome, Italy, 17-20.05.1999, pp. 1541-1552. 84. Kunicki-Goldfinger J.J., Kierzek J., Sartowska B. Utilization of natural radioactivity of potassium for the determination of chemical homogeneity of historical glassware. A case study. 6th International Conference on "Non-destructive Testing and Microanalysis for the Diagnostics and Conservation of the Cultural and Environmental Heritage". Proceedings. Volume II. Rome, Italy, 17-20.05.1999, pp. 1531-1538. 85. Legocka I., Łukaszewska E., Mirkowski K., Nowicki A. Próby modyfikacji tlenku magnezu, tlenku cynku oraz talku niektórymi monomerami winylowymi (Preliminary study of modification of the magnesium oxide, zinc oxide and talc, by radiation method in presence of several vinyl monomers). Materiały XIV Konferencji Naukowej "Modyfikacja Polimerów". Kudowa Zdrój, Poland, 26-30.09.1999, pp. 268-269. 86. Legocka I., Mirkowski K., Nowicki A., Bujnowska E. Modyfikowany radiacyjnie tlenek magnezu i możliwości jego zastosowania do napełniania PE (Magnesium oxide modified by radiation method and its using filling of the polyethylene). Materiały XIV Konferencji Naukowej "Modyfikacja Polimerów". Kudowa Zdrój, Poland, 26-30.09.1999, pp. 78-81. 87. Licki J., Chmielewski A.G., Hier E. Ciągłe i manualne metody pomiaru stężeń zanieczyszczeń w gazach odlotowych w świetle ostatnich uregulowań prawnych (Continuous and manual methods for the measurement of pollutants content in the off gases according to the last ecological regulation). Konferencja Naukowo-Techniczna "Spalanie węgla'99". Materiały konferencyjne. Ustroń-Zawodzie, Poland, 24-26.03.1999, pp. 275-279 88. Ligęza M., Pańczyk E., Rowińska L., Waliś L., Nalepa B. Analysis of trace elements in the alabaster deposits for the determination of the provenance of the Madonna Jackowa of the XIV century sculpture. 6th International Conference on "Non-destructive Testing and Microanalysis for the Diagnostics and Conservation of the Cultural and Environmental Heritage". Proceedings. Volume I. Rome, Italy, 17-20.05.1999, pp. 321-330. 89. Łukasiewicz A., Walls L., Rowińska L., Panasiewicz J. Polyamide and cellulose fibres modified with new polymerized aminotriazole complexes with magnesium acetate and other metals. Materials Letters, 3_£, 108-111 (1999). 90. Machaj B. Modification of the RGR monitor of radon daughters concentration in air. Nukleonika, 44., 3, 479-490 (1999). 91. Machaj B., Urbański P. Continuous measurement of radon concentration in the air with the Lucas cell by periodic sampling. 148 THE INCT PUBLICATIONS IN 1999

Nukleonika, 44,4, 579-594 (1999).

92. Malec-Czechowska K., Migdał W., Owczarczyk H.B. Radiacyjna dekontaminacja surowców i wyrobów kosmetycznych {Decontamination of cosmetics and raw materials by radiation}. V Wiosenna Szkoła Sterylizacji Radiacyjnej Sprzętu Medycznego, Przeszczepów, Farmaceutyków i Kosmetyków. Sterylizacja radiacyjna w Polsce w świetle wymogów Unii Europejskiej. Warszawa, Poland, 27-28.05.1999, p. XI.

93. Malec-Czechowska K., Stachowicz W., Dancewicz A.M., Szot Z. Application of EPR spectrometry, thermoluminescence, analyses of DNA damage and germination power for detection of irradiated foods. Nukleonika, 44, 4, 549-560 (1999).

94. Marciniak B., Bobrowski K., Hug G.L. Reactive intermediates in the sensitized photo-oxidation of sulfur-containing organic compounds. International Workshop on Reactive Intermediates IWRI'99. Book of Abstracts. Szczyrk, Poland, 22-27.08.1999, p. L21.

95. Michalik J., Sadło J., Perlińska J., Danilczuk M., Yamada H. Paramagnetic silver clusters in sodalites. International Workshop on Reactive Intermediates IWRI'99. Book of Abstracts. Szczyrk, Poland, 22-27.08.1999, p. P24. 96. Michalik J., Sadło J., Perlińska J., Danilczuk M., Yamada H. Paramagnetyczne aglomeraty srebra w sodalitach (Paramagnetic silver clusters in sodalites). II Sympozjum Chemii i Techniki Radiacyjnej. Materiały. Lądek Zdrój, Poland, 20-23.09.1999, p. P-15. 97. Michalik J., Sadło J., Shimomura S., Yamada H. Paramagnetic silver clusters in sodalites. Spectroscopy of Transition Metal Ions on Surfaces and Defect Sites in Solids. Workshop. Ysermonde, Nieuwpoort, Belgium, 21-23.03.1999, p. 1.

98. Michaiik J., Sadło J., Shimomura S., Yamada H. Paramagnetic silver clusters in sodalites. 32nd Annual International Meeting: ESR Spectroscopy; Recent Advances and Applications. Abstracts, York, England, 11-15.04.1999, p. P32.

99. Michalik J., Sadło J., Shimomura S., Yamada H. Paramagnetic silver clusters in sodalites with oxyanion. 18th Conference on Modern Magnetic Resonances "RAMIS'99". Abstracts, Poznań-Kiekrz, Poland, 11-15.04.1999, p. P-24.

100. Michalik J., Yamada II., Sadło J., Shimomura S., Takenouchi S., Uchida Y. Paramagnetic silver clusters in sodalites with oxyanions. Conference of the European Clay Groups Association. Euroclay 1999. Program with Abstracts. Kraków, Poland, 5-9.09.1999, p. 112. 101. Migdał W. Jakość mikrobiologiczna przypraw ziołowych dekontaminowanych radiacyjnie. (Microbiological quality of spices decontamination by radiation). Akademia Ekonomiczna w Poznaniu, Zeszyty Naukowe - Seria II, Prace habilitacyjne Z. 156, Poznań 1999,72 p.

102. Migdał W., Owczarczyk H.B. Decontamination of medical herbs by irradiation. FAO/IAEA/WHO International Conference on Ensuring the Safety and Quality of Food through Radiation Processing. Book of Extended Synopses. Antalya, Turkey, 19-22.10.1999, pp. 119-120.

103. Mioduski T. Comment to the Bigeleisen's theory of isotope chemistry of the heavy elements. Comment Inorganic Chemistry, 21, 1-3,175-196 (1999). THE INCT PUBLICATIONS IN 1999 149

104. Mioduski T. Identification of saturating solid phases in the system Ce2(SO4)3-H2O from the solubility data. Journal of Thermal Analysis and Calorimetry, 5J>, 751-763 (1999). 105. Mioduski T. O nauce - Z perspektywy przetomu tysi^cleci (On science - At the turn of the centuries) Poste.py Techniki Ja.drowej, 42, 4, 2-4 (1999). 106. Mirkowski J., Grodkowski J. Measurement system for pulse radiolysis at the linear electron accelerator LAE 13/9. Nukleonika, 44,1, 71-78 (1999). 107. Moroz Z., Sowiriski M., Bouzyk J., Chmielewski A.G. Application of artificial neural nets for the electron beam flue gas treatment control. Nukleonika, 44,3,411-426 (1999). 108. Muller W.U., Strefler C, Wojcik A., Niedereichholz F. Radiation-induced malformations after exposure of murine germ cells in various stages of spermato- genesis. Mutation Research, 425., 99-106 (1999). 109. NarbuttJ. Hydration and solvation of lead(II) acetylacetonate and the coordination number of lead(II). Solvent Extraction and Ion Exchange, 17, 5,1271-1280 (1999). 110. NarbuttJ. Radiochemia u progu drugiego stulecia (Radiochemistry on the verge of its second century). Wiadomo

118. Pańczyk E.( Ligęza M., Waliś L. Application of instrumental neutron activation and X-ray fluorescence analysis to the examination of objects of art. Czechoslovak Journal of Physics, 49, Suppl. SI, 401-410 (1999).

119. Pańczyk E., Ligęza M., Wałiś L. Neutronowa analiza aktywacyjna pomaga w atrybucji malowideł (Help of Neutron Activation Analy- sis in the attribution of paintings). Postępy Techniki Jądrowej, 42, 4, 34-40 (1999).

120. Pene B., Baran S., Hofmann F., Leciejewicz J., Śląski M., Szytuła A., Zygmunt A. Antiferromagnetism of RPtX (R=Ho; Er; X=Si, Ge) compounds. Journal of Physics: Condensed Matter, 11,5631-5642 (1999).

121. Pene B., Baran S., Hofmann F., Leciejewicz J., Śląski M., Szytuła A., Zygmunt A. Antiferromagnetism of RPtX (R=Ho; Er; X=Si, Ge) compounds. 6th International Seminar on Neutron Scattering Investigation in Condensed Matter and 3rd Polish Seminar on Neutron Scattering. Book of Abstracts. Poznań, Poland, 29.04.-1.05.1999, p. [1]. 122. Pene B., Hofmann M., Leciejewicz J., Szytuła A. Commensurate-incommensurate magnetic phase transition in TbCO2Ge2 compound. Journal of Physics: Condensed Matter, U, 7579-7584 (1999).

123. Pene B., Hofmann M., Leciejewicz J., Śląski M., Szytuła A. Magnetic properties of RlrGe (R=Gd-Er) compounds from neutron diffraction and magnetic measure- ments. Journal of Alloys and Compounds, 2SZ, 18-24 (1999). 124. Piekoszewski J., Werner Z., Wieser E., I^angner J., Grötzschel R., Reuther H., Jagielski J. Formation of surface Pd-Ti alloys using the pulsed plasma beams. Nukleonika, 44, 2, 239-246 (1999).

125. Piekoszewski J., Wieser E., Grötzschel R., Reuther H., Werner Z., Langner J. Pulsed plasma beam mixing of Ti and Mo into AI2O3 substrates. Nuclear Instruments and Methods in Physics Research B, 14£, 32-36 (1999). 126. Przybytniak G. Obróbka radiacyjna wyrobów farmaceutycznych (Radiation processing of Pharmaceuticals). V Wiosenna Szkoła Sterylizacji Radiacyjnej Sprzętu Medycznego, Przeszczepów, Farmaceutyków i Kosmetyków. Sterylizacja radiacyjna w Polsce w świetle wymogów Unii Europejskiej. Warszawa, Poland, 27-28.05.1999, p. XIV.

127. Przybytniak G., Ambroż H. Wolne rodniki, ich identyfikacja i oznaczanie (Free radicals, their identification and determination). Materiały Sympozjum "Metody Analityczne w Badaniach Substancji Szkodliwych i Niebezpiecznych. Ciechocinek, Poland, 20-22.10.1999, pp. 45-46. 128. Przybytniak G., Ambroż H.B., Kornacka E. Efektywność przenoszenia centrów paramagnetycznych z DNA na DTT (Efficiency of paramagnetic centres transfer from DNA towards DTT). II Sympozjum Chemii i Techniki Radiacyjnej. Materiały. Lądek Zdrój, Poland, 20-23.09.1999, p. C-11.

129. Przybytniak G.K., Zagórski Z.P., Żuchowska D. Free radicals in electron beam irradiated blends of polyethylene and butadiene-styrene block copolymer. Radiation Physics and Chemistry, 55., 5-6, 655-658 (1999). 130. Pszonicki L., Dudek J. Modifier effects in the determination of arsenic, antimony and bismuth by electrothermal atomic absorption spectrometry. Journal of Analytical Atomic Spectrometry, 14,1755-1760 (1999).

131. Ptasiewicz-Bąk H., Leciejewicz J. Crystal and molecular structure of a Zn(II) complex with pyrazine-2,3-dicarboxylate ligand. THE INCT PUBLICATIONS IN 1999 __ 151_ Polish Journal of Chemistry, 73,1887-1894 (1999). 132. Ptasiewicz-Bqk H., Leciejewicz J. The crystal and molecular structure of a Zn(II) complex with pyrazine-2,3-dicarboxylate ligand. 41st Polish Crystallographic Meeting. Book of Abstracts. Wroclaw, Poland, 24-25.06.1999, p. 91. 133. Ptasiewicz-Bqk H., Leciejewicz J. Crystal and molecular structures of nickel(II) complexes with pyrazine-2,3-dicarboxylic and 3-amino- pyrazine-2-carboxylic acids. Polish Journal of Chemistry, 73, 717-725 (1999). 134. Ptasiewicz-Bqk II., Leciejewicz J. Molecular ribbons in the crystals of a new Cu(II) complex with pyrazine-2,3-dicarboxylate ligand. Polish Journal of Chemistry, 72, 5,853-858 (1999). 135. Pyrzyriska K., Trojanowicz M. Functionalized cellulose sorbents for preconcentration of trace metals in environmental analysis. Critical Reviews in Analytical Chemistry, 29,4, 313-321 (1999). 136. Rafalski A., Zagorski Z.P. Eksperymentalna symulacja widm nadtlenk6w na lancuchach polipropylenu (Experimental simulation of spectra of peroxides on chains of polypropylene). Materiafy XIV Konferencji Naukowej "Modyfikacja Polimer6w". Kudowa Zdroj, Poland, 26-30.09.1999, p. 332. 137. Rahimi H., Naimpour M.A., Abedinzadeh A., Amini A., Kras J. Radiotracer technique for pipeline leak detection in the National Iranian Oil Company. Nukleonika, 44, 3, 491-498 (1999). 138. Sadto J., Bojarski J., Strzelczak G., Michalik J. Radiation effects in poly(ethylene terephthalate) - polypropylene composite materials. Polimery, 44, 3, 226-228 (1999). 139. Sadlo J., Bojarski J., Strzelczak G., Michalik J. Radiation processes in poly(ethylene terephthalate) composite materials. Nukleonika, 44, 1, 59-69 (1999). 140. Siekierski S. Efekty relatywistyczne w chemii (Relativistic effects in chemistry). Poste.py Fizyki, 50,4,175-181 (1999). 141. Skwara W., Pszonicki L. Metody oznaczania krzemu i fosforu za pomoca^ atomowej spektrometrii absorpcyjnej (The methods for determination of silicon and by atomic absorption spectrometry). Nowoczesne Metody Przygotowania Probek i Oznaczania Sladowych IloSci Pierwiastkow. Materiafy VIII Poznanskiego Konwersatorium Analitycznego. Poznan, Poland, 8-9.04.1999, p. 39. 142. Sochanowicz B., Szumiel I., Grqdzka I. Nuclear translocation of the p65 subunit of NF-kB in L5178Y sublines differing in antioxidant defense. Radiation Environmental Biophysics, 38,125-131 (1999). 143. StachowiczW. Sterylizacja wyrob6w medycznych (Sterilization of medical products). V Wiosenna Szkola Sterylizacji Radiacyjnej Sprzeju Medycznego, Przeszczep6w, Farmaceutyk6w i Kosmetyk6w. Sterylizacja radiacyjna w Polsce w Swietle wymog6w Unii Europejskiej. Warszawa, Poland, 27-28.05.1999, p. II. 144. Stachowicz W., Dancewicz A.M., Malec-Czechowska K., Szot Z. Control of irradiated foods in Poland. FAO/IAEA/WHO International Conference on Ensuring the Safety and Quality of Food through Radiation Processing. Book of Extended Synopses. Antalya, Turkey, 19-22.10.1999, pp. 121-122. 152 THE INCT PUBLICATIONS IN 1999 145. Stachowicz W., Michalik J., Ostrowski K., Dziedzic-Godawska A. Electron paramagnetic resonance speclroscopy and irradiation as used for the study on mineralised tissues. 2nd World Congress on Tissue Banking and 8th International Conference of EATB "Allograft Against Disability". Abstracts. Warszawa, Poland, 07-10.10.1999, p. 30. 146. Stachowicz W., Sadto J., Strzelczak G., Michalik J., Bandiera P., Mazzarello V., Montella A., Wojtowicz A., Kaminski A., Ostrowski K. Dating of palaeoanthropological nuragic skeletal tissues using electron paramagnetic resonance (EPR) spectrometry. Italian Journal of Anatomy and Embryology, 104,1,19-31 (1999). 147. Starosta W., Wawszczak D., Sartowska B., Buczkowski M. Investigations of heavy ion tracks in polyethylene naphthalate films. Radiation Measurements, 21, 149-152 (1999). 148. Strzelczak G., Bobrowski K., Michalik J. ESR study of polycrystalline s-methylcysteine and its derivatives. 21st Miller Conference on Radiation Chemistry. Programme & Abstracts. Doorwerth, The Netherlands, 24-29.04.1999, p. 46. 149. Strzelczak G., Bobrowski K., Michalik J. Intermediates in y-irradiated S-methylcysteine derivatives. International Workshop on Reactive Intermediates IWRI'99. Book of Abstracts. Szczyrk, Poland, 22-27.08.1999, p. P43. 150. Szopa Z., Dybczyriski R., Polkowska-Motrenko H. Strategia certyfikacji materiai6w odniesienia na bazie por6wnan mie_dzylaboratoryjnych (The strategy of reference material certification on the basis of interlaboratory comparisons). V Sympozjum "Mie.dzylaboratoryjne badania porownawcze". Leba, Poland, 13-15.09.1999, pp. 213-223. 151. Szytula A., Batanda M., Hofmann M., Leciejewicz J., Kolenda M., Penc B., Zygmunt A. Antiferromagnetic properties of ternary silicides RNiSi (R=Tb-Er). Journal of Magnetism and Magnetic Materials, 191,122-132 (1999) 152. Swiderska-Kowalczyk M., Starosta W., Zoltowski T. Multicounter neutron detector for examination of content and spatial distribution of fissile materials in bulk samples. Nukleonika, 44,4, 619-634 (1999). 153. Trojanowicz M., Jagielska A., Rotkiewicz P., Kierzek A. Flow-injection determination of phenols with tyrosinase amperometric biosensor and data processing by neural network. Chemia Analityczna, 41, 865-878 (1999). 154. Trzeciak A., Gloc-Fudata E., Wojew6dzka M., Blasiak J. Uszkodzenia i naprawa DNA w limfocytach czlowieka eksponowanych na etanol i aldehyd octowy (DNA damage and its repair in human peripheral blood lymphocytes exposed to ethanole and acetaldehyde). XXXV Zjazd Polskiego Towarzystwa Biochemicznego. Streszczenia. Olsztyn, Poland, 13-16.09.1999, p. 95. 155. Trzeciak A., Kowalik J., Wojewodzka M., Blasiak J. DNA damage in human gastric mucosa cells and peripheral blood lymphocytes induced by hexavalent chromium. 7th Conference on Cell Biology. Abstracts. Krakbw, Poland, 9-11.09.1999, p. 67. 156. Trzeciak A., Kowalik J., Wojewodzka M., Btasiak J. Genotoxicity of chromium in human gastric mucosa cells and peripheral blood lymphocytes. Comet Assay Workshop. Book of Abstracts. Smolenice, Slovakia, 29.05.-2.06.1999, p. [1]. 157. Urbariski P., Kowalska E. Radiometric scanner of the titanium foil. THE INCT PUBLICATIONS IN 1999 153 Nukleonika, 44,4,657-660 (1999). 158. Werner Z., Jagielski J., Piekoszewski J., Kubiak L., Giinzel R. Improvement of the wear properties of cutting tools implanted with nitrogen ions. Nukleonika, 44,2, 261-264 (1999). 159. Wisniowski P., Korzeniowska A., Bobrowski K., Richter L., Brede O. Generation of radical cations from phenyl, vinyl and allyl containing thioethers in organic solvents. International Workshop on Reactive Intermediates IWRI'99. Book of Abstracts. Szczyrk, Poland, 22-27.08.1999, p. P50. 160. Wojewodzka M., Kruszewski M., Iwaneriko T., Collins A.R., Szumiel I. Lack of adverse effect of smoking habit on DN A strand breakage and base damage, as revealed by the alkaline comet assay. Mutation Research, 440_, 19-25 (1999). 161. Wojewddzka M., Van der Schans G.P., Szumiel I. DNA repair in radioadapted human lymphocytes studied by the SCGE and ELISA. Neoplasma, 46, Suppl., 40 (1999). 162. Wojewodzka M., Van der Schans G.P., Szumiel I. DNA repair in radioadapted human lymphocytes studied by the SCGE and ELISA. Comet Assay Workshop. Book of Abstracts. Smolenice, Slovakia, 29.05.-2.06.1999, p. [1]. 163. Wqjcik A., Opalka B., Obe G. Analysis of inversions and sister chromatid exchanges in chromosome 3 of human lymphocytes exposed to X-rays. Mutagenesis, 14,6,633-637 (1999). 164. Wojcik A., Shadley J.D., Szumiel 1. Adaptive response in lymphocytes: Is DNA repair involved? Eleventh International Congress of Radiation Research. Vol. 1: Abstracts. Dublin, Ireland, 18-23.07.1999, p. 59. 165. Wojcik A., Szumiel I. Biologiczne dzialanie i ry/yko promieniowania jonizuja^cego (Biological action and risk of ionizing radiation). V Wiosenna Szkola Sterylizacji Radiacyjnej Sprze.tu Medycznego, Przeszczep6w, Farmaceutyk6w i Kosmetyk6w. Sterylizacja radiacyjna w Polsce w Swietle wymog6w Unii Europejskiej. Warszawa, Poland, 27-28.05.1999, p. III. 166. Yamada H., Michalik J., Shimomura S., Uchida Y. Silver atoms and clusters in imogolite fibers. Conference of the European Clay Groups Association. Euroclay 1999. Program with Abstracts. Krakow, Poland, 5-9.09.1999, pp. 147-148. 167. Zagorski Z.P. Dosimctry as an integral part of radiation processing. Proceedings of a Symposium "Techniques for High Dose Dosimetry in Industry, Agriculture and Medicine". Vienna, Austria, 2-5.11.1998. IAEA-TECDOC-1070. IAEA, Vienna 1999, pp. 257-264. 168. Zagorski Z.P. . Niektore zagadnienia sterylizacji radiacyjnej poruszone na tegorocznej konferencji IMRP 11 w Mel- bourne oraz rola koncern6w wielonarodowych w tej dziedzinie (Selected topics of radiation sterili- zation discussed during this year Conference IMRP 11 in Melbourne and the role of multinational companies in that field). V Wiosenna Szkola Sterylizacji Radiacyjnej SprzQtu Medycznego, Przeszczepow, Farmaceutyk6w i Kosmetykdw. Sterylizacja radiacyjna w Polsce w Swietle wymog6w Unii Europejskiej. Warszawa, Poland, 27-28.05.1999, p. XVIII. 169. Zag6rski Z.P. Oddzialywanie promieniowania jonizuja_cego z materia/. Najcze_Sciej stawiane pytania (Interaction of ionizing radiation with the matter. Most popular questions asked). 154 THE INCT PUBLICATIONS IN 1999

V Wiosenna Szkoła Sterylizacji Radiacyjnej Sprzętu Medycznego, Przeszczepów, Farmaceutyków i Kosmetyków. Sterylizacja radiacyjna w Polsce w świetle wymogów Unii Europejskiej. Warszawa, Poland, 27-28.05.1999, p. I.

170. Zagórski Z.P. Odporność radiacyjna betonu: Stosowany aspekt chemii radiacyjnej ciała stałego (Radiation resis- tance of concrete. Applicable aspect of radiation chemistry of solid state). II Sympozjum Chemii i Techniki Radiacyjnej. Materiały. Lądek Zdrój, Poland, 20-23.09.1999, p. C-4.

171. Zagórski Z.P. Pulse radiolysis od solid and rigid systems. In: Properties and Reactions of Radiation Induced Transients. Selected Topics. Ed. J. Mayer. PWN, Warszawa 1999, pp. 219-233.

172. Zagórski Z.P. Rosyjskie służby specjalne i bomba atomowa (Russian secret services and the atomic bomb). Postępy Techniki Jądrowej, 42, 4,47-51 (1999).

173. Zagórski Z.P. Solid state radiation chemistry - features important in basic research and applications. Radiation Physics and Chemistry, 5.4 559-565 (1999).

174. Zakrzewska-Trznadel G., Harasimowicz M., Chmielewski A.G. Concentration of radioactive components in liquid low-level radioactive waste by membrane distilla- tion. Journal of Membrane Science, M2, 257-264 (1999).

175. Zakrzewska-Trznadel G., Ilarasimowicz M., Chmielewski A.G. Uzdatnianie wody do celów kotłowych metodą destylacji membranowej (Conditioning of water for boiler purposes by membrane distillation method). Przemysł Chemiczny, 28, 5, 181-184 (1999).

176. Ziaie F., Stachowicz W., Strzelczak G., Al-Osaimi S. Using bone powder for dosimetric system EPR response under the action of y irradiation. Nukleonika, 44,4, 603-608 (1999).

177. ZimekZ. Akceleratory elektronów dla potrzeb sterylizacji radiacyjnej (ekonomika, perspektywy) (Electron accelerators for radiation sterilization (economics and prospects). V Wiosenna Szkoła Sterylizacji Radiacyjnej Sprzętu Medycznego, Przeszczepów, Farmaceutyków i Kosmetyków. Sterylizacja radiacyjna w Polsce w świetle wymogów Unii Europejskiej. Warszawa, Poland, 27-28.05.1999, p. V.

178. Zimek Z., Kałuska I. Difficulties associated with the validation of radiation sterilization of tissue allografts. 2nd World Congress on Tissue Banking and 8th International Conference of EATB "Allograft Against Disability". Abstracts. Warszawa, Poland, 07-10.10.1999, p. 23.

179. Zimek Z., Kałuska I. Radiation sterilization of medical devices and tissue with electron beam accelerator at INCT. 2nd World Congress on Tissue Banking and 8th International Conference of EATB "Allograft Against Disability". Abstracts. Warszawa, Poland, 07-10.10.1999, p, 28.

180. Zimek Z., Kałuska I. Sterylizacja radiacyjna sprzętu medycznego jednorazowego użytku i przeszczepów (Radiation sterilization of medical devices single use and allografts). Compendium Medycyny, 2,19-21 (1999).

181. Zimek Z., Panta P., Głuszewski W. Radiation processing for pharmaceuticals. Acta Poloniae Pharmaceutica (Drug Research), 5.6. (Suppl.) 5-6 (1999). THE INCT PUBLICATIONS IN 1999 155

182. Zimek Z., Panta P., Kahiska I., Głuszewski W. Radiation processing for Pharmaceuticals. Multidyscyplinarna Konferencja Nauki o Leku. Streszczenia, Muszyna, Poland, 3-5.03.1999, p. P-22. 183. Żuchowska D., Zagórski Z.P. Radiacyjna modyfikacja mieszanin polimerowych (Modification of polymer blends by irradiation). Polimery, 44,7-8, 514-519 (1999).

SUPPLEMENT LIST OF THE INCT PUBLICATIONS IN 1998

184. Cieśla K. The influence of annealing and heavy ion irradiation on multiply melting and crystallization occuring in PBT films. 7th European Symposium on Thermal Analysis and Calorimetry (ESTAC). Book of Abstracts. Bala- tonffired, Hungary, 30.08.-4.09.1998, p. 259. 185. Cieśla K., Svensson E., Eliasson A-C. Application of differential scanning calorimetry in studies of radiation induced defects in starch and flour. 7th European Symposium on Thermal Analysis and Calorimetry (ESTAC). Book of Abstracts. Balatonfured, Hungary, 30.08.-4.09.1998, p. 206. 156 ' THE INCT REPORTS IN 1999

THE INCT REPORTS IN 1999

1. INCT Annual Report 1998. IChTJ, Warszawa 1999, 206 p. 2. Hier E. Dyspersyjny model transportu mediów w radioznacznikowych badaniach pracy wybranych instalacji przemysłowych (A dispersion mode! of transport media in radiotracer investigations on selected of chemical installations). IChTJ, Warszawa 1999. Raporty IChTJ. Seria A nr 1/99,134 p. 3. Kruszewski M. Podłoże odwrotnej krzyżowej oporności komórek L5178Y na promieniowanie jonizujące i nadtlenek wodoru (Cellular determinants of the inverse cross sensitivity of mouse lymphoma L5178Y cell lines to ionizing radiation and hydrogen peroxide). IChTJ, Warszawa 1999. Raporty IChTJ. Seria A nr 2/99,120 p. 4. Malicki W., Stuglik Z. Wyznaczanie energii elektronów w wiązce przemiatanej akceleratora liniowego przez dozymetrię dawki głębinowej (Evaluation of energy of scanned electron beam from linear accelerator by means of depth-dose distribution measurement). IChTJ, Warszawa 1999. Raporty IChTJ. Seria B nr 12/98, 40 p. 5. Chmielewski A.G. Electron beam gaseous pollutants treatment. IChTJ, Warszawa 1999. Raporty IChTJ. Seria B nr 1/99,66 p. 6. Kunicki-Goldfinger J.J., Kierzek J., Kasprzak A.J., Małożewska-Bućko B. XVIII-wiecznc naczynia szklane z hut w Nalibokach i Urzeczu. Badania fizykochemiczne (The 18th century glassware from Naliboki and Urzecze glasshouses. Physico-chemical studies). IChTJ, Warszawa 1999. Raporty IChTJ. Seria B nr 2/99,110 p. 7. Zagórski Z.P. IAEA Conference on Large Radiation Sources in Industry (Warszawa 1959): Which technologies of radiation processing survived and why? IChTJ, Warszawa 1999. Raporty IChTJ. Seria B nr 3/99,16 p. 8. Chmielewski A.G. Environmental effects of fossil fuel combustion. IChTJ, Warszawa 1999. Raporty IChTJ. Seria B nr 4/99, 48 p. 9. Skwara W., Pszonicki L. Oznaczanie krzemu i fosforu metodą absorpcyjnej spektrometrii atomowej z atomizacją płomieniową i elektrotermiczną (Determination of silicon and phosphorus by atomic absorption spectrometry with flame and electrothermal atomization). IChTJ, Warszawa 1999. Raporty IChTJ. Seria B nr 5/99,14 p. 10. Derda M. Izotopy siarki w przyrodzie. Metodyka oznaczania stosunków izotopowych siarki w węglu i ropie naftowej metodą spektrometrii masowej (Sulphur isotopes in nature. Determination of sulphur isotope ratios in coal and petroleum by mass spectrometry). IChTJ, Warszawa 1999. Raporty IChTJ. Seria B nr 6/99,20 p. ll.Mikołajczuk A. Efekty izotopowe siarki w reakcjach chemicznych (Isotope effects of sulfur in chemical reactions). IChTJ, Warszawa 1999. Raporty IChTJ. Seria B nr 7/99, 28 p. NUKLEONIKA 157

NUKLEONIKA THE INTERNATIONAL JOURNAL OF NUCLEAR RESEARCH

EDITORIAL BOARD

Andrzej G. Chmielewski (Editor-in-Chief, Poland), Krzysztof Andrzejewski (Poland), Janusz Z. Beer (USA), Gregory R. Choppin (USA), Bohdan Dziunikowski (Poland), Andrei Gagarinsky (Russia), Alexander van Hook (USA), Zbigniew Jaworowski (Poland), Larry Kevan (USA), Evgeni A. Krasavin (JINR-Dubna), Stanisław Latek (Poland), Sueo Machi (Austria), Jacek Michalik (Poland), Tomasz Mioduski (Poland), James D. Navratil (USA), Shoichi Sato (Japan), Robert H. Schuler (USA), Irena Szumiel (Poland), Piotr Urbański (Poland)

CONTENTS OF No. 1/99 1. Krynicki J., Puton J., Oleniak J., Warchoł S., Rzewuski H. High energy ion implantation profiles. 2. Cebulska-Wasilewska A., Rękas K., Kim J.K. Application of TSH bioindicator for studying the biological efficiency of radiation. 3. Milewska A., Szydłowski J. The influence of the H/D substitution on the viscosity in acetonitrile - decanol solution near the critical point. 4. Plasari E., Thereska J., Leclerc J.P., Villermaux J. Tracer experiments and residence-time distributions in the analysis of industrial units: case studies. 5. Sadło J., Bojarski J., Strzelczak G., Michalik J. Radiation processes in poly(ethylene terephthalate) composite materials. 6. Mirkowski J., Grodkowski J. Measurement system for pulse radiolysis at the linear electron accelerator LAE 13/9. 7. Rzyski B.M., Morato S.P. Fluorescence of Tm doped U2B4O7 glass.

CONTENTS OF No. 2/99 1. Turos A., Stonert A, Breeger B., Wendler E., Wesch W. Thermally activated defect transformations in III-V compound semiconductors. 2. Hereć J., Filiks J., Sielanko J. SIMS study of low energy implantation. 3. Droździel A., Kornarzyński K., Romanek J., Mączka D., Latuszyński A. Positive and negative ion production in the ion sputtering process. 4. Hereć J., Filiks J., Sowa M., Sielanko J., Mączka D. Negative ion source for SIMS application. 5. Jaroszewicz B., Tomaszewski D., Słysz W., Grabieć P., Jung W. Application of simulation tools for design of large area silicon photodetector technology. 6. Kiszczak K. Cold hollow cathode ion source. 158 NUKLEONIKA 7. Konarski P. Sample rotation applied in the SIMS depth profile analysis of layered structures. 8. Latuszynski A., M^czka D. Atom ionization in the high-temperature cavity thermoionizer. 9. Slowko W. Three-dimensional surface imaging by the directional signal detection. 10. Drzazga W., S16wko W. Electron optical properties of retarding lenses for the low voltage SEM. 11. Kulik M., Saied S.O., LiSkiewicz J., Ma.czka D. Oxide layers on implanted GaAs surfaces: X-ray-photoelectron spectroscopy and ellipsometry study. 12. Milchanin O.V., Gaiduk P.I., Komarov F.F. Interaction between pre-existing dislocations in silicon and hydrogen-induced defects introduced by plasma treatment. 13. Nickel F. The energy loss of swift ions in solids. 14. Gaiduk P.I., Komarov F.F., Tishkov V.S., Herre O., Wendler E, Wesch W. Wurtzite InP phase formation during swift Xe ion irradiation. 15. Kamienska-Krzowska B., Tarkowski P. Friction and wear processes modification of ion implanted steel. 16. Komarov F.F., Kamyshan A.S., Mironov A.M. Formation of horizontal and vertical insulation in semiconductors by ion implantation. 17. Krupa D., Baszkiewicz J., Jezierska E., Kozubowski J., Barcz A. Effect of nitrogen, carbon and oxygen ion implantation on the structure and corrosion resistance of OT-4-0 titanium alloy. 18. Mrochek I., Gunzel R., Matz W., Moller W., Anishchik V. Implantation of ions into hard metals. 19. Narojczyk J., Piekoszewski J., Richter E., Werner Z. Wear properties of TiN coated cutting tools implanted with nitrogen ions. 20. Olszyna A., Pawtowski P. Oxygen-free AIN coatings produced from AIN(O) powder in the impulse nitrogen plasma. 21. Piekoszewski J., Werner Z., Wieser E., Langner J., Grotzschel, Reuther H., Jagielski J. Formation of surface Pd-Ti alloys using the pulsed plasma beams. 22. Tarkowski P., Lukasik K., Budzyrtski P., LiSkiewicz J. About possibility of improving durability of metal forming tools by ion implantation. 23. Werbowy A., Pawtowski P., Siwiec J., Szmidt J., Olszyna A., Sokolowska A. AIN layers plasmochemically produced as semiconductors. 24. Werner Z., Jagielski J., Piekoszewski J., Kubiak L., Gunzel R. Improvement of the wear properties of cutting tools implanted with nitrogen ions. 25. Wilk J., Kowalski W. Ion-beam modification of stainless steel surface roughness. 26. Slowinski B. Deep ion implantation: advantages and current problems. 27. Stowiriski B., Wilczyriska T., WiSniewski R. Modification of temperature dependence of manganin resistance using the ion implantation techniques. NUKLEONIKA 159 28. Zukowski P., Partyka J., We.gierek P., Kozak M. Comparison of permittivity of ion implanted silicon and silicon bombared with neutrons. 29. Zukowski P., Partyka J., Wejierek P. Changes in permittivity of silicon implanted through an aluminium layer. 30. Zukowski P., Karwat C, tozak M., LiSkiewicz J. A new method for determining changes in hardness of implanted materials. 31. Da.bekl, Michalak L. Study of CO2 clusters by mass spectrometry. 32. Gront K., Gwizdatta T., Czerbniak J. Channelling of H projectile. 33. Kobzev A.P. Element depth profiling of implanted samples. 34. Pelc A., Michalak L. Electron impact study of argon clusters. 35. Ruzicka J., Saro S., Krupa L., Zrelov P.V., Zrelov V.P., Lapchik E.D., Geissel H., Irnich H., Kozhuha- rov C, Magel A., Miinzenberg G., Nickel F., Scheidenberger C, Schott H.-J., Schwab W., Stohlker T., Voss B. Some peculiarities of the Vavilov-Czerenkov radiation emitted by heavy ions. 36. Zuk J., Kuduk R. Ion beam induced luminescence of porous silicon: a comparative study.

37. Gacek Z.( Mazniewski K. Similarity and differences of certain electrification processes in some fluids. 38. Synowiec Z. Electrical conductivity of implant isolation in GaAs. 39. Marszatek K., Leja E. Industrial Arc based equipment for decorative coating deposition. 40. Komarov A.F., Komarov F.F., Zukowski P., Karwat C, Shukan A.L. Simulation of the process of high dose ion implantation in solid targets. 41. Martan J. Collision cascade as a fractal. 42. Belyi V.A., Komarov F.F. Model of non-continuous track formation in InP under swift ion implantation. 43. Szyszko W. Laser induced diffusion in Ge/Sb-Si films.

CONTENTS OF No. 3/99 1. Zielinska A., Zielinski M., Papiernik-Zieliftska H. Carbon-13 isotope effect for decarboxylation of phenylpropiolic acid (PPA) in orthophosphoric acid. 2. Moroz Z., Sowinski M., Bouzyk J., Chmielewski A.G. Application of artificial neural nets for the EB flue gas treatment control. 3. El-Messiry A.M., El-Said Kh.M. On sensitivity loss of the neutron detectors during long operation of MPR. 4. El-Koliel M.S., Borysiewicz M. Computer program for the Markovian reliability and availability as applied to emergency AC power system configurations of the nuclear power plants. 160 NUKLEONIKA 5. Aziz M. Simulation of aerosol growth by condensation using moving sectional technique. 6. Aziz M., El-Messiry A.M. Safety assessment of the ETRR-2 shielding. 7. Machaj B. Modification of the RGR monitor of radon daughters concentration in air. 8. Rahimi H., Naimpour M.A., Abendinzadeh A., Amini A., Kras" J. Radiotracer technique for pipeline leak detection in the National Iranian Oil Company.

CONTENTS OF No. 4/99 1. Burda J., Drozdowicz K., Gabanska B., Igielski A., Janik W., Kosik M., Krynicka E., Kurowski A., Woznicka U., Zaleski T. Time-dependent neutron field experimental set-up at the pulsed neutron generator in the Institute of Nuclear Physics. 2. Bilewicz A., Siekierski S. Influence of relativistic effects on hydration and hydrolysis of rutherfordium, dubnium and some 6-th row element cations. 3. Zielinska A., Zielinski M. Deuterium kinetic isotope effect for oxidation of perdeuteriated sodium butyrate with manganate in 3 M sodium hydroxide solution. 4. Shmakova N.L., Fadeeva T.A., Krasavin E.A., Komochkov M.M., Abouzeid O.A. Cytogenetic effects of low dose radiation in Chinese hamster cells. 5. Malec-Czechowska K., Stachowicz W., Dancewicz A.M., Szot Z. Application of EPR spectrometry, thermoluminescence, analyses of DNA damage and germination power for detection of irradiated foods. 6. Buraczewska I., Gasiriska A,, Grqdzka I., Jarocewicz N., Sochanowicz B., Szumiel I. Erbstatin-induced increase in apoptosis does not radiosensitize L5178Y cells. 7. Machaj B., Urbanski P. Continuous measurement of radon concentration in the air with the Lucas cell by periodic sampling. 8. Chylinski A., Radoszewski T., Terlikowska-Drozdziel T. New generation of the radionuclide standards. 9. Ziaie F., Stachowicz W., Strzelczak G., Al-Osaimi S. Using bone powder for dosimetric system. EPR response under the action of y irradiation. 10. de C. R. Poli D., de Mesquita C.H. Application of the compartmental analysis theory to the studies of the kinetics of the rainfall infiltra- tion in the unsaturated zone in Abadia de Goia"s. 11. Swiderska-Kowalczyk M., Starosta W., Z61towski T. Multicounter neutron detector for examination of content and spatial distribution of fissile materials in bulk samples. 12. Riesz F, T6th A.L., Rye L., Sfysz W., We.grzecki M. The EBIC study of boundary effects in the Si PIN photodiodes for X-ray detector applications. 13. Rye L., Riesz F. Potential application of the AlGaAs/GaAs heterostructure photodiodes for laser-plasma diagnostics. 14. Urbanski P., Kowalska E. Radiometric scanner of the titanium foil. NUKLEONIKA 161 15. ChruSciel E., Massalski T., Palka K.W., Puchacewicz J., Zorski T. Natural gamma-ray spectral logging - some applications. 16.SikoraT.,CzerwB. Nucleonic measuring systems and devices in the Polish mining industry.

Information INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY NUKLEONIKA Dorodna 16, 03-195 Warszawa, Poland phone: (+48-22) 811-06-56 or 811-30-21 int. 14-91; tlx 813027; fax: (+48-22) 811-15-32; e-mail: [email protected] 162 THE INCT PATENTS AND PATENT APPLICATIONS IN 1999

THE INCT PATENTS AND PATENT APPLICATIONS IN 1999

PATENTS

1. Spos6b otrzymywania radionuklidow itru i indu (Method for obtaining radioyttrium and radioindium). A. Bilewicz, J. Narbutt Polish Patent no. 177065

2. A process for removal of SO2 and NO* from combustion flue gases and an apparatus used therefore. Z. Zimek, A.G. Chmielewski, I. Artiuch, G. Lysov, N. Frank Korean Patent no. 233773

PATENT APPLICATIONS

1. Spos6b efektywnego usuwania zawieszonych w cieczach osad6w, zwlaszcza biologicznych osad6w czyn- nych i urzqdzenie do realizacji tego sposobu (Method for effective removal of precipitates suspended in liquids, especially of biologically active precipitates and an apparatus therefore). A.G. Chmielewski, Z. Czempinski, A. Owczarczyk, J. Palige, P. Turowski P.333991

2. Nowe sorbenty krzemionkowe wiqzqce efektywnie metale ci^zkie (New siliceous sorbents effectively binding heavy metals). A. Lukasiewicz, L. Rowiriska, L. Walis" P. 336188

3. Spos6b zwiqkszenia efektywnos'ci oczyszczania promieniotworczych s"ciek6w nisko i Srednio aktywnych zat^zanych metodq odwr6conej osmozy (Method for increased effectiveness of purification of low and medium level radioactive wastes concentrated by means of reverse osmosis). A.G. Chmielewski, M. Harasimowicz, B. Tyminski, G. Zakrzewska-Trznadel P. 336861 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1999 163

CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1999

1. INTERNATIONAL SYMPOSIUM ON "CREATIVE ELECTRONS"- RADIATION CHEMISTRY AND TECHNOLOGY IN RESEARCH AND INDUSTRIAL APPLI- CATIONS, 7-8 JUNE 1999, WARSZAWA, POLAND

Organized by Institute of Nuclear Chemistry and Technology Organizing Committee: Z. Zimek, Ph.D.; Prof. J. Michalik, Ph.D., D.Sc; Prof. K. Bobrowski, Ph.D., D.Sc; W. Gniszewski, M.Sc. (Secretary)

OPENING PLENARY • Opening Symposium L. WaliS (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • PAA President Opening Address J. Niewodniczanski (National Atomic Energy Agency, Warszawa, Poland) • Accelerator LAE 10 Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

KYENOTE PRESENTATIONS • Scientific research perspectives with the new pulse radiolysis system at the electron accelerator LAE 10 K. Bobrowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Development of radiation technologies at the Institute of Nuclear Chemistry and Technology A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

SESSIONS Radiation chemistry - basic and applied research Chairman: K. Bobrowski (Institute of Nuclear Chemistry and Technology) • Reaction spectroscopy in Leipzig - concept, equipment and examples M. Brede (Universitat Leipzig, Germany) • Application of pulse radiolysis technique in photochemical studies B. Marciniak (Adam Mickiewicz University in Poznari, Poland) • Excitation energy transfer and radical processes in gas phase pulse radiolysis A. J6wko (Agricultural and Teachers University, Siedlce, Poland) • Pulse radiolysis of aqueous solution of polymeric systems J. Rosiak (Technical University of L6dz, Poland) • Relevance of pulse radiolysis in protein reactivity studies Ch. Hou6e-Levin (Paris-Sud University, Orsay, France) • Geometry-dependent intermolecular hydrogen atoms transfer in radical cations J. Ge,bicki (Technical University of L6dz, Poland)

Radiation chemistry - basic and applied research Chairman: A.G. Chmielewski (Institute of Nuclear Chemistry and Technology) • "OH-induced radical chemistry in sulfur-containing amino acids and peptides K. Bobrowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT 164 IN 1999 • Theoretical study on decomposition halogenated hydrocarbons in dry air under influence of electron beam H. Nichipor (Institute of Radiation, Physical and Chemical Problems, Academy of Sciences, Belarus) • Silver clusters in sodalites J. Michalik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Specifics of solid state radiation chemistry Z.P. Zag6rski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Application of PE additives modified by radiation I. Legocka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Electron accelerators for radiation chemistry and technology Chairman: Z. Zimek (Institute of Nuclear Chemistry and Technology) • The influence of the electron gun parameters on properties of electron pulses in LAE10 accelerator Z. Dzwigalski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Pulse power supplies in LAE 10 electron accelerator S. Bulka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Accelerators for radiation sterilization and radiation processing developed in NPK LUC NIIEFA M. Demskij (Scientific Research Institute of Electrophysical Apparatus, St. Petersburg, Russia) • Electron beam for industrial applications and environmental issues K. Mizusawa (Nissin High Voltage Co. Ltd., Kyoto, Japan) • Status, applications and future development of ELV accelerators N.K. Kuksanov (Institute of Nuclear Physics, Novosibirsk, Russia) • Powerful industrial RF accelerator with energy up to 5 MeV and beam power up to 50 kW Auslender V. (Institute of Nuclear Physics, Novosibirsk, Russia) • Current apporach to design of high power electron accelerators to match actual requirements of radiation technology in Poland S. Kulinski (Institute of Nuclear Studies, Swierk, Poland) • Evaluation of accelerator technology implementation through the various experience of COFRAR in- stallations H. de Rocquigny (COFRAR SA, Versailles, France) • Economic consideration and progress tendencies in accelerator technology Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

2. TECHNICAL REVIEW MEETING ON INDUSTRIAL DEMONSTRATION PLANT FOR ELECTRON BEAM FLUE GAS, 22-23 JUNE 1999, WARSZAWA, POLAND Organized by Institute of Nuclear Chemistry and Technology, International Atomic Energy Agency

LECTURES • Internal structures of project realization for construction and operation of e-b installation at EPS POMORZANY R. Kostrzewski (Dolna Odra Power Plant Group, Nowe Czarnowo, Poland) • Present status of construction of the industrial e-b installation at EPS POMORZANY A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), Z. Wacek Energobudowa S.A., Opole, Poland) • Up data news from Chubu electricpower station about construction of e-b installation for flue gases purification M. Tanaka (Chubu Electric Power Co., Nagoya, Japan) • Recent developments of air pollution control in USA N. Frank (International Business Consultants, USA) CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1999 ' 165 • Final construction of flue gases conditioning unit at POMORZANY e-b installation B. Tymiriski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Construction of ammonia water storage, ammonia preparation and dosage unit B. Tymiriski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Reaction vessels and accelerators Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), M. Romanowski (Study and Design Nuclear Technique Office PRO ATOM, Warszawa, Poland) • Collection of by-product. Planed pilot plant experiments. Agricultural tests of by-product utility E. Iller (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Control and monitoring system for POMORZANY e-b installation J. Licki (Institute of Atomic Energy, Swierk, Poland)

3. V WIOSENNA SZKOLA STERYLIZACJI RADIACYJNEJ SPRZETU MEDYCZ- NEGO, PRZESZCZEPOW, FARMACEUTYK6W I KOSMETYKOW (TRAINING COURSE ON RADIATION STERILIZATION OF MEDICAL DEVICES, IMPLANT MATERIALS, PHARMACEUTICAL AND COSMETICS), 27-28 MAY 1999, WAR- SZAWA, POLAND Organized by Institute of Nuclear Chemistry and Technology Organizing Committee: Prof. A.G. Chmielewski, Ph.D., D.Sc. (Chairman); Z. Zimek, Ph.D.; I. Katuska, M.Sc; W. Ghiszewski, M.Sc.

LECTURES • Oddziatywanie promieniowania jonizuja_cego z materia_ (Effects of the ionizing radiation on the matter) Z.P. Zag6rski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Sterylizacja wyrob6w medycznych (Sterilization of medical devices) W. Stachowicz (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Biologiczne dzialanie i ryzyko promieniowania jonizuja_cego (Biological action and risk of ionizing ra- diation) A. W6jcik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Mikrobiologiczne aspekty sterylizacji radiacyjnej (Microbiological aspects of radiation sterilization) E. Czerniawski (University of L6dz, Poland) • Akceleratory elektronow dla potrzeb sterylizacji radiacyjnej - ekonomika, perspektywy (Electron accele- rators for radiation sterilization needs - economics, perspectives) Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Sterylizacja w zrodlach gamma (Sterilization in gamma sources) W. Bogus (University of L6dz, Poland) • Normy europejskie dotycza_ce sterylizacji radiacyjnej (European standards concerning radiation sterili- zation) I. Katuska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Sterylizacja radiacyjna wyrobtfw medycznych w IChTJ ( Radiation sterilization of medical devices at the INCT) I. Kahiska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Metoda okres"lania dawki sterylizacyjnej dla wyrob6w medycznych jednorazowego uzytku wyjalawianych radiacyjnie na przykladzie wyrob6w firmy Balton (Sterilization dose determination method for medical devices single use based on the example of Balton's products) D. Lachiewicz (Balton, Warszawa, Poland) • Wybrane aspecty GMP w przemys'le farmaceutycznym (Selected aspects of GMP in pharmaceutical in- dustry) Z. Lukaszkiewicz, D. Prokopczyk (Institute for Drugs, Warszawa, Poland) CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT 166 IN 1999 • Radiacyjna dekontaminacja ziol i wyrobow kosmetycznych (Radiation decontamination of herbs and cosmetics) K. Malec-Czechowska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Odpornos'c' radiacyjna folii polimerowych oraz membran mikrofiltracyjnych (Radiation resistance of polimeric foils and microfiltration membranes) M. Buczkowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Materiary medyczne - rejestracja i inne formy dopuszczenia do obrotu (Medical materials - their regis- tration and other forms of their release to the market) T. Achmatowicz (Institute for Drugs, Warszawa, Poland) • Obrobka radiacyjna wyrob6w farmaceutycznych (Radiation treatment of pharmaceutical products) G. Przybytniak (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Kontrola analityczna Iek6w sterylizowanych radiacyjnie (Analytical control of radiation sterilized drugs) B. Marciniec (Medical Academy in Poznafi, Poland) • Sterylizacja radiacyjna biostatycznych przeszczep6w tkankowych (Radiation sterilization of biostatic allografts) A. Dziedzic-Godawska (Medical Academy in Warsaw, Poland) • Sztuczne materiafy implatacyjne - rola biomaterialow w inzynierii tkankowej (Artificial implant materials - the role of biomaterials in tissue engineering) M. Lewandowska-Szumiel (Medical Academy in Warsaw, Poland) • Sterylizacja radiacyjna w s"wietle 1.1th International Meeting on Radiation Processing 1999 Melbourne, Australia (Radiation sterilization as presented at 11th International Meeting on Radiation Processing 1999 Melbourne, Australia) Z.P. Zag6rski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Zastosowanie obr6bki radiacyjnej w produkcji przylepcow medycznych (Application of radiation pro- cessing for medical adhesive production) A. Wnuk (Viscoplast S.A, Wroclaw, Poland), W. Wojtynska (Industrial Chemistry Research Institute, Warszawa, Poland) • Radiacyjna inzynieria biomaterialowa (Radiation biomaterial engineering) J. Rosiak (Technical University of L6dz, Poland) • PVC - w wyrobach medycznych jednorazowego uzytku - zalety i wady wynikaja_ce z zastosowania (PVC used for medical devices single use - advantages and disadvantages result from application) B. Swierz-Motysia (Industrial Chemistry Research Institute, Warszawa, Poland) • Dozymetria wiqzki elektronow akceleratorowych (Electron beam dosimetry) P. Panta, W. Gluszewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Przemyslowe zastosowanie wi^zki elektron6w (Industrial application of electron beam) A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Ph.D./D.Sc. THESES 167

Ph.D./D.Sc. THESES

Ph.D. THESES

1. Andrzej Rafalski, M.Sc. Produkty nietrwałe radiolizy propylenu (Unstable products of the radiolysis or propylene) supervisor: Prof. Zbigniew P. Zagórski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, 07.10.1999

2. Zbigniew Samczyński, M.Sc. Rozdzielcze i analityczne zastosowanie jonitów amfoterycznych (Separation and analytical application of amphoterics ionites) supervisor: Prof. Rajmund Dybczyński, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, 09.12.1999

D.Sc. THESES

1. Andrzej Wójcik, Ph.D. Badania zjawiska popromiennej odpowiedzi adaptacyjnej (Studies on the phenomenon of radioadaptive response) Institute of Biochemistry and Biophysics, Polish Academy of Sciences 168 EDUCATION

EDUCATION

Ph.D. PROGRAMME IN CHEMISTRY

The Institute of Nuclear Chemistry and Technology holds a four year's Ph.D. degree programme to graduates of chemical, physical and biological departments of universities, to graduates of medical uni- versities and to engineers in chemical technology and material science The main areas of the programme are: • chemistry of radioactive elements and isotope effects, • coordination chemistry, • chemistry of separation and analytical methods, • radiation chemistry and biochemistry, • chemistry of fast processes, • application of nuclear methods in chemical and environmental research and in material science, • chemistry of radicals. The candidates accepted for the forementioned programme can be employed in the Institute. The candidates can apply for a doctorial scholarship. Each participant takes part in a 45 h course of lectures of fundamental physical chemistry and a 30 h specialization course. He/she is obliged to deliver a lecture on the 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 National Education, are: • submission of a formal dissertation, summarizing original research contributions suitable for publica- tion; • final examination and public defense of the dissertation thesis. Applicants for the Ph.D. degree programme are accepted throughout the year. Detailed information can be obtained from Admission Secretary, Ewa Gniazdowska, M.Sc. (phone: (+48-22) 811-27-35). In 1999 there were the following lecture series: • "The chemistry of elements" - Prof. Slawomir Siekierski (Institute of Nuclear Chemistry and Tech- nology), • "Fundamentals of radiation chemistry' - Prof. Zbigniew Zagorski (Institute of Nuclear Chemistry and Technology), • "Synthesis and properties of superheavy elements" - Prof. Adam Sobiczewski (Soltan Institute for Nuclear Studies).

PRACTICAL TRAINING OF STUDENTS

Numer of Insitution Country Period participants

Ecole des Mines de Nantes France 2 3 months

Stanislaw Staszic Academy of Mining and Metallurgy Poland 6 2 weeks

Warsaw University of Technology Poland 15 one-day practice

Technical School of Chemistry No 3 Poland 4 1 month (Warszawa)

Collective Technical School of Electronics and Me- Poland 2 1 month chanics (Warszawa) (one week per year) RESEARCH PROJECTS AND CONTRACTS 169

RESEARCH PROJECTS AND CONTRACTS

RESEARCH PROJECTS GRANTED BY THE POLISH STATE COMMITTEE FOR SCIENTIFIC RESEARCH IN 1999 AND IN PREVIOUS YEARS

1. Newe wood preservatives based on polymerized aminotriazole complexes with copper. supervisor: Prof. Andrzej Lukasiewicz, Ph.D., D.Sc. 2. Differential scanning calorimetry and X-ray diffraction studies of the physico-chemical transformation occurring in the polyester films under influence of heavy ions irradiation. supervisor: Krystyna Cies"la, Ph.D. 3. Influence of relativistic effect on chemical properties of the heaviest elements. supervisor: Assoc.Prof. Aleksander Bilewicz, Ph.D.. D.Sc. 4. Even-odd effect in separation of the isotopes of f-electron elements in the three electron exchange reactions. supervisor: Wojciech Dembinski, Ph.D. 5. Hydration of oxaalkanes in aqueous solutions. supervisor: Prof. Jerzy Narbutt, Ph.D., D.Sc. 6. Separation analytical application of amphoteric ion exchange resin retardion 11A 8. supervisor: Prof. Rajmund Dybczynski, Ph.D., D.Sc. 7. Investigation of modifiers used for the determination of elements of the Groups V and VI by graphite furnace atomic absorption spectrometry. supervisor: Prof. Leon Pszonicki, Ph.D., D.Sc. 8. Studying of the significance of DNA double-strand break repair in the adaptive response of human lymphocytes. supervisor: Maria Wojewodzka, Ph.D. 9. Analysis of centromeres in micronuclei by FISH for biological dosimetry. supervisor: Assoc.Prof. Andrzej Wojcik, Ph.D., D.Sc. 10. Optimization of radiation removal process of SO2 and NO* from flue gases containing high concentration of SO2. (supervision of IEA PhD fellow) supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. 11. Electron beam processing technology for modification of various types of cellulose mass for preparation of derivatives. supervisor: Edward Iller, Ph.D. 12. Influence of the structural changes in membrana-penetrant system on permeation process using synchrotron methods. supervisor: Assoc.Prof. Helena Grigoriew, Ph.D., D.Sc. 13. Radiation processing of polyolefines and their composites devoted to thermoshrinkable products. supervisor: Zbigniew Zimek, Ph.D.

IMPLEMENTATION PROJECTS GRANTED BY THE POLISH STATE COMMITTEE FOR SCIENTIFIC RESEARCH IN 1999

1. Thermo-melt glue polymer composites with adhesive properties for heat-shrinkable products. 3T 09B 544 96 C/2871 2. Irradiation method for microbiological decontamination of herbal raw materials. 5 PO6G 004 96 C/2870 3. Instruments for measurements of radon concentration. 8T10C016 97C/3615 170 RESEARCH PROJECTS AND CONTRACTS 4. Small dimensions universal electrofilter for inorganic hygroscopic salts capture. 8T10A083 98 5. New Polish certified reference materials of biological origin for inorganic trace analysis: tea leaves and mixture Polish herbs. 3T09A00199C/4265 6. Development of activity and dose rate gauge of Ru-106 beta sources for irradiation of eye cancer. 8T11E04 099C/4311

GOVERNMENT STRATEGIC PROGRAMME

The management of radioactive wastes and burnt nuclear fuel 1. Elaboration and studies on novel engineered barriers preventing migration of most toxic radionuclides from nuclear waste repositories. SPR-4-4b supervisor: Prof. Jerzy Narbutt, Ph.D., D.Sc. 2. Concentration of liquid low- and medium-level radioactive wastes by membrane methods. SPR-4-1 supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

IAEA RESEARCH CONTRACTS IN 1999

1. Preparation and certification of the new certified reference material VIRGINIA TOBACCO LEAVES and development of neutron activation analysis (NAA) methods for checking the homogeneity. 7192/R2/RB principal investigator: Prof. Rajmund Dybczynski, Ph.D., D.Sc. 2. Materials for in-situ monitoring of light water reactor (LWR) water chemistry by optical methods. 8426/RB principal investigator: Leon Fuks, Ph.D. 3. Thin layer alanine dosimeter with optical spectrophotometric evaluation. 8533/RB principal investigator: Prof. Zbigniew P. Zag6rski, Ph.D., D.Sc. 4. Decontamination of herbal raw materials and herbal drugs by irradiation. 10355/ReguIar Budget Fund principal investigator: Wojciech Migdal, Ph.D. 5. Tracer study of dynamic characteristics of natural industrial sewage receivers as element of ecological hazard assessment. 10061/Regular Budget Fund principal investigator: Andrzej Owczarczyk, Ph.D.

IAEA TECHNICAL CONTRACTS IN 1999

1. Industrial scale demonstration plant for electron beam purification of flue gases. POL/8/014 2. Control laboratories for radiation processing. POL/8/16

EUROPEAN COMMISSION RESEARCH PROJECTS IN 1999

1. Development of heavy duty reactor window for industrial scale removal of NOX and SO2 from flue gas by electron beam treatment. IC15-CT97-0711 supervisor: Prof. Jerzy Piekoszewski, Ph.D., D.Sc. RESEARCH PROJECTS AND CONTRACTS 171 2. Accreditation for high dose measurement. EU INCO Copernicus Project IC I5-CT96-0824 supervisor: Zofia Stuglik, Ph.D.

OTHER FOREIGN CONTRACTS IN 1999

1. Development of sol-gel process for coating of NiO cathodes (used in molten carbonate fuel cells) with lithium cobaltite. 12811 Contract with ENEA, Italy principal investigator: Andrzej Deptula, Ph.D. 2. Set for ABSR leakage systems: analog module preamplifier and discriminator H.U. power supply board D1160 control unit board with display and keyboard, transmission unit. Contract with Itaiservice and Consulting Ltd., United Kingdom principal investigator: Prof. Piotr Urbariski, Ph.D., D.Sc. 3. Production of integrated circuit, resistors and crystal oscillators. Contract with NESSCO Ltd., Aberdeen, United Kingdom principal investigator: Prof. Piotr Urbariski, Ph.D., D.Sc. 4. Evaluation of technical conditions and radiation processing of rubber sheets. Contract with COFRAR, Versailles, France 172 LIST OF VISITORS TO THE INCT IN 1999

LIST OF VISITORS TO THE INCT IN 1999

Name Institution Country Period 1. 3achir Aioub Atomic Energy Commision of Syria Syria 01.09-29.12 2. Saud Mohammed Institute of Atomic Energy Research Saudi 01.02-30.04 Al-Osaimi Arabia 3. Sukarman Aminjoyo Yogyakarta Nuclear Research Centre Indonesia 05.12-12.12 4. Klaus Dieter Asmus University of Notre Dame USA 02.10-05-10 5. Vadim Auslendcr Institute of Nuclear Physics, Siberian Branch of Russia 05.06-15.06 Russian Academy of Science, Novosibirsk 6. Pawel Baranczewski Pharmacia, Uppsala Sweden 13.09 7. Ortwin Brede University of Leipzig Germany 07.06-11.06 8. Kirsti Bredholt Morwegian Radiation Protection Authority, Norway 26.04 Oslo 9. Witold Brostow University of North Texas USA 17.09 10. Elisabeth Bruckman University Clinics, Essen Germany 23.09 11. Dawid Brown University of Huddersfield Great 12.11-15.11 Britain 12. Freddy Callens University of Ghent Belgium 20.09-26.09 13. Mikhaid Demskij Scientific Research Institute of Electrophysical Russia 06.06-10.06 Apparatus, St. Petersburg 14. Jacek Dziewiriski Los Alamos National Laboratory USA 09.06-11.06 15. Aleksander Fainchtein Institute ENERGOSTAL Ukraine 15.08-27.08 16. Leonid Fomin Insitute of Electrophysical Equipment, St. Pe- Russia 06.06-10.06 tersburg 17. Norman Frank International Atomic Energy Agency expert United 21.06-03.07 Nations International Business Consultants USA 21.11-04.12 18. Ud-Din Ghiyas Pakistan Institute of Nuclear Science and Tech- Pakistan 15.11-31.12 nology, Islamabad 19. Anatolij Gryzlov State Research and Production Corporation Russia 06.06-12.06 "TORIJ", Moscow 20. Omer Harraga Tajoura Nuclear Research Centre Libya 01.01-23.02 21. Nor'Paiza Moh. Malaysian Institute for Nuclear Technology Re- Malaysia 28.05-30.05 Hasan search 22. Amzad Hossain Bangladesh Atomic Energy Comission Bangladesh 18.05-24.05 23. Chantal Houee-Levin University Paris-Sud France 06.06-13.06 24. Gordon L. Hug Radiation Laboratory University of Notre Dame USA 19.02-22.02 01.03-02.03 25. Garanse Humez Ecole dc Nines, de Nantes France 18.05-12.08 26. Eberhard Janata Hahn Meitner Institut, Berlin Germany 05.12-11.12 27. Nikolay Kuksanov Institute of Nuclear Physics, Siberian Branch of Russia 05.06-15.06 Russian Academy of Science, Novosibirsk 28. Mike Kuperberg Florida State University USA 10.11 29. Jozef Kuruc Comenius University, Bratislava Slovak 24.10-29.10 Republic LIST OF VISITORS TO THE INCT IN 1999 173

30. Antoine L'Eplattenier Ecole de Nines, de Nantes France 03.05-05.08 31. Jingyu Luo Tsinghua University China 22.11-28.11 32. Georgi Lysov State Research and Production Corporation Russia 07.10-09.10 "TORIJ", Moscow 33. Sueo Machi International Atomic Energy Agency United 21.06-25.06 Nations 34. Paul Mathys University of Ghent Belgium 20.09-26.09 35. J. Meerlins Florida State University USA 10.11 36. Hirohito Nakazawa National Institute for Research in Inorganic Ma- Japan 04.09-12.09 terials, Tsukuba 37. Wladimir Nazarov State Research and Production Corporation Russia 07.10-09.10 "TORIJ", Moscow 38. Henrieta Nichipor Institute of Radiation Physical and Chemical Belarus 18.01-30.01 Problems, Academy of Sciences of Belarus 03.10-16.10 19.11-21.11 04.12-10.12 39. Akiro Okuyama Banyu Tsukuba Research Institute Japan 16.05 40. Ivar Olovsson University of Uppsala Sweden 01.09-02.09 41. Oleg Orelovitch Joint Institute for Nuclear Research, Dubna Russia 17.01-30.01 24.09-30.09 42. Aleksander Pavielev State Research and Production Corporation Russia 06.06-12.06 "TORIJ", Moscow 43. Reynaldo V. Philippine Nuclear Research Institute Philippines 28.05 Pedregosa 44. Aleksy Pikajev Institute for Physical Chemistry, Russian Aca- Russia 31.08 demy of Sciences, Moscow 45. Samy Remita University Paris V France 30.01-06.02 46. Lothar Richter University of Leipzig Germany 07.06-11.06 47. Henry de Rocquigny COFRAR SA, Versaille France 17.02 07.06-09.06 48. Hommam Mohammed Egyptian Nuclear Materials Authority Egypt 25.04-20.07 Serag 49. Bernard Siret Lab-Lyon France 06.01-07.01 50. Christian Streffer University Clinics, Essen Germany 04.05-08.05 51. Sudjatmoko Yogyakarta Nuclear Research Centre Indonesia 19.03-26.03 52. Martyn Symons De Monfort University, Leicester Great 04.10-11.10 Britain 53. Kenji Tamura National Institute for Research in Inorganic Ma- Japan 04.09-12.09 terials, Tsukuba 54. T. Tanaka International Atomic Energy Agency United 21.06-26.06 Nations 55. Nikolaj Taralenko Institute of Nuclear Physics, Siberian Branch of Russia 17.09-19.09 Russian Academy of Science, Novosibirsk 56. Benny Theng University of Landcare Now Zcland 01.09-0309 57. Tsurugi International Atomic Energy Agency United 21.06-26.06 Nations 58. Andriej Uszakov State Research and Production Corporation Russia 07.10-09.10 "TORIJ", Moscow 59. Nicolas Varmenot University Paris V France 30.01-13.02 09.05-21.05 60. Sri Wahyuni National Atomic Energy Agency Indonesia 30.08-01.12 174 LIST OF VISITORS TO THE INCT IN 1999

61. Irene White De Monfort University, Leicester Great 04.10-11.10 Britain 62. Hirohisa Yamada National Institute for Research in Inorganic Ma- Japan 04.09-12.09 terials, Tsukuba 63. Svetlana Yarcheva Institute ENERGOSTAL Ukraine 03.05-02.06 64. Malgorzata University Leiden Holland 18.06 Zdzienicka 65. Farhood Ziaie Nuclear Research Center for Agriculture and Iran 01.03-31.07 Medicine, Karaj THE INCT SEMINARS IN 1999 175

THE INCT SEMINARS IN 1999

1. Prof. Klaus-Dieter Asmus (Notre Dame Radiation Laboratory, Indiana, USA) Free radical induced degradation of amino acids. 2. Prof. Freddy Callens (University of Ghent, Belgium) Single crystal and power EPR/ENDOR of transition metal ion complexes in photographically relevant materials.

3. Prof. Andrzej G. Chmielewski, Dr. Halina Polkowska-Motrenko, Wojciech Starosta, M.Sc, Dr. Ryszard Wierzchnicki (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Koncepcja akredytowanego Laboratorium Jadrowych Technik Analitycznych dla zastosowari w medycy- nie, przemys'le i ochronie Srodowiska (Acquision conceptions for the Laboratory of Nuclear Analytical Techniques for use in medicine, industry and environmental protection). 4. Dr. Wojciech Dembinski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Udzial pola j^drowego w chemicznych efektach izotopowych (Contribution of nuclear field to chemical isotope effects). 5. Prof. Krystyna Dyrek (Jagiellonian University, Krakow, Poland) Mozliwos'ci i ograniczenia spektroskopii EPR w badaniach rial stafych (Possibilities and limitations of EPR spectroscopy in studying solids).

6. Jacek Dziewiriski, M.Sc. (Los Alamos National Laboratory, New Mexico, USA) Zastosowanie technik elektrochemicznych do przerobki odpad6w radioaktywnych (Application of electrochemical techniques to radioactive waste disposal). 7. Assoc. Prof. Jerzy Herbich (Institute of Physical Chemistry, Polish Academy of Sciences, Warszawa, Poland) Fotoindukowane przeniesienie elektronu. Aspekty strukturalne i wpfyw Srodowiska (Photoinductive transfer of electron. Structural aspects and influence of the environment).

8. Prof. Jacek Kijefiski (Warsaw University of Technology, Poland) Rodnikowe przemiany zwi^zk6w organicznych na tlenkowych powierzchniach jonowych (Radical trans- formations of organic compounds on oxide ionic surfaces). 9. Dr. Marcin Kruszewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Podloze odwrotnej krzyzowej opornos"ci kom6rek L5178Y na promieniowanie jonizujqce i nadtlenek wodoru (Mechanism of inverse cross resistance of L5178Y cell lines to ionizing radiation and hydrogen peroxide).

10. Prof. Hiromoto Nakazawa (Institute for Research in Inorganic Materials, Tsukuba, Japan) Clays in chemical evolution. 11. Prof. Aleksy K. Pikajev (Institute of Physical Chemistry, Russian Academy of Sciences, Moscow, Russia) Radiation treatment of waste water. 12. Dr. Wadaw Stachowicz, Kazimiera Malec-Czechowska, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Droga do akredytacji Samodzielnego Laboratorium Identyfikacji Napromieniowanej Zywnos'ci (Way to the acquisition for the Independent Laboratory for Identification of Irradiated Food).

13. Prof. Martyn C.R. Symons (De Monfort University, Leicester, United Kingdom) Electron movement through DNA, proteins and in whole cells. 176 THE INCT SEMINARS IN 1999 14. Dr. Ewa Szajdziriska (L6dz Technical University, Poland) Struktura i dynamika jonomer6w i modelowych ukladtiw micelarnych. Badania z wykorzystaniem prob- nik6w molekularnych (Structure and dynamics of ionomers and model micellar systems. Studies with the use of molecular samplers). 15. Prof. Jong-Sung Yu (Hannam University, Taejon, Korea) Combinatorial development of anode and cathode electrocatalyst in direct methanol fuel cell. 16. Prof. Zbigniew P. Zag6rski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Los Alamos - legenda i terazniejszos'c' (Los Alamos - legend and the present). 17. Prof. Malgorzata Zdziennicka (Leiden University, Holland) Promieniowrazliwe mutanty kom6rek ssaktiw (Radiosensitivity of mutants of mammalian cells). SEMINARS DELIVERED OUT OF THE INCTIN 1999 177

SEMINARS DELIVERED OUT OF THE INCT IN 1999

1. Hanna Ambroz Damages and repairs of irradiated DNA, generally accepted and controversial facts. De Monfort University, Leicester, United Kingdom, 29.12.1999 2. Krzysztof Bobrowski Reactive intermediates during OH oxidation of methionine-containing peptides. Radiation Laboratory, University of Notre Dame, Indiana, USA, 22.06.1999 3. Krzysztof Bobrowski Oxidation processes in sulphur-containing model peptides. Laboratoire de Chimie et Biochimie Pharmacologiques et Toxicologiques, Universite Rene Descartes, Paris, France, 17.09.1999 4. Andrzej G. Chmielewski Chemia atmosfery a nowoczesne technologic oczyszczania gazow powstaja.cych przy spalaniu paliw ko- palnych (The chemistry of atmosphere and modern purification technologies of gases formed during combustion of fossil fuels). Konferencja dla doradcow metodycznych chemii (Conference for methodical advisors in chemistry), Debe, Poland, 19.03.1999 5. Andrzej G. Chmielewski Spalanie paliw kopalnych a chemia atmosfery (Fossil fuel combustion and atmosphere chemistry). Stowarzyszenie Elektryk6w Polskich (Association of Polish Electrical Engineers), Warszawa, Poland, 11.05.1999 6. Andrzej G. Chmielewski Membrane prevaporation as a means of isotope separation of O17, O18, D and T from waters. Chemistry Department, University of Tennessee, Knoxville, USA, 13.10.1999 7. Iwona Gra.dzka Rola mitochondriow w procesie apoptozy (The role of mitochondria in apoptosis). Zaklad Biochemii i Medycyny Dos\viadczalnej, Centrum Zdrowia Dziecka (Department of Bioche- mistry and Experimental Medicine, Child's Health Center), Warszawa, Poland, 29.01.1999 8. Marcin Kruszewski Podtoze odwrotnej krzyzowej wrazliwos'ci kom6rkowej linii kom6rek L5178Y na promieniowanie joni- zuja_ce i nadtlenek wodoru (Mechanizm of inverse cross sensitivity of L5178Y cell lines to ionizing ra- diation and hydrogen peroxide). Instytut Biochemii i Biofizyki PAN (Institute of Biochemistry and Biophysics, Polish Academy of Sciences), Warszawa, Poland, 07.09.1999 9. Marcin Kruszewski Regulacja metabolizmu jon6w zelaza w kombrkach nieerytroidalnych (Iron ion homeostasis in non erythroidal cells). Instytut Medycyny Pracy i Zdrowia Srodowiskowego (Institute of Occupational Medicine and Envi- ronmental Health), Sosnowiec, Poland, 16.11.1999 10. Marcin Kruszewski Liczba wywolanych przez nadtlenek wodoru uszkodzeri DNA zalezy od poziomu wolnych jonow zelaza (Extent of H2O2 induced DNA damage depends on labile iron pool). Centrum Onkologii (Oncology Center), Gliwice, Poland, 26-27.12.1999 178 SEMINARS DELIVERED OUT OF THE INCT IN 1999 11. Marcin Kruszewski Podłoże odwrotnej krzyżowej wrażliwości linii komórek L5178Y na promieniowanie jonizujące i nad- tlenek wodoru (Mechanizm of inverse cross sensitivity of L5178Y cell lines to ionizing radiation and hydrogen peroxide). Komisja Radiobiologii i Ochrony Radiologicznej Komitetu Fizyki Medycznej PAN (Radiobiology and Radiological Protection Commission, Medical Physics Committee, Polish Academy of Sciences), War- szawa, Poland, 02.12.1999

12. Jacek Michalik Transition metal agglomeration in mesoporous materials. National Institute for Research in Inorganic Materials, Tsukuba, Japan, 5.02.1999

13. Jacek Michalik Paramagnetic silver clusters in molecular sieves. Magnetic Resonance Seminar, Weizmann Institute of Science, Rehovot, Israel, 5.11.1999

14. Tomasz Mioduski Czy należy obawiać się energetyki jądrowej? (Should we be afraid of nuclear power?) Instytut Chemii, Wyższa Szkoła Pedagogiczna (Institute of Chemistry, Pedagogical University), Często- chowa, Poland, 17.11.1999

15. Jerzy Narbutt Perspektywy badań radiochemicznych w Polsce (Perspective of radiochemical studies in Poland). Wydział Chemii, Uniwersytet Warszawski (Faculty of Chemistry, University of Warsaw), Poland, 16.04.1999

16. Sławomir Siekierski Efekty relatywistyczne w chemii (Relativistic effect in chemistry). Polskie Towarzystwo Chemiczne (Polish Chemical Society), Poznań, Poland, 8-9.03.1999

17. Irena Szumiel Sygnalizacja komórkowa w odpowiedzi na promieniowanie jonizujące (Cellular signalling in the res- ponse to ionizing radiation). Instytut Biologii Doświadczalnej PAN (Institute of Experimental Biology, Polish Academy of Sciences), Warszawa, Poland, 28.01.1999

18. Irena Szumiel Uszkodzenia DNA i mechanizmy naprawy (DNA damage and repair). Instytut Biostruktury Akademii Medycznej (Institute of Biostructure, Medical Academy in Warsaw), Warszawa, Poland, 13.12.1999 -

19. Marek Trojanowicz Decomposition of selected organic pollutants in waters by ionizing radiation for environmental pro- tection. Institute of Energy and Nuclear Research (IPEN), Sao Paulo, Brazylia, 27.05.1999

20. Marek Trojanowicz Flow injection potentiometry for speciation in environmental samples. Institute of Chemistry, Catholic Pontifical University, Rio de Janeiro, Brazil, 28.05.1999

21. Marek Trojanowicz Decomposition of selected organic pollutants in waters by ionizing radiation for environmental purposes. International Atomic Energy Agency, Vienna, Austria, 24.06.1999

22. Andrzej Wójcik Ryzyko niskich dawek promieniowania (Risk of low doses of ionising radiation). Instytut Biologii, Wyższa Szkoła Pedagogiczna (Institute of Biology, Pedagogical University), Kielce, Poland, 25.05.1999 SEMINARS DELIVERED OUT OF THE INCT IN 1999 179 23. Zbigniew Pawei Zagorski Produkty natury - blogoslawieristwa i niebczpieczenstwa (Natural products - blessings or dangers). Centrum Studi6w nad Cztowiekiem i Srodowiskiem, Uniwersytet Slaski (Centre of Studies on Manking and Environment, Silesian University), Katowice, Poland, 18.02.1999 24. Zbigniew Pawet Zagorski A comparison of radiolysis chemistry in solid vs. liquid state. Los Alamos National Laboratory, New Mexico, USA, 4.04.1999. 25. Zbigniew Pawel Zagorski Red atom and cold war as seen from behind the curtain. Los Alamos National Laboratory, New Mexico, USA, 5.04.1999 26. Zbigniew Pawel Zag6rski Los Alamos National Laboratory - radiochemia i odpady (Los Alamos National Laboratory - radio- chemistry and waste treatment) Wydzial Chemii, Uniwersytet Warszawski (Faculty of Chemistry, University of Warsaw), Poland, 17.12.1999 280 INDEX OF THE AUTHORS

INDEX OF THE AUTHORS

E Alvani Carlo 82 Eliasson Ann-Charlotte 49 Ambroż Hanna B. 20, 21 Amenitsch Heinz 88,90 Antoniak Waldemar 133 Fiedler Rudolf 59 B

Barbossa Carla 40 Garkushalgor 123 Barson Stephen D. 122,124 Gasińska Anna 99,100 Bartak Jakub 134 Głuszewski Wojciech 32,35, 40 Berkowski Marek 41 Gniazdowska Ewa 85 Bernstorff Sigrid 88 Goretta Kenneth C. 78 Berrely Sueli I. 32 Grabias Agnieszka 123 Bilewicz Aleksander 60, 64 Grądzka Iwona 99,104,106 Bobrowski Krzysztof 19, 23, 25 Grigoriew Helena 88, 90 Bojarski Jerzy 30, 54 Grötzschel Rrainer 124 Boużyk Elżbieta 109 Brede Ortwin 19 H Brignocchi Aldo 80 Brown David 27 Hakoda Teruyuki 116 Bruckmann Elisabeth 105 Harasimowicz Marian 113 Buczkowski Marek 125 Hashimoto Shoji 116 Bulka Sylwester 116 Hofmann Michael 92 Buraczewska Iwona 99,100,104,106 Holcman Jerzy 25 Hołderna-Kędzia Elżbieta 51 Hug Gordon L. 23

Casadio Sergio 82 I Chebotarev Volodia V. 123 Chmielewski Andrzej G. 82,88,90,113,114,116,122,124 Hier Edward 114 Chwastowska Jadwiga 72,73 Iwaneńko Teresa 109 Cieśla Krystyna 38,40,49 Croce Fausto 80 Jarocewicz Neila 99 D Jaworska Alicja 103 Dancewicz Antoni M. 47,48 K Danilczuk Marek 27 Danko Bożena 66, 76 Kaczmarek Sławomir M. 41,42,47 De Angelis Paula 103 Kasprzak Aleksandra 130 Dembiński Wojciech 59 Kevan Larry 27 Deptuła Andrzej 78, 80,82 Kędzia Bogdan 51 Derda Małgorzata 117 Kierzek Joachim 129,130 Di Bartolomeo Angelo 80 Kisielewski Jarosław 42,47 Dobrowolski Piotr 85 Kolenda Małgorzata 92 Drzewicz Przemysław 32 Kolitsch Andreas 122 Dudek Jakub 70 Kopcewicz Michał 123 Dybczyński Rajmund 66,74,76 Kornacka Ewa 20,21 Dźwigalski Zygmunt 138 Korzeniowska-Sobczuk Anna 19 INDEX OF THE AUTHORS 181 Kowalska Ewa 137 Kozubek Halina 23 Krejzler Jadwiga 60, 61 Paluchowska Beata 86, 92 Kruszewski Marcin 99,104, 109 Panta Przemysław P. 32,35 Kubica Krystyna 114 PańczykEwa 127 Kulisa Krzysztof 74 Pawlukojć Andrzej 91 Kunicki-Goldfinger Jerzy 129,130 Pene Bogusław 92 Kwaśny Mirosław 42,47 Piekoszewski Jerzy 122,123,124 PieńkosJanP. 134 Polkowska-Motrenko Halina 74,76 Poniński Marek 59 Langner Jerzy 123,124 Poznański Jarosław 25 Leciejewicz Janusz 91, 92, 93, 94, 95 Przybytniak Grażyna 20, 21,44, 54 Lehner Katarzyna 48 Pszonicki Leon 70,71 L'Eplattenier Antoine 137 Ptasiewicz-Bąk Halina 93, 94,95 Licki Janusz 114,124 Ligęza Maria 127 R Lipiński Paweł 109 Rafalski Andrzej 37,44 Rahier Hubert 38 ReitanJon 103 Richter Edgar 122,124 Lada Wiesława 78,80,82 Richter Lothar 19 Łukasiewicz Andrzej 121 Rogowska Adrianna 72 Łukasiewicz Tadeusz 42 Ronci Fabio 80 Rowińska Luzja 121 M Rzewuski Henryk 42 Machaj Bronisław 135 Madajczyk Danuta 51 Majchrowski Andrzej 47 Sadło Jarosław 30,38,54 Malec-Czechowska Kazimiera 47, 48 Sadowska-Bratek Monika 73 Małożewska-Bućko Bożena 129 Samczyński Zbigniew 66 Marciniak Bronisław 23 Sampa Maria H.O. 32 MaurinJanK. 86,92 Sartowska Bożena 82,123,124,125 Michalik Jacek 27, 30, 38 Sereno Alberto 40 Migdał Wojciech 51, 52 Siekierski Sławomir 62 Mikołajczuk Agnieszka 117 Skeldon Peter 122,124 Mioduski Tomasz 65 Skwara Witold 71 Moroz Zbigniew 41,42 Sochanowicz Barbara 99,102 Müller Wolfgang-Ulrich 108 Sołtyk Wojciech 118,120 Stachowicz Wacław 38,47,48 N Stanislawski Jacek 124 Starosta Wojciech 94,95,123,125 Nałęcz-Jawecki Grzegorz 32 Sterlińska Elżbieta 72,73 Narbutt Jerzy 60,61, 85, 86 Streffer Christian 108 Nichipor Henrieta 116 Strzelczak Grażyna 30, 35, 38 Niedereichholz Frauke 108 Stuglik Zofia 42,43 Sun Yongxia 114,116 O Szot Zbigniew 47,48 Szumiel Irena 99,100,102, 103 Obe Günter 105,107 Szymczyk Władysław 123,124 Olczak Tadeusz 78,82 Szytuła Andrzej 92 Olsen Goril 103 Ołdak Tomasz 104 Opałka Bertram 107 Ostapczuk Anna 114,116 Świerz-Motysia Barbara 54 Owczarczyk Andrzej 117,118,120 Świętosławski Jacek 52 Owczarczyk Hanna B. 51,52 Świętosławski Janusz 52 182 INDEX OF THE AUTHORS Świstowski Edward 133 Wiśniowski Paweł 19 Włodzimirska Barbara 64 Wojewódzka Maria 106 Wojtkowska Jolanta 42 Tereshin Vladimir I. 123 Wojtyńska Elżbieta K. 35 Thompson George E. 122,124 Wolińska-Grabczyk Aleksandra 88 Trojanowicz Marek 32 Wójcik Andrzej 105,107,108 Tymiński Bogdan 113 Wrońska Teresa 47

U Y

Urbański Piotr 133,135,137 Yu Jong-Sung 27 W WahyuniSri 32 Walendziak Jolanta 118,120 Zagórski Zbigniew P. 22,37, 44 WaliśLech 121,123,127 Zakrzewska-Trznadel Grażyna 38,113 Warchoł Stanisław 41 Zimek Zbigniew 35, 54,116,138 Wawszczak Danuta 125 Werner Zbigniew 122,123,124 Wierzchnicki Ryszard 117 Wierzchowski Kazimierz L. 25 Żebrowska Teresa 109 Wieser Egbert 122,124 Żuchowska Danuta 44 INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY Dorodna 16, 03-195 Warszawa, Poland Phone: (+48)-(22) 811-06-56 Fax: (+48)-(22) 811-15-32 Telex: 813027 ichtj pi E-mail: [email protected]