PL9902258
ISSN 1425-204X
INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY
(27 no Iff] /a} IT 1998 I 30-44 EDITORS Wiktor Smuiek, Ph.D. Bozena Bursa
PRINTING Sylwester Wojtas
© Copyright by the Institute of Nuclear Chemistry and Technology, Warszawa 1999 All rights reserved CONTENTS
GENERAL INFORMATION 9 MANAGEMENT OF THE INSTITUTE 11 MANAGING STAFF OF THE INSTITUTE 11 HEADS OF THE INCT DEPARTMENTS 11 PROFESSORS AND SCIENTIFIC COUNCIL 12 PROFESSORS 12 ASSOCIATE PROFESSORS 13 ASSISTANT PROFFESSORS (Ph.D.) 13 SCIENTIFIC COUNCIL (1995-1999) 15 HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (1995-1999) 16 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 17 PHOTOOXIDATION OF METHIONINE DERIVATIVES IN AQUEOUS SOLUTIONS K. Bobrowski, G.L. Hug, B. Marciniak 19
HYDROXYL RADICAL INDUCED OXIDATION OF (x-(METHYLTHIO)ACETAMIDE IN AQUEOUS SOLUTIONS P. WiSniowski, K. Bobrowski 20
SILVER CLUSTERS IN ZIC-4 ZEOLITES J. Michalik, Jong-Sung Yu, J. Sadio 21
ESR STUDY OF POLYCRYSTALLINE TRIPEPTIDES G. Strzelczak, K. Bobrowski, J. Michalik 24
EPR STUDY OF PARAMAGNETIC PRODUCTS IN DRUGS FOLLOWING y-STERILISATION H.B. Ambroz, E.M. Kornacka, B. Marciniec, G. Przybytniak 26
MODIFICATION OF DNA RADIOLYSIS BY DTT AT CRYOGENIC TEMPERATURES H.B. Ambroz, E.M. Kornacka, G. Przybytniak 27
THEORETICAL STUDY ON DECOMPOSITION OF ETHYL CHLORIDE IN DRY AIR UNDER INFLUENCE OF ELECTRON BEAM H. Nichipor, E. Dashouk, A.G. Chmielewski, Z. Zimek, S. Buika 28
EFFECT OF SELECTED INORGANIC SCAVENGERS ON RADIOLYTIC DEGRADATION OF 2,4-DICHLOROPHENOL P. Drzewicz, P.P. Panta, W. GJuszewski, M. Trojanowicz 30
RADIATION YIELD OF MULTI-IONIZATION SPURS IN SOLID ALANINE Z.P. Zagorski 33
FREE RADICALS IN EB IRRADIATED BLENDS OF POLYETHYLENE AND BUTADIENE-STYRENE BLOCK COPOLYMER G.K. Przybytnialc, Z.P. Zagorski, D. Zuchowska 34
A PULSE RADIOLYSIS STUDY ON SINGLE CRYSTALS OF a-ALANINE Z.P. Zagorski, K. Sehested 36
RADIATION CHEMISTRY OF SOLID THIOSULFATE. I. OPTICAL ABSORPTION SPECTRA Z.P. Zagorski, A. Rafalski 38
RADIATION CHEMISTRY OF VIRGIN POLYPROPYLENE A. Rafalski 41
EFFECTS OF GAMMA IRRADIATION AND ANNEALING TREATMENTS ON THE PERFORMANCE OF Cr;Tm;Ho:YAG LASERS S.M. Kaczmarek, W. Zendzian, T. Lukasiewicz, K. St^pka, Z. Moroz, S. Warchoi 43 HIGH ENERGY ION IMPLANTATION PROFILES J. Krynicki, J. Puton, J. Oleniak, S. Warchol, H. Rzewuski 45
DRS QUANTIFICATION OF ABSORBED RADIATION DOSE INDICATED BY LABELS Z.P. Zagorski, A. Rafalski 46
A THIN, COMPOSITE SODIUM CHLORIDE DOSIMETER WITH DIFFUSE REFLECTED LIGHT SPECTROPHOTOMETRIC READ OUT Z.P. Zag6rski, A. Rafalski . 47
ION BEAM DOSIMETRY. ABSOLUTE METHOD BASED ON ENERGY AND FLUENCE MEASUREMENTS Z. Stuglik 49
ALAN1NE/POLIMER RODS WITH LOW CONCENTRATION OF DL-oc-ALANINE FOR ROUTINE ELECTRON BEAM DOSIMETRY Z. Stuglik, T. Bryl-Sandelewska 50
RE-INVESTIGATION OF PVC FOILS USED FOR ROUTINE ELECTRON BEAM DOSIMETRY IN INCT Z. Stuglik . 51
MICROCRYSTALLINE L-a- AND DL-a-ALANINE IRRADIATED WITH GAMMA RAY AND HEAVY IONS AND ANALYZED BY MEANS OF INSTRUMENTAL METHODS Z. Stuglik, A. Dindune, M. Burzytiska-Szyszko, L. Actida 52
EVALUATION OF ENERGY OF SCANNED ELECTRON BEAM FROM LINEAR ACCELERATOR BY MEANS OF DEPTH-DOSE DISTRIBUTION MEASUREMENT W. Malicki, Z. Stuglik 53
OPTICAL PROPERTIES OF GAMMA IRRADIATED ARTIFICIAL SAPPHIRE AND YTTRIA STABILIZED ZIRCONIA SPECTROSCOPIC WINDOWS L. Fuks, C. Degueldre 54
PRELIMINARY APPLICATION OF MODULATED DIFFERENTIAL SCANNING CALORIMETRY IN STUDIES OF HEAVY ION IRRADIATED POLYESTER FILMS K. CieSla, M. Ribeiro 56
APPLICATION OF WAXS DIFFRACTION IN STUDIES OF CRYSTALLINITY CHANGES IN HEAVY ION IRRADIATED POLYESTER FILMS K. CieSla 57
DIFFERENTIAL SCANNING CALORIMETRY STUDIES OF ANNEALING AND HEAVY ION IRRADIATION INFLUENCE ON MELTING AND CRYSTALLIZATION PROCESSES IN POLYETHYLENE TEREPHTHALATE) K. Cie^la, E. Ferain, R. Legras, W. Starosta 59
RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 61
DETERMINATION OF TRACE ELEMENTS IN ALABASTER BY NEUTRON ACTIVATION ANALYSIS L. Rowiriska, E. Paiiczyk, L. WalH, M. Lig^za, B. Nalepa 63
ANALYSIS OF TRACE ELEMENTS IN LEAD WHITE OF PAINTINGS OF THE SILESIAN SCHOOL FROM THE XVth CENTURY E. Pariczyk, J. Olszewska, L. Rowinska, L. Walis 64
DETERMINATION OF CHEMICAL HOMOGENEITY OF HISTORICAL GLASSWARE. A CASE STUDY J.J. Kunicki-Goldfinger, J. Kierzek, B. Sartowska 67
A CHEMICAL SEPARATION SCHEME FOR 24Na - A DECAY PRODUCT OF THE CLUSTER RADIOACTIVITY OF 233U B. BartoS, A. Bilewicz 70
FRACTIONAT1ON OF YTTERBIUM ISOTOPES IN THE Yb(III)-ACETATE'Yb-AMALGAM SYSTEM. A SEVEN ISOTOPE TRIAL W. Dembiriski, M. Poninski, R. Fiedler 70
HYDRATION AND SOLVATION OF LEAD(II) ACETYLACETONATE AND THE COORDINATION NUMBER OF LEAD(II) J. Narbutt 71 INCREASE OF THE COORDINATION NUMBER OF TRIVALENT p- AND d-BLOCK METAL IONS IN NEUTRAL TROPOLONATES BY ADDUCT FORMATION WITH TRIOCTYLPHOSPHINE OXIDE. THEORETICAL AND THERMODYNAMIC EVIDENCE J. Narbutt, M. Czerwinski, J. Krejzler 73
IMPLICATIONS OF THE NEW THEORY OF ISOTOPE CHEMISTRY OF THE HEAVY ELEMENTS T. Mioduski 77
AQUATION IN SOLID PHASES OF THE Ln2(S04)j-H2O SYSTEMS T. Mioduski 77
INTERLABORATORY COMPARISON OF THE DETERMINATION OF 226Ra AND a8Ra IN SAMPLES SIMULATING COAL MINE WATER J. Narbutt, L. Fuks 79
+ 2+ THERMAL CONVERSION OF Li -Mn ACETATE-ASCORBATE GELS TO LiMn2O4 FOR ELECTROCHEMICAL APPLICATIONS A. Deptula, T. Olczak, W. Lada, F. Croce 80
PREPARATION OF CALCIUM PHOSPHATE BIOMATERIALS (POWDERS, MONOLITHS, COATINGS AND FIBERS) 2+ 3 + FROM Ca -PO4 -NHi -OH-ASCORBIC ACID-H2O BY COMPLEX SOL-GEL PROCESS (CSGP) A. Deptuia, W. Lada, T. Olczak, B. Sartowska, R.Z. LeGeros, J.P. LeGeros 84
THE DYNAMICAL PATTERN OF THE 3-AMINO-2-PYRAZINE ACID MOLECULE BY INELASTIC NEUTRON SCATTERING, RAMAN SPECTROSCOPY AND AB INITIO CALCULATIONS A. Pawlukojc, I. Natkaniec, Z. Malarski, J. Leciejewicz 87
NEUTRON DIFFRACTION STUDY OF ANTIFERROMAGNETIC ORDERING IN HoPtSi, ErPtSi AND ErPtGe S. Baran, M. Hofinann, J. Leciejewicz, B. Penc, A. Szytula 88
CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS OF HETEROCYCLIC CARBOXYLIC ACIDS. PART XXIII. THE CRYSTAL STRUCTURE OF NICKEL(II) COMPLEX WITH PYRAZINE-2,3-DICARBOXYLIC ACID H. Ptasiewicz-Ba_k, J. Leciejewicz 89
CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS OF HETEROCYCLIC CARBOXYLIC ACIDS. PART XXIV. THE CRYSTAL STRUCTURE OF Cu(II) COMPLEX WITH PYRAZINE-2.3-DICARBOXYLIC ACID H. Ptasiewicz-Ba_k, }. Leciejewicz 90
CRYSTAL CHEMISTRY OF COORDINATION COMPOUDS WITH HETEROCYCLIC CARBOXYLIC ACIDS. PART XXV. THE CRYSTAL STRUCTURE OF CALCIUM(II) COMPLEX WITH 5-METHYLPYRAZINE-2-CARBOXYLIC ACID H. Ptasiewicz-Bak, J. Leciejewicz 91
CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLIC ACIDS. PART XXVI. THE CRYSTAL STRUCTURE OF MANGANESE(II) COMPLEX WITH FURAN-3-CARBOXYLATE ANIONS B. Paluchowska, J.K. Maurin, J. Leciejewicz 92
SAXS STUDY OF THE INFLUENCE OF SOLVENTS ON THE STRUCTURE OF POLYURETHANE-BASED MEMBRANES H. Grigoriew, A. Wolinska-Grabczyk, A.G. Chmielewski, J. DomagaJa 93
KINETICS OF STRUCTURAL CHANGES IN POLYMER MEMBRANES H. Grigoriew, A.G. Chmielewski, H. Amenitsch, S. Bernstorff, J. Domagala 94
A STUDY ON ANION EXCHANGE THERMODYNAMICS AND THE EFFECT OF COLUMN TEMPERATURE ON THE QUALITY OF CHROMATOGRAPHIC SEPARATIONS IN ISOCRAT1C ION CHROMATOGRAPHY K. Kulisa, R. Dybczynski 95
SORPTION OF HEAVY METALS ON HYDROXYAPATITES J. Chwastowska, E. Sterlinska, M. Sadowska-Bratek 96
EFFECT OF GASEOUS CHLORINE AND HYDROCHLORIDE ON THE As-Pd AND Sb-Pd COMPOUNDS DURING THEIR ATOMISATION IN A GRAPHITE FURNACE L. Pszonicki, J. Dudek 98
DETERMINATION OF SILICON AND PHOSPHORUS BY FLAME AND ELECTROTHERMAL ATOMIC ABSORPTION SPECTROMETRY W. Skwara, L. Pszonicki 99
INVESTIGATION ON POSSIBILITIES OF DETERMINATION OF SOME PRECIOUS METALS IN GEOLOGICAL AND ENVIRONMENTAL SAMPLES BY NEUTRON ACTIVATION ANALYSIS Z. Samczyriski, B. Danko, R. Dybczyriski 100 RADIOBIOLOGY 103 CERAMIDE IS NOT INVOLVED IN NUCLEAR TRANSLOCATION OF NF-KB IN L5178Y SUBLINES B. Sochanowicz, I. Szumiel 105
INDUCTION OF DNA BREAKAGE IN X-IRRADIATED NUCLEOIDS SELECTIVELY STRIPPED OF NUCLEAR PROTEINS IN TWO MOUSE LYMPHOMA CELL LINES DIFFERING IN RADIOSENSITIVITY M. Kruszewski, T, Iwaneriko . 106
CYTOSOLIC LABILE IRON POOL SIZE CORRESPONDS WITH THE SENSITIVITY OF L5178Y SUBLINES TO OXIDATIVE DAMAGE P. Lipinski, H. Retmariska, B. Sochanowicz, M. Kruszewski 107
DIFFERENTIAL INACTIVATION OF DNA-DEPENDENT PROTEIN KINASE IN IRRADIATED REPAIR-COMPETENT AND REPAIR-DEFICIENT L5178Y SUBLINES B. Sochanowicz, M. Kruszewski, I. Szumiel 108
LACK OF ADVERSE EFFECT OF SMOKING HABIT ON DNA STRAND BREAKAGE AND BASE DAMAGE M. Wojew6dzka, M. Kruszewski, T. Iwanenko, A.R. Collins, I. Szumiel 109
POLY(ADP-RIBOSE) METABOLISM IN TWO L5178Y MURINE LYMPHOMA SUBLINES EXPOSED TO X-RAYS H.E. Kleczkowska, I. Szumiel, F.R. Althaus 110
INHIBITION OF POLY(ADP-RIBOSYLATION) SIMILARLY AFFECTS CAMPTOTHECIN-TREATED L5178Y-R AND -S CELLS I. Gradzka, I. Szumiel 111
TELOMERE SIGNALS IN TWO L5178Y MOUSE LYMPHOMA CELL LINES A. Wojcik, E. Bouzyk, I. Szumiel, Ch. Streffer 113
PREFERENTIAL SEGREGATION OF A MARKER CHROMOSOME 14 IN MOUSE RECOMBINANT INBRED STRAINS DERIVED FROM THE KE AND CBA/Kw STRAINS M. Lenartowicz, A. Wojcik 113
SISTER CHROMATID DIFFERENTIATION WITH BIOTIN-dUTP E. Bruckmann, A. Wojcik, G. Obe 114
OXIDATIVE DAMAGE IN DIFFERENTIALLY HYDROGEN PEROXIDE SENSITIVE L5178Y SUBLINES CULTURED IN SELENIUM-SUPPLEMENTED MEDIUM E. Bouzyk 115
NUCLEAR TECHNOLOGIES AND METHODS 117 PROCESS ENGINEERING 119 INTEGRATED CONTROL MONITORING SYSTEM FOR ELECTRON-BEAM INSTALLATION FOR FLUE GAS PURIFICATION FROM SO2 AND NO* AT THE ELECTRIC POWER STATION "POMORZANY" A.G. Chmielewski, E. Iller, J. Licki, B. Tymihski 119
APPLICATION OF TRACER TECHNIQUES FOR INDUSTRIAL SUPPLY WATER AND WASTEWATER SYSTEM EXAMINATION A. Owczarczyk, h Palige, R. Wierzchnicki 120
TRACER INVESTIGATIONS OF SEDIMENTATION PROCESSES AFTER BIOLOGICAL TREATMENT OF WASTEWATER A.G. Chmielewski, A. Owczarczyk, J. Palige 121
CONCENTRATION OF LIQUID LOW- AND MEDIUMACTIVE LEVEL RADIOACTIVE WASTES (LLRW AND MLRW) USING MEMBRANE METHODS A.G. Chmielewski, M. Harasimowicz, B. Tymiriski, G. Zakrzewska-Trznadel !22
CONCENTRATION OF LIQUID LOW-LEVEL RADIOACTIVE WASTE BY MEMBRANE DISTILLATION - PILOT PLANT EXPERIMENTS G. Zakrzewska-Trznadel, M. Harasimowicz, A.G. Chmielewski 123
MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS 125 DOUBLE INTERFACIAL LAYERS FOR CERAMIC/METAL BRAZE JOINTS MADE BY HIGH INTENSITY PULSED PLASMA BEAMS AND ARC PVD TECHNIQUES J. Piekoszewski, J. StanisJawski, R. Grdtzschel 125 FORMATION OF SURFACE Pd-Ti ALLOYS USING PULSED PLASMA BEAMS J. Piekoszewski, Z. Werner, E. Wieser, J. Langner, R. GrOtzschel, H. Reuther , . 126
KINETICS OF THE PULSED EROSION DEPOSITION PROCESS INDUCED BY HIGH INTENSITY PLASMA BEAMS J. Piekoszewski, J. Stanisiawski, R. GrStzschet, E. Wieser, Z. Werner 127
SPECIAL ISOTOPE METHOD OF LEAKPROOF CONTROL OF TECHNOLOGICAL OBJECTS J. KraS, S. Myczkowski 128
STUDIES ON NEW POLYMERIC COMPLEXES OF AMINOTR1AZOLE WITH MAGNESIUM A. Lukasiewicz, L. Walii, L. Rowinska 129
THE 18™ CENTURY GLASSWARE FROM NALIBOKI AND URZECZE GLASSHOUSES. PHYSICO-CHEMICAL STUDIES ].h Kunicki-Goldfinger, J. Kierzek, A.J. Kasprzak, B. Maiozewska-Buiko 130
DETERMINATION OF SURFACE CHARGE DENSITY FOR PARTICLE TRACK MEMBRANES D. Wawszczak, W. Starosta, V.V. Berezkin, M. Buczkowski 132
LABORATORY OF ISOTOPE RATIO MASS SPECTROMETRY R. Wierzchnicki 133
LABORATORY FOR POROUS MATERIALS EXAMINATION M. Buczkowski, H. Grigoriew, B. Sartowska, D. Wawszczak, G. Zakrzewska-Trznadel 134
NUCLEONIC CONTROL SYSTEMS 135 ACTIVITY OF RADON DECAY PRODUCTS SIMULATION AS THE BASIS FOR OPTIMIZATION OF RADON DAUGHTERS CONCENTRATION MONITOR IN AIR B. Machaj 135
A MEASUREMENTS PROGRAMME FOR RADON DECAY PRODUCTS IN A RADON CHAMBER T. Radoszewski 137
RADIOMETRIC SCANNER FOR TITANIUM FOIL P. Urbariski, E. Kowalska 138
APPLICATION OF HEXAGONAL WELL DETECTOR FOR DETERMINATION OF MASS AND SPATIAL DISTRIBUTION OF NEUTRON RADIATION SOURCES INSIDE BULK SAMPLES M. Swiderska-Kowalczyk, W. Starosta, T. Zoitowski 139
MATHEMATICAL MODEL OF THE MOSSBAUER SPECTRUM IN THE TRANSMISSION GEOMETRY W. Starosta 141
APPLICATION OF PARTICLE TRACK MEMBRANES FOR DETERMINATION OF MICROIMPURITIES DISTRIBUTION IN ENVIRONMENTAL WATER SAMPLES M. Buczkowski, D. Wawszczak, W. Starosta, B. Sartowska 142
DETERMINATION OF CARBON CONTENT IN COAL AND ASH BY XRF J. Parus, J. Kierzek, B. Maiozewska-Bucko 143
THE INCT PUBLICATIONS IN 1998 145
THE INCT REPORTS IN 1998 169 NUKLEONIKA 171 THE INCT PATENTS AND PATENT APPLICATIONS IN 1998 175 PATENTS 175 PATENT APPLICATIONS 175 UTILITY MODELS 175 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1998 176
Ph.D./D.Sc. THESES 192 RESEARCH PROJECTS AND CONTRACTS 193 RESEARCH PROJECTS GRANTED BY THE POLISH STATE COMMITTEE FOR SCIENTIFIC RESEARCH IN 1998 AND IN PREVIOUS YEARS 193 IMPLEMENTATION PROJECTS GRANTED BY THE POLISH STATE COMMITTEE FOR SCIENTIFIC RESEARCH IN 1998 194 GOVERNMENTAL STRATEGIC PROGRAMME 194 IAEA RESEARCH CONTRACTS IN 1998 194 IAEA TECHNICAL CONTRACTS IN 1998 195 EUROPEAN COMMISSION RESEARCH PROJECTS IN 1998 195 OTHER FOREIGN CONTRACTS IN 1998 195 LIST OF VISITORS TO THE INCT IN 1998 197
THE INCT SEMINARS IN 1998 199
SEMINARS DELIVERED OUT OF THE INCT IN 1998 200
COMPUTER NETWORK IN THE INCT 203
INDEX OF THE AUTHORS 204 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 later 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 oftheINRinl983. The fundamental research on radiobiology, radio- and coordination chemistry and radiation chemistry is continued. In 1998 Jacek Michalik, Ph.D., D.Sc. and Krzysztof Bobrowski, Ph.D., D.Sc. obtained Professor titles from President of Poland. Mrs. Bozena Danko received her Ph.D. degree and Dr Aleksander Bilewicz his D.Sc. both in 1998 and both from the Scientific Council of the INCT. The Institute offers academic and research programmes for Ph.D. and D.Sc. thesis in chemistry. In 1998 10 postgraduate students started doctoral studies in the Institute. Institute is one of the most advanced science and technology centres working on development of technological 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 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 1998 the Institute organized a national conference on radiochemistry and nuclear chemistry entitled "On the Centenary of the Discovery of Polonium and Radium", held in Kazimierz Dolny. The Institute participated in the organization of a national symposium on "Nuclear Technology in Industry, Medicine, Agriculture and Environmental Protection", held at the Academy of Mining and Metallurgy in Krakow. The Institute, together with the Faculty of Chemistry, Adam Mickiewicz University in Poznan, organized a workshop on "Reactive Intermediates in Sulfur Chemistry". The School of Radiation Sterilization is periodically conducted. Professor Slawomir Siekierski has published a book "The Chemistry of Elements", the book being a textbook of inorganic chemistry for students and post-graduate students. JO GENERAL INFORMATION Scientific workers of the Institute prepared, as co-authors, several chapters in the book "Environmental Application of Ionizing Radiation" (Eds. WJ. Cooper, R.D. Curry, K.E. O'Shea. John Wiley & Sons, New York, 1998). Students from Ecole de Mines de Nantes (France), 6 fellowship holders from the IAEA were trained at the Institute. 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 Strategic Governmental Programme (SPR-4) "Treatment of radioactive wastes and burned nuclear fuel". 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 group 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 was 62. The Polish Section of the International Nuclear System (INIS) was situated in the INCT till the end of 1998. The Institute is the editor of NUKLEONIKA - 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 Walis, 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 Kazmirska
HEADS OF THE INCT DEPARTMENTS
• Department of Nuclear Methods of Material • Department of Analytical Chemistry Engineering Prof. Rajmund Dybczyiiski, Ph.D., D.Sc. Assoc.Prof. Lech Walis, 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 and • Pilot Plant for Food Irradiation Methods Wojciech Migdal, Ph.D. Prof. Piotr Urbanski, Ph.D., D.Sc. • Laboratory for Detection of Irradiated • Department of Radiochemistry Foodstuffs Assoc.Prof. Jerzy Narbutt, Ph.D., D.Sc. Wactaw 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. 12 PROFESSORS AND SCIENTIFIC COUNCIL
PROFESSORS AND SCIENTIFIC COUNCIL
PROFESSORS
1. Ambroz Hanna B. physical and radiation chemistry, biological chemistry, photochemistry
2. Bobrowski Krzysztof radiation chemistry, photochemistry, biophysics
3. Chmielewski Andrzej G. chemical and process engineering, nuclear chemical engineering, isotope chemistry
4. Chwastowska Jadwiga analytical chemistry
5. Dancewicz Antoni M. biochemistry, radiobiology
6. Dybczynski Rajmund analytical chemistry
7.|FideIis Irenaj physical chemistry, coordination chemistry of lanthanides and actinides
8. Leciejewicz Janusz crystallography, solid state physics
9. Lukasiewicz Andrzej material chemistry
10. Michalik Jacek radiation chemistry, surface chemistry, radical chemistry
11. Piekoszewski Jerzy solid state physics, material science
12. Pszonicki Leon analytical chemistry
13. Radoszewski Toniasz metrology of radionuclides
14. Rzewuski Henryk solid state physics, semiconductor physics
15. Siekierski Slawomir physical chemistry, inorganic chemistry
16. Szot Zbigniew radiobiology
17. Szumiellrena cellular radiobiology PROFESSORS AND SCIENTIFIC COUNCIL 13 18. Trojanowicz Marek analytical chemistry
19. Urbanski Piotr radiometric methods, industrial measurement equipment, metrology
20. Zag6rski Zbigniew P. physical chemistry, radiation chemistry, electrochemistry
ASSOCIATE PROFESSORS
1. Bilewicz Aleksander radiochemistry, inorganic chemistry
2. Grigoriew Helena solid state physics, diffraction research of non-crystalline matter
3. Legocka Izabella polymer technology
4. Mioduski Tomasz lanthanide and actinide chemistry
5. Narbutt Jerzy radiochemistry, coordination chemistry, physical chemistry
6. Parus Jerzy analytical chemistry
7. WaliS Lech material science, material engineering
8. Zdttowski Tadeusz nuclear physics
ASSISTANT PROFESSORS (Ph.D.)
1. Borkowski Marian 8. Dembiriski Wojciecfa radiochemistry, inorganic chemistry isotope chemistry
2BouzykElzbieta 9. Deptula Andrzej biology chemistry
3. Bryl-Sandelewska Teresa 10. Dobrowolski Andrzej radiation chemistry chemistry
4. Buczkowski Marek 11. Do Hoang Cuong physics nuclear physics
5. Bukowski Piotr 12. Dzwigalski Zygmunt high voltage electronics, electron injectors, mechanics gas lasers 6. CieSla Krystyna 13.FuksLeon physical chemistry, solid state reactions chemistry 7. Danko Bozena 15. Grqdzka Iwona analytical chemistry biolog}' 14 PROFESSORS AND SCIENTIFIC COUNCIL 16. Grodkowski Jan 36. Przybytniak Grazyna radiation chemistry radiation chemistry
17. Harasimowicz Marian 37. Ptasiewicz-Bajk Halina technical nuclear physics, theory of elementary physics particles 38. Skwara Witold 18. Iller Edward analytical chemistry chemical and process engineering 39. Sochanowicz Barbara 19. Jaworska Alicja biology biology 40. Stachowicz Wadaw 20. Kierzek Joachim radiation chemistry, EPR spectroscopy physics
21. Kleczkowska Hanna 41. Strzelczak Grazyna biology radiation chemistry, radical chemistry
22. Krejzler Jadwiga 42.StuglikZofia inorganic chemistry radiation chemistry
23. Kruszewski Marcin 43. Szpilowski Stanisiaw biology chemistry
24. Krynicki Janusz 44. Tyminski Bogdan solid state physics chemistry
25. Machaj Bronisiaw 45. Urbanski Tadeusz electronics, radiometric methods chemistry
26. Migdal Wojciech 46. Walicka Malgorzata chemistry biology 27. Mirkowski Jacek nuclear and medical electronics 47. Warchol Stanisiaw solid state physics 28. Nowicki Andrzej organic chemistry and technology, high- 48. Wqsowicz Tomasz temperature technology radiation chemistry, surface chemistry, radical chemistry 29. Owczarczyk Andrzej chemistry 49. Wierzchnicki Ryszard chemical engineering 30. Owczarczyk Hanna B. biology 50. Wojewodzka Maria biology 31. Palige Jacek metallurgy 51. W6jcik Andrzej 32. Panta Przemystaw P. cytogenetics nuclear chemistry 52. Wronska Teresa 33. Pawlukojc Andrzej chemistry physics 53. Zakrzewska-Trznadel Grazyna 34. Pogocki Dariusz process and chemical engineering radiation chemistry, pulse radiolysis 54. Zimek Zbigniew 35. Polkowska-Motrenko Halina electronics, accelerator techniques, radiation analytical chemistry processing PROFESSORS AND SCIENTIFIC COUNCIL 15 55. Zebrowska Teresa 56. Zmijewska Wanda biology analytical chemistry
SCIENTIFIC COUNCIL (1995-1999)
1. Prof. Hanna B. Ambroz, Ph.D., D.Sc. 13. Prof. Kazimierz Korbel, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Stanislaw Staszic Academy of Mining and physical and radiation chemistry, biological Metallurgy chemistry, photochemistry nuclear electronics, nuclear technical physics
2. Prof. Krzysztof Bobrowski, Ph.D., D.Sc. 14. Janusz Kras, M.Sc. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology radiation chemistry, photochemistry, biophysics radioisotope diagnostic methods for engines and industrial installations 3. Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 15. Gabriel Kuc, M.Sc. chemical and process engineering, nuclear Institute of Nuclear Chemistry and Technology chemical engineering, isotope chemistry radiation chemistry
4. Prof. Jadwiga Chwastowska, Ph.D., D.Sc. 16. Prof. Janusz Lipkowski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Polish Academy of Sciences, Institute of analytical chemistry Physical Chemistry physico-chemical methods of analysis 5. Prof. Rajmund Dybczynski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 17. Prof. Andrzej Lukasiewicz, Ph.D., D.Sc. analytical chemistry Institute of Nuclear Chemistry and Technology material chemistry 6. Zyta Glebowicz Institute of Nuclear Chemistry and Technology 18. Prof. Jozef Mayer, Ph.D., D.Sc. staff representative Lodz Technical University 7. Ewa Gniazdowska, M.Sc. physical and radiation chemistry Institute of Nuclear Chemistry and Technology 19. Prof. Jacek Michalik, Ph.D., D.Sc. physical chemistry of solutions (Co-chairman) 8. Edward Iller, Ph.D. Institute of Nuclear Chemistry and Technology radiation chemistry, surface chemistry, radical Institute of Nuclear Chemistry and Technology chemistry chemical and process engineering 20. Assoc.Prof. Jerzy Narbutt, Ph.D., D.Sc. 9. Prof. Janusz Jurczak, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Polish Academy of Sciences, Institute of Organic radiochemistry, coordination chemistry, physical Chemistry; University of Warsaw chemistry organic chemistry, stereochemistry
10. Antoni Kalicki, M.Sc. 23. Dariusz Pogocki, Ph.D. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology radiometric methods, industrial measurement radiation chemistry, pulse radiolysis equipment, metrology 22.|Prof. Jaw Przyluski, Ph.D., D.Sc. 11. Iwona Kaiuska, M.Sc. Warsaw University of Technology Institute of Nuclear Chemistry and Technology chemistry, solid state technology radiation chemistry 23. Prof. Leon Pszonicki, Ph.D., D.Sc. 12. Barbara Kazmierska (Chairman) Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology staff representative analytical chemistry 16 PROFESSORS AND SCIENTIFIC COUNCIL 24. Prof. Henryk Rzewuski, Ph.D., D.Sc. 31. Prof. Piotr Urbanski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology solid state physics, semiconductor physics radiometric methods, industrial measurement equipment, metrology 25. Zbigniew Samczynski, M.Sc. Institute of Nuclear Chemistry and Technology 32. Assoc.Prof. Lech Walis, Ph.D. analytical chemistry Institute of Nuclear Chemistry and Technology material science, material engineering 26. Prof. Slawomir Siekierski, Ph.D. Institute of Nuclear Chemistry and Technology 33. Prof. Stanislaw Wronski, Ph.D., D.Sc. physical chemistry, inorganic chemistry Warsaw University of Technology chemical engineering 27. Jan Skajster Institute of Nuclear Chemistry and Technology 34. Prof. Zbigniew P. Zag6rski, Ph.D., D.Sc. chemical technology Institute of Nuclear Chemistry and Technology physical chemistry, radiation chemistry, 28. Prof. Irena Szumiel, Ph.D., D.Sc. electrochemistry (Co-chairman) Institute of Nuclear Chemistry and Technology 35. WiesJaw Zielinski, M.Sc. cellular radiobiology Institute of Nuclear Chemistry and Technology staff representative 29. Prof. Jan Tacikowski, Ph.D. (Co-chairman) 36. Wanda Zmijewska, Ph.D. Institute of Precision Mechanics Institute of Nuclear Chemistry and Technology physical metallurgy and heat treatment of metals analytical chemistry
30. Prof. Marek Trojanowicz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology analytical chemistry
HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (1995-1999)
1. Prof. Maria Kopec, Ph.D., D.Sc. 2. Prof. Antoni M. Dancewicz, Ph.D., D.Sc. Institute of Haematology and Blood Transfusion Institute of Nuclear Chemistry and Technology hematology, radiobiology biochemistry, radiobiology RADIATION CHEMISTRY AND PHYSICS RADIATION TECHNOLOGIES
felt BLAtf RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 19 PHOTOOXIDATION OF METHIONINE DERIVATIVES IN AQUEOUS SOLUTIONS
Krzysztof Bobrowski, Gordon L. Hug", Bronislaw Marciniak2' 11 Radiation Laboratory, University of Notre Dame, Notre Dame, USA 2/Adam Mickiewicz University, Poznan, Poland
Neighbouring groups appear to have a major influence from the quenching events. Fig.l shows a spectral on the course of oxidative attack on organic sulfur resolution at time delay of 150 ns following the compounds. This is illustrated by a large variation in quenching of triplet CB by methyl ester of methionine the primary quantum yields of products following the at pH 6.44. From the concentration profiles, quantum quenching of benzophenone triplets by multifunctional yields for the intermediates were determined. Table 1 thioethers [1-6]. When triplet states oxidize thioethers, shows quantum yields of transients following the total there is a branching of processes with electron transfer quenching of the CB triplet by methionine derivatives, extrapolated to the end of the laser flash. Branching followed by back electron transfer, escape of radical ions or proton transfer and escape of neutral radicals. AA The factors contributing to the relative importance of these reaction channels are of interest both for basic Composite 1h chemistry and for biological systems. • Data In this work we investigate how the escape of 1 0.030 o Kely! radical radical ions from the reaction cage is affected by the stability of the species representing the nominal sulfur A Table 1. Quantum yields of transients following the total quenching of the CB triplet, extrapolated to the end of the laser flash Quencher pH N-Ac-Met-NH2 6.60 0.19 0.07 0.088 0 5.3' 0.39 0 *0.04 0.17 H-Met-OMe 6.4" 0.39 0 =0.04 0.20 9.89 0 0.43 0.04 0.28 H-Met-NH2 5.24 0.38 0 0.07. 0.12 9.74 0 0.48 0.10 0.28 Met-Gly 6.0 0.39 RO.OI 0.02 0.15 11.1 0.06 0.55 0.01-0.04 0.51 Gly-Met 5.93 0.25 0.13 0.19 0 10.9 0.08 0.32 0.19 0 5.2 0.15 0.18 0.19 0 Pro-Met 7.42 0.14 0.18 0.18 0 11.1 0.23 0.38 0.06 0 ' Average of two or more independent experiments v/ithin a narrow range ofpH's about the nominal pH. The experiments were independent in the sense that they performed with different operators and solutions and different times, but with the same laser system. 20 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 3CB* "(-NHa)" CT, CT2 CT, NH, CBH-... r CB'«... CB"-... S*- ! "CH, "bET *CH, NHo CBH- + aS "sep CBH- + CB + k' CB+ NH0 CB" CBH- S+- r- CB- (S,N)+ Scheme ratios were evaluated for the decay of the charge- nitrogen electron pair. A modified scheme of quenching transfer complex by the competing processes of back including an additional channel for the decay of CT electron transfer, proton transfer and escape of radical complex was proposed to account for the pH effects ions. A systematic decrease was observed in the observed. quantum yields for the escape of radical ions along with a correlated increase in the proton-transfer yields. References The enhanced propensity of the sulfur radical cations [1]. Marciniak B., Bobrowski K., Hug G.L.: J. Phys. Chem., 98, to deprotonate is due to deprotonation at the carbon 4854-4860(1994). adjacent to the sufur-cationic site and at the unsubsti- [2], Bobrowski K., Marciniak B., Hug G.L.: J. Am. Chem. Soc, tuted amino group when present. The involvement of 114, 10279-10288 (1992). [3]. Marciniak B., Hug G.L., Bobrowski K., Kozubek H.: J. Phys. protons on the amino groups was implicated by the Chem., 99,13560-13568(1995). correlation of the quantum yields of ketyl radical [4]. Hug G.L., Marciniak B., Bobrowski K.: J. Phys. Chem., 97, formation in the photochemistry experiments with the 11937-11943(1996). rate constants for the reaction of the CB radical anion [5]. Bobrowski K., Hug G.L., Marciniak B., Miller B., Schoneich with the sulfur-containing substrates in pulse radi- Ch.: J. Am. Chem. Soc, 119, 8000-8011 (1997). olysis experiments. With this reaction channel it is [6]. Hug G.L., Marciniak B., Bobrowski K.: J. Photochem. Photo- now possible to understand the formation of (S.'. N)+ biol., 95, 81-96(1996). [7]. Monig J., Goslich R., Asmus K.-D.: Ber. Bunsenges. Phys. at pH's below the pKa of the amino groups of the Chem., 90,115-121 (1986). substituted methionines. After an intra-cage proton [8]. Bobrowski K., Pogocki D., Schoneich Ch.: J. Phys. Chem., 97, transfer the electron pair on the amino group becomes 13677-13684(1993). free, and the sulfur-centered radical cation can form [9]. Hug G.L., Bobrowski K., Kozubek H., Marciniak B.: Photo- a three-electron, two-centered bond with the free chem. Photobiol., 68, 785-796 (1998). HYDROXYL RADICAL INDUCED OXIDATION OF a-(METHYLTHIO)ACETAMIDE IN AQUEOUS SOLUTIONS Pawet Wisniowski, Krzysztof Bobrowski The *OH-induced oxidation of a-(methy!thio)acet- sulfur-centered radical cations (>S+*) indicated amide (a-MTA) does not proceed at neutral pH via through the lack of formation of the intermolecularly RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 21 three-electron-bonded (S.\ S)+ radical cations even at to the yields of formaldehyde obtained after y-nradi- high concentration of the solute. This is in contrast to ation of N2O-saturated aqueous solutions containing experiments performed in acidic pH where almost 10"2 M of (alkylthio)ethanol derivatives [2,3]. The exclusive formation of the dimeric radical cations of mechanism leading to the formation of formaldehyde a-MTA was observed. These obsevations were involves also an intramolecular hydrogen transfer rationalized by the occurrence of two competitive within hydroxysulfuranyl radical from the adjacent processes of hydroxysulfuranyl radicals: proton- hydroxyl group(s) [2]. catalyzed elimination of hydroxide ions and intra- Table 1. Radiation chemical yields (G values) of carbon dioxide molecular hydrogen transfer via a six-membered (CO2) obtained after y-radiation of N2O-saturated aqueous transition structure [1]. The latter process leads to the solutions at various pH's containing 10'2 M a-(MTA). formation of imine radicals. These radicals are pH G(CO2) PH G(CO2) expected to undergo ^-fragmentation into a-(alkyl- 0 0 3 1.66 thio)alkyl radicals and isocyanate. In aqueous sol- 0.5 0 3.5 1.65 utions isocyanate undergoes simultaneous hydrolysis 1 0 4 2.02 and the Hoffman rearrangement, leading to ammonia 1.5 0.24 4.5 1.95 and carbon dioxide. 1.8 0.65 5 1.64 2 Decreasing yields of carbon dioxide with parallelly 0.76 6 1.95 2.5 1.03 7 1.73 increasing yields of inter-molecularly three-electron- bonded (S.\S)+ radical cations can be expected with decreasing pH. This conclusion is based on an increasingly favorable competition of proton attack 0.3. • • • resulted in the formation of sulfur-centered radical cations (>S+#) (which does not lead to carbon dioxide) / • • with an intramolecular hydrogen transfer. In the 0.2- /• present study the quantitative carbon dioxide analysis • was achieved employing a gas chromatographic head- 0.1 . space technique. The G-values were calculated from J the straight lines derived by plotting the measured 1 carbon dioxide concentrations vs. applied radiation 0.0- dose for five different doses. The final yields of carbon dioxide, measured as a function of pH, after y- irradiation of N2O-saturated aqueous solutions con- pH 2 Fig.l. Efficiency of decarboxylation (expressed as G(CO2)cxp/ taining 10" M of a-MTA, are summarized in Table 1. 2 High CO yields (-1.7-2.0) are derived for experi- GCOH)PH in N2O-saturated solutions of a-MTA (10" M) at 2 various pH. ments carried out over the pH range 4-7, accounting for ca. 30% of initially available hydroxyl radicals. References For better asssessment of decarboxylation yields, the [1], Bobrowski K., Hug G.L., Schdneich Ch., MarciniakB., Wtinio- G(CO2) values were normalized to the total initial wski P.: Res. Chem. Interm., 25 (1999) (in print). radiation chemical yield of hydroxyl radicals at [2]. Schoneich Ch., Bobrowski K.: J. Am. Chem. Soc, 115, 6538- 6547 (1993). a particular pH. The respective data are illustrated in [3]. Pogocki D., Wisniowski p., Bobrowski K.: manuscript in prep- Fig.l. It is remarkable that the yields of CO2 are close aration. SILVER CLUSTERS IN ZK-4 ZEOLITES Jacek Michalik, Jong-Sung Yu", Jaroslaw Sadlo PL9902196 " Hannam University, Taejon, Korea n+ Introduction stabilize paramagnetic silver hexamer - Ag6 , where The size-dependent properties of metal nanoclusters are n = 1,3,5 for paramagnetic species [1-4]. It was of considerable interest with respect to '.fundamental postulated that hexameric silver clusters are trapped knowledge and possible applications in catalysis and inside sodalite cages of zeolite A [2]. However, silver nanotechnology. The unique cluster properties originate hexamers have been never observed in zeolite X or Y from the size-dependent distribution of the electron although the faujasite structure is also composed with energy levels and in quantum-size effects. sodalite cages [5]. Silver exchanged Na-A and K-A zeolites reduced To understand the reason of such differences we chemically or radiolytically show a unique ability to studied radiation induced silver clusters in ZK-4 22 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES zeolites which have the same framework structure as corresponds to a 20% decrease of the total cation zeolite A but Si/Al ratios higher than 1 and therefore capacity, the ESR spectrum at 230 K reveals, besides a lower cation capacity. Ag2"1" singlet, a weak multiplet O and a singlet M The structure of zeolite A is composed of sodalite (Fig.2a). The spectrum O is too weak for a satisfactory cages and a-cages with diameters 0.66 nm and simulation and we were unable to assign it to any 1.14 nm, respectively. The entrance to the sodalite unit particular silver cluster. Isotropic singlet M with is only possible through a hexagonal window with giso= 2.0086 is characteristic for a Conduction Electron a diameter of 0.23 nm. There are three preferential Spin Resonance (CESR) signal, which represents sites for Ag+ cations in zeolite A structure: first in the metallic particles with diameters in the range 3-10 nm. plane of the hexagonal window, second - slightly The formation of metallic clusters proves that displaced from the hexagonal window into sodalite migration of silver atoms along zeolite channels is cage and third - displaced into a-cage. effective even at 230 K. In dehydrated zeolites with Results and discussion low cation capacity the channels and cages are quite empty which should facilitate silver atom migration. Linde 4A zeolite with silver loadings higher than 2 Ag+ per unit cell dehydrated at 130°C and y-irradiated at 77 K shows after annealing at 230 K the ESR AgNa-ZK-4/dehydrated n+ septet: Ais0 = 6.7 mT, giso = 2.0033 of Ag6 cluster located inside sodalite cages (Fig.la). The same signal is observed in AgNa-A (Si/Al = 1) zeolite synthesized in Hannam University laboratory. However, its inten- sity at 230 K is about four times lower than in a com- mercial Linde 4A zeolite. Because of that a dominant signal in the synthetic sample is an anisotropic singlet: Si/Al = 1.2 gii = 2.316 and g± = 2.056 of Ag2+ cations. AgNa-A/dehydrated Uncle 4A r • I Ag2+:g,, / A synthetic A I A b JW— Ag2 275 300 325 350 375 LU [mT] Fig,2. ESR spectra of dehydrated ZK-4 zeolites with a) Si/Al = 1.2 and b) Si/Al = 1.4 irradiated at 77 K and annealed at 230 K. i * In irradiated zeolites with Si/Al = 1.4 after an- nealing at 230 K, the ESR spectrum shows a singlet of 2+ 300 320 340 360 380 Ag cation and a triplet with Aiso = 31.6 mT and giS0 = + [mT] 1.991 of silver dimer, Ag2 (Fig.2b). The outer lines of Fig. I. ESR spectra of dehydrated a) Linde 4A zeolite and b) triplet show additional splittings which probably result synthetic zeolite irradiated at 77 K and annealed at 230 K. + from an interaction between Ag2 and the nearby In AgNa-ZK-4 zeolites hexameric silver is not cation, Ag+. The central line of triplet is splitted into stabilized at all. When Si/AI ratio is 1.2, which two lines by a second order interaction. It is interesting RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 23 that a further increase of temperature does not lead to It is worth noting that in zeolites with lower cation the formation of a silver trimer Ag32+ but to the decay capacity (Si/Al = 1.4) silver tetramers are formed at of the dimer. lower temperature and decay faster than in zeolites The ESR results clearly show that even a small with higher cation capacity (Si/Al = 1.2) (Fig.3). The decrease of zeolite cation capacity (higher Si/Al ratio) intensities of Ag43+ quintet and Ag° doublet are strongly affects a silver agglomeration process inside comparable already at 135 K in ZK-4 with Si/Al = 1.4, zeolite cages. Two factors could be responsible for whereas in the sample with Si/Al = 1.2 Ag° doublet is that: still dominant at 140 K. However, in zeolite with Si/Al + 1. smaller amount of Ag cations located primarily in = 1.2, Ag4 is observed even at 250 K when for a sodalite cages. higher Si/Al ratio the silver tetramer decays complete- 2. less Na+ cations blocking hexagonal windows ly above 230 K. The kinetics of Ag° transformation which makes easier Ag° migration out of sodalite and Ag43+ decay clearly shows that atom and cluster cages. migration is faster in zeolites with lower cation + As a result smaller cation species (Ag2 ) are formed capacity. 3+ inside (3-cages and bigger metallic clusters (Agn) are Silver tetramers, Ag4 are also formed in y-irradi- stabilized on the surface of zeolite crystallites. ated AgNa-ZK-4 zeolites exposed to methanol. The 3+ In hydrated zeolites AgNa-ZK-4 or in zeolites behaviour of Ag4 clusters in the presence of meth- exposed to water after dehydration silver tetramers are anol is similar as in the presence of water. stabilized effectively for a sample with Si/Al = 1.2 as To answer the question whether water or methanol well as with Si/Al = 1.4. In AgNa-ZK-4 zeolites molecules are involved in Ag43+ stabilization in zeolite exposed to D2O and y-irradiated at 77 K initially structure the Electron Spin Echo Envelope Modulation formed Ag° atoms (ESR doublet: Aiso = 55.7 mT, giso = (ESEEM) studies have been carried out. This method 3+ 1.992) are gradually transformed to Ag4 clusters is particularly well adapted for studying powder (ESR pentet: Ais0 = 13.9 mT, giso = 1.968) during spectra in high surface area solids. By analyzing the thermal annealing (Fig.3). The agglomeration modulation signal associated with a very weak proceeds by the reaction with Ag+ cations: electron-nuclear dipolar interaction it is possible to locate a paramagnetic species with respect to various surface atoms and with respect to adsorbate molecules. AgNa-ZK-4/D2O AgNa-ZK-4/D2O Si/Al = 1.2 Ag° Si/Al = 1.4 Ag° 135 K 140 K I 1 1 i i i I 11 1 1 1 l 275 300 325 350 375 275 300 325 350 375 [mT] [mT] Fig.3. ESR spectra of AgNa-ZK-4/D2O with a) Si/Al = 1.2 and b) Si/Al = 1.4 irradiated at 77 K. 24 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES In other words the analysis of modulation makes it wards Ag43+ which positions hydroxyl groups close to possible to determine the coordination geometry of hexagonal windows. The Ag43+ cluster interacts with paramagnetic species with adsorbate molecules. In one methanol molecule in zeolite with Si/Al = 1.2 and ESEEM spectroscopy specifically deutered molecules with two methanols for Si/Al = 1.4. are often used to study ligand orientation. To study Conclusion 3+ coordination geometry of Ag4 cluster we exposed In contrast to AgNa-A zeolite, hexameric silver is not AgNa-ZK-4 zeolites to D2O or CD3OH and CH3OD stabilized in AgNa-ZK-4 zeolites although the lattice adsorbates. From the simulations of the modulation structure of both zeolites is identical. It proves that patterns on the echo decay curves we determined the relatively small changes in Si/Al ratio affects drasti- number of deuterium nuclei and the interacting cally the silver agglomeration process in zeolites with 3+ distances between unpaired electron in Ag4 cluster the same framework structure. It was postulated earlier n+ + and deuterium nuclei in all studied systems. The data that for Ag6 formation six Ag cations have to be are summarized in Table. present in sodalite cage before y-irradiation. The 3+ Table. Results of ESEEM simulations for deutered adsorbates formation of Ag4 cluster in AgNa-ZK-4 zeolites AgNa-ZK-4 N atoms R[nm] A [MHz] exposed to water suggested that in ZK-4 with Si/Al = 1.2 and 1.4 only four Ag+ cations are located D O 2 primarily in sodalite cages. Si/At = 1.2 2 0.265 0.23 Si/Al = 1.4 4 0.332 0.025 The differences in coordination geometries of CDjOH adsorbed molecules revealed by ESEEM for zeolites Si/Al=1.2 3 0.392 0.02 with Si/Al = 1.2 and 1.4 can be related to different Si/Al =1.4 6 0.410 0.04 cation capacities. In zeolites with the lower cation CH3OD capacity (higher Si/Al ratio) there is a more free space Si/Al =1.2 1 0.345 0.03 in the cages, therefore a bigger number of adsorbate Si/Al = 1.4 2 0.385 0.01 molecules can interact directly with the silver + The simulated spectra indicate that in AgNa-ZK- tetramer. For the high cation capacity, Na co-cations 4/D O with Si/Al = 1.2 tetrameric silver interacts with block some hexagonal windows and less adsorbate 2 molecules is able to migrate to the positions making an one D2O molecule at a distance of 0.265 nm sug- gesting that both species are located in the same interaction possible. 3+ sodalite cage. For Si/Al = 1.4, Ag4 interacts with two References more distant water molecules. They are located outside [1]. Hermerschmidt D., Haul D.: Ber. Bunsenges. Phys. Chem., 84, the sodalite cage, possibly close to the hexagonal win- 902 (1980). dows, with their molecular dipoles oriented towards [2]. Morton J.R., Preston K.F.: J. Magn. Reson., 68, 121 (1986). silver cluster inside P-cage. [3]. Michaiik J., Kevan L.: J. Am. Chem. Soc, 108, 4247 (1986). [4], Schoonheydt R., Leeman H.: 3. Phys. Chem., 93,2048 (1989). The arrangement of methanol molecules in a-cages [5]. Sadlo J., W^sowicz T., Michaiik J.: Radiat. Phys. Chem., 45, is similar. Their molecular dipoles are oriented to- 909 (1995). ESR STUDY OF POLYCRYSTALLINE TRIPEPTIDES Grazyna Strzelczak, Krzysztof Bobrowski, Jacek Michaiik io Knowledge of the reaction mechanisms and kinetics of of methionine residues (Met-Gly-Met, Met-Met-Met, radical processes in biological relevant compounds Met-Gly-Met-Met) in order to provide comparisons i§ such as amino acids and oligopeptides is a necessary with dipeptides and homopeptides containing methionine. jQ_ prerequisite to better understanding the processes oc- The gamma irradiated at 77 K polycrystalline curring in more complex systems of biological import- methionine-containing tripeptides with doses of 5 kGy ance, i.e. polypeptides and proteins. were investigated by electron spin resonance spectro- In our previous works [1,2,3] we have established scopy. that the character of radicals produced in dipeptides The radicals formed were identified over the containing methionine depends on the location of the temperature range 77-293 K using a Bruker ESP-300 methionine residue with respect to the terminal spectrometer equipped with a cryostat and a variable functions. temperature unit. In this work, we extend the study to polycrystalline The ESR spectra were analysed by a computer oligopeptides containing methionine in varied location simulation (using ESR-software kindly provided by with respect to the terminal functions (Gly-Gly-Met, Dr. D.L. Dulling from NIEHS LMB National Institute Gly-Met-Gly, Met-Gly-Gly) and with a varied number of Health, USA). RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 25 Carbon dioxide analysis was performed by a gas Generally, radicals formed by hydrogen abstraction chromatography technique (Perkin Elmer 8700). from the C-terminal amino acid residue are observed Anion radicals formed by the addition of an at room temperature. (Fig.2) [4]. electron to the carbonyl group of the peptide bond are the major components observed at 77 K in all peptides 293K and a second anisotropic singlet assigned to the mono- meric sulphur radical cation (S+"). Warming the samples of oligopeptides containing adjacent methionyl residues (Met-Met-Met, Met-Gly- Met-Met) to 110 K we have observed dimeric radical -CONH-CH-COO" cations with an intramolecular three electron bond Met-Met-Met 95 K -CONH-C-COO" J\ CH, CH2 S CH, 2,5 mT Fig.2. Experimental ESR spectra of H-abstracion radicals at the o> carbon: 1. for peptides with C-terminal glycine residue (top), 2. for peptides with C-terminal methionine residue (bottom). However, in Met-Gly-Met and Met-Gly-Met-Met the most stable species at room temperature are H- abstraction radicals from the internal glycine residue 110 K x4 / —~T-CONHT—• / /S"""S\ N \ / H3C CH3 Fig.l. Experimental ESR spectra of: superposition of anion radical and monomeric sulphur radical cation (S+1) (top) and dimeric radical cation (S.'.S)+ (bottom). Deamination and decarboxylation radicals and Fig.3. Experimental ESR spectra recorded at room temperature for a(alkylthio)alkyl radicals (in oligopeptides with N-ter- peptides Met-Gly-Met and Met-Gly-Met-Met. minal metionine residue) were detected at 180-250 K. (Fig.3). Formation of these radicals is due to the low Carbon dioxide was identified in all oligopeptides value of dissociation energy of a-C-H bond (DC-H) in (Table 1). the glycine residue. Table 1. Yields of decarboxylation (experessed in G^units) in poly- o crystalline methionine-containing peptides Peptide G iA/WW>— NH-nbH-C-vtw Gly-Gly-Met 2.31 Gly-Met-Gly 0.93 Met-Gly-Gly 2.69 Met-Gly-Met 0.75 Met-Met-Met 1.03 Met-Gly-Met-Met 2.53 26 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES This value was calculated by an ab initio study in References a series of model glycyl peptides [5], The DC-H for the [1]. Burlinska G., Wajowicz T., Michaiik J., Bobrowski K.: Mol. 1 internal glycyl residue was established as 348 kJ mol" . Phys. Rep., 6,134(1994). The low value of DC-H is due to the captodative [2]. Burlinska G., Michaiik J., Bobrowski K.: Radiat. Phys. Chem., stabilizing effect of the electron-donating XNH- and 43,425(1994). electron-withdrawing -C(=O)Y groups. It means that [3], Strzelczak-Burlinska G., Bobrowski K., Pogocki D., Michaiik the oc-C position will be vulnerable to H-atom J.: Nukleonika, 42,2,333 (1997). [4], Strzelczak G., Bobrowski K., Kozubek H., Michaiik J.: Nukleo- abstraction by radicals, for which the parent nika, 44, 3 (1999) (in press). compounds have bond dissociation energies in excess [5], Armstrong D.A., Yu D., Rauk A.: Can. J. Chem., 74, 1192 of350kJmor'. (1996). EPR STUDY OF PARAMAGNETIC PRODUCTS IN DRUGS FOLLOWING y-STERILISATION Hanna B. Ambroi, Ewa M. Kornacka, Barbara Marciniec17, Grazyna Przybytniak :CO " Department of Pharmaceutical Chemistry, University of Medical Science, Poznan, Poland :o j CO Various drugs, cytostatic (MP, AZA, AA, IA), anti- [1,2]. One of the most critical point of the radiation cancerigenic (FA, TX), regulating blood circulation treatment is a possibility of chemical and physical (NF, NT, NM) and others, have been investigated by alterations which can lead to some undesirable EPR for searching if they contain or can easily form changes, e.g. to a loss of their biological activity [3,4]. stable paramagnetic species following sterilisation by We report an EPR study of free radicals trapped in ionising radiation. The method has been particularly microcrystalline lattices of powdered drugs, detected recommended for unstable substances, thermolabile or in irradiated samples. They are characteristic "solid- chemically reactive ones, which can hardly be state spectra", often composed and anisotropic. The sterilised by other methods (thermal or chemical) results of the EPR examinations are displayed in Table 1. Table 1. Data of generated free radicals in irradiated drugs Symbol name Radical concentration g Factor Comments spins g^'x 10'6 [KP] Clozapine 4.3 2.0044 singlet AHPP= 1.07 mT [IB] Indobufen 12.8 g'= 2.0025 probably fine splitting g" = 2.0023 doublet, a(H) = 1.54 mT [TX] Tamo-xifen Citrate 4.6 2.0066 narrow singlet AHPP = 0.91 mT [KK] Ketoconasole 9.0 g' =2.0035 a(H)=1.76mT g"= 2.0026 poor resolution [KAS] Mesalazine 12.8 2.0037 broad singlet AHPP = 2.32 mT gi = 2.0096 the same shape of spectrum prior and [NT] Nitrendipine 11.9 gl = 1.9845 post-irradiation, a(N) = 1.5 mT giso = 2.0012 gi = 2.0097 [NF] Nifedipine 14.4 gl =1.9848 signal similar as in VI giso = 2.0014 g'j: = 2.0097 [NM] Nimodipine 2.1 g1l= 1.9852 some features similar as in VI and VII &» = 2.0015 g"= 2.0048 [FA] Flutamide 6.0 2.0046 singlet, AHFP= 1.06 mT [IA] Ifosfamide 45.4 2.0030 a(N)=1.25mT [AA] Amino-giutethimine 5.6 2.0051 at least two radicals of various life time [MZ] Metronidazole 6.2 2.0033 broad singlet and resolved spectrum, a(2N) = 0.96 mT [OZ] Ornidazole 5.1 g' = 2.0033 a(2N) = 0.96 mT, AHPP = 2.21 mT g" = 2.0050 broad singlet gl =2.0236 [MP] Mercaptopurine 11.0 gi = 2.0048 anisotropic signal gi» = 2.0110 [AZA] Azathioprine 8.9 giso = 2.0051 anisotropic signal RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 27 The concentrations of stable free radicals present in patients in aqueous solutions cannot exist any longer irradiated samples vary from 2 to 45 x 1016 spins g"1. as free radicals if they are carbon-, oxygen- and The higher concentration of radicals, generated at the sulphur-centred ones. They convert fast into stable same absorbed dose of radiation, proves a higher non-paramagnetic products. The only nitroxy radicals sensitivity of the drug for y-irradiation, however the can be stable longer, e.g. for hours, as it is known from efficiency of microcrystalline matrices for trapping spin trapping experiments. In order to assess if the paramagnetic species has to be considered as well. radicals remain a threat to the health of patients, their Radical populations and structures which determine structure and concentration in drugs sterilised by y- their reactivity depend on specific character of the radiation as well as their life-time should be studied chemical and consequently biological properties of the [5]. drugs. There is no doubt that the influence of some substituents on spin population is stronger than others. References The most significant group increasing radical concen- [1]. Dam A.M., Gazso L.G., Kaewpila S., Maschek I.: Radiat. Phys. tration is the presence of P = 0(0), carboxyl, ester or Chem., 47, 515-517(1996). sulphur-containing substituents. However it is not [2]. Varshoey L., Patel K.M.: Radiat. Phys. Chem., 43, 471-480 (1994). possible to predict the radiation effects and stabilities [3], Jacobs G.P., Wills P.A.: Radiat. Phys. Chem., 31, 685-691 of radicals even if compounds are similar, as minor (1988). changes in molecular structure can have a significant [4]. Phillips G.O.: IAEA Bulletin, 1, 19-23 (1994). influence on observed processes. It should be kept in [5]. Marciniec B., Ambroi H., Ogrodowczyk M., Przybytniak G., mind that y-sterilised medicines which are taken by Kornacka E.: Die Pharmazie (in press). MODIFICATION OF DNA RADIOLYSIS BY DTT AT CRYOGENIC TEMPERATURES Hanna B. Ambroz, Ewa M. Kornacka, Grazyna Przybytniak PL9902199 In an indirect effect of ionising irradiation on DNA, \ DPPH thiols are known as efficient radioprotectors which not only scavenge hydroxyl radicals but also repair dam- ages following hydrogen donor processes [e.g. 1,2]. (A) The role of these species on a direct effect of radiation is less explored and ambiguous. The aim of our study was to find the consequences of the dithiotreitol (DTI1) influence on DNA radiolysis at low tempera- tures. It is expected that in frozen aqueous solutions DNA together with thioalcohol are at high concentra- tion in the separated phase from aqueous aggregates, i.e. microcrystals of water and the formation of *OH in ice do not effect changes observed in DNA [3]. The participation of DTT in the DNA radiolysis at concentrations of 10, 100 and 1000 mM was studied by EPR at temperatures ranging from 77 K to 223 K. An example of recorded spectra is depicted in Fig.l. A quantitative analysis of the results applying APOLLO software [4] reveals that thymine intermediates to some degree depend on presence of DTT as an increase of an thioalcohol concentration to 1000 mM results in the reduction of protonated radical anion TH" (5-thymyl) to a half of the initial population (Fig.2). On the other hand, on annealing between 193 and 203 K, the thiyl radical RS* is formed due to repair processes of DNA. It seems that the TH* radical is then converted (at least partially) into a TH2 stable 2.5 mT product. The other possible mechanism is an electron transfer from primary product T~* to RSH, protonation of the formed intermediate, and subsequently the Fig.!. EPR spectra of irradiated to a dose of 10 kGy frozen aqueous solutions of DNA (100 mg/ml) in presence of 100 mM DTT production of RS* and H2. As can be distinctly seen in (A) at 77 K, (B) at 183 K, (C) at 203 K and (D) at 223 K. 28 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES Fig.2C, for high concentrations of DTT the thiyl radical is formed also as a primary product and its decay starts at about 160 K. It influences the total radical concentration which varies depending on DTT contents (Fig.2A, B and C), and reduces population of RS* at higher temperatures. Contrary to Sevilla's suggestions [5] no reaction of guanine radical cation with thiolate group G+* + RS* -» G + RS" is observed. The reason of the low reactivity of DTT towards DNA is probably due to lack of electrostatic forces between DTT and DNA. The cationic thiols (e.g. amino groups are present in their molecules) behave as counterions, condense in the vicinity of nucleic acids and demonstrate a high ability in the protection of DNA [6]. The DTT molecule is uncharged and under such circumstances its localisation at the DNA chain is less favoured. References [1]. Fahey R.C.: Pharmac. Ther., 39, 101-108 (1988). [2]. Priitz W.A.: Int. J. Radiat. Biol., 56, 21-33 (1989). [3]. Gregoli S., Olast M., Bertinghamps A.: Radiat. Res., 89, 238- 254(1982). 140 160 180 200 220 [4]. Dusemund B.: Ph.D. Thesis, University of Saarland 1997. temperature / K [5], Wang W., Sevilla M.D.: Int. J. Radiat. Biol.,66,683-695 (1994). Fig.2. The total and component radical concentrations formed in [6]. Zheng S., Newton G.L., Ward J.F., Fahey R.C.: Radiat. Res., frozen aqueous solutions of DNA in presence of (A) 10 mM 130, 183-193 (1992). DTT, (B) 10 mM DTT and (C) 1000 mM DTT. The curves represent: total radical cone. (-•-), thiyl radical (-V-), thymyl radical (-+-) and other radicals (-•-). THEORETICAL STUDY ON DECOMPOSITION OF ETHYL CHLORIDE IN DRY AIR UNDER INFLUENCE OF ELECTRON BEAM iO Henrieta Nichipor1', Elena Dashouk", Andrzej G. Chmielewski, Zbigniew Zimek, Sylwester Bulka 11 IRPCP, Academy of Sciences of the Republic of Belarus, Minsk-Sosny, Belarus 15 The decomposition kinetics of C2H5C1 under the C2H5C1 + O :=> OH + products; k=l .2-10* cmVmolec. s electron beam influence have been published recently (3) in [1]. Experiments were performed in dry air under In the published work [1] the transformation pressure P = 1 at and at 300 K. The initial C H C1 2 5 mechanism of C H and C2H4CI to final products, like concentration was changed in the range 200-2100 ppm 2 5 CO, CO , HC1, has been described. and at a dose level up to 300 kGy was applied. The 2 Having in mind the published results [1] a theoreti- mechanism of C H C1 decomposition process has been 2 S cal model of C H C1 decomposition in dry air under proposed by the authors in [1]. According to their 2 5 the influence of electron beam has been elaborated. assumption, electrons during the ionization process of The different initial C H C1 concentration (200-2100 the gas mixture under treatment are being termalized 2 ? ppm) and a dose within the range 30-300 kGy have and then react with C H C1 in a dissociative 2 5 been used during calculations. The model applies the attachment process following the formula [2]: chemistry of positive and negative ions, their recombi- 13 e + C2H5C1 => C2H5 + Cl"; k=2-7-10- cmVmolec. s (1) nation and chemistry of radicals. Totally 275 reactions for 81 particles have been used in the model. The Cl" ions react in recombination processes with positive ions and became Cl atoms that decompose Computer calculations were performed on the basis of elaborated model for the experimental conditions C2H5C1 in the reaction according to [3]: described in the literature [1] using a Kinetic program. 42 QH5CI + Cl => GH4CI + HC1; k=6.8-10 cmVmolec. s (2) The main positive ions which participate in the + + Another channel of C2H5C1 decomposition can be recombination process are as follow: O2 ; C2HSC1 ; + + described as [4]: NO ; NO2 . The main negative ions are: O2"; Cl"; RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 29 NO2"; NO3"; Cl2"; CO3". The electrons dissociative cant process for the decomposition of C2HSC1 is attachment process to oxygen molecules takes place defined as reaction (2) leading to the following according to the reactions [5]: reaction [6]: 31 6 2 9 + N2=>O2" + N2;k=1.6-10" cm /molec. s (4) O2" + HC1 => HO2 + Cr, k= 1.6-10- cnrVmolec. s (6) 30 6 2 It should also be noticed that even at a low HC1 + O2 => O2" + O2; k=2.5-10- cm /molec. s (5) concentration, when the negative charge from O2" is The O2" ions are being formed as a result of the transferred to NO2 and NO to form the negative ions above reactions. It should be noticed that only small 3 part of electrons takes part in reaction (1). Reaction (1) NCVand NO3", the formation of Cl" ions takes place as was found as an important channel responsible for a result of the following reactions [6]: 9 3 C2H5CI decomposition according to the assumption NCV + HC1 =>cr + HNO2;k=1.4a0- cm /molec.s (7) 12 described in the literature [1]. A much more signifi- NO3" + HC1 => Cr + HNO3; k=10" cnvVmolec. s (8) 10000" Caculated decomposition of ethyl chloride E 204.9 ppm a, a. 344 ppm E 604.9 ppm O 1000 23 1025.9 ppm 1230 ppm 1489.7 ppm .0i 1795ppm 2113.2 ppm 10 15 20 25 30 35 Dose [MRad] 10000T Electron beam decomposition of ethyl chloride I 1000 Q- vi u O U 15 20 35 Dose [MRad] Fig.l. Concentration of ethyl chloride vs. electron beam dose level. A - calculated data, B - experimental data [1], 30 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES The presence of Cl-ions initiates a chain process in the probable that some important processes have not been gas mixture in the above described experimental included to the theoretical model. As an example it is conditions (1). The recombination process of Cl" ions not quite obvious (no literature data) whether the leads to the formation of CI atoms and then, according C2H5CI" ions can be formed and how they can to reaction (2) to HC1. In the second stage HCI reacts participate in reactions occurring in the gas mixture. with the O2"; NO2"; NO3" negative ions and then Cl- The computer calculations revealed that the ions are formed again. Due to the chain reaction the formation of HCI increases the decomposition process +10 +n concentration of Cl atoms grows up to 10 -10 of C2H5CI due to the reaction of HCI with the negative 3 molec./cm leading to a significant decomposition of O2"; NO2" and NO3" ions. Slowing down of the C2H5CI within the dose range up to 300 kGy. decomposition process of C2H5C1 by a higher HCI According to experimental data this decomposition concentration at a higher dose level was suggested by takes place at a dose below 50 kGy, when the chain the authors of experimental work [1]. This could be reaction is not intense enough. We can explain this by possible if the following reaction would happen: the formation of Cl atoms caused by the reaction of + e + HCl =>HCr (11) C2H5C1 (the main positive ion), with O{ (the main 9 3 negative ion) at a low dose level. As it was proved with rate constant higher than 10" cm /molec. s. But, experimentally such recombination may lead to the as it was published in the literature [7], for the electron following products: energy range 0.1-2 eV, the electron reacts with HCI according to the formula: + (9) e + HCI => H + C1-; k=10"ll-l(r10 cnrVmolec. s (12) (10) Therefore HCI is not slowing down the decompos- Results and discussion ition process of C2HSC1 in the experimental conditions The calculation results of the decomposition kinetics described in the literature [1]. This is also proved by of C2H5Cl in dry air under the influence of electron the results of calculations performed with the elabor- beam are displayed in Fig.lA. Fig.IB shows the data ated model. obtained experimentally [1]. The temperature, gas pressure and range of initial C2H5CI concentration and References dose range were equal. As it can be noticed from [1]. Vitale S.A. et al., Radiat. Phys. Chem., 49,421 (1997). a comparison of the calculated and experimental data, [2]. Petrovie Z. L. et al., J. Chem. Phys., 90, 3145 (1989). the elaborated model allows to obtain quantitatively [3]. Kaiser E.W. et al., J. Phys. Chem., 96, 303 (1992). [4]. Kerron J.T. et al., J. Phys. Chem. Ref. Data, 2, 467 (1973). similar results as in experiments, but the degree of [5], Penetrante B.M. etal., Phys. Lett., A209, 69 (1995). C2H5CI decomposition is significantly higher in the [6]. Albritton D.L., Atomic Data Nucl, Data Tables, 22, 1,1 (1978). experimental results at a certain dose level. It is quite [7]. Petrovic ZX. et al., J. Appl. Phys., 64, 1625 (1989). EFFECT OF SELECTED INORGANIC SCAVENGERS ON RADIOLYTIC DEGRADATION OF 2,4-DICHLOROPHENOL Przemyslaw Drzewicz, Przemyslaw P. Panta, Wojciech Gluszewski, Marek Trojanowicz IS The environmental applications of ionizing radiation solution, dose of radiation and on the presence of IS include the removal of pollutants from industrial flue oxygen or ozone. In real samples of water or wastes gases, degradation of organic pollutants and removal also the presence of naturally occurring scavengers of of heavy metal ions from water and wastewater, as radiation should be taken into account. This was not well as from contaminated soils [1], In case of water discussed extensively in the literature. Bicarbonate is and wastes, among recently published works one can a strong scavenger of e"aq and *OH, whereas the nitrate find papers on the use of ionizing radiation for degra- is a scavenger of e"aq and H' [10]. In case of p- dation of polychlorinated biphenyls [2], removal of chlorophenol both these scavengers did not affect sig- lead and mercury from water [3], for treating a waste nificantly the efficiency of radiolytic decomposition water from molasses processing [4], and for the elim- [8], however, in N2O saturated solutions it was ob- ination of organochlorine in a pulp mill effluent [5]. served that the dehalogenation of monochlorophenols Because chlorophenols belong to the most frequently by y-irradiation is much less effective [6], occurring organic pollutants their radiolytic degrada- 2,4-dichlorophenol (2,4-DCP) belongs to the most tion for environmental purposes was discussed recent- toxic chlorophenols, hence this compound was se- ly in several papers [6-9]. lected for detailed studies of various factors affecting The effectiveness of radiolytic degradation of its radiolytic degradation. It was already shown that chlorophenols depends on the acidity of irradiated pH of irradiated aqueous solution of 2,4-DCP affects RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 31 both effectiveness and mechanism of dehalogenation pH5.1 pH 10.7 [11]. In this work the effect of the presence of the bicarbonate and nitrate scavengers on the radiolysis of 2,4-DCP has been investigated. As a source of y-radiation a 60Co source Issledova- tel with a dose rate of 4 kGy h"1 and a mean energy of 1.25 MeV was used. Aqueous solutions of 2,4-DCP were irradiated in 100 ml glass conical flasks. Deter- minations of products of radiolysis were carried out by reversed phase HPLC with Intersil ODS2 (Chrom- pack) and Spherisorb ODS1 (Knauer) columns and a water/acetonitrile/methanol (40:30:30) eluent con- U LJ 1 taining 2 g I" citric acid, and by gradient ion-chroma- Fig.l. Chromatograms obtained for 20 mg/1 solution of 2,4-di- tography with electrochemical suppression and an chlorophenol irradiated with a lkGy dose at different pH in anion exchange column Ion-Pac ASH from Dionex. aerated solutions. HPLC conditions: Spherisorb ODS1 As it was shown earlier [11] pH of the irradiated column, eluent as mentioned in the text, flow rate 1.5 solutions at doses up to 1 kGy has a significant effect ml/min, injection volume 20 ml, UV detection at 280 ran. Irradiated samples were preconcentrated on Baker phenyl on the efficiency of radiolysis. At higher doses this columns. Observed retention times (min) correspond to: effect is negligible and 2,4-DCP undergoes complete 1.18 - hydroquinone, 1.58 - catechol, 1.9 - phenol, 2.21 - degradation. In the whole examined range, pH affects 2-chlorophenol, 2.60 - 3-chlorophenol, 2.69 - 2,6-dichloro- the mechanism of radiolysis, which is illustrated by phenol, 3.30-2,4-DCP. chromatograms recorded at a 1 kGy dose using the The concentration of these active radicals is also Spherisorb column (Fig.l). From these data and also affected by the presence of various scavengers. In this from those obtained with the Intersil column it was study an effect of the presence of bicarbonate in the found that at pH 3 mostly dihydroxybenzenes and 3- range 50-250 mg/1 and nitrate at 10 mg/1 was investi- chlorophenol are formed. At pH 5 to 7 in larger gated. Aerated 20 mg/1 solutions of 2,4-DCP of pH 7 amounts an unsubstituted phenol in formed, and es- were irradiated using doses from the fraction of kGy pecially a large chromatographic signal was observed up to 10 kGy. The example chromatograms recorded for 3-CP at low radiation doses. At pH 10.7 mostly with the Intersil ODS2 column are shown in Fig.2. As catechol is formed but also a small amount of 2,6- it is indicated by data in Table 1 a dose of 1 kGy is not dichlorophenol was found. Changes of the mechanism sufficient to decompose 2,4-DCP in the presence of of dehalogenation are connected with the changes of the examined scavengers, however, at 5 kGy the concentration of the radicals formed from water at degradation process occurs practically with a 100% different pH. efficiency. 6 B 6 min i 1 Fig.2. Chromatograms obtained for 20 mg/1 solutions of 2,4-dichlorophenol at pH 7 irradiated with a i kGy dose in the presence of 50 mg/1 of bicarbonate (A), 250 mg/1 of bicarbonate (B), and 10 mg/1 of nitrate (C). HPLC conditions: Intersil ODS2 column, eluent as mentioned in the text, flow rate 1.5 m!/min, injection volume 20 ml, UV detection at 280 ran. Irradiated samples were preconcentrated on the Baker phenyl columns. Peak assignment: 1 - resorcinol, 2 - phenol, 3 - 2-chlorophenol, 4 - 3-chlorophenol, 5 - unknown, 6 - 2,4-DCP. 32 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES Table 1. Efficiency of radiolytic degradation of 2,4-dichlorophenol tion of bicarbonate where in the whole range of doses in 20 mg/1 solutions at pH 7.0 in the presence of different from 1 to 10 kGy almost complete radiolysis of 2,4- scavengers at various doses of radiation DCP occurs, the main products being catechol and Scavenger Efficiency of degradation, % unsubstituted phenol. The latter is decomposed IkGy 5kGy lOkGy completely at 5 kGy. An increase of bicarbonate 95 100 100 concentration leads to a decrease of efficiency of Nitrate 10 mg/1 53 . 100 dehalogenation and to an increase of concentration of Bicarbonate 50 mg/1 84 100, 100 monochlorophenols in the irradiated samples. At the 150 mg/1 66 100 100 highest bicarbonate concentration level (250 mg/1) 250 mg/1 40 92 100 even at a 10 kGy dose after irradiation phenol, 2-CP The presence of various concentrations of and catechol were found in the solution. bicarbonate at different doses of irradiation essentially affects the products of radiolytic decomposition of In the presence of 10 mg/1 of nitrate at pH 7 at 0.5 2,4-DCP (Fig.3). At pH 7 and at a suitable concentra- kGy dose only a 20% efficiency of radiolysis of 2,4- DCP was observed, whereas at 1 kGy the figure was 1.6X10' 53%. At these low doses among the products of radiolysis an unknown compound (peak 5 in Fig.2) predominated, and beside this also the presence of 2-CP and 3-CP was observed. Incomplete dehalogena- tion was also confirmed by the determination of ionized chloride in a reaction mixture after irradiation with ion-chromatography. At 10 kGy where complete degradation of 2,4-DCP takes place, the only non- decomposed products were hydroquinone and catechol. Results of these studies indicate that the presence 12 3 4 5 6 7 8 10 of scavengers influences the efficiency of radiolytic Dose, kGy degradation of 2,4-dichlorophenol more significantly 1,6x10? than the changes of pH even in a very broad range. -O- 1,2-B«ni«n»d»ol -O-phtnol The degree of dehalogenation and content of unsub- B -A— 2-chfecphenol 1.2x10' stituted phenol and dihydroxybenzenes is a complex function of three factors: pH of irradiated solution, applied dose and the content and kind of present scavengers. This has to be considered in practical application of this technology for environmental purposes. References [1]. Cooper W.J. ed.: Environmental applications of ionizing radi- 123456789 10 ation. Wiley, New York 1998. [2]. Mucka V., Silber R., Kropacek M., Pospisil M., Klisky V.: Radiat. Phys. Chem., 50, 5, 503-510 (1997). [3]. Chaychian M, Al-Sheikhly M., Silverman J., McLaughlin W.L.: Radiat. Phys. Chem., S3, 145-150 (1998). [4]. Gehringer P., Fiedler H.: Radiat. Phys. Chem., 52, 345-349 (1998). [5]. Taghipour F., Evans G.J.: Environ. Sci. Technol., 30, 5, 1558- 1564(1996). [6], Schmid S., Krajnik P., Quint R. M., Solar S.: Radiat. Phys. Chem., 50, 5,493-502(1997). [7], Trojanowicz M., Chudziak A., Bryl-Sandelewska T.: J. Radio- anal. Nucl. Chem., 224, 1-2, 131-136(1997). [8], Bettoli M.G., Ravanelli M., Tositti L., Tubertini O., Guzzi L., Martinotti W., Queirazza G., Tamba M.: Radiat. Phys. Chem., 8 9 10 52, 1-6,327-331 (1998). Dose, kGy [9], Fang X., He Y., Liu J., Wu J.: Radiat. Phys. Chem., S3, 411- Fig.3. Chromatographic signals observed for main the products of 415(1998). radiolytic degradation of 2,4-DCP detected by HPLC at [10]. Cooper W.J., Nickelsen M.G., Meacham D.E., Cadavid E.M., different doses of g radiation for a 20 mg/1 solution of 2,4- Waite T.D., Kurucz C.N.: J. Environ. Sci. Health A, 27, 1, DCP at pH 7 in the presence of 50 (A), 150 (B) and 250 (C) 219-244(1992). mg/1 bicarbonate. HPLC data obtained with the Intersil [11]. Trojanowicz M., Drzevvicz P., Panta P., Gluszewski W.: INCT column. Annual Report 1997, pp. 25-27. PL9902202 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 33 RADIATION YIELD OF MULTI-IONIZATION SPURS IN SOLID ALANINE Zbigniew P. Zag6rski Deposition of ionization energy in spurs, not alanine irradiated with low LET radiations (y rays and resembling the deposition of energy in photochemis- 1-10 MeV electrons), because that can lead to more try, occurs in any state of condensation of the matter, precise comparison between water and alanine radi- because it results from the basis of radiation physics. ation chemistry. The key problem is the determination The independence of single ionization spurs, produc- of debris of alanine molecule which can be ascribed to ing reactive radiolysis products and large spurs with multi-ionization spurs only. Ammonia belongs both to "molecular" products has been considered as a canon debris and to products of deamination in single ioniz- in the early history of radiolysis of water, but it is ation spurs and therefore its yield cannot be used for almost forgotten now, unfortunately also in consider- estimation of multi-ionization spurs. The main product ation of radiolytic mechanisms in other media. One of of multi-ionization spurs is carbon dioxide, because the most frequently investigated recently, apparently participation of decarboxylation of alanine in single- a simple system, i.e. of crystalline a-alanine, is seldom ionization spurs is negligible. Carbon dioxide is there- approached from the point of view of spurs in it, as it fore not produced in single ionization spurs, which are was a common treatment of results in water and the source of deaminated radical anion exclusively. aqueous solutions, several decades ago. Early avail- A study has been carried out to determine the yield able experimental data on the free radical yield of of CO2 in low LET irradiated solid a-L-alanine. deaminated alanine in the function of LET value of Crystals irradiated in air-free ampoules, closed by applied radiation show an astonishing similarity to the silicone rubber membranes, were dissolved in carbon same function in water radiolysis. Yields of the radical dioxide free aqueous solution of perchloric acid, anion CH3C*HCO2~ formed by deamination of alanine introduced by a syringe. Dissolution of crystals was molecule and determined by EPR measurement, necessary, because full recovery of CO2 from the plotted versus the LET values, coincide with radical lattice by thermal treatment is not possible and heating yields in water [1]. Coincidence of the radical anion creates new undesired reactions. Ammonia formed in yield of CH3C*HCO2" vs. LET with those for water all types of spurs is kept bounded in acidic solution. shows the effect of single ionization spurs only, The concentration of carbon dioxide in the gas phase leading to deamination without deeper destruction of above the solution is in equilibrium with its concentra- the affected alanine molecule. Multi-ionization spurs tion in the solution. A sample of the gas phase is taken are formed far from single-ionization sites, in places of for gas chromatographic determination of CO2. the crystalline lattice where ionizing particles are Exactly the same procedure was repeated with reaching their final range and deposit energy in con- unirradiated alanine, with the addition of increasing centrated locations, inside single molecule. The latter amounts NaHCC>3 as the standard of CO2 and results cannot absorb much more energy than causing simple were recalculated on hand of calibration curve. As it deamination without destruction and decomposes into was expected, the radiation yield of carbon dioxide debris. Larger spurs involve two or more neighbouring was independent of the dose as it should be in the case molecules, causing larger islands of debris. The debris of the spur, and amounted both, for the case of cobalt neither produce EPR signals [2], nor show spectro- 60 y radiation and for 10 MeV electrons, to Gnr. = photometric UV-VIS spectra [3,4], At a higher LET 0.95+0.09 per 100 eV of absorbed energy (old units value the participation of multi-ionization increases are used to make easier comparisons with old spur and the effects of single-ionization spurs are lower. At chemistry). One could expect a slight increase of the the same time the concentration of energy in the spur yield at very high doses, when overlapping of spurs originating from heavy ion beams reaches amounts can take place. However, the dose could not be qualifying them as thermal spikes. Single ionization increased more than to 100 kGy, because polymers spurs are formed around thermal spikes, but they show used in the experimental arrangement were lowering their resistance towards radiation and loosing their a slightly deformed shape of the EPR signal due to proper mechanical and rheological properties. The thermally disturbed lattice and also show faster partial determined value of the yield of multi-ionization spur decay with time, being formed in the region of higher is very interesting not only because of the similarity to temperature. At low LET values of radiation, fading of the molecular products yield in water, which are also the concentration of the radicals is negligible for products of multi-ionization spurs. months, but in the case of heavy ion beams, the If the free radical yield of CH3CHCO2", which is starting decay is substantial and requires measure- the product of a single ionization spur, is 3.3 ments to be done immediately after the irradiation. molecules per 100 eV of absorbed energy and the CO The most important question is the quantitative esti- 2 yield is 0.95 (main product of decomposition of mation of participation of multi-ionization spurs in alanine in the multi-ionization spur) per 100 eV of 34 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES absorbed energy, one can estimate that about 80% of References the absorbed energy is distributed in single ionization [1]. Zag6rski Z.P.: INCT Annual Report 1995, pp. 29-31. spurs and 20% in more than one ionization per one [2]. Przybytniak G.K., Zag6rski Z.P.: Orientation of crystals in molecule of alanine. alanine dosimeter assesed by DRS, as seen in EPR spectra evealuation, J. Radioanal. Nucl. Chem., Lett., 212, 373 (1996). Part of the research reported in the paper was [3]. Zagbrski Z.P., Rafalski A.: A thin alanine-PE film dosimetry supported by the International Atomic Energy Agency system with DRS evaluation, J. Radioanal. Nucl. Chem., (Research Grant 8553/R1). Articl., 196, 97(1995). [4]. Zagorski Z.P., Przybytniak G.K.: Optical properties of the rad- Support by the IAEA is gratefully acknowledged. ical anion derived from a-alanine by deamination, Nukleonika, 42, 373 (1997). FREE RADICALS IN EB IRRADIATED BLENDS OF POLYETHYLENE AND BUTADIENE-STYRENE BLOCK COPOLYMER 1 iCO Grazyna K. Przybytniak, Zbigniew P. Zag6rski, Danuta Zuchowska ' " Institute of Organic and Polymer Technology, Wroclaw University of Technology, Wrociaw, Poland M Blends of polymers are prepared for the purpose of radiation crosslinked tubes and tapes in our Institute. achieving unique physical properties, differing from For comparison some other grades of PE were irradi- those of pure constituents. Resulting materials are also ated and investigated like Malen. The second compo- interesting from the point of view of physical chemis- nent was SBS - block copolymer styrene-butadiene- try. Conclusions drawn from basic research can help styrene (Shell Chemical Co, grade Kraton D). It con- to modify chosen blends as concerns both the compo- tains 29% of styrene and has the density of 0.94 g cm"3. sition and technology of production. Investigation of Blends were prepared in three proportions: radiation chemistry of blends has therefore a double 25%PE/75% SBS, 50%PE/50% SBS and 75%PE/25% aspect: technological one, involving possible im- SBS. The macroscopically homogeneous mixture of proving of properties of the material for applications components was obtained applying three times extru- and the aspect of basic research. Our research is aimed sion at a temperature of 170°C and then moulding and at these directions, technological and basic and the shaping into threads for EPR measurements, flat object of study are blends of polyethylene (PE) and squares 20 mm x 20 mm for spectrophotometric styrene-butadiene-styrene copolymers (SBS), prepared measurements by diffuse reflection spectroscopy in various proportions. These blends are already inves- (DRS, results described in another paper) and into tigated for mechanical and material properties and the specific shapes for mechanical experiments. influence of high doses of ionizing radiation on their Irradiations were made under a beam of 10 MeV quality is known. It has revealed the fact that the blend electrons generated in the high power linear electron has new properties that could not be expected if the accelerator LAE 13/9. The beam was monoenergetical additivity principle would have been valid. Investiga- due to the bending by 270 degrees and scanned over tion of the origin of that phenomenon demanded a conveyor of controlled speed, adjusting the dose. deeper insight into the radiation chemistry of blends. The power of scanned beam was 6 kW, pulses were of On the one side of the row of proportions of composi- 5.5 us duration. Individual pulses overlapped on the tion we have 100% of PE, of known radiation samples due to scanning (5 Hz frequency) and the chemistry, on the opposite one, 100% of the SBS of movement of the conveyor. The whole dose was poorly known radiation chemistry, but expected to be supplied in a time shorter than 1 minute. The starting interesting from radiation chemistry point of view, temperature of irradiation was 25°C and increased because of protection effect exhibited by styrene during irradiation, due to the adiabatic character of moieties in the polymer. In the intermediate range delivery of energy to the value resulting from the there are separated phases of PE and SBS. A highly specific heat of the object. In the case of PE and a developed interface allows the electron and hydrogen dose of 30 kGy it was by 17 K [1]. Due to a signifi- transport. The boundary between very different phases cant heat effect, higher doses were supplied by split may be a site of grafting, responsible for the occur- close technique, i.e. subsequent portions of dose were rence of new properties. The present investigation supplied after 20 minutes, needed to cool down the describes esperiments on radiation effects, as seen by sample in a stream of air. The EPR measurements EPR spectroscopy. were started 20 minutes after the irradiation in the case Blends were prepared from two basic materials: PE of a single dose of 30 kGy. - high density polyethylene (BASF, Lupoien 1812D) Irradiated samples were placed in EPR tubes and which is used also commercially for the production of inserted into a rectangular TE 102 cavity of the EPR RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 35 spectrometer Bruker ESR 300. Measurements were completely. carried out at a modulation frequency of 100 kHz, Irradiated SBS shows one kind of radical, of the amplitude modulation of 0.4 mT, sweep width of 20 mT spectrum in the shape of a quartet of hyperfine and microwave power of 20 mW, 2 mW and 0.02 mW. splitting equal AiS0= 1.1 mT. This asymmetric signal Concentration of free radicals was estimated by seems to exhibit anisotropic interaction of two comparing, at room temperature, spectra of irradiated equivalent hydrogen atoms characterized by gj. = samples with that of a standard DPPH-benzene sol- 2.0065 and g|| = 2.0006. The observed intermediate ution. The number of accumulations and amplification does not change into another paramagnetic product, was always adjusted according to the intensity of the because the spectra recorded just after irradiation and signal. The deconvolution of spectra and their analysis after several days, in the wide range of microwave was performed, assisted by the program Apollo [2]. At power (0.02-20 mW) preserve the same shape. The the present state of our research all measurements concentration of paramagnetic centers is, in the case of were done at room temperature. First, the spectra were all doses, several times lower than in PE. Styrene recorded in a minute time resolution: later the lapses moiety contributes to dissipation of absorbed ioniz- of time were extended to hours and days. ation energy without chemical effects and also exhibits Figs. 1 and 2 show changes of EPR spectra, de- a protection effect on the radiolysis of butadiene pending on composition of the blend, dose and time moiety. Stability of radicals in SBS is higher than in elapsed after irradiation. Characteristic peroxide EPR PE. The spectrum of SBS is different from the spectra signals, known in many polymers irradiated in air or observed for polystyrene, for which the splitting of exhibited to oxygen after irradiation in vacuum were triplet is about 1.7 mT, corresponding to a radical in not observed. If present in our systems, their concen- which the unpaired spin is localized on the carbon trations were too low to be unambiguosly detected. bounded to the benzene ring (c.f. [3]). The spectra observed in radiolysis of PE are superpo- Spectra of blends 75%PE/25% SBS, 50%PE/50% sition of alkyl, allyl and polyenyl radicals. Although SBS and 25%PE/75%SBS recorded immediately after they consist of multiplete lines with poorly resolved irradiation are not linear-additively composed from the hyperfine structure, the presence of alkyl radical after spectra of constituents, Fig.IB. There is a significant a dose of 30 kGy is visible, whereas for higher doses participation of signals characteristic for principal the dominant component of signals is that one origin- constituents, but proportions of PE radicals are totally ating from the allyl radical (Fig.lA). At low doses, the different from that observed for pure component. The decay of the allyl radical is faster than of the alkyl source of observed discrepancies is not the formation radical and after 3.5 h the allyl radical disappears of a new kind of radical or radical pairs which could (A) (B) after irradiation 75% PE; 25% SBS .5 h after irradiation 50% PE ; 50% SBS 25% PE ; 75% SBS 2.5 mT Fig. 1. (A) - EPR spectra of PE. (B) - EPR spectra in blends of PE/SBS in various proportions. 36 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES exhibit a fine interaction. Recorded after a few hours IS upon irradiation changes are due to the lack of a sig- exp. nificant decrease of the allyl radical population and the growing relative contribution of alkyl radicals, even 85% (A) : 15% (B) for a dose as high as 120 kGy. No conversion of alkyl into allyl radical was found. Assuming that allyl radicals are produced by migration of alkyl radicals to exp. double bonds, this observation may provide evidence that unsaturation of PE in blends is inhibited. The 60% (A) : 40% (B) other way of alkyl radical decay is recombination or diffusion towards surface. Signals obtained for samples tn exp. one and three days after irradiation can be recon- structed from experimental spectrum A for PE and spectrum B for SBS applying for deconvolution t 50% (A) : 50% (B) a- proportions demonstrated in Fig.2. No other constitu- 8 ents were found. Relative contributions of constituents (A) obtained for spectra measured after one day of storage result from (i) initial amount of radicals formed in (B) constituents, (ii) different rates of their decays and (iii) 8 various proportions of parent spectra formed by 2.5 mT transformation of original radicals. Fig.2. Deconvolved spectra. Experimental spectra of samples irra- The important conclusions, from the point of view diated to the dose of 60 kGy and measured after 24 hours. of physico-chemistry of polymers, is that radiation A (PE) and B (SBS) - constituents spectra. induced processes are not a simple sum of processes References occurring in constituents of the blend, in spite of their [1]. Zagorski Z.P.: Thermal and electrostatic aspects of radiation physical separation of phases. Presented results will be processing of polymers. In: Radiation processing of polymers. compared with other findings obtained in the same Eds. A. Singh, J. Silvermans. Hanser Publishers, Munich 1992. system by different methods of investigation and also [2]. Dusemund B.: Ph.D. Thesis, University of Saarland 1997. by the same methods in similar systems. [3]. Garrett R.W., Hill D.J.T., Le T.T., O'Doneell J.H., Pomery P.J.: Radiat. Phys. Chern., 39, 215 (1992). A PULSE RADIOLYSIS STUDY ON SINGLE CRYSTALS OF a-ALANINE Zbigniew P. Zagorski, Knud Sehested1' " Ris0 National Laboratory, DK-40Q0 Roskilde, Denmark ICNJ Investigation of radiation chemistry of solid, crystal- sometimes called erroneously "alanine radical", IS line a-alanine has been limited in recent decades whereas it is the "alanine derived radical anion". The ! mainly to the study of stable radical anion derived EPR method of measuring the concentration of the from deamination of this amino acid and measuring its radical anion, mentioned above is difficult to perform concentration by the EPR method. The main purpose properly and gives results of diminished precission if was dosimetric application, which has reached even crystals of alanine are oriented in the sample. That is the stage of an international standard [1], in spite of the case with thin layers of alanine, e.g. in the shape of some unexplained phenomena, evidently connected polymeric films containing alanine microcrystals [3]. with unknown radiation chemistry of solid alanine. Therefore other methods were tried to measure the Application of higher LET radiations [2] could not concentration, insensitive to the orientation of radicals. solve the problems, as the phenomena in tracks of high An attempt to find a better analytical method and energy heavy ions (thermal spikes) belong rather to at the same time to explore the radiation chemistry of the high temperature chemistry of alanine than to alanine, started with the measurement of optical radiation chemistry of single ionization spurs. The properties, i.e. the absorption spectrum of the alanine neglect of chemistry of the system started already with derived radical (Xmm = 350 nm), first by diffuse the formula of a-alanine written incorrectly: reflection spectrophotometry (DRS) [4], in powdered CH3CHNH2COOH, although it is well known from crystals. That approach, excellent for dosimetry of NMR measurements that a-alanine in crystalline form electron beam irradiations, could not reveal the molar + has the formula CH3CHNH3 CO2", i.e. it occurs as a extinction coefficient of the radical anion. The deter- zwitter ion. The radical anion formed by deamination mination of s became possible with the preparation of of a-alanine has the formula CH3C"HCO2~ and is single crystals of a-alanine, and the conventional RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 37 spectrophotometric measurements. As the radiation single ionization spurs. In our case of a not very yield of the radical anion was known, the result [5] complicated spectrum, one single crystal is sufficient was e = 1100 MT'cm"1. This is very close to the s value for recording of five spectra. of the same but short lived radical anion observed by pulse radiolysis of aqueous solution of propionate or ZPZ piyat*], ZSp pull, mw oyttti (6mm), pull 32-33 chloropropionate by H, resp. Cl abstraction. The half 0.14 live of the radical in the solution is ca. 12 orders of 0.12- magnitude shorter than in the solid state. The successful measurement of optical properties of the alanine derived radical anion in a single crystal suggested the use of time resolved spectrophotometry, i.e. solid state pulse radiolysis [6]. The latter can be carried out without ceil, if the sample is in the shape of a single crystal or glass and is not hygroscopic or sensitive to oxygen. Alanine fulfils these conditions. Sufficiently large crystals of commercial reagent grade L-a-alanine, have been grown from saturated aqueous 0.00- solution by slow evaporation at room temperature. .•0.02-, , , , , , , , Transparent crystals with a light path of at least 5 mm •0.002 -4.00) 0,000 8.001 COOS 0.0U 0.0O4 0.004 0.001 0.007 0.00* were positioned in the beam of electrons. Orientation MCondt according to crystallographic axis was not necessary, Fig.l. Record of optical density of an L-a-alanine single crystal, at as the optical spectrum does not depend on the angular a temperature of 32°C. arrangement in the measuring instrument. A single Spectra constructed from the decays show a broad crystal may be kept at temperatures slightly lower or band just after the pulse (Fig.2), which changes moderately higher than ambient by passing thermo- according to the first order kinetics into the well stated air around it. The 2.5 fas pulses were used known spectrum of the free radical anion CH3C'HC(V throughout the study. With low doses of radiation, one recorded conventionally from irradiated single crystals crystal is sufficient to record ca. 50 single kinetics, of L-a-alanine [5]. The broad band indicates the pres- without changing. The problem of the maximum ence of different energy states of the complex under number of shots to one solid sample is common in the process of deamination. The average oscillator solid state pulse radiolysis. strength is higher than in the case of the stable, Fig. 1 presents typical kinetic curves of formation deaminated radical. Unexpected, a comparatively long and decay of the intermediate in the crystal. The half- life of the cage which contains the radical product of life time of the first order decay is rather long, 1.5 ms deamination and ammonia, opens new possibilities of at room temperature, which is common in the case of explanation of final products and yields in radiation transients in solid state matrices. The capacity of the chemistry of amino acids. The product of deamination, crystal for the number of shots is determined by the i.e. ammonia stays in the cage long enough to enter level of noise which can be tolerated from the point of reactions, before starting to leave the cage by view of the limit of accepted precission. This limita- diffusion. Closer investigation of such phenomena tion occurs earlier than the risk of complication from demands an experimental approach different than pulse the overlapping of accumulated stable radicals and radiolysis. Upper spectrum: Just alter the pulse 4- I 4 4. 4- 4. I Lower spectrum: 5 ms, and lonser after the pulse 0.07- q nm Fig.2. Spectra constructed from kinetic curves of the decay of the complex under deamination. 38 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES The easiness to measure temperature dependence energy which helps to start the deamination process of the decay of the transient complex of alanine under and formation of the free radical anion. The decay of deamination allows to estimate the activation energy the complex under deamination is depending on the of decay, in the narrow range of temperatures (20- temperature, probably involving more or less advanced 55°C) at the time being: it is 0.25 eV/molecule. Until reconstruction of the alanine molecule. Ammonia now, only the temperature coefficient of the response formed in multi-ionization spurs does not play any of alanine-based dosimeters was known, but it never role in the reconstruction, because debris are very far has been investigated in order to explain the from single ionization spurs. mechanism responsible for its rather high value. The Full text of the research appeared in [8]. ASTM standard [1], as well as its proposed revision, This research was supported in part by the still under discussion, states the value of +0.18%/K. The International Dose Assurance System (Inter- International Atomic Energy Agency (research grant national Atomic Energy Agency) uses the value of 8533/R1). +0.24%/K. A substantial difference between values References indicates a poor recognition of basic phenomena in [1]. Standard practice for use of the alanine - EPR dosimetry system irradiated alanine. As the pulse radiolysis has revealed ASTM Standard E 1607-94, 1994. a possible way of explanation, further studies should [2], Hansen J.W., Olsen K.J., Wille M: Rad. Prot. Dosim., 19, 43 be carried out at wider range of temperatures starting (1987). at 77 K as well as probing the temperature range [3]. Przybytniak G.K., Zagorski, Z.P.: J. Radioanal. Nucl. Chem., above 55°C. Lett., 212, 373 (1996). [4]. Zagorski Z.P, Rafalski A.: J. Radioanal. Nucl. Chem., Articl., One has to stress that all phenomena described in 196,97(1995). the present paper are connected with single ionization [5]. Zagorski Z.P., Przybytniak G.K.: Nukleonika, 42,2,373 (1997). spurs, which dominate in low LET irradiations. Only [6]. Zagorski Z.P.: Pulse radiolysis of solid and rigid systems. In: about 20% of absorbed radiation energy appears in Properties and reactions of radiation induced transients - selected multi-ionization spurs [7], 80% of alanine molecules topics. Ed. J. Mayer. PWN, Warszawa 1999, pp. 219-233. [7]. Zag6rski Z.P.: Radiat. Phys. Chem. (1999) (accepted for print). affected by the ionization energy appear in single [8]. Zagorski Z.P., Sehested K.: J. Radioanal. Nucl. Chem., 232, ionization spurs. They contain the excess of 10-15 eV 139(1998). RADIATION CHEMISTRY OF SOLID THIOSULFATE. I. OPTICAL ABSORPTION SPECTRA PL9902205 Zbigniew P. Zagorski, Andrzej Rafalski The present research is a part of statutory research on The hydrated thiosulfate (Na2S2O3-5H2O), has solid state radiation chemistry. At the same time it is been used and the anhydrous salt. Both reagents were connected with water occurring in different solid used without further purification and used as supplied forms. Investigation on similar systems started with except of mechanical sieving to select uniform grain aqueous clathrates [1-4]. The paper [3] has announced size, that improves the precission of diffuse reflected a specific behavior of sodium thiosulfate which shows spectrophotometry (DRS). Irradiations were made an intensive yellow-orange coloration of irradiated with a 10 MeV scanned electron beam from a linear crystals, which lasts for several hours. The present accelerator, usually at a dose of 30 kGy. That is the paper describes more experiments on the subject, maximum dose which may be applied adiabatically trying to identify intermediates and mechanisms of without excesive heating of the sample. Absorption reactions, including not only optical but taking into spectra were recorded by diffuse reflection spectro- account also older EPR measurements known from the photometry (DRS) on a Perkin-Elmer spectrophoto- literature. EPR investigations on thiosulfate are men- meter Lambda 9 equipped with the light integrating tioned by Symons [5] together with investigations sphere. Otherwise optical spectra of species formed in on dithionate and tetrathionate anions. This author irradiation of anhydrous Na2S2O3 were impossible to suggests that the radical anion derived from thiosulfate record. The DRS method proved its advantage in solid 3 anion, after primary ionization act is [*S2O3] ~ rather state radiation chemistry, because the technique of than [°S2O3]~. Indirect relations to the topic, but measurement, i.e. irradiated sample vs. unirradiated, connected with optical spectra may be found in papers compensates any peculiarities of diffusion and reflec- [6,7] on pulse radiolysis studies in aqueous solution tion of light beam by the sample, due to its texture. 3 showing the formation of "S2O3" (£375 = 1.72-10 M"' The method has proved its excellency in such different 1 2 cm" ) (from S2O3 " + OH). systems as in the investigation of CH3*CHCO2~ radical RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 39 anion derived from deamination of alanine [8] and in reported in the next publication. Spectra of the the exploration of radiation chemistry of unprocessed, intermediate in the anhydrous salt shows unchanged raw (virgin) polypropylene [9]. wavelength during the decay, whereas the maximum of absorption in hydrated salt shows a slight blue shift Irradiated Na2S2O3-5H2O shows intensive yellow- orange color induced by radiation, whereas the during decay. The blue shift is an artefact because the anhydrous salt shows a slight yellowish tint only. The band is composed of at least two bands of similar absorption spectra are shown in Figs. 1 and 2, respect- wavelengths. At the shorter wavelength part of the ively. The spectrum of anhydrous thiosulfate proves curve, the formation of a new absorption is visible, or that the slight yellowish tint is caused by a longer a more stable species is forming from the transient. wavelength tail of the intensive band in UV. Its The intermediate in hydrated thiosulfate does not intensity is comparable to the visible band in the case change into radiation generated intermediate in the of hydrated thiosulfate. anhydrous salt. X: Ih26k»; 788,8 - 198.8 m; pis Sit: int 1.88; ord -0.278 - B.2446 PR The interpretation has to be initiated with the Inf: Ha2$293'S2Q 26 US? el vt 8 kGy.22.B6.S6. understanding of the thiosulfate anion. It is colorless, 2.75- in spite of combination of two sulfur atoms of differ- ent conformation of electrons. Thiosulfate ion should 2.15 exhibit electronic spectrum in the visible range of spectrum. Now we are able to show that thiosulfate has an intensive absorption, but located in UV. Fig.3 shows, that its absorption spectrum contrasts with the lack of absorption of sulfate ions, to which thiosulfate ion is formally similar (one oxygen is exchanged by a sulfur ion). Absorption in UV is very intensive and looks practically like a UV cut-off filter, starting at -0.25 320 nm and exhibiting a total absorption at 270 nm. 200.0 300.0 400.0 500.0 GOO.O 700.0 nm X; IiosM; 488.8 - 136.9 ret; pis ill; itri 1,88; ord 4.4353 - 78.348 M Fig.l. Absorption spectrum of Na2S2O3- 5H2O, 10 MeV EB irradi- lnf:HsSS203 21.86.98 ated (26 kGy), DRS measured against unirradiated salt of the 80.0T same polycrystallimty. Absorption is expressed in Kubelka- Munk equation units (FR). Spectrum recorded 100 h after irradiation is indicated. Irradiation and measurements at room temperature. Sample kept in dark. X: Tb2Skc«; 768.6 - 193.8 m; pts 5(1; inf 1.88! ord -8,831 - B.7493 M Inf: Ha2S203 25 kGy el vs B kGy,22.8S.98. 2.01 0.0 200.0 250.0 nm Fig.3, Transmision spectrum of anhydrous sodium thiosulfate, DRS measured against BaSO4 as the standard of whiteness in UV- Vis. The spectrum of hydrated thiosulfate is practically identical, indicating that the aqueous moiety does not partici- pate in absorption. Sodium sulfate is completely transparent 300.0 400.0 500.0 600.0 700.0 in the UV region. nm The primary act of ionization in anhydrous Fig.2. Absorption spectrum of Na2S2O3 irradiated (26 kGy), DRS measured against unirradiated salt of the same polycrystal- thiosulfate consists of detachment of electron from the linity. Absorption is expressed in Kubelka-Munk equation anion which is the main constituent of the system, units (FR). Spectrum recorded !00 h after irradiation is interacting with high energy quanta or particles. indicated. Detachment of a single electron produces isolated Kinetics of the decay of transients is different. The small spurs, connected with absorption of 80% of total absorption at a wavelength of X = 360 nm in anhydrous absorbed energy, as determined by absolute calor- thiosulfate decays slowly with tV2 - 80 h, but the imetric dosimetry. The remaining 20% is deposited as visible intensive color in hydrated thiosulfate disap- multi-ionization spurs, participating in the creation of pears much more rapidly with an estimated half life congested ionizations, leading to the formation of time of ca.ti/2 = 9 h at room temperature. The unusual- debris of the molecules. As usual, these debris are of ly low temperature coefficient of decay rate will be low reactivity and detection of their presence and 40 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES identity is difficult, especially in view of their low thiosulfate, the anion produces debris due to the high concentration in comparison to much pronounced local concentration of energy. Multi-ionization spurs presence of reactive products of single ionization in aqueous moiety of the hydrate can produce H2O2 spurs. Localization of single ionization spurs is practi- and H2 this being considered as not very important at cally limited to the S2O32"" anion representing all the present stage of investigation of phenomena in the electrons of the lowest binding energy. The stable hydro-moiety. The initial act of ionization, i.e. the structure changes into *S2O3~ which may be under- formation of holes and electrons is followed by rapid stood as a hole delocalized over the anion. Excitations consecutive reactions which lead to different paths in of unpaired electron in the radical anion are proposed comparison to the case of anhydrous thiosulfate. There as the origin of optical electron absorption spectrum in is no band ascribed to S2O3~ in the UV region in the UV (probably n -» n*), with a short tail reaching into spectrum of the irradiated Na2S2O3-5H2O. The close the visible range. The delocalization of electron and neighbourhood of thiosulfate anion and water moieties lack of a possible reaction partner explains rather long makes easy the energy and material transfer. Therefore time of life of the radical. The geminate electron, the transient complex [*S2O3-H2O]" seems to be detached in the act of ionization is, most probably, responsible for the 418 nm absorption. The red shift of stabilized temporarily in a trap outside the anion, e.g. absorption in the hydrated salt in comparison to the in an anion vacancy, which is expected to be present anhydrous one is understandable because of larger in the Na2S2O3 crystalline lattice. Considering the size oscillator size responsible for the electronic spectrum. of the anion vacancy, the trapped electron can show its The initial ionization of the thiosulfate moiety leads absorption in the far IR region only, thus being rapidly to the same species due to the close neighbour- difficult to detection. As both the "hole" and electron hood of water molecule. Therefore the band observed are comparatively stable, the reaction of recombina- in irradiated anhydrous thiosulfate does not survive to tion is slow, explaining the long half life time of the observation. Comparatively rapid disappearance of the radical anion. To summarize: the absorption with a transient in hydrated thiosulfate is due to the low maximum at 360 nm is due to the radical anion "S2(V. stability of the complex [*S203-H2O]~ and an better There is a striking analogy of this absorption band to availability of electrons for geminate reaction. They the absorption described by Dogliotti and Hayon [7] are localized temporarily in a variety of traps, mainly also to 'S2O3" radical anion, but obtained in time in aqueous moiety of the compound. Interpretation of resolved flash photolysis studies on aqueous solutions our optical spectra obtained in irradiated anhydrous of sodium thiosulfate. Na2S2O3 is consistent with a previous interpretation of early measurements of EPR spectra. However, we are The expected radical yield of *S2C>3~ generated tending rather to ascribe the formula of the main during the delivery of dose of 30 kGy to solid 3 radical product to *S2O3" and not to "S2O3 ~. The Na2S2O3 cannot be higher than G = 5 per 100 eV of absorbed energy. This upper limit means that in 1 g of formation of the latter in the radiation process is sodium thiosulfate irradiated at a dose of 30 kGy, difficult to imagine from the point of view of radiation 6 chemistry. Thus we are coming back to earlier ideas, 15.36 • 10" moles of *S2O3~ is formed, i.e. the maxi- mum possible concentration of the radical ion is like that by Morton [11], who postulated "one minus" radical anion, eliminating at the same time more exotic 25.6 mM, distributed in the matrix of Na2S2O3, which is 10.5 M. (1 liter of sodium thiosulfate has the mass assumptions, i.e. that radiation can break the S-S bond of 1.667 kg). Therefore one radical occurs per 412 in thiosulfate. molecules of the parent anion; it is of the order of References common situations in most radiation processing tech- nologies and so called high dose dosimetry. This [1]. Zagorski, Z.P.: J. Phys. Chem., 90,957 (1986). concentration is still far from overlapping of single [2]. Zagorski, Z.P.: J. Phys. Chem., 91,734, (1987). [3]. Zagorski, Z.P.: J. Phys. Chem., 91,972 (1987). ionization spurs. [4]. Zagorski, Z.P.: J. Inclusion Comp. Mol. Recognition in Chem., The explanation of radiation induced phenomena 7,569(1989). in hydrated thiosulfate is more difficult. This time the [5]. Symons, M.C.R.: J. Chem. Soc. Dalton Trans., 10, 1468 primary act of ionization is distributed statistically (1979). 2 [6]. Adams, G.E., Boag, J.W. and Michael, B.D.: Trans. Faraday between the S2O3 ~ anion and five water molecules in + Soc, 61, 1674 (1965). the vicinity of it and Na cations. Typically for [7]. Dogliotti, L., Hayon, E.: J. Phys. Chem., 72,1800 (1968). hydrates (and aqueous clathrates), water molecules are [8]. Zagorski, Z.P., Przybytniak, G.K.: Nukleonika, 42, 2, 373 more tightly packed than in ice. The density of (1997). [9]. Zagdrski, Z.P., Rafalski, A.: Radiat. Phys. Chem., 52, 257 Na2S2O3 • 5H2O is 1.729 g/ml, i.e. is higher than the density of anhydrous sodium thiosulfate (1.667 g/ml). (1998). [10]. Zag6rski, Z.P., Sehested, K.: J. Radioanal. Nucl. Chem., 232, Ca. 20% of energy goes, as usually into multi- 139(1998). ionization spurs. As in the case of the anhydrous [11]. Morton, J.R.: J. Phys. Chem., 71, 89 (1967). RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 41 RADIATION CHEMISTRY OF VIRGIN POLYPROPYLENE Andrzej Rafalski PL9902206 Polypropylene (PP) belongs to the group of unstable absorption spectra, and helped to avoid preparation of polymers which cannot be processed and applied transparent samples of doubtful composition. without additives. Radiation chemistry of processed Investigation of polypropylene of highly developed polypropylene is therefore considered in fact as the interface of particles, which were in contact with the radiation chemistry of complicated multicomponent gas phase over them, has helped to recognize reac- systems, usually in addition influenced by thermally tions, which in the case of polypropylene films of changed polypropylene. Investigation on radiation small surface area, exposed to the gas phase, do not chemistry of stabilized PP is not conclusive because show interactions with gases with sufficient radiation the response to the radiation induced effects is yields. strongly influenced by radiation chemistry of additives Industrial polypropylene was acquired from an and their complexes with PP. The virgin PP cannot be industrial production line as described in paper [1], processed into transparent samples without additives Usage of gamma radiation was limited; high power and therefore optical absorption spectra had to be electron accelerators were principal sources of ioniz- made by diffuse reflection spectrophotometry (DRS). ing radiation, as described in [1], For EPR measure- Identification of chromophoric groups has been done ments a conventional Bruker EMS 104 ESR spectro- by comparison with low M.W. peroxides and ketone meter-analyser was used. compounds combined with PP. Decay of peroxides in Two other techniques (spectrophotometry of far UV observed optically was correlated with the powders and gravimetric study of reactions with decay of EPR signals. Chain oxidation of irradiated PP oxygen) were not typical. Diffuse Reflection Spectro- exposed to air, lasting for months, was followed photometry (DRS) has been used for measuring the gravimetrically, that proved to be more convenient and absorption spectra of irradiated polypropylene precise in comparison with the manometric method. powders. A physical basis of the measurement and an On the contrary to more stable polymers, which instrumental approach is presented separately. The can be processed into transparent samples without DRS method is constantly being developed and changes of basic chemistry and physical properties of, improved and now every firm producing high quality the material, research on radiation chemistry of spectrophotometers offers additional attachments for polypropylene is difficult. Every attempt to process DRS measurements. We have concluded from a polypropylene, e.g. thermally or by dissolution/evap- comparison of results obtained for irradiated samples oration into a form convenient for investigation, is on different types of spectrophotometers that only connected with the modification of chemical compo- those instruments, which provide a double beam of sition and polymeric structure. For that reason the light measurement at the same time on a reference and number of papers on radiation chemistry of pure irradiated sample, are useful in radiation research. The polypropylene is small in comparison with papers on reference is an unirradiated sample of the same texture polypropylene with additives. as the irradiated one. Therefore all phenomena due to Looking into radiation induced reactions in virgin the optically complicated surface of the sample are PP, one has to resign conventional optical UV-VIS compensated in the resulting absorption spectrum, methods, because samples of transparent polypropyl- which shows only absorption of these species which ene with additives cannot be considered as the pure are formed or changed during irradiation. polypropylene. To overcome that difficulty, a tech- The difficulty which existed previously, i.e. the nology has been proposed consisting in the possibility to carry out measurements only around preparation of transparent films, followed by the room temperature has been overcome recently. extraction of low molecular weight additives and Kodaira in Tsukuba, Japan [2] has demonstrated now products of thermally decomposed polypropylene. DRS records made at 77 K. Another difficulty of the However, a reasonably full removal of these corn- DRS method, i.e. the quantification of absorption pounds is impossible, the procedure may be con- remains not fully solved. The parameter of light sidered acceptable if the film after extraction is diffusion in the Kubelka-Munk equation is difficult to impregnated with a high concentration of new com- estimate. The method is fully precise as concerns the pounds fulfilling the role of scavenger of reactive determination of wavelengths of absorption, but only products of radiolysis like in radiation chemistry of semiquantitative in the estimation of intensities. Full liquids. Another approach has been applied in our precision can be reached only in the case when the Laboratory consisting in application of diffuse material is additionally prepared in transparent form as reflection spectrophotometry to virgin polypropylene it was possible in the case of irradiated low molecular in powder form, which enables to measure the compound [3]. Full quantification of spectra even in 42 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES the case of polymeric materials will be reached after investigated system, because molar extinction coeffi- further development of experimental techniques. cients are too low in the IR region to detect low One of aims of our DRS measurements on irradi- concentrations of peroxides and ketones. ated virgin polypropylene was an attempt to correlate the EPR detection of peroxide decays with UV ab- sorption spectra of peroxide moieties in polypropylene chains. EPR signals disappear with the decay of peroxides and simultaneously the disappearance of far-UV optical absorption is observed (Fig.l). If irradiated polypropylene is in contact with air, the chain reaction of oxidation proceeds producing ketone moieties on the polypropylene chains. The near UV band in the spectrum is attributed to ketone groups (Fig.2 shows the sequence of changes of spectra). Both interpretations have been preceded by modelling 0.0 240.0 260.0 280.0 300.0 of supposed chemical changes in polypropylene. nm Peroxides located on polypropylene chains were simu- Fig.2. DRS records of optical absorption of irradiated polypropyl- lated by a soaking standard polypropylene powder ene, exposed to air. An increase of absorption in the 260- with hexane solution of tertbutyl hydroperoxide and 280 nm is attributed to ketone groups in the polypropylene ditertbutylperoxide which were adsorbed on the chain. The time of measurements: 1 -just after irradiation, 2 surface of microparticles of the polymer. As the - after 60 days, 3 - after 525 days. reference served polypropylene soaked with hexane. Another non-typical method is a simplified The absorption was observed in far UV, close to the measurement of oxygen absorption kinetics. One can final full absorption, for l<190 nm, like in the case of find in the literature descriptions of measurement of irradiated PP when the EPR signal is still present. oxygen absorption consisting in the determination of Maxima of peroxides and hydroperoxides are not well oxygen pressure above the irradiated material developed, but the absorption at 200-220 nm shows (manometric method). We have found the pressure the presence of peroxides and hydroperoxides. measuring method difficult to apply and insufficiently 0.0 precise. A better method was the gravimetric one, -•- EPR realized with modern electronic balances of much better precision in comparison to old ones. The -•- DRS gravimetric method is superior in our case because of substantial increases of weight, reaching almost 1 mg per day and 20 g of polypropylene at the beginning of oxidation process. The new approach offered free choice in adjusting the composition and pressure of gas above irradiated polypropylene. The G value of oxygen absorption and formation of ketone groups on polypropylene chains was up to 12 nmole J"1, depending on the dose and the time elapsed from 50 100 irradiation. Once initiated, the chain reaction proceeds time [hours] for months. Consumption of oxygen and formation of Fig.l. Comparison of decays of the EPR signal attributed to peroxides and decays of the far-UV optical absorption as ketone moieties are not influenced by the humidity of measured by DRS as a function of time. At longer times the air. far-UV absorption of peroxides is disturbed by the tail of ketone groups absorption with a maximum in the near-UV This is a part of authors Ph.D. thesis; supervisor - region. Professor Z.P. Zagorski. The ketone moiety was modelled in a similar way References by soaking polypropylene grains with methanol sol- [1]. Zag6rski Z.P., Rafalski A.: Diffuse reflectance spectrophoto- ution of di-isopropylketone and di-isobutylketone. The metry in polypropylene radiolysis study. Radiat. Phys. Chem. reference was polypropylene soaked with methanol. 48, 595 (1996). Both ketones show the absorption in the 260-280 nm [2]. Kodaira T., Tsukuba, Japan, private communication, Sept. band, corresponding to the sequence of DRS absorp- 1998. tion spectra in irradiated polypropylene (Fig.2). The [3]. Zag6rski Z.P., Przybytniak G.K.: Optical properties of the rad- ical anion derived from a-alanine by deamination, Nukleonika, DRS-UV absorption method is superior to IR in the 42,373 (1997). PL9902207 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 43 EFFECTS OF GAMMA IRRADIATION AND ANNEALING TREATMENTS ON THE PERFORMANCE OF Cr;Tm;Ho:YAG LASERS Slawomir M. Kaczmarek1', Waldemar Zendzian", Tadeusz Lukasiewicz2"3', Krzysztof Stfpka17, Zbigniew Moroz4', Staoislaw Warchol2'5' " Institute of Optoelectronics, Military University of Technology, Warszawa, Poland 21 Institute of Electronic Materials Technology, Warszawa, Poland 3/ Institute of Applied Physics, Military University of Technology, Warszawa, Poland 4/ Softan Institute for Nuclear Studies, Otwock-&wierk, Poland 51 Institute of Nuclear Chemistry and Technology, Warszawa, Poland Quite often many solid-state lasers are designed to To measure the optical output, a laser power supply work in strong external fields of ionizing radiation (Analog Modulus) was used. The rod was placed in (e.g. cosmic rays, gammas, electrons, neutrons). For a Quantron K-1041 head with a diffusive reflector and example, instruments in orbital space missions are water cooling. Measurements were carried out by subjected to integrated radiation doses, which can pumping the rod with a sequence of pulses of width reach upwards of 103 Gy over a 5-year period and are 700 ms and frequency f = 1 Hz. conceivably higher for non-earth based missions [1]. The "as grown" sample was exposed to 106 Gy of Therefore, a study of the degradation induced in their gamma-rays and next annealed at 400°C in air then active materials by such radiation is highly relevant. irradiated a second time with 106 Gy and annealed at Studies of Cr;Tm;Ho:YAG (CTH:YAG) crystals sub- 1400°C in air for 3 h. Finally, the sample was once jected to ionizing radiation have been reported in more irradiated with 105 Gy and, then subjected to many publications [2-7]. a sequence of ten UV pulses from the xenon lamp The main goal of the present work is to study in (pulse energy: 90 J, period: 10 s). In the last irra- more detail the mechanisms of the irradiation induced diation, we studied how each pulse influences the changes of the optical properties of CTH:YAG absorptive properties of the crystal. As a result of the crystals. gamma-ray exposure of the sample, the AA bands Crystal samples were produced in the Institute of appear. They are mainly observed on the short-wave Electronic Materials Technology by the Czochralski edge and are shown in Fig. 1. Annealing of the crystal method. A detailed description of the growth process at 400°C in air fully bleaches the radiative colour of such crystals is given by Z.Frukacz and Z.Mierczyk centres as illustrated by curve 2 in Fig.l. This curve [8]. Spectroscopic studies were carried out on parallel plate samples of 0.77 mm thickness, cut from the CTH:YAG crystal perpendicularly to the growth axis in the <111> plane and polished on both sides. Measurements of the transmission in the range of 190- 1100 nm were made with a LAMBDA-2 (Perkin- Elmer) spectrophotometer for the samples before and after processing (gamma irradiation or thermal anneal- ing). The additional absorption (AA) coefficient was 1 —7 irradiation WGy then calculated from formula [3]: AK(A,)= 1/d - In Tj/T 2 — »mea!ing si 530"C 2 s 3 T irradiatioo 10 Gy [I/cm] where d = sample thickness; Ti,T2 = trans- missions of the samples before and after processing, respectively. Gamma irradiations were carried out in a *°Co 0 100 200 300 400 5OQ 600 700 800 SCO 1000 1100 chamber with an efficiency of 1.7 Gy s"1 in this 5 6 Institute. The gamma dose varied between 10 and 10 Fig.!. AA vs. wavelenght for CTH:YAG sample: 1 - y-irradiation Gy. For the crystals subjected to different processing with a dose of 106 Gy, 2 - thermal annealing at 400°C in air 5 (annealing, gamma irradiation) the influence of UV and 3 - y-irradiation with a dose of 10 Gy. irradiation from a xenon lamp on the colour centres appears to be almost a mirror-reflection of curve 1, the was investigated. For this purpose a pulsed light latter describing the response of the "as grown" crystal source (xenon discharge lamp) was used. Each sample to the gamma irradiation with 106 Gy. The intensity of was irradiated by a sequence of ten pulses, each of the AA bands depends on the gamma dose, as is energy 90 J, with a separation of 10 s between pulses. illustrated by curves 1 and 3. At 430 nm the AA Laser emission studies were carried out for a CTH: intensity is 0.2 (cm"1) for 106 Gy and 0.15 (cm"1) for YAG rod of length 1 = 67.3 mm and diameter f = 4 mm. 105 Gy. Annealing at high temperature (1400 °C) leads 44 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES to the changes in the AA-spectrum shown by curve 2 150 -i in Fig.2. 1i after r 10s Gyo('as grown'crystal 21 after annealing at 800% 3h in air 3.0-• 120- 'A after annealing at 1400-C in air and ^irradiation T 10^y a «T after anneaSng at 40ffC3h in air 2.5- 2.0 90- Cr,Tm,Ho:YAG 1at%, 5,Tat%,0.36aL% l=67,3mm,L =255mm red m -700ms 60 t 30 0.0 •0,5- 120 140 160 ISO 200 220 -1.0- Pump energy [J] -1,5 Fig.4. Optical output of CTH:YAG laser after: y-irradiation with a 200 300 *0O 500 600 700 800 900 1000 1100 dose of 105 Gy, after annealing at 800°C in air, after annealing at 1400°C in air, and after y-irradiation with a dose of 10s Gy for the same CTH:YAG rod with a lenght of Fig.2. AA bands in CTH:YAG sample after: 1 - y-irradiation with 67.3 mm and f = 4 mm. a dose of 106 Gy, 2 - annealing at 1400°C in air and 3 - y- irradiation with a dose of 105 Gy. are shown in Fig.4. Four optical outputs were obtained The influence of UV radiation on the sample for the CTH:YAG laser rod. After anealing at 800°C previously annealed and gamma irradiated, is shown a decrease of the threshold energy of about 20 J is observed, in comparison with an "as grown" crystal in Fig.3. Additional absorption bands, in particular at 5 430 and 600 nm, are seen. In general, these bands irradiated with 10 Gy. Subsequent annealing at 1400°C in air and then (after optical polishing of the rod faces correspond to those obtained by gamma irradiation s of the "as grown" crystal, suggesting that UV radiation only) irradiation of the same sample with 10 Gy caused a rise of the threshold energy to 134 J and an 0,30-1 increase of the differential efficiency to 0.169%. Annealing at 400°C caused relaxation of the radiative colour centres and a lowering the differential effi- ciency of the laser. References [1]. Rose T.S., Hopkins M.S., Fields R.A.: IEEE J. Quantum Electron., 31,9(1995). [2]. Kaczmarek S., Mierczyk Z., Kopczynski K., Matkovskii A.O., SugakD.Yu., FrukaczZ.: Proc. Intermol. Interact. Matter, 134- 141 (1995). [3]. Kaczmarek S., Matkovskii A.O., Mierczyk Z., Kopczynski K., Sugak D.Yu., Durygin A.N., Frukacz Z.: Acta Phys. Pol., A90, 2,285-294(1996). [4]. Matkowski A.O., Sugak D.J., Vakiv M., Durygin A., Kaczmarek S., Kopczynski K., Frukacz Z., Pukasiewicz T.: 0 100 200 300 400 500 600 700 800 900 1000 1100 Proceedings of SPIE, 1997, Vol. 3178, pp. 273-278. [5]. Zmija J., Majchrowski A., Rutkowski J., Zieliriski ).: Growth Fig.3. Additional absorption bands of the CTH:YAG crystal and characterization. Conf. on Solid State Crystals, Materials irradiated by UV, after earlier annealing at 1400°C and Science and Applications, Zakopane, Poland, October 7-11, gamma irradiation with 106 Gy. 1996. [6], Matkowski A.O., Sugak D. Yu., Durygin A.N., Kaczmarek S., 4+ 3+ changes the valence of the Cr to Cr . It seems Kopczynski K., Mierczyk Z., Frukacz Z., Lukasiewicz T., reasonable that the following interaction scheme takes Shakhov A.P.: Radiation effects in laser crystals, Opt. Mat., 6, place: UV+Fe2+ -» ((e") + Fe3+); (e' + Cr4+ -> Cr 3+). 353-358 (1996). That is, UV is ionizing the Fe2+ ions and the resulting [7]. Kaczmarek S., Kopczynski K., Lukasiewicz T., Frukacz Z., 4+ Piramidowicz R., Matkovskii A.O., Sugak D.Y., Durygin A.N.: electrons are captured by the Cr . The influence of Proceedings of SPIE, 1997, Vol. 3186, pp. 129-134. gamma irradiation and annealing on the laser emission [8]. Frukacz Z., Mierczyk Z.: Mat. Elektr., 22, 69 (1994). PL990290R 45 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES uu HIGH ENERGY ION IMPLANTATION PROFILES Janusz Krynicki, Jaroslaw Puton1', Janusz Oleniak2', Stanistaw Warchol, Henryk Rzewuski " Military University of Technology, Warszawa, Poland 21 Department of Chemical and Process Engineering, Warsaw Technical University, Warszawa, Poland A new computer program for depth distribution has been drawn with a solid line. In Fig.lb the respect- calculations of high energy ions implanted into solids' ive results for a linearly decreasing concentration of has been presented. It provides a possibility of the implanted Sb+ ions inward the crystals are plotted. obtaining any shape of the implanted ion profiles for Table 1. The implantation sequences obtained for the two assumed high energy ions assuming, that the correlation profiles between the Rp and ARP is known. In particular, it ProfiJeNo. 1 Profile No. 2 provides a high computer efficiency while maintaining Energy; Dose Energy Dose a high degree of accuracy. [keV] [x 1015 cm"2] _JkeV]__ [xl0lscrn2l To illustrate applicability and reliability of the 40 0.26 25 0.56 program a number of representative calculations have 95 0.68 90 1.15 200 1.5 been performed. High energy Sb+ ion implantation 170 0.88 270 1.32 340 1.4 into Si crystals was performed for the case of flat and 480 3.64 L 460 1.0 linear implantation profiles. Rutherford Backscattering Spectroscopy has been Energy (MeV) used to determine depth distributions of the implanted 1.1 1.2 1.3 1.4 ions. It was found that very good agreement is held -RUMPsvm. between the assumed theoretical profiles and a •o 5 .A Si imp!. Sb measured ion distributions. To perform an optimization procedure of implant- ation sequences, a computational program has been elaborated in view of realization of the required depth 'S 3 distribution profile in a crystal. The results of optimization, with a possible correction by the user, can be presented on the display screen either in the form of a table with all implant- ation sequences or as an equivalent plot representing the impurity distribution in a crystal. 600 650 700 750 800 In this paper, according to its major objective, a fit of the implanted ion distribution to two kinds of profiles has been assumed: Energy (MeV) 1. a flat profile (i.e. a constant concentration of atoms 1.1 1.2 1.3 1.4 in a crystal) from the surface up to the depth of 2000 A, and then decreasing to the zero impurity - RUMP svm. b . O Si imp), Sb concentration inward a further 1000 A. 2. a linearly decreasing concentration of the im- planted ions from the surface of a crystal, starting from 0.7% to the zero impurity concentration at a distance of 2500 A in the bulk. r The data for the projected range Rp and the O •) standard deviation ARp for ion energies have been acquired from the calculations performed, using the program TRIM'91 [1]. In this program five sequences of implantations have been assumed. The results of this calculation are presented in Table 3. 600 ~7§0 730^ 880C 0 Fig.la shows a random spectrum obtained for the Channel implanted Sb+ ions. In this case, the flat depth distribu- Fig.l. RBS spectrum (circles or triangles) of the implanted Sb'' ions tion over a given distance was assumed. and the calculated spectrum (solid lines) which has been In the same Fig., the spectrum obtained from a obtained, assuming the following profiles: a) constant concentration of the implanted atoms from the surface down computer simulation using the RUMP program [2] to 3000 A inwards, b) linear decrease of the implanted atom which was adapted particularly for the RBS spectra, concen-tration from the surface down to 2500 A inwards. 46 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 1.0 0.9 a 0.8 Wo.6 TO.Sr 0.3 0.2 +\ 0.1 \ x + 0.0 • 0 700 1400 2100 2800 3500 700 1400 2100 2800 3500 Depth [A] Depth [A] Fig.2. Assumed theoretical profiles (dashed lines) and the corresponding experimental distributions (crosses) of the Sb atoms concentrations in silicon: a) flat profile - No. 1, b) linear profile - No. 2. For both cases there is very good agreement be- relates the energies of the implanted ions with their tween the assumed theoretical profile and the experi- ranges and standard deviations of the Gaussian dis- mentally obtained distribution of the implanted Sb tributions. atoms in silicon which was shown in Figs. 2a and 2b. It is very likely that similar results can be obtained for References some other materials and implanted ions. The only [1], Biersack J.: TRIM'91, Berlin 1991. condition is to have a reliable characteristics which [2]. Doolittle L.R.: Nucl. Instr. Meth., B9,334 (1995). DRS QUANTIFICATION OF ABSORBED RADIATION DOSE INDICATED BYLABELS Zbigniew P. Zagorski, Andrze j Rafatski -Mi PL9902209 Dosimetry is an integral part of radiation processing gested isodose curves in electron beam radiation [1]. The most important is the quantitative dosimetry processing. of precision and accuracy demanded by a particular As far as it is known, the quantification of label radiation technology. Parallely to the precise dosimetry, a dose indicators have not been proposed yet in publi- qualitative or semiquantitative dosimetry in the shape cations or in ASTM standards. The development of of labels or indicators, usually attached to the standard stopped 9 years ago, due to the difficulties in irradiated object, is applied. reaching consensus in that complicated standard [2]. Many chemical systems are proposed and some of The conventional spectrophotometry cannot be them commercially produced as selfadhesive labels, applied for quantification, because it would demand described in publications and in patents. They are dissolution of the dye preparation etc., making the usually basing on the combinations of dyes with a dosimetric procedure unacceptable. The only mode of polymer base, most often there are acid-base operation is a non-damaging measurement by diffuse indicators embedded in a matrix with a chorine reflected light spectrophotometry. The development of containing compound. A simple radiation induced that branch of spectrophotometry is nowadays very reaction causes the release of HC1, which reacts with wide and proper laboratory and hand-held instruments a colour pH indicator with obvious results. Other are available. systems are possible, but they always involve the for- Our measurements have used two widely used mation of a new colour, easy to notice and comparable labels - with one or more dyes compositions. Optical by nacked eye with standards. The estimate is a half- density in the DRS mode were measured with a quantitative and sometimes even qualitative, when the Lambda 9 spectrophotometer, Perkin Elmer equipped label becomes a go-no-go indicator for an easy check with a light integration sphere. The reference was if the object has been irradiated or not. always un irradiated label, which has a deciding advan- Labels produced commercially have a uniform tage over other DRS systems which use measurements composition and thickness, therefore they should be against the standard whiteness (BaSO4). That technol- a subject of improved application by a more precise ogy of measurement proved its veracity in many cases measurement of optical density, than a visual compari- of radiation research [e.g. 3,4]. son. Additional argument is the flatness and low Figs. 1-3 show examples of quantification of irra- thickness of the label, corroborating with highly con- diated labels. The negative absorption in Fig.3 means RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 47 Z: sti26i$2; 658,8 - 458,B m; )>ts 281'. tot 1.86; ord -i.W - 3.8212 R 8.8 - 288,8 m: pts 681: int 1.88: ori -B.31B - 1.5824 FS Irf: Etiju Indicator us S k^ za key el 1.60" 5.0" o.o 400.0 500.0 600.0 700.0 800.0 450.0 nm nm Fig.l. Set of absorption spectra of irradiated Etigam indicator. Fig.3. Set of absorption spectra in double dye system: 1 - 120 Gy, Absorption spectra refer to doses indicated. All absorptions 2 - 350 Gy, 3 - 1170 Gy, 4 - 2340 Gy. All absorptions are are measured against the unirradiated labels as reference. measured against the unirradiated labels as reference. that the yellow dye in the composite is destroyed and the red dye is formed instead. Fig.3 is convincing that the measurement shows the difference of the intensity of the colour, whereas the differences of colours are no longer recognizable by eye. References [1]. Zagbrski Z.P.: Dosimetry as an integral part of radiation pro- cessing. In: International Symposium on Techniques for High- Dose Dosimetry in Industry, Agriculture and Medicine, Vienna, 2-5 November, 1998. IAEA-SM-356/23 (in print). [2]. Standard practice for use of a radiochromic label dosimetry system. Standard under development E10.01, J. Am. Soc. for Testing and Materials (ASTM) 1990. [3]. Zagorsk) Z.P., Rafalski A.: Diffuse reflectance spectrophoto- metry in polypropylene radiolysis study. Radiat. Phys. Chem., 30 40 48,595(1996). dose [kGy] [4]. Zagorski Z.P., Rafalski, A.: Free radicals in irradiated unstabil- ized polypropylene, as seen by diffuse reflection absorption- Fig.2. Calibration curve for DRS quantitated Etigam indicator. spectrophotometry, Radiat. Phys. Chem., 52,257 (1998). A THIN, COMPOSITE SODIUM CHLORIDE DOSIMETER WITH DIFFUSE REFLECTED LIGHT SPECTROPHOTOMETRIC READ OUT Zbigniew P. Zagorski, Andrzej Rafalski The contemporary dosimetry for radiation processing Our interest concentrated on the F-centers (color is based on solid state radiation chemistry. Specific centers) in irradiated alkaline halides. Known for more lo characteristics of electron beam (EB) processing, than one hundred years, and even longer from namely congested isodoses, i.e. unfortunate hetero- mineralogy as pleochroic circles, they are now geneity of the radiation field, demands thin layer understood as due to radiation released electrons, dosimeters. The most popular solid dosimeter, which trapped in anionic vacancies of halides. The frequency consist of the EPR-determined free radical anion of electron oscillations is determined by the size of the CH3C"HCO2~ formed by deamination of alanine, is elementary cell, i.e. of the size of the anionic vacancy. difficult to realize precisely in a thin geometry, due to Thus, the absorption band of light in irradiated the difficult to avoid, naturally preferred but undesired rubidium bromide is in infrared, whereas in lithium orientation of crystals in the matrix (Przybytniak, fluoride lies in UV, therefore the color is not visible. Zagorski [1]). Introduction of optical measurement of The irradiated sodium chloride is bright yellow. The the same radical anion, by diffuse reflection specrro- absorption of light is connected with redistribution and phophotometry (DRS) helped to neglect the crystalline removal of electrons from their traps. Therefore the anisotropy of alanine dosimeter (Zagorski, Rafalski [2] color is not permanent, but the bleaching effect is and references therein). The interesting results gained different for different salts. The case of two similar by this version of thin layer EB dosimetry made us to salts - potassium and sodium chlorides is a good look for other systems suitable for EB dosimetry. example, because the violet colored KCI is bleached 48 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES easier in the daylight than NaCl. For these reasons conveyor of controlled speed (Zag6rski [6]). This linac NaCl has been selected for further investigation. is routinely used for commercial radiation processing. Optical absorption by electrons trapped in natural Another linac for routine radiation processing has anionic vacancies in NaCl has been used for the been also used, of energy limited to 10 MeV, as well construction of a dosimeter for radiation processing. as a van de Graaff electron accelerator of maximum Although NaCl has not been used yet as the energy of 2 MeV with the possibility of energy of dosimeter in the way we are proposing, one has to electrons reduced to 100 keV. For the purpose of 60 mention that there have been some approaches to the comparison, the y radiation from Co, high intensity 1 application of electrons trapped in halides in (5 kGy h" ) source has been used. dosimetry. Thus, McLaughlin et al. [3] proposed to measure their concentration by conventional UV i spectrophotometry of irradiated LiF single crystals. 1 These centers are not easily bleached by ordinary A electric bulb light. The method, which demanded expensive single crystals, did not find wider applica- tion. A more popular approach using irradiated sodium /A \ chloride consists in measurement of the lyolumine- / ' scent light emitted during dissolution of irradiated J, / sodium chloride crystals in water. The system has 1 been developed mainly by Indian workers (e.g. Patil et J5: / al. [4]) and has found applications, although there is \ ^ no information about the compatibility with demands 1^ K imposed by EB processing, concerning the thin layer thickness of the dosimeter and resulting precision of the response to the most popular doses applied in — ,r— 1i i processing. 300 400 500 600 700 nm To meet the demands of electron beam processing, Fig.I. Absorption spectra (DRS) of NaCI/polyethylene irradiated characterized by congestion of isodoses, the active with scanned EB (10 MeV) to doses from 20 (second lowest part of the dosimeter, microcrystals of NaCl are thin line curve), to 40, to 60 kGy (upper curve), combined embedded in polyethylene, forming a 0.3 mm thick with absorption spectrum, of 10 MeV EB irradiated single crystal of NaCl, obtained by Owaki et al. [5] (lowest thick film, in which isodoses from 10 MeV electrons do not line curve. The absorption below 300 nm in our NaCI/PE exceed ±2% difference in dose. The NaCl composite composite is due to radiation induced oxidation products of with polyethylene has been prepared as a film in polyethylene. It is more intensive at a low dose rate of y Brabender devices typical for polymer research, by irradiation (see full text of the paper, to be published). repeated mixing and extrusion. The dosimetric film is The dosimetric work allows some basic con- opaque and the optical density at the wavelength clusions. The first question to be answered is the A.max = 465 nm, i.e. the maximum absorption of the Fl veracity of the measurement of F-centers spectra in band, is measured by diffuse reflected light spectro- conditions far away from conventional. As a compari- hotometry (DRS) on a routine spectrophotometer, in son we have chosen the spectra obtained by Owaki et the matter of minutes after irradiation. The measure- al. [5] on single crystals of NaCl irradiated with ment is executed against the unirradiated film as refer- electron beams of 10 MeV energy to doses similar to ence, thus increasing the accuracy, by compensation of ours, applied for the purpose of radiation processing. signals not belonging to the absorption of F-centers. Fig.l shows Owaki's and our results combined on the The spectrum obtained in such a way is identical with same wavelength scale. The exact overlap of maxima the spectrum of F-centers in irradiated single crystals of bands is a proof of veracity of spectral measurement of NaCl. Comparison of our spectra with single crystal of absorption of trapped electrons in anionic va- spectra recorded by Owaki [5] is shown in Fig.l. The cancies, in spite of extremely different conditions: calibration curve of the height of the band is almost » large NaCl single crystals vs. microcrystals linear vs. dose in the range of several tens of crushed and sieved to the size of ca 10 fim, kilograys. Because ordinary grades of sodium chloride • neat single crystals vs. polycrystalline powder may be used, the resulting dosimeter is very cheap, embedded in polyethylene, allowing thorough mapping of the irradiation field in • optical absorption measured by conventional single objects of complicated geometry. beam spectrophotometry with an analytical beam The main, mostly used irradiation source was of light passing through the crystal vs. optical a linear electron accelerator of 5-13 MeV energy and absorption measured by double beam diffuse light 6-9 kW power in the beam. The latter could be used as reflection spectrophotometry with one beam falling the straight beam, or a scanned beam, of more mono- on the sample of irradiated film and the second energetic spectrum, for irradiation of samples on the probing the unirradiated film from the same batch. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 49 The energy of electrons which were used to minutes from taking the dosimeter from the irradiated generate the trapped electrons should not play any role object on the conveyor. Dosimetric films may be (except for the geometry of energy deposition) stored as the documentation of processing, in a black because only the electrons of last generation, ther- paper envelope, because day light causes bleaching of malized to a low value of energy are trapped in F centers. There is also a natural bleaching caused by anionic vacancies. The comparison between the effect vibrations of the lattice, therefore the films have to be of 10 MeV and 0.1 MeV electrons will be shown in stored at room temperature, preferably in an air- a full version of the paper. The maxima of bands (kmm conditioned laboratory. Every batch of dosimeters is = 465 nm and Xmm = 720 nm) are the same and so is calibrated for the natural decay of the absorption, the relation of the heights of two bands which are therefore in the case of a (rare) need one can recon- exactly the same. The first band is identical with many struct the dose. The exact corrections for bleaching are times described band of Fl center identified by accompanying particular batches of dosimetric film. electron trapped in a single CV anion vacancy. The The temporary increase of temperature during accel- nature of the lower energy band is not clear. It does erator irradiation, which is of adiabatic nature not play any role in dosimetry and will be discussed in (Zagorski [7]) is incorporated into a calibration curve. another part of the studies on radiation chemistry of There are no unusually high temperatures in the sodium chloride. The unknown, as yet nature of the irradiation room itself which is always routinely air- second band does not interfere with the application of cooled because irradiated objects are very often our system to the dosimetry of any radiations - y or sensitive to heat (e.g. hydrogels). electrons of any energy, using the first band. Acknowledgments As it is the case with all secondary dosimeters, Part of the investigation was supported by the neither the alanine, nor the NaCl are absolute International Atomic Energy Agency under the dosimeters and have to be calibrated. The Fricke Research Contract No. 8533/R1. dosimeter may be realized in the absolute version, by recalculation of measured optical density to the dose References on hand of known radiation yield of iron(III) and the [1], Przybytniak G.K., Zag6rski Z.P.: Orientation of crystals in molar extinction coefficient of that species. A similar alanine dosimeter assessed by DRS, as seen in EPR spectra procedure in the case of alanine and NaCl is theoreti- evaluation., J. Radioanal. Nucl. Chem., Lett, 212, 373 (1996). [2]. Zagorski Z.P., Rafalski A.: A thin aianine-polyethylene film cally possible, but the accuracy of the result would be dosimetry system with diffuse reflection spectrophotometric doubtful. evaluation, J. Radioanal. Nucl. Chem., Articl., 196, 97 (1995). Although the NaCl-polyethylene film could have [3], McLaughlin W.L., Miller A., Ellis S.C., Kapsar B.M.: Radi- been made even thinner, the thickness of 0.3 mm is ation-induced color centers in LiF for dosimetry at high sufficient to cover isodoses from 10 MeV electrons absorbed dose rates, Nucl. Instr. Meth., 175, 17 (1980). [4]. Patil S.F., Ravishankar D., Bhatia P., Chowdhary I.B.: Chemi- differing less than by ±2% which is satisfactory from cal effects induced by Y-irradiated salts in aqueous medium, Int. the point of view of the overall precision of measure- J. Appl. Radiat. Isot, 35,459 (1984). ment of the field which is dramatically inferior to the [5]. Owaki S., Koyama S., Takahashi M., Karaada M., Suzuki R.: more homogenous fields achieved in the v-processing Metallic Na formation in/on NaCi crystals with irradiation by technology, especially in large irradiation plants, electron or vacuum ultraviolet photons, Radiat. Phys. Chem., 49,609(1997). where the boxes are traveling through regions of doses [6]. Zagorski Z.P.: Dependence of depth-dose curves on the energy of different dose rate, thus averaging the integrated spectrum, of 5 to 13 MeV electron beams, Radiat. Phys. Chem., dose. 22,409(1983). Radiation processing demands dosimetric results [7J. Zagdrski Z.P.: Thermal and electrostatic aspects of radiation processing of polymers. In: Radiation processing of polymers. as quickly as possible. The proposed dosimeter is Eds. A. Singh, I Silverman. Hanser Publishers, Munich 1992, faster than any other and the result is obtained in 10 pp. 271-287. ION BEAM DOSIMETRY. ABSOLUTE METHOD BASED ON ENERGY AND FLUENCE MEASUREMENTS ZofiaStuglik PL9902211 Nevertheless much modern instruments, cyclotrons done rather seldom. This results partly from a hard still hold a relevant position giving intensive and good access to cyclotrons, partly - from experimental quality beams of different ions with an energy in the difficulties, among them - dosimetry. Secondary range 1-100 MeV/amu. Such beams are used in atomic methods, useful and commonly used in low-LET and nuclear physics, material science, biology and experiments lose their versatile character in a high- medicine. Chemical studies with ion beams have been LET area. This is connected mainly with the LET- 50 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES dependence of the G-values. "The dosimetric answers" all of the ions instead 12C. For the light ions we have 12 to the same dose are different not only for different used the wair-values as for C. The errors connected ions with the same energy, but also for the identical with such an assumption did not exceed 1 -2%. In the ions with different energies. case of heavy ions - we calibrated our ionization The absolute methods could be divided in two chamber immediately on track detectors [1]. This classes: approach led to the situation similar as for the particle a) calorimetric methods, registration regime. b) methods based on energy and fluence measure- Energy in the vacuum, Eo was measured by means ments. of a semiconductor detector situated in the arm of a The calorimetric methods cannot be used as on- vacuum pipe and bombarded by the ions scattered with line methods or for external beams of the ions with an Au-foil. The scattering angle and energy losses were low or intermediate energy. The methods based on taken into account when evaluating the value of ion energy and fluence measurements have not such energy. shortcomings and are more frequently used. Energy on the surface of the sample, Es, was We employed one of such methods with good calculated as Eo minus energy losses in the target results in the course of radiation experiments on a system. The losses were calculated from the stopping power data (tables [2] or computer programs [3]) and U-400 cyclotron (KHIPTI facility, JINR, Dubna). We U n 2+ 12 2+ 18 2+ 22 3+ 24 3+ were changing from -10% for 113 MeV B up to used ion beams of B , C , O , Ne , Mg 59 40Ca5+, 52Cr6+, s6Fe6+ and 59Co7+ with a specific energy -50% for 397 MeV Co (for the same target configur- ranging from 2 to 11 MeV/amu. The ions were ation). extracted from a cyclotron chamber by means of The overall accuracy of dose determination for the charge exchange in thin graphite foils and went into light ions (B, C) was evaluated as 5-6% and for the the atmosphere through Al (-10 urn) or Ti (~4 um) heavy ones (Co, Fe) as 10-15%. windows. The fluences were measured by means of We checked our evaluations for the light ions by a 3-electrode, thin ionization chamber (Al; 5.6 um, air means of experiments with a Fricke dosimeter ir- 12 2+ at atmospheric pressure, air gaps -0.5 mm) situated radiated by the C ions with an energy of 120 MeV just under the vacuum window. Because of rather high and 105 MeV [4]. There were some data for such fluxes (108-109 pps) it was impossible to work at a system investigated by other scientists. The discrep- a particle registration regime. Instead, we have worked ancy between our data and the previous ones were in a current registration regime and the total fluence within the predicted accuracy range. was calculated from the formula: A full text of the work will be published in [5], 1 1 1 ALANINE/POLIMER RODS WITH LOW CONCENTRATION OF DL-oc-ALANINE FOR ROUTINE ELECTRON BEAM DOSIMETRY CM Zofia Stuglik, Teresa Bryl-Sandelewska iCNI :Cv| IS Radiation facilities using linear electron beam acceler- « for checking the dose settled for the irradiated ators demand careful dosimetry at three stages: product at least at the beginning, in the middle and (i) facility qualification, at the end of the run. (ii) product qualification, Alanine-polimer rods are useless for stages (i) and (iii) radiation processing. (ii) since they are too thick to dose distribution measurements. Instead, they are very useful for routine In the last case we have to use dosimeters: dose control at stage (iii). • for checking day-to-day stability of the accelerator Alanine dosimetry is considered to be expensive and transport system (before any run), because of an analytical device (EPR spectrometer) RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 51 and alanine costs. This is a misconception. The cost of was designed to be well-matched to the EMS-104 small dosimetry-dedicated EPR-spectrometers is cavity. actually at the level of UV7VIS spectrophotometers We have investigated: and there are at least two possibilities to diminish the • shape and stability of EPR-signals from a polymer cost of the dosimeters considerably. Firstly, we can matrix, alanine, and alanine-polimer rods, use a cheap, racemic form of alanine instead of an • stability of EPR-signal for various doses of gamma expensive, chiral one (such an approach has been and electron radiation, applied at some commercial dosimeters). Secondly - • dispersion of the EPR-signal amplitudes for we can use alanine-polimer mixtures at a low concen- dosimeters irradiated with the same dose, tration of the sensitive material. This way is quite new. • angular dependence of EPR-signal, Two years ago we started our experiments with • influence of heating of irradiated samples on EPR- DL-oc-alanine-polimer rods with the concentration of signal stability, alanine ~10% [1]. At the moment we are sure that it is a good direction. The EPR method is so sensitive that • signal-to-dose dependence for gamma and electron even working with low-concetration samples we still beams (calibration curves). keep a high reserve of sensitivity. The results are in preparation for publication. In all experiments an EMS-104 (Broker) EPR- Reference spectrometer was used as an analytical instrument. So, [1]. Stuglik Z., Bryl-Sandelewska T., Mirkowski K.: INCT Annual the shape of dosimeters (rods, 03 mm, 35 mm long) Report 1997, p. 104. RE-INVESTIGATION OF PVC FOILS USED FOR ROUTINE ELECTRON BEAM DOSIMETRY IN INCT Zofia Stuglik PL9902213 Even PVC-foils are not listed by international or advantage of PVC-foils is their low cost and a pos- ASTM standards as reliable high-dose dosimeters but sibility to evaluate an approximate dose also by eye nevertheless we have used them in this Institute for (non-irradiated foil is transparent, irradiated one - more than twenty years with positive results. A big brown). The main disadvantage is the instability of 10,6kGy 17,6 kGy Elektronika LAE 13/9 0.18 8 days 1 month 27 h 0.16 24 h 0.35- 0.3 '[ (-j • | - i-r—rT~l I ! I j I 1~T 360.0 380.0 400.0 420.U 360-0 38O.o 400.0 420. Fig.l. Absorption spectra of irradiated and heated (30 min, 70°C) PVC foils measured during one month after irradiation. 52 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES dosimetric signal. We confirmed the finding of work [1] that the The PVC foil actually used in the Institute position of the peak used for dosimetric measurements (producer: Staufen, Germany, type 37; 0.25 mm thick) (398 nm just after irradiation and heating) shifts was recommended by Zofia Bulhak after a detailed towards shorter wavelengths (394 nm). Time at which study of many kind of foils [1]. The procedure of the peak achieves a new position is different for electron beam dosimetry with PVC foils was also different samples. The new position is stable for at elaborated by her. According to this procedure the ir- least 1-2 months. radiated foils should be heated for 30 min at 70°C and For all investigated samples the optical absorption analyzed (absorption density measurement at 398 nm) measured at the peak value diminishes by about 11%- 30 min after. The last demand is hard to perform when 14% during the first day after irradiation. Then the many read-outs should be done at the same time. time dependence differs from sample to sample. The Because of that, the knowledge about the time vari- dosimetric signal can be quite stable (2% - 4%) in the ations of dosimetric signal is an important question. time range from 1 day to 1 month (Fig.lA) but also - Recently we obtained (IAEA Project POL/8/016) evidently unstable (Fig.IB). The reason for these kind a high quality UV/VIS spectrophotometer (CINTRA of differences and the question of long-term stability 40, GBC, Australia) which enabled us to start work on of PVC dosimeters will be investigated in the future. re-investigation of routine PVC dosimeters. In this contribution we present some results dealing with time Reference variations of a dosimetric signal. [1]. Buihak Z.: Ph.D. Thesis, 1976. MICROCRYSTALLINE L-a- AND DL-a-ALANINE IRRADIATED WITH GAMMA RAY AND HEAVY IONS AND ANALYZED BY MEANS OF INSTRUMENTAL METHODS Zofia Stuglik, Antonija Dindune1', Maja Burzynska-Szyszko2', Liene Actida1' " Institute of Inorganic Chemistry, Latvian Academy of Sciences, Salaspils, Latvia 5s=jI 5S) 2/ Department of Material Science and Engineering, Warsaw University of Technology, Warszawa, Poland Two forms of macrocrystalline cc-alanine: L-a- (chiral) investigated them by means of X-ray diffractometry, and DL-cc- (racemat) are commonly used as dosimetric IR spectroscopy and thermogravimetric methods materials. Both alanines crystalize in an orthorhombic (DTA, DTG, TG). The irradiations were performed at system and - what is interesting - have nearly identical the 1NCT, Warsaw and the JINR, Dubna, Russia. The cell dimensions. The space groups are: P2i212] for measurements were done at the HCh LAN, Salaspils, L- crystals and Pna2[ for DL-form [1]. Latvia and at the Warsaw University of Technology. The well-known, stable EPR signal observed in Comparison of the results for DL-a-alanine and irradiated microcrystalline alanine is commonly ascribed L-a-alanine led to an interesting finding. The conse- to CH3CH*COO- radicals formed after the break-up of quences of irradiation seem to be different for racemic C-N bond. The second product is an ammonium and chiral forms. molecule, NH3. Its radiation yield is about 4 molecules IR. and X-ray spectra of irradiated and non- perl00eV[2], irradiated DL-a-alanine are practically undistinguish- Another one, small and gaseous in normal able. On the contrary, for L-a-alanine we observed conditions molecule, formed during the radiolysis of measurable differences for IR spectra in the range 1 1 alanine, is CO2. The latter has been detected by many 3100-2500 cm' and 1660-1485 cm' and also some authors, but its radiation yield is much lower than that changes in the X-ray spectra. The later ones can be ofG(NH3). interpreted as some changes in atom positions but Some authors suggest existence of an additional always inside the same, orthorhombic cell. species with low molecular weight as products of the We have not observed any significant differences radiation destruction of alanine ("debris") [3] but between the samples irradiated with gamma rays and without experimental support. the ion beams. The question was at what extend the generation of The work is continued and its first part is in gaseous products inside the microcrystals leads to preparation for publication. measurable changes of their physico-chemical para- References meters? [I]. Simpson H.J., Marsh R.E.: Acta Cryst., 20, 550-555 (1966). We irradiated L-a- and DL-a-alanine micro- 60 [2]. Van Laere K., Buysse J., Berkvens P.: Int. J. Appl. Radiat. Isot., crystals with Co gamma rays (D ~ 480 kGy) and 41), 885-891 (1990). 40 2 heavy ions ( Ar, 370 MeV, Wojciech Malicki, Zofia Stuglik Research on intrdducting the usage of a measuring- RIS0 (High Dose Reference Laboratory, Denmark), method for the determination of electron beam energy was obtained. Detailed results have been already of an industrial accelerator in accordance with the published [4]. understanding used in ASTM Standard E 1649 [1], was undertaken. The method is based on the character- ..... -a- - -• — ..... isation of depth-dose distribution in a reference •-- material. In the next step, based on earlier [2] empiri- •*- cally determined dependencies, calculations were ...... ± carried out of two statistical parameters of energy: the •-- ± . most probable energy and the average energy. Taking E.'•8,0 nun Z» )mn into account that the energy of accelerator can be set t -12, ..... P— in the range 6-11 MeV, metallic aluminium was 4 r E,= O.lx(O.2 + 5.09 R,) " chosen as the absorbency reference material. For dose \- :-. -- 20RJ0) - — •r .... •- — measurements thin-layer radiochromic films were ...... — ... — ..r •••••" ... used. Application of the reference material in the form — ... — : •^ - •-- of wedge, and measurement of dose on a continuous ...... strip were found to be especially useful. Use of a spectrophotometer with a build-in automatic feeder for "• such a long strip [3] also was very useful for reading- -"• - y units ] ...... out depth-dose distribution. A special aluminium -• •«- ' H wedge in the stair form was made (see Fig. 1). An ;; :ii ...... • 8 — — .... example of the spectrum of depth-dose distribution in —: — ft" _..: — :;: •:..-. "~ -•: ELECTRON BEAM — • - ;'- -. • r.T ~: -r 1 v K - • -- 24,38 liiillliilllJ • K SO .«f •_-_ J DEFIH IN ALUMINIUM [mm] i . " i i.i i. .i -i- ...i j Fig.2. Depth-dose distribution curve, where is: Ep [MeV] - most probable energy, Ea [MeV] - average energy, Rp [mm] - T practical range, R50 [mm] - half-value depth. References [1]. Standard practice for dosimetry in an electron beam facility for radiation processing at energies between 300 keV and 25 MeV. i ASTM Standard E 1649-94, 1994. - 300 mm • [2]. Stopping powers for electrons and positrons. International Fig.l. The absorbencies aluminium wedge: I - top view (the slit for Commission on Radiation Units and Measurements (ICRU). dosimeter strip is seen), 2 - side view. Report no. 37, 1984. [3]. Machaj B., Stuglik Z., Panta P., Katuska I., Bryl-Sandelewska such a wedge is shown in Fig.2. It is very interesting T., Strzalkowski J., Malicki W.: Computerized PVC absorbance that the effects of surface changes in the region of the reader as the device for quick detection of dose distribution on, stair edges are visible in considerable depths of the under and inside the electron irradiated object. IAEA- wedge. Good agreement of measurements with TECDOC-1023. IAEA, Vienna 1998. comparative measurements in water and in the [4]. Malicki W., Stuglik Z.: Wyznaczanie energii elektronow w wiazce przemiatanej akceleratora liniowego poprzez dozyme- aluminium wedge of lineal inclination, provided by trie. dawki glebinowej. Raporty ICHTJ. Seria B nr 12/98. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES OPTICAL PROPERTIES OF GAMMA IRRADIATED ARTIFICIAL SAPPHIRE AND YTTRIA STABILIZED ZIRCONIA SPECTROSCOPIC WINDOWS SCO 1 : T— Leon Fuks, Claude Degueldre ' I CM ;CM 11 Paul Scherrer Institute; 5232 Villigen PSI, Switzerland It has been already shown that a continuous, non- color of c-YSZ samples changed rapidly from totally invasive monitoring of the formation of corrosion transparent to transparent yellowish-brown at the dose layer in a nuclear reactor operating mode can be range 3-10 kGy. Selected values of optical trans- effectively performed using optical spectroscopy. A mission, obtained for the AO and c-YSZ specimens novel technique for monitoring the oxide layer growth irradiated with different doses are presented in Figs. 1 on-line, reflectance spectroscopy (RS), seems to be and 3. one of the most attractive. Its development, verifica- As one can see from Fig.l, the spectra of irradiated tion and application was recently reported [1,2]. One AO samples differ only slightly from that of non- of the crucial points for the reliable optical measure- irradiated material. A broad plateau in the transpar- ments is a long-term stability of window material in ency range of 500-1000 nm seems to be stable, and the presence of reactor cooling water. The window transmission coefficients are close to 100%, indepen- should be transparent and must form a pressure/tem- dently of the radiation dose. On the contrary, a signifi- perature barrier for a long time. Considering the cant decrease in the transparency upon y-irradiation requirements (BWR operating conditions, thermo- can be observed below 400 nm. These data seem to be mechanical stress, optical transparency, and commer- in good agreement with those presented by Orlinski et cial availability), a-aluminium oxide (AO) in the form al. [4]. of artificial sapphire and cubic single crystals of zirconium oxide stabilized with yttria (c-YSZ) have 100-1 been chosen as the most promising window materials on the basis of both the initial literature search and 75- 150 kGy preliminary experimental tests. The present investigations were undertaken to study the influence of y-radiation on the UV-Vis-NIR light transmission through both the optical materials mentioned above. The problem is of importance I 25H because numerous corrosion products can be released into the circulating reactor coolant, and some of them 0- can be neutron-activated. It is known that a major part 200 400 600 800 1000 of the total dose of radiation emitted by the primary wavelengths, nm circuit water (about 450 Sv/year) comes from the 16N 16 16 radioisotope produced in the O(n,p) N reaction, as 100-j well as from the slCr, 54Mn, s9Fe, S8Co and especially from 60Co. 75- Investigated specimens were irradiated in the Paul Scherrer Institute with various doses of y-radiation at room temperature in a channel of the 60Co-source 1 (Gammacell 220, AECL, Canada). The smallest dose v> of radiation was 0.5 kGy and the highest -150 kGy. 2 25 UV-Vis-NIR spectra measured were smoothed 900 nm; 700 nm; using the Savitzky-Oolay method [3] which performs 500 nm; 300 nm a local polynomial regression to determine the 0 25 50 75 100 125 150 smoothed value for each data point. The residual dose, kGy spectra, i.e. the difference spectra of irradiated and Fig.l. Transmission spectra of the irradiated artificial sapphire in non-irradiated samples, were deconvoluted into comparison with the non-irradiated material (upper plot). separate gaussian peaks. It has been already shown Changes of optical transmission with increasing y-radiation that because of strong light absorption in water, only dose (lower plot). the region of wavelengths below 1000 nm should be Fig.2 presents selected residual spectra calculated examined [1]. for the sapphire window irradiated at selected doses. It has been observed that the color of AO The spectra show two separate absorption bands in the specimens did not change significantly after y- regions of 300 and 400 nm, preceding the plateau irradiation up to Dy = 150 kGy. On the contrary, the starting from about 600 nm. It has already been shown RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 55 that y-irradiation of oc-AO causes the generation of 100- OkGy hole centers with an absorption band close to 400 nm (about 3.1 eV) and electron centers in the UV region [5]. Therefore, the observed slight decrease of trans- mission of sapphire windows due to the irradiation can be related to creation of optical centers as a result of appearing lattice defects. 0,150-1 0,100- 400 600 800 1000 wavelengths, nm 0,050- 100 0,000 200 400 600 800 1000 c •3 50- wavelengths, nm .2 CO a 25 0,050- a 900 nm; o 700 nm; 500 nm 0 0 25 50 75 100 125 150 dose, kGy 0,025- Fig.3. Transmission spectra of the irradiated yttria-stabilized zirconia in comparison with the non-irradiated material (upper plot). i Changes of optical transmission with increasing y-radiation dose (lower plot). 0,000- 150 kGy 0,300- 200 400 600 800 1000 wavelengths, nm Fig.2. Residual optical absorption spectra for artificial sapphire ir- 0,200 radiated with selected doses of y-radiation (upper plot). Deconvolution of peaks for spectrum attributed to 5 kGy dose (lower plot). 0,100- The dose dependence of light transmission through the c-YSZ window is presented in Fig.3. It can be seen 0,000- that the lower end of the transparency plateau shifts from 400 to 700 nm. The plateau shifts only for low 400 600 800 1000 Y-radiation doses (3-10 kGy). Greater doses, up to wavelengths, nm 150 kGy do not influence the lower end position. The 388 nm transmission coefficients on the plateau do not practi- cally depend on the radiation dose. 0,150- As one can see from Fig.4, residual spectra calculated for y-irradiated c-YSZ in the region of 350- 0,100- 1000 nm show one broad absorption peak with a maxi- o mum around 395-405 nm (i.e. for transitions with an % 0,050- energy of about 3.1 eV). It corresponds well to the value of 3.2 eV (395 nm) reported by Dietrich et al. [6] and is thought to be responsible for the yellowish- 0,000- brown colorization of polycrystalline yttria-stabilized tetragonal zirconia. The spectral peak at 3.2 eV has 400 6Q0 800 1000 been described by Dietrich as related to transition wavelengths, nm occurring in an unknown extrinsic defect, associated Fig.4. Residual optical absorption spectra for yttria-stabilized zirconia irradiated with selected doses of y-radiation (upper plot). with tracer ionic impurities in the zirconia poly- Deconvolution of peaks for spectrum attributed to 5 kGy crystal. dose (lower plot). 56 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES Because of requirements of optical measurement' References conditions (temperature of about 300°C), the samples [1]. Degueldre C, Fuks L., Schenker E.: In-line measurement of the of both investigated materials were heated (starting oxide layer build-up on zircaloy under Boiling Water Reactor from 150°C) after several consecutive irradiations. (BWR) conditions using diffuse reflection spectroscopy, Meas. It has been found that only heating at above 210°C Sci. Techno!., 9, 809-815 (1998). causes a permanent decolorization of zirconia [2]. Degueldre C, Fuks L., Schenker E.: Pre-oxidation of stainless steel, a study by diffuse reflection spectroscopy, Appl. Surface windows. Optical transmission spectra recorded for Sci., 134,254-262(1998). both heated specimens were similar to those for non- [3]. Savitzky A., Golay M.J.E.: Smoothing and differentiation of irradiated samples. It can be suggested that in-line data by simplified least squares procedures, Anal. Chem., 36, optical monitoring of the corrosion process occurring 1627-1639 (1964). in the nuclear installations operating under the BWR [4]. Orlinski D.V., Al'tovsky I.V., Bazilevskaya T.A., Gritsyna V.T., conditions can be performed applying both artificial In'kov V.I., Ivanin I.A., Koval'chuk V.D., Krasil'nikov A.V., Pavlov D.V., Tarabrin Yu.A., Turchin S.I., Vojtsenya V.S., sapphire and yttria-stabilized zirconia windows. Yudin I.L.: Preliminary results of window radiation resistance This research was supported in parts by the investigations, J. Nucl. Mat, 212-215, 1059-1064 (1994). International Atomic Energy Agency (Research [5]. Crawford J.H., Jr.: A review of neutron radiation damage on corundum crystals, J. Nucl. Mater., 108-109, 644-654 (1982). Contract No. POL-8426), the Polish State Committee [6]. Dietrich A., Heimann R.B., WiHmann G.: The colour of for Scientific Research (KBN) and the Swiss Federal medical-grade zirconia (Y-TZP), J. Mater. Sci.: Mater, in Nuclear Safety Inspectorate (HSK). Medicine, 7, 559-565(1996). PRELIMINARY APPLICATION OF MODULATED DIFFERENTIAL SCANNING CALORIMETRY IN STUDIES OF HEAVY ION IRRADIATED POLYESTER FILMS Krystyna Ciesla, Madeleine Ribeiro1' " Laboratoire de Thermodynamique et Genie Chimique, Universite Blaise Pascal, Clermond-Ferrand 2, France is Modulated differential scanning calorimetry (MDSC) a subsequent evaporization of the solvent. The is a modern thermal analysis enabling separation of granulate was kindly supplied by Dr. Karolina the reversible and non-reversible processes occurring Grzebieniak from the Institute of Chemical Fibres in simultaneously during heating or cooling of a sample Lodz, Poland. Part of this film was irradiated with Ar [1,2]. In this method the sample is heated with a ions (5.5 MeV/amu, 5 x 1011 ions/cm2) in the Centre modulated heating rate, while in the traditional differ- du Recherche du Cyclotron in Louvain-la-Neuve. ential scanning calorimetry (DSC), the constant heating MDSC measurements were done applying a Metier- rate is applied. Mathematical elaboration of the raw Toledo Star system in the temperature range from MDSC signal enabled us to calculate separately 25°C to 250°C in the heating-cooling-heating cycles. a reversible heat flow, a non-reversible heat flow and The heating was carried out with a modulated heating also a total heat flow. rate (an average heating rate 2°/min), while cooling Traditional DSC enabled to observe the differences was realised with a constant rate of 10°/min. In the in Tg transformations and relaxation in the amorphous first step the modulation type, enabling a proper state, occurring in thin films prepared from separation of signals of the reversible heat flow and of copolymers of poly(etylene terephthalate) with lactic non-reversible heat flow, was selected. acid, initial and irradiated with heavy ion. These two Application of the MDSC method enable us to processes occur simultaneously during heating of the observe separately Tg transformation (on the revers- samples, therefore it is not possible to determine ible heat flow curve) and the endothermal process of exactly the heat of endothermal process, change in the structural relaxation in the amorphous state (on the specific heat and characteristic temperatures of both non-reversible heat flow curve) occurring simulta- processes. Moreover, it was difficult sometimes to neously in the temperature range up to 90°C. The separate the processes of cold crystallization (exo- superposition of thermal effects of these processes is thermal) and melting (endothermal), due to their broad observed on the total heat flow curve, corresponding thermal effects with indistinct boundaries. At present, to the traditional DSC signal (Fig.l). The method an attempt is made to investigate the processes made also possible to calculate the reversible and non- occurring in such films applying the MDSC method. reversible contribution to enthalpy of melting and to The film under examinations was prepared by obtain a good separation of cold crystallization and dissolution of polymer granulate (containing 34.3 wt% melting, occurring during the second heating (Fig.2). of lactic acid) in a chloroform solution. Then the sol- In the case of irradiated sample the lower temperature ution was put into a glass substrate followed by of glass transition and a smaller heat of melting RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 57 (mainly non-reversible contribution) were observed, as 0.75 well as a bigger heat of cold crystallization were detected during the second heating. 0.6 0.5 r 0.45 0.4 non-reversible heat flow I 0.3 0.15 5I 0.2 0.1 20 40 60 80 100 120 140 180 180 200 220 240 260 temperature, C Fig.2. Total, reversible and non-reversible heat flow recorded for the initial film during the second heating. In particular, the 0 I 1 1 < 1 i i i ' • ' ' \ enthalpy of cold crystallization was determined as equal to 20 40 60 80 100 120 140 160 180 200 220 240 260 11.9 J/g (non reversible heat flow), while reversible and temperature, C non-reversible contributions found for the enthalpy of Fig.l. Total, reversible and non-reversible heat flow recorded for melting were equal to 10.4 and 15.3 J/g. For the irradiated the initial film during the first heating. The values of total film, the values of 17.9, 15.3 and 7.4 were found, enthalpy of melting was equal to 35.5 J/g, while the values respectively. reversible and non-reversible contributions were equal to 22.10 and 13.4 J/g. In the case of irradiated film the values References obtained were 25.0, 13.1 and 10.9, respectively. The [i]. Reading M., Elliott D., Hill V.L.: A new approach to the cal- midpoint of Tg transition was observed at 55.5°C and orimetric investigation of physical and chemical transitions, J. 51.9°C, while the non-reversible contribution to structural Thermal Anal., 40,949-955 (1993). relaxation was equal to 11.1 and 8.2 J/g in case of the initial [2]. Reading M, Luget A., Wilson R.: Modulated differential and irradiated film, respectively. scanning calorimetry, Thermochim. Acta, 238,295-307 (1994). APPLICATION OF WAXS DIFFRACTION IN STUDIES OF CRYSTALLINITY CHANGES IN HEAVY ION IRRADIATED POLYESTER FILMS jco Krystyna CieSla ici is WAXS diffraction was applied in studies of the effect (for PET films) and 5 x I01' (for PBT films) ions/cm2. of heavy ion irradiation on the crystalline phase WAXS measurements were carried out using an Q- content in polyethylene terephthalate) (PET) and HZG4-C X-ray diffractometer applying CuK 10 • 2"0 ' 3'0 4"0 5*0 6'0 7( 2 theta degree Fig.l. WAXS diffraction patterns of PET films: 1 - amorphous PETl film (melted at 300°C, moulded at 30°C), 2 - semi- crystalline initial film PET2 (melted at 300°C, moulded at 30°C, annealed at 210°C for 5.5 h), 3 - the film irradiated with Ar ions (5.5 MeV/amu, 2x10" ions/cmz). The measure- ments were done applying CUK<, radiation. An attempt was made to solve the WAXS pattern of PET semicrystalline films, applying the Hindeleh- 0 Johnson method [2], assuming the presence of several 8 18 28 38 crystalline reflections and 2 amorphous reflections in 2 theta degree Fig.2. Comparison of diffraction patterns of the highly crystalline the pattern. An example of the pattern solution is c shown in Fig. 3. The crystallinity indices calculated on initial PBT film (melted at 260 C, moulded at 20°C, annealed at 200°C for 3.5 h) and of the film irradiated with Ar ions the basis of the above solutions were equal to 0.468 (5.5 MeV/amu, 5x10" ions/cm2). The value of relative and to 0.334, for the initial and the irradiated films, crystallinity index was determined as equal to 0.77 for the respectively. The volume crystallinity indices were irradiated sample, while the crystallinity index was assumed determined as being equal to 0.492 and to 0.373, as 1.00 for the initial sample. The volume crystallinity indices were calculated as equal to 0.266 and 0.174 and the respectively. crystallinity indices calculated on the basis of the heat of Relative crystallinity indices xd were calculated for melting were equal to 0.266 and 0.174, repectively in the the PBT films on the basis of WAXS patterns, by case of the initial and the irradiated samples. 700 20 30 40 50 60 70 2 theta, degree Fig.3. Solution of diffraction pattern of the initial PET2 film (melted at 300°C, moulded at 30°C, annealed at 210°C for 5.5 h). The experimentally found scattering curve is shown as a grey shadow line, while the calculated scattering curve is shown as a thin black line. RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES 59 References Poland, 2-5 December, 1998 (in press). [2], Rabiej S., WJochowicz A.: Angew. Makromol. Chem., 175, 81- [1]. Ciesla K.: Application of WAXS diffraction in studies of crystallinity changes in heavy ion irradiated polyester films. In: 97(1990). Proceedings of the Fourth International Workshop on X-ray [3], Wakelin J.H., Virgin, J.H.S., Crystal E.: J. Appl. Phys., 30, Investigations of Polymer Structure, XIPS'98, Bielsko-Biaia, 1654(1959). DIFFERENTIAL SCANNING CALORIMETRY STUDIES OF ANNEALING AND HEAVY ION IRRADIATION INFLUENCE ON MELTING AND CRYSTALLIZATION PROCESSES IN POLYETHYLENE TEREPHTHALATE) Krystyna CieSla, Etienne Ferain1', Roger Legras1', Wojciech Starosta is !/ Unite des Hauts Polymeres, University Catholique de Louvain, Louvain-la-Neuve, Belgium IS ID- In our earlier work differential scanning calorimetry selected and irradiated with Ar ions (5.5 MeV, ca. 2 x ^^ enabled to observe the differences in melting and 1010 ions/cm2). Moreover, the films prepared from |^= crystallization processes occurring in thin biaxially PET and four co-polymers of PET with oligo-1,4- ' stretched poly(etylene terephthalate) (PET) films, oxybutylenediol (PTMEG) [3] (30-50 ^m thick), con- (unirradiated) and heavy ion irradiated [1,2]. Studies taining 10-40 wt% of PTMEG, were obtained from the of physico-chemical changes occurring under heavy Szczecin Technical University. These films were ion irradiation were at present continued for non irradiated with Ar ions applying a fluence of 7 x 10u oriented PET films displaying various crystallinities. ions/cm2. The work is connected with the search for new Two sets of DSC measurements were performed in materials for heavy ion detectors and particle track heating-cooling-heating cycles. Heating-cooling-heat- membranes (PTM). ing rates 10-10-10°/min were applied in set I, while A series of PET films (90-100 \xm thick) were in set II rates of 10-80-107min were used. The prepared. WAXS results show that the films display differences were observed between melting, crystal- different crystallinities. PET amorphous films were lization and glass transition processes occurring in obtained by melting of commercial granulate (Elana, particular PET films and between these processes Poland) and moulding the ribbons in a calender. The occurring in the reference and irradiated films during semicrystalline films were prepared by annealing in first heating, cooling and the second heating. The vacuum of amorphous films, applying different tem- examples of DSC curves are presented in Figs. 1, 2. In peratures and time of annealing. Four PET films were particular, a single narrow endothermal effect of 7,74 Perkin-Elmer Thermal Analysis 7.5 6.0 initial D. | 6.5 o | 6.0 I 5.5 5.0 4.0 40 60 80 100 120 140 160 180 200 220 240 260 280 temperature, °C Fig.l. DSC curves recorded during the second heating of 30-50 urn thick PET-PTMEG (containing 40% of PTMEG (Mw = 650 Daltons) film and the product irradiated with Ar ions (5.5 meV/amu) applying a fluence of 7 x 10'' ions/cm2. 60 RADIATION CHEMISTRY AND PHYSICS, RADIATION TECHNOLOGIES melting was noticed during the first heating of the highly crystalline PET film, while in the case of the initial amorphous films the cold crystallization exo- thermal effect preceeding a broad melting effect was additionally noticed. Broad and small effects of melting observed for PET-PTMEG films, indicate a small amount of the crystalline phase content. Peak and onset temperatures, shape of thermal effect and enthalpy, calculated for the processes occurring in the irradiated films differ from those observed for the initial samples. In particular, the differences between 13 crystallization occurring during cooling of the melted 100 120 140 160 180 200 220 240 260 irradiated and the appropriate initial film were bigger temperature, °C in the case of the highly crystalline film, as compared 27 b to those observed in the case of the amorphous one 26 (Fig.2). The influence was noticed of the thermal history (fast cooling or cooling with a rate of 10°/min) p. s 25 on the processes occurring during the second heating. © e 24 Decrease in crystallinity in the semicrystalline PET and PET-PTMEG films after irradiation can be g 23 concluded, on the basis of WAXS diffractogramms and FTIR patterns. Decrease in volume crystallinity eg 22 was also stated on the basis of density data. The 21 initial significant chemical changes were found in the case of the PET-PTMEG films by the GPC method. 20 100 120 140 160 180 200 220 240 260 References temperature, °C [1]. Cies'la K., Trautmann Ch., Vansant E.F.: DSC examinations of Fig.2. Comparison of exothermal efects of crystallization occurring heavy ion irradiated thin polymer foils, Nukleonika, 40,3, 141- during cooling of the melted initial and irradiated PET films. 152(1995). The values of densities and of volume crystallinities xv [2], [2]. Ciesia K., Starosta W.: Heavy ions track structure in a PETP, calculated for the initial and irradiated films, respectively, are Nucl. Instr. Meth. Phys. Res. B, 105,115-119 (1995). 3 3 as follows: a) 1332 g cm' (amorphous film xv = 0.009 g cm" ) [3]. El Fray M., Sionecki J.: Multiblock co-polymers consisting of 3 3 and 1.288 g cm' ; b) 1.399 g cm" (highly crystalline film, polyester and polyaliphatic blocks, Angew. Makromol. Chem., 3 xv = 0.492 and 1.383 g cm" (x» = 0.373). 234,103-117(1996). RADIOCHEMISTRY STABLE ISOTOPES NUCLEAR ANALYTICAL METHODS CHEMISTRY IN GENERAL NEXT PASEfS) left RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 63 DETERMINATION OF TRACE ELEMENTS IN ALABASTER BY NEUTRON ACTIVATION ANALYSIS 1 1 Luzja Rowinska, Ewa PaAczyk, Lech Walis, Maria Lig^za ', Boiena Nalepa ' iO ;CM 17 Academy of Fine Arts, Krak6w, Poland IS There are many works of art made of alabaster the alabasters from Poland contain high concentrations of authors of which as well as the centres in which they trace elements. This makes it possible to answer the were created are unknown. The only criterion used for question if unknown sculptures present in Poland are dating a sculpture is the style of the epoche or artist. made of native or imported alabaster. For this purpose Isotope methods, in particular neutron activation a catalogue containing data on the content of trace analysis can furnish data for estimation of the elements in alabasters originating from various mines sculpture origin. By comparing the content of trace is necessary. The main centres of manufacturing ala- elements in alabasters and in the alabaster of the baster sculptures in the Middle Ages were Normandy, examined sculpture it is possible to estimate where the Westphaly, North Netherlands and England. sculpture comes from, because the content of trace In this work concentrations of trace elements in elements in alabasters significantly differs. According alabasters coming from four mines located along the to [1] the concentration of trace elements in alabasters line Cracow-Lvov and in a sample taken from the from England is very low. On the other hand sculpture Phillippi's Epitaph were determined. Table 1. Avarage concentrations of trace elements in alabaster [g/g] Alabaster deposit from quarry Element Z6rawno Krak6w Lagiewniki Lopuszka Wielka Ruczaj Zdrdj Phillippis Epitaph Na 7.89E-05 3.32E-05 4.00E-05 3.06E-05 6.01E-05 K 3.41E-05 7.89E-05 6.30E-05 5.49E-05 5.02E-05 Sc 1.49E-08 1.84E-08 1.61E-08 1.21E-08 1.I0E-08 Cr 1.04E-05 9.67E-06 1.05E-05 1.00E-05 7.96E-06 Mn 1.41E-05 9.33E-06 9.04E-06 6.93E-06 5.47E-06 Fe 1.32E-04 1.59E-04 1.50E-04 1.38E-04 8.24E-05 Co 2.06E-06 1.60E-07 1.36E-07 1.55E-07 1.62E-07 Zn 1.20E-06 7.54E-07 7.08E-07 8.01E-07 1.11E-06 As 1.08E-06 1.19E-06 1.01E-06 8.39E-07 8.43E-07 Br 3.88E-06 2.22E-06 7.96E-05 4.59E-06 5.29E-06 Sr 2.16E-02 1.28E-02 1.71E-02 1.67E-02 1.44E-02 Zr 7.38E-05 4.72E-05 4.67E-05 4.33E-05 7.92E-05 Ag 7.73E-08 1.38E-08 2.01E-08 2.73E-08 1.67E-08 Sb 1.24E-06 8.30E-07 7.01E-07 7.44E-07 1.15E-06 Cs 1.39E-07 8.10E-08 4.73E-07 3.26E-07 1.58E-07 Ba 3.61E-06 4.43E-06 4.06E-06 4.74E-06 2.84E-06 La 1.16E-07 I.87E-07 1.45E-07 1.14E-07 8.49E-08 Ce 8.23E-07 6.89E-07 7.25E-07 5.35E-07 2.86E-07 Sm 2.96E-08 3.29E-08 3.46E-08 2.14E-08 2.40E-08 W 1.93E-05 1.82E-05 4.21E-07 4.49E-07 2.99E-07 Au 2.83E-09 I.30E-09 5.90E-10 8.74E-10 7.81E-10 Hg - - 2.17E-07 2.98E-07 3.26E-07 Ca* 1.51E+4 1.37E+04 1.54E+04 1.52E+04 1.17E+04 * Relative Ca concentration in alabaster [counts/min/g], photopeak - 1297 keV 64 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL Tree Diagram for 5 Cases Ward's method Euclidean distance 0.009 0.008 0.007 | 0.006 J 0.005 ^ 0.004 jg 0.003 J 0.002 0.001 0.000 1 1 C 4 C 3 C 5 C 2 C 1 Fig. 1. Analysis of clusters for alabaster samples described by 22 features. Samples of alabasters from the mines, of a weight detector (ORTEC) coupled to a CANBERRA S 100 of 200 g were ground in an agate grinder. Samples of analyser controlled by an IBM computer. a weight of 50 mg were taken for analysis. The The concentration of 23 elements occurring in samples together with standards of 22 elements were Polish alabasters was determined. The results are irradiated in the nuclear reactor Maria at Swierk, at shown in Table 1. The obtained results were subjected a thermal neutron flux of 8 x 1013 n/ cm2 s for 24 h. As to multiparameter statistical analysis. The result of this a result of nuclear reactions in the alabaster (packed analysis is presented in Fig.l. The similarity of the cryptocrystalline form of calcium sulphate), under the alabasters originating from the five sources shows the applied conditions of irradiation the following radio- following order: most similar to each other are alabas- isotopes are obtained: 46Ca (n,y ) -» 47Ca -> 47Sc. ters from the mines Lopuszka Wielka and Ruczaj The half-lives of 47Ca and 47Sc are 4.53 and 3.4 Zdroj; then come the alabasters from Krakow Lagiew- days, respectively. The reaction cross sections amount niki and Phillippi's Epitaph, while the alabaster from to 0.3 and 0.25 barn, respectively. 47Ca emits gamma the Z6rawno mine is least similar to the above alabas- rays of energies of 810 and 1290 keV. 47Sc emits ters (based on the content of Mn, Co, Zn, Sr, Zr, Ag, gamma rays of an energy of 160 keV. Due to the low Cs and Au). The obtained results indicate that the natural abundance (0.003) of the isotope 46Ca the sculpture Phillippi's Epitaph could have been made of radiation intensity from its isotopes is low. Formation alabaster from Polish quarries. of radioactive isotopes of oxygen and sulfur is not Reference very probable, which makes easier the determination [1]. Beasley S.M.: The attribution of alabaster tomb carvings to of impurities of calcium sulphate. The irradiated Medieval Schools. Analytical and typographical problems. samples were measured by means of an HP germanium Further study. Thesis, Univ. of Bradford, 1978 (unpublished). ANALYSIS OF TRACE ELEMENTS IN LEAD WHITE OF PAINTINGS OF THE SILESIAN SCHOOL FROM THE XVth CENTURY Ewa Panczyk, Justyna Olszewska1', Luzja Rowinska, Lech Walis •CM "institute for Conservation and Restoration of Cultural Property, Nicholas Copernicus University, Torun, Poland S IS 1. Introduction (beginning from 1834) by zinc white and later (in the = _J Lead white has been one of the most frequently used XXth century) by titanium white. = Q. pigments for the last twenty centuries. The purity of There are three ways of classifying lead white: this pigment is directly connected with the develop- • examination of the impurity level by determining ment of manufacturing and purification of lead. The the concentration of elements, method of manufacturing of lead did not significantly • examination of the change of the isotope ratio change until the XVIIIth century. However, because pb206/pb204j of high toxicity lead white was gradually substituted • examination of the modification of the crystal RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 65 structure. was connected with the master who created among The crystal structure and the impurity level of other things, St. Barbara's Altar (National Museum in major elements are characteristic of the manufacturing Warsaw) which is one of the most valuable examples method, while isotope ratios and trace impurities are of the late-gothic painting in the Middle Europe. The connected with the origin of the mineral. By deter- other one collaborated with H. Pleydenwurfft, the mining the trace elements it is possible to date a paint- author of, among other things, the altar of the ing and determine its origin. It is possible to identify Wroclaw Cathedral. The samples of lead white repainted fragments and conservation steps which is of examined in this work were taken from paintings prime importance to art historians. . attributed to masters of the latter workshop. The On the basis of quantitative determination of trace characteristics of the samples is shown in Table 1. elements in lead white from paintings of XV-XIXth 3. Determination of trace element concentration in centuries it has been found that cisalpine lead white, lead white samples which occurs also in Venetian paintings, exhibits The analysis of lead white was carried out by INAA higher concentrations of copper and manganese and using standards of the elements to be determined. lower concentrations of silver and antimony than 3.1. Preparation of samples and standards transalpine white used in Northern Europe [1]. Samples of lead white were collected after examin- It is also of interest to answer the question if the ation of the technological structure and preservation trace element pattern in lead white and ground is state of the paintings. It is very difficult to take characteristic of and unique for the examined object or a sample containing pure lead white. Even small typical for materials used in another important clearly white surfaces contain, at the best, lead white European workshop which might have influenced the mixed with a medium e.g. linseed oil. Contamination master of the painting in question. with other pigments can take place in the process of In the Department of Nuclear Methods and Ma- painting (due to the use of dirty brush or in order to terial Engineering of this Institute in the collaboration obtain a shade of the white). with the Department of Conservation of Paintings and After removal of vernix 1-5 samples of the weight Polychromed Sculpture of Nicholas Copernicus Uni- of 0.1-0.5 mg were taken from original spots of the versity in Torun there have been carried out systematic object (possibly without admixtures of other pigments) studies on panel paintings of masters of the Silesian directly to quartz ampoules. School of the XVth century now stored in the National Museums in Warsaw and Wroclaw. The samples were weighed and the ampoules were sealed and packed. A packet contained 7 samples and The determination of trace elements was carried 47 standards of the elements to be determined (Na, K, out by instrumental reactor neutron activation analysis Sc, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, (1NAA), one of the most sensitive methods for the Rb, Sr, Zr, Mo, Ru, Ag, Cd, Sn, Sb, Te, Cs, Ba, La, determination of the elemental composition of ma- Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Yb, Lu, Hf, Ta, terials without chemical separation. W, Ir, Au, Hg, Th and 238U). Small volumes (0.001 ml) 2. Characteristics of the examined objects of solutions of the elements, arranged in suitable In the Silesian School of the XVth century there were groups, were placed in quartz ampoules, evaporated to two independent painting workshops. One of them dryness and the ampoules were then sealed. Addi- Table 1. Description of the samples examined Sample Name of painting Sampling site identification number Adoration of the Child, 1 Altar from St. Peter and Paul's church at Strzegom 1486/87 Blue wing of the kneeling Angel, right side Annunciation, white jewels on the golden trimming 2 of Archangel Gabriel's overcoat Altar from Our Lady's Church at Piasek in Wroclaw 1485 Whipping, grey beard of the man standing behind 3 (Phot.l.) the balustrade Prince Wactaw Zaganski's Epitaph from St. Barbara's Apostle's white garment, right side of the picture 4 church in Wroclaw Votive painting Mournful Christ offered up by Good the Hieronim's white garment 5 Father from St. Elisabeth's church in Wroclaw Andrzej Steinberg's Epitaph from St. Stanislaw and St. Stanislaw's white garment 6 Waclaw's Parish church at Swidnica Offering up, H. Pleydenwurfft White garment 7 66 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL tional standards of zinc (1 mg), Sn (10 mg), Fe (10 mg) ment parameters are presented in Table 2. Altogether and Ni (1 mg) were packed in an aluminium foil. Each 8 measurements were carried out for each sample. batch of samples contained also standards of Sc and Fourty seven elements were identified and determined. Au as neutron flux monitors. Table 2. Irradiation and measurement parameters Neutron flux 8x 10'3 n/cm2s Irradiation time 24 hours Cooling time 1 day 6 days 20-30 days 60 days Measuring time 1000 s 3200 s 7200 s 10000 s 4. Discussion of the results The trace elements dominating in the examined lead white samples are: Fe, Cu, Sb and Hg. The content of zinc is by one order of magnitude lower. The concen- tration level of Ag is similar except for the samples taken from the Altar of St. Peter and Paul's Church at Strzegom 1486/87. The Mn/Ag concentration ratio in the samples taken from objects No 1 and 2 is <1 and from objects No 3,4, 5 and >1. In order to determine the degree of similarity of the objects examined an analysis of clusters using the .' STAT1STICA (StatSoft) program was carried out. The J analysis is based on the distances between the objects in the property space (the dimension of the space is equal to the number of properties). Each object can be described by means of a certain number of properties, which can be presented as real numbers - in our case the concentration of individual elements in the exam- ined lead white sample [5]. The cluster analysis was carrie.d out for all the elements determined. The results of this analysis for 7 objects described by 32 proper- ties, are presented as a dendrogram in Fig.l. Phot.l. Fragment of Altar from Our Lady's Church at Piasek in Wroclaw, 1485 (sampling site is marked by arrow). It follows from the analysis that the lead white samples taken from the painting Offering up by 3.2. Irradiation and activity measurements of samples H. Pleydenwurfft (7) are very similar to the samples The irradiation was carried out in the Maria reactor at taken from the Altar from Our Lady's Church at 13 2 Swierk, at a thermal neutron flux of 8 x 10 n/cm s. Piasek in Wroclaw 1485 and Prince Waciaw Zagan- The samples were irradiated for 24 hours and cooled s'ki's Epitaph from St. Barbara's church at Wroclaw. for 8 hours. After removal of the packaging the irradi- The remaining samples taken from the Altar of St. ated samples were washed with (1:1) HC1 solution, Peter and Paul's Church at Strzegom, the votive followed by alcohol in order to remove surface con- painting the Mournful Christ Offered Up by God the tamination. The standards were washed out from the Father from St. Elisabeth's church in Wroclaw, ampoules or in the case of Sc and Au dissolved Andrzej Steinberg's Epitaph from St. Stanistaw and together with the aluminium foil. Definite volumes Waciaw's parish church at Swidnica form a separate (0.01-0.1 ml) of the solutions were transferred to flat cluster area. vessels and evaporated to dryness. The activity For a full comparison of the objects it will be measurements of the samples and standards were necessary to carry out analysis of additional samples carried out using an HP Ge detector (of an active taken from a larger number of art objects originating 3 volume of 80 cm and resolution of 1.95 keV for 1333 from painting workshops approximate to the circle of 60 keV Co ) coupled with a SI00 Canberra analyser artists whose works are examined in the present work controlled by an IBM/PS-2 computer. The analysis of because the analysis of trace elements is the more complex gamma-ray spectra was carried out using a valuable the higher is the number of diversity of the micro SAMPO program. The irradiation and measure- objects examined. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 67 Tree Diagram for 7 Cases Ward's method Euclidean distances 18000 16000 « 14000 2 12000 .22 ® 10000 ao jg 8000 B j 6000 4000 2000 0 C_7 C_4 C_3 C 6 C 5 C 2 C 1 Fig.l. Dendrogram of 7lh lead white samples described by 46 features. References from sacral paintings of the fifteenth century determined by instrumental neutron activation analysis, Nukleonika, 37,4, 29- [1]. Fleming S.1: Authenticity in art. London 1975. 41 (1992). [2]. Sayre E.V.: Activation analysis applications in art and archaeol- [4]. Currie L.A.: Anal. Chem., 40, 586-591 (1968). ogy, Adv. Activ. Anal., 2, 155-184 (1972). [5]. Harbottle G.: Activation analysis in archaeology, Radiochem., [3]. Pariczyk E., Lige.za M., Wails' L.: Trace elements in lead white 3,33-72(1976). DETERMINATION OF CHEMICAL HOMOGENEITY OF HISTORICAL GLASSWARE. A CASE STUDY Jerzy J. Kunicki-Goldfinger, Joachim Kierzek, Bozena Sartowska PL9902222 1. Introduction A subject of the present communication is Workers conducting physico-chemical studies of art constituted by historic glass - a material that, at least pieces often face a situation when only a single, in its uncorroded part, is considered as a relatively usually very small, analytical sample may be actually homogeneous substance, particularly when we deal collected from the investigated object. The location of with modern luxury colourless hollow glassware free a sampling site, relying on many factors, also cannot of apparent technological impairments. Due to the be unrestricted. Depending on the problem that needs brittleness of the material and because of frequent to be resolved, an analysis of a single specimen instances of objects being irreplaceable or having high collected from the investigated object allows one to commercial value, as well as of aesthetic and perhaps acquire more or less reliable data concerning the entire still other reasons, museum curators rarely allow object. With the assumption that the sampling oper- anyone to collect specimens of glass objects for ation as well as the selection of a test method and the physico-chemical testing. And even if they do, they testing itself have been conducted properly, the ac- allow to collect only the smallest possible sample. quired result must be solely referred to the single Similar objections also concern many non-destructive specimen being tested. It is only after the whole methods of surface analysis. This is due to the fact interpretation procedure, that a certain degree of gen- that, in order to determine the composition of the bulk eralization is allowed, enabling a characterization of of glass, these methods call for a removal of corroded the object on the basis of that single analytical result. surface layers of different chemical composition. This interpretation procedure takes into account, Certain modern analytical techniques require among others, numerous data of a non-physico- collection of very small samples. An open question chemical nature as well as results of the studies remains how representative these samples are with conducted on different objects. In such a case an respect to the whole of the investigated objects. There assumption is made that the sample has been is no exaggeration in a statement that the degree of representative for the entire volume of the substance representativeness of samples decreases with de- (object). creasing of both the number and the size of the 68 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL samples [1]. among which only one concerns a utilization of We will now move to the title case - an instance of natural radioactivity of potassium [5]. glass characterised by a high degree of chemical The following are the natural abundance values of inhomogeneity. The results of chemical analyses of three potassium isotopes: 39K - 93.08%, "°K - 0.0119%, three specimens sampled from this object have shown 4IK - 6.91%. Only the isotope 40K is radioactive, with a large spread. Therefore, in order to prove a thesis of its half-life amounting to 1.28 x 109 years. Therefore, the inhomogeneity of the glass, non-destructive, taking into account the entire history of glassmaking, radiometric techniques were used. the relative content of this isotope may be assumed constant. The radiations emitted are beta particles with 2. Description of the object 1314 keV endpoint energy (89.3% yield), gamma rays The object of interest is a colourless, faceted, baluster of 1460.8 keV energy (10.5% yield) and characteristic stem of luxury goblet, attributed to Lubaczow glass- Ar X-rays following the electron capture. house (south-east of Poland) and dated approximately to 1730. The object, presented in Fig.l, comes from 4.1. Gamma ray spectrometry - determination of the the collection of National Museum in Warsaw (inven- average concentration of potassium in glass tory No. SZSmag. 486). The preserved fragment is The measurement of 1460.8 keV gamma radiation 1.2 cm long, has a maximum diameter of 4.5 cm and on from the radioisotope 40K was performed using a visual inspection exhibits no signs of corrosion. Since gamma ray spectrometric system equipped with an only a stem, with a knob have been preserved, it is HPGe detector with a resolution of 1.91 keV and a possible to collect samples from both fracture mirrors. relative detection efficiency of 92.4% for the 1.33 MeV The analyses have shown that the piece is made from gamma line. Since the 1460.8 keV peak is contained in potash-lime glass. Nevertheless, the results exhibited the natural background, a passive shield was used. large spread. A complete set of results is presented A procedure, especially elaborated for this purpose, elsewhere [2]. In the present work it is only the has been used in order to assure a non-destructive concentration of potassium that is used to disclose the character of the measurements. In addition, the inhomogeneity of the glass. following calibration procedure has been applied. First, the measurement was carried out on a specially prepared mould with the object inside and then it was repeated on the same mould filled with powdered potassium sulphate. The details of the measurement calibration are given in a separate work [6]. The 'j'. application of gamma spectrometry allowed us to determine the average concentration of potassium in the glass which, with respect to K2O, amounted to 14.9%. Fig.l. Stem of a goblet, Lubaczow, c. 1730. 4.2. Autoradiography - homogeneity studies of the 3. Analyses of the samples glass Three specimens have been collected from the differ- In autoradiography the role of detector is played by ent sampling sites of the object and transferred to a special emulsion in which, under the irradiation, different laboratories in order to subject them to ana- a latent image is recorded. After chemical processing lytical testing using different methods. The specimens this image is transformed into a real one. A degree of were collected at different times and particular results darkening of the emulsion is proportional to the were already presented on different occasions. The intensity of radiation which, in turn, depends on the results of K2O analysis are presented in Table, see [2]. quantity of the investigated element. Table Testing was carried out with the help of a pressure method using X-ray photographic films D7, manufac- Sample No. Method K O, wt% 2 tured by Agfa-Gevaert. Exposure time amounted to 1 flame photometry >20 150 days. Densitometric measurements were carried 2 EPMA 17.80 out using an optical microdensitometer Mark II Cs, 3 ASA 14.82 manufactured by Joyce & Loebl, equipped with a standard wedge B770. Net optical density D , directly 4. Utilization of natural potassium radioactivity n th connected to the concentration of potassium in the The glasses produced before the end of the 18 investigated object, was calculated using the equation: century contained a radioactive nuclide, namely 40K. The problem of utilizing the natural radioactivity of Dn = Dc-Dt (1) historic glasses received very little attention. Only where Dt denotes the average optical density of an a few communications have been reported [3,4,5], unexposed photographic film (background) and Dc RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 69 denotes the optical density of the radiograph of the 5. Conclusions investigated object. Optically, the homogeneous historic glass may The dependence of Dn on the K2O content in the nevertheless exhibit large chemical inhomogeneity of glass was calculated basing on numerous measure- its material. The K2O content in various spots of the ments carried out on standard glasses of known discussed object could oscillate between 13% and concentration of potassium. Further details of the 20% (or even more) by weight. As a consequence, method as well as the discussion of its sensitivity with differences in the content of other components of the respect to various ranges of potassium concentration glass must also have occurred, which was reflected in are presented elsewhere [2,7]. a large dispersion of the results of chemical analyses 4.2.1. Autoradiography of the discussed goblet stem of samples collected from different places. Both the form and the size of photographic films were Although the presence of such inhomogeneities is fixed to fit the flat surfaces of the stem. Auto- not a common phenomenon in the luxury glassware of radiographs of an uneven darkening were obtained. the 18lh century, it appears that we should treat many Fig.2 presents the auto radio graph taken from the of the results of the single sample analyses with surface, marked "X" in Fig.l. Apart from the marks of caution, especially in those cases when one must give an expertise concerning the entire object on the basis of such a single measurement. The autoradiographic method, although a long lasting one, enables a recording of an uneven distribution of potassium in the glass, thus allowing one to determine its chemical inhomogeneities. With its help a concentration of potassium on the surfaces corresponding to different levels of the darkening of Fig.2. Autoradiograph taken from the surface marked "X" in Fig.l. the glass edges, three areas of various degree of a photographic plate may be estimated. darkening, marked with letters A, B and C, could be Gamma spectrometry, on the other hand, enables distinguished. One of the photometric lines crossing the determination of the average concentration of the areas A, B and C is shown in Fig.3. The analysis potassium across the investigated object. of the autoradiograph and of the photometric curves Both methods are non-destructive and do not allowed us to state that: require sampling. Both are based on the measurement of natural radioactivity of the glass and this is why • the average K O content in the areas marked with 2 they could be applied only in those cases where one of letter A may be estimated to amount to approxi- the components of the glass is a radioactive nuclide. mately 13%; • the area marked with letter C corresponded to the References K2O content of approximately 16%, while the [1]. Stern W.B.: The composition of Roman glass. Problems of non- strongly darkened area marked with letter B destructive analysis. In: Annales du lie Congres de corresponded to the K2O content of approximately l'Association Internationale pour l'Histoire du Verre (Bale 20%. 1988). AIHV, Amsterdam 1990, pp. 37-41. A similar inhomogeneiry has also been recorded in [2], Kunicki-Goldfinger J.J.: Nieniszcza.ce metody badan zabytko- wych szkie) i szkliw ceramicznych, Doctoral thesis. Nicholas other surfaces of the discussed stem. Copernicus University, Torun 1998. [3], Murray S., Haggith J.: The estimation of uranium in colored A glasses, J. Glass Studies, 15, 184-186 (1973). [4]. Festag J.G., Gentner W., Miiller 0.: Search for uranium and chemical constituents in ancient Roman mosaics. In: Applications of nuclear methods in the field of works of art. International Congress - Rome and Venice 1973. Accademia Nazionale Dei Lincei, Rome 1976, pp. 493-503. [5]. Hudson A.P., Newton R.: A means for the in-situ identification of Medieval glass by the detection of its natural radioactivity, Archaeometry, 18, 2, 229-232 (1976). [6], Kunicki-Goldfinger J.J., Kierzek J.: Non-destructive analysis of potassium in ancient glass on the basis of its natural gamma activity, Glass Sci. Technol. - Glastechnische Berichte, 71, 11, 332-335(1988). [7]. Kunicki-Goldfinger J.J., Kierzek J., Sartowska B.: Oznaczanie potasu w zabytkowych szklach metodami radiometrycznymi. In: Krajowe Sympozjum Technika Ja.drowa w Przemysle, Medycynie, Rolnictwie i Ochronie Srodowiska. Referaty, 16- Fig.3. Photometric line crossing the areas A, B and C in Fig.2. 18.09.1998, Krakow, Poland, pp. 308-313. 70 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL A CHEMICAL SEPARATION SCHEME FOR 24Na - A DECAY PRODUCT OF THE CLUSTER RADIOACTIVITY OF 233U Barbara Bartos, Aleksander Bilewicz PL9902223 233U is theoretically expected to decay by the 24Ne and impregnated with HDEHP. Then tracers of 22Na and 25Ne cluster emission leading to 208-209Pb, with a 224Ra with decay products were added at the top of the predicted partial half-life being in the range 3 x 1016 - column. The effluent from the teflon-HDEHP column 3 x lO17 y. Price et al. [1] in a 582 days experiment, was passed through three ion-exchange columns in using a track-recording phosphate glass detector regis- series. The first column was filled with Dowex 50Wx8 tering heavy ions emission from a thin 233U film. From and the second with cryptomelane-type hydrous the experiment, the measured partial half-life was 2 x manganese dioxide. Both columns were predicted to 1017 y. Our calculations show that 2 g of thorium efficiently remove the decay products of 233U such as should contain, in equilibrium, about 100 atoms of 225Ac, 225Ra, 213Bi and 209Pb. The third column was 0.5 Wl HNO3 Fs teflon impregnated HDEHP Fig. 1. Flow scheme of the separation of micro-amounts of sodium from weight quantities of uranium. 24Na (tic = 15.0 h) due to the (J decay of 24Ne. The packed with a composite ion exchanger containing goal of the present work was to separate a few tens of polyantimonic acid, which sorbed selectively the Na+ the 24Na nuclides from about 2 g of 233U and to ions. The third column was placed inside the cavity of determine in this way the efficiency of the decay the detector. The system was tested in a continuous 233U- 209 long time experiment. The sodium yield was always To achieve this goal we have devised a separation greater than 95%. The decontamination factors were scheme of submicro-amounts of sodium from 2 g of greater than 105 for uranium, 224Ra, 2l2Pb and 2l2Bi. uranium and its decay products (Fig.l). Simulation experiments were made with natural uranium and Reference 224 212 212 22 Ra, Pb, Bi and Na labels. Uranium nitrate [1]. Price P.B., Moody K.J., Hulet E.K., Bonnetti R., Migliorino C: was loaded on a column filled with teflon fine grains Phys. Rev. C, 43, 1781 (1990). FRACTIONATION OF YTTERBIUM ISOTOPES IN THE Yb(III)-ACETATE/Yb- AMALGAM SYSTEM. A SEVEN ISOTOPE TRIAL Wojciech Dembinski, Marek Poninski, Rudolf Fiedler17 11 PL9902224 Safeguards Analytical Laboratory, IAEA, Vienna, Austria Continuing our studies [1] on ytterbium isotope we determined the unit separation factors for all Yb separation in the Yb(IlI) acetate/Yb amalgam system isotopes. The exchange reaction is: RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 71 m 172 172% Yb(Ac)3+ Yb(Hg) <-> '"Yb(Ac)3 isotopes. The even odd effect, SO/E, as defined by The unit separation factor is defined as Nishisawa et al. [2], is visible only when the triad m 172 m 172 171,174,176 yb is taken int0 account. The value of eO/E for q = ( Yb/ Yb)Hg/( Yb/ Yb)ac where m means mass 171 number 168,170,171,173,174,176. The unit separation Yb is -0.00052. This value is to be compared with -0.00075 obtained in our previous measurement [1]. gain is 6 = q - 1 « ln(q). The isotopic analysis was 173 performed using a mass spectrometer with a multi- The even-odd effect of Yb, if exists, is covered by collector system (Finnigam MAT262). The precision error of measurement. of the measured isotopic ratio was 0.07% (1SD) or An interesting sequence of data is observed when better. the series of even-even pairs (Am = 2) is considered. The results are shown in Figure. The data for I68Yb The values of the separation gains are O.OO13±5% for 172/174 is excluded because an unexpectedly high value of i7o/n2Ybi 00010±5% for Yb and 0.0014+7% for 174/176 separation factor was found. This finding, will be Yb. The differences are probably related to the discussed later. nuclear field shift addend (sfS) in the total chemical 0.15 isotope effect. The isotope shifts observed in atomic spectra of ytterbium support such conclusion. As it is 0.10 known [3] the optical isotope shift of ytterbium is mostly due to the field shift (the mass shift can be 0.05 neglected) and is expressed by a change in the nuclear \ » 0.00 mean square radius. The respective values of S^) for the series mentioned above are 0.120 frn2 for Z -0.06 \ """V), 0.034 fm2 for 172/1748(r2), and 0.089 fm2 for l74/1768 The value of the unit mass separation factor, eU; [1]. Dembiiiski W., Poniriski M., FiedJer R.: Sep. Sci. Techn., 33, defined as the mean of the even isotope separation 14,2101-2112(1998). factors (excluding 168Yb) was found to be 0.00059 and [2]. Nishisawa K., Nakamura K., Yamamoto T., Masuda T.: Solv. Extr. Ion. Exch., 12, 5, 1073-1084 (1984). was nearly the same as the experimental unit mass [3]. King W. H.: Isotope shifts in atomic spectra. Pergamon Press, separation factor calculated for the series of six New York-London 1984, pp. 142-143. HYDRATION AND SOLVATION OF LEAD(II) ACETYLACETONATE AND THE COORDINATION NUMBER OF LEAD(II) Jerzy Narbutt A great variety of coordination numbers (CN) of Pb" observation was, however, not explained and little and structures of its complexes have been reported [1], work has appeared subsequently, in particular that depending on the character of the 6s2 electrons. The focused on hydration and solvation of lead(II) large ionic radius of Pb" results from the lone electron complexes. pair occupying 6s orbital, but the radius decreases to The aim of the present work was to explain, why IV a value compared with that of Pb when the pair bis(acetylacetonato)lead(II) is relatively easily extracted enters a hybrid orbital and becomes stereochemically from aqueous solutions to organic solvents, specifical- active. Solvent extraction provides evidence for ly, whether its good extraction can be related to the hydration and solvation of metal complexes in character of the lone electron pair (is it stereo- solution and makes it possible to evaluate the extent of chemically active or non-active?). In fact, there are no their coordinative unsaturation (if any). This in turn data in the literature on the molecular structure of allows us to conclude on CN and the radius of the Pb(acac)2 [3]). central metal ion. Shigematsu and Tabushi [2] pointed To reach the goal, thermodynamics of water - out that extraction of Pb(acac) was higher than 2 toluene partition of Pb(acac)2 was investigated and expected from the large ionic radius of Pb". That discussed in terms of hydration of the chelate in the 72 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL aqueous phase, and synergistic effect of trioctyl- phosphine oxide (TOPO) on Pb(acac)2 partition was studied, making it possible to determine formation constants of the respective inner-sphere adducts. To make interpretation of the results easier, a similar chelate but with no lone electron pair on the central metal ion - bis(acetylacetonato)zinc(II) - was also studied for comparison. Partition constants, P, of the neutral chelates were determined at the pH values close to the centres of the plateau regions [4] with the use of radiotracers 212Pb [5] and 65Zn. The enthalpy of partition, AH0, was determined by the temperature coefficient method (Table 1). -4 0.5 log |TOPO] Table 1. Partition constants, standard enthalpies and entropies of partition of Pb(acac)2 and Zn(acac)2; in the system water - Fig. The effect of molar concentration of TOPO on partition of toluene®. Formation constants of their TOPO adducts in Zn(acac>2 and Pb(acac)2 between toluene and water at 25°C. toluene®. The lines are the best fit curves calculated with the parameters taken from Table 1. M(acac)2 M(acac>2-nTOPO The relatively high coordinative saturation of Pb2+ 0 0 M P AH * AS " n in the chelate must be the result of its small ionic Pb 2.6 21.6 80 0.98 0.99 radius. The Pb2+ ion in a weak complex has a large + 0.3 ±1.6 + 6 ±0.08 ±0.11 ionic radius, 119 pm [6], because the radius is then Zn 0.17 63.0 197 0.99 2.87 determined by the radius of the 6s orbital. On the other ±0.02 ±1.6 ±6 ±0.02 ±0.05 hand, in a strong complex the two 6s electrons enter ®Based on molarities. Temperature 25°C. The error limits denote the hybrid orbital (stereochemically active lone pair is 2+ two standard deviations; *kJmor'; "Jmol"' K"!. formed). The ionic radius of Pb is then determined 4+ Figure shows the effect of concentration of TOPO by the 5d shell, and is therefore close to that of Pb in the organic phase on the distribution of Pb(acac)2 ion, i.e. 78 pm [6]. An indirect literature argument for 2+ and Zn(acac)2 between toluene and water. For the case the small Pb radius in the present case is the of only one adduct M(acac)2 • nTOPO existing in the similarity of stability constants of zinc and lead acetyl- organic phase, the following equation holds: acetonates in the aqueous phase: log Pi = 4.7 and 4.5; log p2 = 8.3 and 7.2, respectively [7], which may be logf—-ll = logp.'2,n •nlog[TOPO] (1) interpreted in terms of similar radii of the central metal ions: Zn2+and Pb2+. where D denotes the distribution ratio of a given This is, however, insufficient to explain why it is chelate (in the presence of TOPO), P - its partition more difficult to increase CN for Pb11 than for Zn" in 11 constant, p2,n is the formation constant of the n-th the chelate, because the ionic radius of Zn is still adduct, and [TOPO] - molar concentration of TOPO in smaller (74 pm [6]). There are also two other reasons: the organic phase. The relationship (1) fitted to the (1) the stereochemically active lone pair which data sets shows (Table 1) that acetylacetonates of both occupies room in the first coordination sphere of Pb" lead and zinc form 1:1 adducts, and that the Zn(acac)2 • and hinders the following basic Hgand to be 1 TOPO adduct is over 10 kJ mol" more stable than coordinated, and (2) the expected higher promotion n Pb(acac)2 • TOPO. energy of Pb than of Zn" to the valence state All the results can easily be explained in terms of corresponding to CN 5. To increase CN, each ion much higher coordinative saturation of Pb(acac)2 as engages in hybridization its nd orbital of high energy. 2+ compared to that of Zn(acac)2, i.e. lower tendency to For Pb two 6d orbitals must be used because the increase CN in the chelate by Pb2+ than by Zn2+. stereochemically active lone pair of Pb2+ in the chelate Because of that, the Pb2+ ion in the chelate has a low already implies the sp3d hybridization. Strong tendency to form a coordination bond with water relativistic stabilization of the 6s orbital of Pb2+ [8] molecule(s) in the aqueous phase. Therefore, partition makes the 6s-6d gap greater than the 4s-4d gap for 2+ 3 2 2+ constant of Pb(acac)2 is distinctly higher while the Zn , so the sp d hybridization in the case of Pb is standard enthalpy and entropy of partition - much much less probable than the sp3d hybridization in the 2+ smaller than those of Zn(acac)2 which is strongly case of Zn . inner-sphere hydrated in the aqueous phase. For the Additional studies on proton-acceptor ability of same reason Pb(acac) is less prone to form inner- 2 Pb(acac)2 were carried out to find additional evidence sphere adducts in the organic phase, even with TOPO for stereochemical activity of the lone pair. Distribu- - one of the strongest electron-donor ligands. tion of Pb(acac)2 and Zn(acac)2 between water and RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 73 carbon tetrachloride - chloroform mixtures was inves- extractability of the chelate, pointed out in ref. [2], tigated as a function of the mole fraction of the latter. disappears. The details of the present work are given The observation of a similar solvation of both chelates in paper [10], with chloroform allowed us to conclude that the The research was supported by the Polish State stereochemically active lone pair (if any) only slightly Committee for Scientific Research (KBN), under grant enhances proton-acceptor properties of the lead(IT) No. 3 T09A 016 09. chelate. Recapitulating, the thermodynamic data based on References liquid-liquid distribution do not explicitly confirm, but [1]. Harrison P.G. !n: Comprehensive coordination chemistry, Vol. bring strong indirect evidence for the hypothesis that 3. Eds. G. Wilkinson, R.D. Giltard, J.A. McCleverty. Pergamon there is a stereochemically active lone electron pair of Press, Oxford 1987, p. 183. the central Pb2+ ion in a neutral acetylacetonate complex. [2]. Shigematsu T., Tabushi M.: Bull. Inst. Chem. Res. Kyoto The direct evidence results from our X-ray diffraction Univ., 39,35 (1961). [3]. Holloway C.E., Melnik M.: Main Group Met. Chem., 20, 399 studies [9], still in progress. The assumption that the u (1997). decreased ionic radius of Pb in the chelate and the [4]. Narbutt J.: Polish J. Chem., 67, 293 (1993). occupation of a coordination site by the lone pair make [5]. Narbutt J., Bilewicz A.: Appl. Radiat. Isot., 49, 89 (1998). it difficult for the ion to attain the formal coordination [6]. Shannon R.D.: Acta Crystallogr., A32, 751 (1976). number greater than 4, very well explains the experi- [7]. Stary J., Liljenzin J.O.: Pure Appl. Chem., 54,2557 (1982). [8]. Pyykk6 P.: Chem. Rev., 88, 563 (1988). mental results. The inconsistency between the [9]. Narbutt J., Paluchowska B., Maurin J.: to be published. seemingly large radius of lead(II) and the good [10]. Narbutt J.: Solv. Extr. Ion Exch., 17, 5 (1999) (in press). INCREASE OF THE COORDINATION NUMBER OF TRIVALENT p- AND d-BLOCK METAL IONS IN NEUTRAL TROPOLONATES BY ADDUCT FORMATION WITH TRIOCTYLPHOSPHINE OXIDE. THEORETICAL AND THERMODYNAMIC EVIDENCE Jerzy Narbutt, Marian Czerwinski", Jadwiga Krejzler " Chemistry Institute, Pedagogical University, Cze_stochowa. Poland PL9902225 The ability to increase coordination number (CN) by neutral chelates with bidentate ligands is influenced by metal ions in complexes is of both theoretical and the properties of ions with either completely filled or practical significance. Various approaches are used to empty d orbitals, i.e. d10 or d° ions. We assumed that describe coordination stereochemistry of metal com- ions with empty (n-l)d orbitals easily accessible for plexes: geometrical, electrostatic and those accounting hybridization would attain CN 7 more eagerly than d10 for electronic structure of metal ions. Geometrical ions which have much less accessible nd orbitals. For- models consider not only the size of metal ion and mation energies or stability constants of adducts (mixed- ligand atoms but also the ligand structure. We assume ligand complexes) of neutral metal chelates and an that there are four main factors which influence CN of auxiliary neutral ligand were considered as a measure a central metal ion of a given valency in chelate of the tendency to increase CN of the central metal complexes with bidentate ligands of given donor ion. Trivalent Group 13 ions of a large range of radii - atoms. Two od these factors relate to ligand properties, gallium, indium and thallium - were studied. Scarcity i.e. its pKa and bite. Recently, on the example of of data on their mixed-ligand complexes [2] affected scandium chelates, we demonstrated that CN six of the the choice. For the sake of comparison, chelates and central metal ion can be increased to seven by adducts of two d-block ions, Sc and Y, similar in radii coordination of an additional basic monodentate to In and Tl, respectively, were also studied. ligand, either in weak complexes with flexible ligands Tropolonate anion was selected as a short-bite (of low pKa), or in complexes with short-bite ligands bidentate ligand, and trioctylphosphine oxide (TOPO) where small bite angles make easy to create a room for - as an auxiliary monodentate ligand. Such a choice the seventh ligand by contraction of the bidentate enabled studies of the system both by quantum ligands around the ion, without any significant change chemistry calculations and experimentally. The results in their structure [1]. In the present paper we focus our of theoretical calculations of formation energies were attention on the metal-dependent factors affecting CN, compared with the experimental stability constants of i.e. radius and electronic structure of metal ion. the adducts, determined from the synergistic effect of The aim of this work was to explain how the ten- TOPO, exerted on transfer of the metal tropolonates dency to increase CN of a central metal ion in stable from an aqueous to an organic phase. 74 RAD10CHEM1STRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL al Table 1. Optimized (GAUSSIAN 94) geometry of the chelates Vl(adik)3' Parameter Distances [pm] Angles [deg] w (change)'"' M-OA M-OB M-Oc 0-0 M-O™po O-M-0 M-O-P L-M-L Ga 190.3 202.5 198.1 - 189.7 - - - 302.3|dI 227.5 198.5 217.4 214.0 217.2 266.3 204.6 70.6 137.4 145.8 In 241.8 226.6 226.1 268.7 75.1 104.8 265.6 73.6 98.9 (+1.3 and 8.5%) (+0.2%) (-2.7%) 235.1 236.7 234.6 276.7 226.1 71.8 132.5 138.4 Tl 236.8 244.3 241.1 276.6 70.2 110.3 278.5 71.7 100.5 (+1.6 and 3.6%) (-0.2%) (-3.4%) 217.0 215.5 213.7 260.7 206.7 7.1.0 138.7 147.2 Sc 231.5 223.6 225.5 261.6 73.1 102.5 262.2 73.2 98.1 (+1.0 and 6.4%) (+1.0%) (-3.2%) 234.4 232.2 234.4 267.9 222.7 67.9 139.9 139.6 Y 244.8 241.0 237.9 268.2 69.2 106.6 266.8 68.8 102.5 (+1.2 and 4.5%) (+1.2%) (-1.7%) |bl '"' Capital letters A, B, C refer to the particular adik Iigand; The changi;e of a given parameter in the M(adik)3 • TMPO adduct related to that in the chelate; M interligand angle determined by the centres of the C-C bonds in two adik ligands and the metal ion;i optimization algorithm. The charge density has been Fig.l. Optimized structure of the [Y(adik)3-TMPO] adduct. The obtained from Mulliken overlap population. All of the darkest circles denote oxygen atoms. calculations were carried out using relativistic effec- metal ion the three adik ligands have to be contracted, tive core potential. Promotion energies were computed followed by a decrease of their bite angles and elonga- within the approach of complete active space self- tion of the M-0 bonds. The distortion of a chelate consistent field (CAS SCF) [4]. The first stage of work molecule depends on the radius of the metal ion. comprized optimization of geometry of the chelates Strong deformation of ligands bonded to the smallest [M(adik)3], of the ligand TMPO and of their adducts metal ion studied, i.e. in [Ga(adik)3], results in adlk [M(adik)3-TMPO] (Table 1). The optimized para- breaking one of the six Ga-O bonds and preserving meters of the chelates with M = Sc, Ga, In well CN 6 for Gam in the adduct (Table 1). A moderate correspond with the experimental data for crystalline distortion of the calculated chelate structure has been tropolonates [5]. Stable adduct structures with CN 7 observed in the adducts with the metal ions of have been attained for Sc, In, Tl and Y (Fig.l), but not intermediate radii, In and Sc, while the smallest - for for Ga. the largest metal ions studied, Tl and Y. The different The calculation results confirm that coordination distortions of the chelates are also reflected in the of the seventh ligand is accompanied by rearrange- calculated energies of their structural changes upon ments in the chelate structure. To make room for this adduct formation. Also the TMPO molecule in the ligand in the first coordination sphere of the central adduct becomes slightly distorted. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 75 Table 2. Calculated (GAUSSIAN 94) energies (in atomic units) of: chelate formation, adduct formation, structure change of the chelates, deformation of TMPO, interaction of adduct components, sind promotion to V?; experimental partition constants of metal tropolonates and stability constants of their adducts with TOPO! Shannon's ionic radii for CN 6, r-, [7], (in pm). pM 1 1 M n -Ef.ch -Ec,»d Estr Edef -Bim E^ logpw " Ga 62.0 0.2905 0.0187W - - - - 38 ±3 no adduct In 80.0 0.2827 0.0328 0.0504 0.0034 0.0868 0.148 39 ±3 0.77 ±0.12 Tl 88.5 0.1562 0.0365 0.0241 ^0.0031 0.0637 0.148 - 1.06±0.16 Sc 74.5 1.0290 0.0422 0.0358 0.0031 0.0829 0.005 <0.4 4.07 ± 0.05 Y 90 0.4761 0.0532 0.0261 0.0031 0.0809 0.002 - large? w in the system water - carbon tetrachloride, 25°C, molar concentration scale;!bI in carbon tetrachloride, 25°C, molar concentration scale; the value for Sc taken from ref. [1];w broken Ga-0 bond, open chelate ring. The energies of chelate formation, EfiCh, and of explained in terms of hybridization theory. Because of adduct formation, Ef,ad, can be calculated after full lower energies of (n-l)rf than nd orbitals of an ion, optimization of all the components and computing promotion energy required to transform a p-block 2 their total energies. Table 2 shows that the negative metal ion to the valence state V6 (rw'npW Ef,ch values decrease (become less negative) in the hybridization) is expected to be much higher than that following order: Sc > Y > In > Tl. This order reflects: for a d-block metal ion [(n-l)c/2ns'ry?3]. Particularly m (1) the Ef>Ch gain by Sc and In chelates, due to a greater high promotion energy may be expected for Tl charge density on the smaller metal ions, which is an whose 6s and 6pm orbitals are strongly stabilized and inverse function of ionic radius; and (2) the Ef,ch loss 6d - destabilized, due to the filled 4/ shell and by In and Tl chelates. Shannon's ionic radii [6] for CN relativistic effects [7]. This explains why the p-block 6 are given in Table 2. On the other hand, the adduct metal chelates are less stable than those of d-block formation energies decrease in the different order: Y > ones (Table 2). Also the promotion energy E6n, related Sc > Tl > In, and the sequence of the Ef,a(j values to the transfer from V<; to V7, is expected to be much obtained theoretically is in agreement with the experi- higher for p-block elements (nj'n/?W3) than for d- mental sequence of stability constants of the adducts. block ones [(n-l)c/3ns'n/?3], which should be reflected in the energy of adduct formation. High E /7 values for We assume that the Efia(i value can be expressed as 6 the sum of terms related to the energy of structure p-block elements and low for d-block elements, calculated for single isolated atoms (Table 2), are in change of the chelate, Estr, and that of structure de- formation of TMPO, Edef, upon adduct formation, and agreement with the above considerations. However, as being calculated by a method not involving DFT, the to the energy of interaction, Eint, between the com- ponents of the changed (deformed) structures. E6/7 values cannot be directly compared with the other energies listed in Table 2. Ef d = E + E +E (1) >a str def im Formation of the M-O™po bond is accompanied The values Estr (and Edef) were calculated (Table 2) by changes in charge distribution, in particular by as the differences between the total energies of a given electron transfer from TMPO to [M(ctdik)3]. The M(adik)3 (or TMPO) molecule of the changed (de- dipole moments of adducts are much greater than that formed) structure and that of the optimized structure. of TMPO alone. Their sequence (Y > Sc > In > Tl) The energy of interaction, Eint, between the molecules does not exactly correspond to the charge transfer of M(adik)3 and TMPO of such new structures was sequence (Sc > Y > In > Tl), probably because of calculated as the difference between the total energy more effective charge separation in the adducts with of the adduct and those of its components of the new larger ions (Y, Ti). structures. The E^, values only slightly differ from one Formation of molecular adducts in solution, i.e. another (except for Tl). The decisive contribution to determination of their composition and stability Ef,ad originates from Estr, which can be considered in constants can also be studied by numerous experimen- the first approximation as being due to the effect of the tal techniques. Solvent extraction is particularity use- ion size. The low values of the energy of structure ful in the case of adducts formed by amphiphilic change of the [Tl(adik)3] chelate, lower than that of neutral metal chelates and neutral hydrophobic ligands, [Y(ctdik)3], and of interaction energy between e.g. TOPO. The chelate, [MLm], formed in an aqueous m+ [Tl(adik)3] and TMPO, much less negative than those solution by a metal ion, M , and a bidentate organic for the other adducts, (Table 2), require a plausible ligand in the anionic form, L", is partly transferred to explanation. an organic phase upon contacting the solutions. The The second metal-dependent factor affecting CN of transfer of the metal ion can be enhanced by formation central metal ions is expected to relate to their of molecular adducts [MLm-iB] of the stability con- electronic structure. Greater tendency to form stants Pn,,;, where B denotes an auxiliary neutral [M(ocdik)3] chelates and their TMPO adducts by hydrophobic ligand present in the organic phase: d-block metal ions than by p-block ones can be MLra + iB <=> MLm- iB (2) 76 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL Distribution ratio of the metal, defined as the ratio each of them very close to Do over the whole range of of molar concentrations of its all chemical forms in the TOPO concentrations studied (Fig.2). This shows that organic and in the aqueous phase, is given as: [Ga(trop)3] forms no TOPO adducts which is not surprising in view of small size and d]0 electronic D = - (3) configuration of the ion. The order of the p3|i values is therefore Sc » Tl > In (> Ga), very well corresponding with the sequence Square brackets in formulae (3) and (4) denote the of the theoretically calculated adduct formation molar concentrations. For the case of only one adduct energies Ef>aj (Table 2). Although there are no experi- MLm-B predominating in the organic phase we obtain: mental data on stability of the yttrium tropolonate adduct, we can easily assume that it is much more (4) stable than that of scandium. That is because Y(III) of a large radius forms coordinatively unsaturated where Do denotes the distribution ratio in the absence chelates with ligands of even larger bite, e.g. ofTOPO in the system. acetylacetonate, while scandium acetylacetonate is Fig.2 shows the effect of TOPO concentration on coordinatively saturated [8]. Although the respective the distribution of tropolonates of Ga, In and Tl(III) TOPO adducts have not been described, a high CN of between an aqueous phase and carbon tetrachloride. Ym can be concluded from reported [9] formation of The distribution ratios were measured with the use of anionic species [Y(acac)4]" and very low partition m radiotracers. Because of slow hydrolysis of Tl even constants of [Y(acac)3] which evidence strong inner- at pH 2, the D values for thallium were determined by sphere hydration of the chelate. [Y(trop)3] would extrapolation to the zero time in back extraction. An exhibit still higher tendency to increase CN. increase of D with increasing TOPO concentration One could expect that the order of stabilities of shows that both [In(trop) ] and [Tl(trop) ] form 3 3 inner-sphere hydrates of the chelates studied is similar adducts with TOPO. The antagonistic effect observed to the order of their p i values. The ability to form in extraction of thallium at TOPO concentrations 3i inner-sphere hydrates by isostructural metal chelates is greater than 0.2 mol dm"3 is due to association approximatively reflected by the order of their between TOPO and tropolone and to the resulting partition constants, P, defined as the ratio of molar partial dissociation of [Tl(trop)3] to charged species at concentrations of the neutral chelate in the organic and low pH of the experiment. aqueous phase at equilibrium. The experimental P 0.6 values (Table 2) for the [Sc(trop)3] - [In(trop)3] pair well correspond to this relationship, but unexpectedly the value for [In(trop)3] is not much lower but equal to that for [Ga(trop)3]. This can be interpreted by stronger outer-sphere hydration of gallium tropolonate due to [8] smaller ionic radius of Ga3+ than that of In3+, which compensates the effect of (weak) inner-sphere hydration of [In(trop)3]. The P value for [Tl(trop)3] could not be determined because of fast hydrolysis of Tl(III) at higher pH. In conclusion we state that the coordination number of a central metal ion in a neutral chelate with -2 -1.5 -1 -0.5 bidentate ligands increases upon formation of an log [TOPO] inner-sphere molecular adduct by the chelate and an Fig.2. Effect of TOPO concentration (mol dm'3) on extraction of electron-donor ligand. The tendency to increase CN [M(trop>3] chelates from water to carbon tetrachloride at strongly depends on the metal ion, in particular on its 25°C.M = Ga, InandTl. radius and electronic structure. The larger the radius Least square fitting by means of eq. (4) gives the the lower energy required for intraligand deformation stability constants of the [M(trop)3-TOPO] adducts (M accompanying structure change of the chelate, and = In and Tl) shown in Table 2. Both adducts are much greater the tendency to form such adducts. If the ion is weaker than that formed by [Sc(trop)3]. Under the too small the chelate does not form adducts. On the conditions of gallium extraction (2 mol dm"3 HC1 as other hand, a much greater tendency to form adducts the aqueous phase) not only [Ga(trop)3] but also and to increase CN by ions of d-block than p-block solvated chloride, [GaCl3-3TOPO], appears in the metals points out to the importance of promotion organic phase at higher TOPO concentrations. After energy to a higher valence state of the ion, which deducting from the D values the contribution from the depends on the availability of its unoccupied d orbitals latter, we have obtained a set of corrected D values for hybridization. RADI0CHEM1STRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 77 The research was supported by the Polish State [4]. Roos B.O. In: Methods of computational molecular physics. Eds. G.H.F. Dierksen, S. Wilson. Reidel, Dordrecht, The Committee for Scientific Research (KBN), under grant Netherlands 1979. No.3T09A016 09. [5]. Anderson T.J., Neuman M.A., Melson G.A.: Inorg. Chem., 13, 158-163 (1974); Nepveu F., Jasanada F., Walz L.: Inorg. References Chim. Acta, 211, 141-147 (1993). [1]. Narbutt J., Krejzler J.: Inorg. Chim. Acta, 286, 175-180 (1999). [6]. Shannon R.D.: Acta Crystallogr., A32,751 (1976). [2], Tuck D.G., In: Chemistry of aluminium, gallium, indium and [7], PyykkS P.: Chem. Rev., 88, 563-594 (1988). thallium. Ed. A.J. Downs. Blackie Academic & Professional, [8]. Narbutt J., Barto^ B., Siekierski S.: Solv. Extr. Ion Exch., 12, London 1993, pp. 430-473. 1001-1011(1994). [3]. Pople J.A. et al: GAUSSIAN 94, Revision D.3, Gaussian, Inc., [9]. Suzuki N., Kodera J., Imura H.: Inorg. Chim. Acta, 128, 261- Pittsburgh PA 1995. 266(1987). IMPLICATIONS OF THE NEW THEORY OF ISOTOPE CHEMISTRY OF THE HEAVY ELEMENTS Tomasz Mioduski PL9902226 The recent theory of Bigeleisen of isotope chemistry isms are explained in detail [2]. It is indicated that the of the heavy elements [1] is developed and explicitly uranium ions involved in the Chemex and Asahi tech- specified [2]. Its consequences are discussed [2] in nologies [3] must have the outermost electrons on the terms of nuclear charge size and shape variations, s or p orbitals in the respective organic or resin phase mass formula, even-odd and odd-odd effects, magic complexes, and on the f orbitals in the uranium species numbers, nuclear field shift vs. resulting contraction or of the aqueous phase: U3+ - [Rn]5f3 vs. U4+ - expansion of the s, p, d and f shells, and corresponding [Rnjed'ys'Sf0 for the Chemex cascade solvent extrac- 4+ 2 2+ 6 2 2 variations of the isotope ionic radii and isotope tion, and U - [Rn]5f vs. 0=Lfe0 -6p 7tV\,G ga u5f° ionization potentials. 6d°7s° for the Asahi process where the complexes At the same orbitals of the outermost electrons, the adsorbed by the anion exchange resin correspond to effects of even-odd, odd-odd, magic and doubly magic the organic phase species. It is concluded that the nuclei, as accompanied by a decrease of the nuclear isotope ions of the heavy elements which have the charge size, are of the same sign. This means that outermost electrons the d5/2 or f7/2 and fS/2 subshells in these effects alter the chemical equilibria of the the organic phase species and on the s or p1/2 orbitals isotope exchange in the same direction. An expansion in the aqueous phase complexes should display the of the nuclear charge distribution, usually associated inverse chemical isotopic effect in comparison with with the addition of neutrons to a nucleus, causes all that reported for the chemical uranium enrichment. the s orbitals, and to a lesser extent all the p1/2 orbitals, to expand which results in a less effective screening of References the nucleus. In consequence, the outer d and all the f [1]. Bigeleisen J.: J. Am. Chem. Soc, 118, 3676 (1996). orbitals become less diffuse, i.e. they contract. [2]. Mioduski T.: Gloss to the Bigeleisen's theory of isotope chemis- The emphasis is given to the uranium isotope try of the heavy elements, Comments Inorg. Chem. (in press). chemistry whose theoretical foundations and mechan- [3]. Mioduski T.: Wiadom. Chem., 50, 701 (1996). AQUATION IN SOLID PHASES OF THE Ln2(SO4)3-H2O SYSTEMS == Tomasz Mioduski j CM Critical analysis of about 250 source papers, which lanthanide(HI) ions and labile, though stoichiometric contain surprisingly divergent data on the solubility in and integer, hydration number, h. The present report IS the RE2(SO4)3-H2O (RE = Ln, Y, Sc) systems, has been and the corresponding paper [1] are the completion of IS done. These divergencies, reaching in some cases a wearing work on the title systems. It encompasses all a few hundred %, at the experimental imprecision the rare earth sulphate systems, except those dealing claimed to be ±1-2%, cannot be removed by rejecting with the Sc2(SO4)3- hH2O [2], Ce2(S04y hH2O [3] evident gross errors. They must be traced to incorrect and Eu(SO4)3 [4] systems, discussed previously. identification of saturating solid phases, due to Thermodynamics and mechanisms of solution/ unfortunate occurrence of metastable equilibria. The crystallization are discussed [1] and the solubility solid phases must have diversified aquation of the equations for over 30 solid phases, Ln2(SO4)3 • hH2O, 78 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL Table. Solubility in the Ln2(SO4)3-H2O systems at 273-373 K a b 11 e Ln2(SOi)3-hH2O ' AH^UkJ/mol)' Solubility equation ' m in moles of anhydrous salt/kg H2O, and T(K) La h = 9a -68.3+2.3 lnm = -8.83 + 1644/T La h = 8a -82.3 ±1.8 lnm = -9.74 + 1980/T La h = 6 or 5a -106 ±15 In m =-10.75+ 2550/T La h = 2" -548 ±23 In m = -39.0 + 13200/T La h=16b -2.5 ±1.2 lnm = -3.16 + 60/T Pr h = 8a -104 ±3.5 In m =-10.25+2500AT Pr h= 12" -59.5 ±5.5 In m = -6.45 + 1430/T Pr h = 2b -373 ±94 In m = -28.5 + 9000/T Nd h=88 -96.8 + 2.8 In m =-10.23+2328/T Nd h = 8b(p-form?) -98.0 ± 4.7 In m =-10.18+ 2356/T Nd h=12b -47.8 ± 2.0 lnm = -6.32+1150/T Nd h= 10b -71.5 + 6.9 lnm = -8.15 + 1720/T Nd h = 5b -169 + 20 In m =-15.43+ 4055/T Nd h = 2b -285 ± 6 In m =-21.27+ 6847/T Sm h = 83 -69.5 ±4.7 In m = -9.03 + 1672/T Sm h = 8b(p-form?) -65.7 In m = -8.66+ 1580/T Sm h= 12" -30.2 ±2.0 In m =-6.10 + 726^ Sm h = 5b -176 ±10 In m = -15.50 + 4224/T Sm h = 2b or 0 -729 + 300 lnm = -39.9+17500/T Eu h = 8" -63 ±5 In m =-8.46+ 1510/T Gd h = 8a -59.2 ±2.6 In m= -8.11 + 1424/T Gd h = 8b(p-form?) -53.4 ±1.6 In m = -7.43 + 1284/T Tb h = 8a -66.5 ±0.6 In m = -8.51 + 1600/T Dy h=8a -80 ±5 In m =-9.23+ 19iO/T Ho h = 8b -102+11 lnm = -11.46 + 2700/T Er h=8a -121 In m =-11.74+ 2900/T Tm h = 8a -124 lnm = -11.47 + 2980/T Yb h = 8* -152 ±10 lnm = -12.81+3650/T Yb h= 12 or llb -93 ±3 In m =-8.54 + 2233/T Lu h = 8 or 6b -186 In m =-15.46+ 4472H" Y h = 8a -120 ±15 In m =-11.80+ 2893/T Y h = 8b(|J-form?) -96.3 ± 10.3 lnm = -9.37 + 2318AT Y h=12b -19.7 ±1.9 lnm = -3.48+473.3/T Y h = 2b -518 ±62 In m =-32.54 + 12470/T Pm, Am16 h = 8b -83 lnm = -9.64 + 2086n"f ' Recommended values; b Tentative values; c At the confidence level p = 0.95; d The overall uncertainty in the h and In m values corresponds to that for the solution enthalpy estimator values;" Transition points in the In m vs. 1/T graph and the equilibrium solid phases of the lowest solubility at a given temperature result directly from the solubility smoothing equations;f This is an interpolation between the respective values for the Nd and Sm sulphate octahydrates, and it must be treated with a moderate confidence as based upon the Shannon's ionic radii. Almost the same solubility smoothing equation is valid also for the Cm sulphate octahydrate, as estimated in a similar way, while these for the respective Bk and Cf sulphate hydrates should be analogous with the equations for the sulphate hydrates of Sm and Eu, respectively. at 273-373 K are evaluated and listed in Table. The 2H2O, Nd2(SO4)3 • 12H2O, Nd2(SO4)3 10H2O, Nd2(SO4)3 • solubility equations give implicitly transition points, 2H2O, Sm2(SO4)3 • 12H2O, Sm2(SO4)3 • 2H2O, Yb^SO^j • stability ranges and crystallization fields of the (11-12)H2O, Y2(SO4)3 • 12H2O and Y2(SO4)3 • 2 H2O. hydrates under consideration. As previously [2], some In addition, by analogy with the respective experi- new hydrates with the corresponding solubility equa- mental data for the lanthanide sulphate systems, the tions have been revealed from the critically evaluated aqueous solubility for some unavailable, but pre- solubility data. These hydrates, the existence of which sumably stable, octahydrates has been estimated, i.e. adequately explains the divergencies in the solubility for Pm2(SO4)3- 8H2O, Am2(SO4)r 8H2O, Cm2(SO4)3- data, are as follows: La2(SO4)3 • (5-6)H2O, La2(SO4)3 • 8H2O, Bk2(SO4)3- 8H2O and Cf2(SO4)3- 8H2O. The 2H2O, La2(SO4)3 16H2O, Pr2(SO4)3 12H2O, Pr2(SO4)3 • solubility data for the (Ln or An)2(SO4)3-H2O systems RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 79 are also of practical interest, e.g. for treatment of ous solutions of lanthanide(III) sulphates from the solubility radioactive wastes containing lanthanide fission prod- data, Chem. Anal. (Warsaw), 43,457 (1998). [2]. Mioduski T.: J. Radioanal. Nucl. Chem., Lett., 165,9 (1992). ucts and transuranium actinides. [3]. Mioduski T.: Identification of saturating solid phases in the References Ce2(SO,i)3-HjO system from the solubility data, J. Thermal Anal, (in press). [1]. Mioduski T.: Identification of saturating solid phases in aque- [4]. Mioduski T.: Comments Inorg. Chem., 19, 231 (1997). INTERLABORATORY COMPARISON OF THE DETERMINATION OF 226Ra AND 228Ra IN SAMPLES SIMULATING COAL MINE WATER Jerzy Narbutt, Leon Fuks :oo Long-lived radium isotopes, 226Ra and 228Ra, present tion of radium in simulated coal mine waters has been i in mine waters, and their radioactive decay products organized by the National Atomic Energy Agency of are considered as an important natural hazard in the Poland, with the participation of 9 radiometry labora- Polish coal mining industry [1,2]. The concentration tories from 8 Polish research institutes and univer- of 226Ra in waste waters pumped out from deep hard sities. This Institute was instructed to prepare samples coal mines in Upper Silesia reaches up to 300 Bq dm"3 and to carry out a comparison. [1]. This results in local radioactive contaminations of A series of six saline solutions containing both the natural environment. A system of monitoring radium isotopes at concentrations met in the genuine natural radiation has been developed and introduced in coal mine waters were prepared and distributed all Polish coal mines [3]. Reliable measurements are between the participants of the experiment. The results of primary importance for implementation of a quality of determinations, supplied by the participants, have assurance system in laboratories dealing with radio- been evaluated and discussed in relation to the activity determinations. International experiments were analytical methods used, and to the experience of already organized, with the participation of Polish participants. To secure anonymity of the participanting laboratories, on an interlaboratory comparison of the laboratories, the particular results presented in this determination of natural radionuclides, including paper have been denoted with code numbers known to radium, in environmental samples [2]. The present the organizers only. national interlaboratory comparison of the determina- An example of the results obtained, together with =«E . 5 2 w- • Ifc- g * 5J: JZ 'EC- • • -XT 5 10- I 1 - 0,1 - — mean values —r~ —r~ 1 11 10 12 Laboratory code Fig.l. Distribution of the results of the analysis of 226Ra concentration in samples: Q - 1, O - 2, A - 4, V - 5 and 0 - 6; and of their standard deviations, supplied by the participants. The dashed lines denote the mean experimental concentrations, and the arrows - the organizers' values. 80 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL their uncertainties (equal to two standard deviations of participants can be divided into three main groups: the mean values), supplied by the participants, is 1. Coprecipitation with BaSO4) followed by measure- presented in Fig.l. One of the laboratories has ments using: a) a spectrometry, b) a,p liquid delivered four sets of results for 2MRa, obtained by scintillation counting, and c) y spectrometry; means of different methods. All these results have 2. Direct y spectrometry measurements in Marinelli been considered as independent and denoted with vessels; different laboratory code numbers. 3. Emanation method (for 226Ra), followed by The results obtained from the individual partici- measurements (a spectrometry or liquid scintil- pants of the experiment have been analyzed according lation) of radon and/or its descendents. to the directions of the International Union of Pure and Satisfactory results have been obtained with the Applied Chemistry (IUPAC), the International Stan- use of methods 1 (a and b) and 3. The measurements dardization Organization (ISO) and the Association of based on y spectrometry of either 226Ra or the decay Official Analytical Chemists (AOAC): International products of both radium isotopes (214Pb, 2I4Bi, 228Ac) Harmonized Protocol for the Proficiency Testing of are, as a rule, less accurate. (Chemical) Analytical Laboratories [4]. Results of the Preparation of this interlaboratory comparison individual determinations can be classified as satisfac- experiment and the results have been described in tory, for the values of so called z-score para- detail in Ref. [5]. meter I Zi I < 2, questionable for 2 < | Zj !_< 3 and unsatisfactory for zjl > 3, where z, = (Xj-X^o*1, X; References denotes the result reported by i-th participant, X is the [1]. Jaworowski Z., In: The environmental behaviour of radium. assigned value, and a is the target value for standard Technical Report Series no. 310, vol. 2. IAEA, Vienna 1990, pp. 97-112. deviation. [2]. Cha-iupnik S,, Lebecka J., Mielnikow A., Michalik B., Skubacz In the present experiment practically all the partici- K., Lipowczan A.: Nukleonika, 40,4,45 (1995). pants met a proficiency criterion at the accepted target [3]. Instrukcja wprowadzenia kontroli narazenia radiacyjnego od value CT = 0.1 X. A few best laboratories met a more naturalnych substancji promieniotworczych w kopalniach we.- rigorous proficiency criterion at the target value 0 = gla kamiennego. Wspolnota We.gla Kamiennego, Katowice 1988 (in Polish). 0.05 X. [4], Thompson M., Wood R.: Pure Appl. Chem., 65, 2123 (1993). The analytical methods for radium, used by the [5]. Narbutt I, Fuks L.: Nukleonika, 43, 4, 469 (1998). THERMAL CONVERSION OF Li+-Mn2+ ACETATE-ASCORBATE GELS TO LiMn2O4 FOR ELECTROCHEMICAL APPLICATIONS Andrzej Deptula, Tadeusz Olczak, Wieslawa Lada, Fausto Croce1' " Department of Chemistry, University "La Sapienza", Roma, Italy Spinels of LiMn2O4 type are currently under intensive foaming and self-ignition phenomena. investigations due to their potential applicability as The starting aqueous solutions were prepared cathodic material for Li rechargeable batteries. Li-ion according to the following molar concentrations: Li- + + batteries can be exploited in many different practical acetate 3.68; Mn-acetate 1.57; NH4 and Li hydroxides applications mainly thanks to their very high energy 12.1 and 4.6, respectively. The starting sol-solutions density and capacity. In particular, it has recently (SS) were prepared utilizing two different routes: became evident that this kind of battery might be route I consisted in adding ascorbic acid (ASC) to the usefully utilized to power electric vehicles. starting solutions of Li and Mn acetates (Ac), after In a previous paper [1] we have described a new having adjusted their pH to alkaline values utilizing variant of sol-gel process (CSGP) to synthesize Lio.55. aqueous ammonia. Route II, instead, consisted in + i.nMn2O4+5 having satisfactory electrochemical adding LiOH to a solution of Mn and NH4 acetates properties. The CSGP utilize ascorbic acid as a very containing ascorbic acid. As a variant of route I some strong complexing agent with strong reducing preparations were obtained utilizing LiOH instead of properties. In the case of LiMn2O4 spinels we LiAc (route IA). Finally in few cases also HNO3 was observed that the thermal treatment of Li-Mn gels is added to the starting solutions. Detailed flow chart for a very complex process which involves foaming and the preparation of gels is shown in Fig.l. often self-ignition. In the present study we have In a previous work [1] we observed intensive pursued the goal of trying to elucidate some aspects of foaming from concentrate sols during their heating the thermal transformation of the gels into final (even if a very slow heating rate - <0.5°C/min - was crystalline spinels, paying a special attention to the utilized). This phenomenon is a clear consequence of RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL Li Ac (I) or MnAcr—> Dissolving LiOH (IA] <-H2O Dissolving ASC > Mn AC2 ^complex solution ASC NH4OH—> Sol 4- complex solution NH4A0—> formation Sol formation LiOH NH4OH > •I* complex sol •complex sol Evaporation under vacuum Evaporation under vacuum 1 concentrated sol -^concentrated sol Gelation and drying Gelation and drying 4- dried gel, shard dned gel, shard Self-ignition Self-ignition Grinding Grinding gel powders 4- gel powders Calcination, 400°C- 8 h Calcination, 400°C- 8 h 4- calcined powders 4- calcined powders LiMn2O4 LiMn2O4 Irregularly shaped powders Irregularly shaped powders Variant I and IA Variant II Fig.l. Flow chart for preparation of LiMn2O4 by CSGP. intensive gas evolution from sols or, more correctly, In order to find the influence of both the preparation from melted gels. In fact we have noticed that while method of the gels and the quantity of ASC added on the sols are fluid in the temperature range 110-160°C the composition and self-ignition temperature an analysis they solidify at room temperature. The foam is formed was performed of solidification (Table 1). It can be by the gases produced as a consequence of the thermal noticed that there is no simple relationship between the decomposition of the organic compounds present in carbon content and SIT. For example, samples 3 and 6 the sols. Subsequently, the decomposition of the foam both having a very similar composition have very differ- itself cause its simultaneous solidification. P. Sepulveda ent SIT. Moreover, it was observed that LiNi0.5Coo.5 described all these very complex processes in a review geis (e.g. sample No. 7) have always much higher SIT paper [2]. However, this author explained it as a result despite a similar content of organic compounds. of rapid viscosity increase during sol-to gel trans- This fact seems to indicate that Mn species exert formation. Elsewhere it has been described that catalytic action during the oxidation of both ASC and foaming, harmful from the practical point of view, can products of its decomposition. The experimental ob- be limited by the use of a very long ageing step at servation that during the decomposition of ASC elevated temperatures (further heating of gels results powders self-ignition was not observed further sub- in a violent self-ignition). stantiates this hypothesis. Table 3. Gel preparation*, chemical analysis and self-ignition temperature (SIT) Sample Variant Molar ratio in % self-ignition Note** No. SS ASC:XMe %C %H %N Li2O+ (SIT) °C (observation at SIT) +MnO 1 I 0.1 29.93 3.92 1.40 30.8 278 no foaming 2 I 0.2 31.32 3.68 2.27 31.1 276 limited foaming 3 I 0.4 33.95 3.70 3.75 27.8 250 no foaming 3a I 0.45 - 0.20 - 400°C,8h 4 II . 0.1 30.05 3.76 0.82 32.5 266 limited foaming 5 II 0.2 31.66 3.80 1.56 32.1 262 foaming 6 II 0.4 33.75 3.79 3.05 28.2 308 limited foaming 7*** I 33.62 3.99 4.44 440 limited foaming *sols were heated at 60°C for 5 days; at 13S°C for 6 days (solidification was observed), at 145"C for 2 days; ' foaming: approx. 2 increase in volume, limited foaming: approx. 1/2 increase in volume; *** LiNi0.sCo0.5 gel prepared according to [3]. 82 RAD10CHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL Representative thermal decomposition traces of gels noting is that self-ignition was also not observed in the prepared by methods I and II as reported in Table 1 case of thin film preparation utilizing this system [1]. and ascorbic acid are shown in Figs. 2 and 3. The first We are prone to the hypothesis that a critical mass is necessary to start self-ignition. The self-ignition process discussed above seems to be quite similar to the "combustion synthesis" of ce- ramic material recently reported in the literature [4,5]. However, in this latter case the addition of a fuel (e.g. esss urea) and of an oxidizer (e.g. nitrates) was necessary DTA 4^ to obtain the combustion. On the contrary, no such endo additives were necessary for self-ignition of the ascorbate gels examined in this work. In fact, TG carbonaceous species formed during ACS decomposi- %Am tion, are very reactive and even the atmospheric 10 1 \ oxygen is sufficient to start the ignition. To further X \ X investigate this aspect we have carried out some 20 experiments in which HNO was added to the samples. X \ 3 X 30 % \ As shown in Fig.3, the thermal decomposition of these It samples is similar to that of samples without HNO3. 40 A v It However it can be observed that the addition of HNO3 X \ delays the formation of the foam. Moreover, it can be 50 \ » \ noticed that the foam self-ignition temperature of the \\ 60 •* samples containing HNO3 decreases probably, as i a result of a faster combustion rate caused by the addi- M 70 tion of an oxidizer. \ K 80 \ X X 90 V K 300 500 700 900 temperature, °C Fig.2. Thermal decomposition of ASC (xxx) and LiMn acetate A ascorbate gels (—, Table 2, No. 2; —No. 4). 'Y 'A exotherm process, occurring around 35O°C can be ,7 ^ ascribed to acetate decomposition. The second - around 500°C, can be ascribed to the decomposition, by oxidation, of the non volatile ascorbate ligand. Moreover, a catalytic effect of the Mn species seems \ to be confirmed by the gels lower temperature 20 \ decomposition with respect to that of pure ASC. Mn |\ species seem to play a key role, during the subsequent 30 **\\ heating step, for the early crystalline phase formation, \\\\ as shown in Fig.4. It is worth noting here that the 40 formation of the spinel structure starts at 200°C and 50 after self-ignition it is almost completed. A hypothesis « can be put forward here that the synthesis of these 60 \ 1 materials is facilitated due to the non formation of the x - ... 1 carbonates (absence of v3CO3 - 875 cm" IR band). In 70 contrast, for example, with the LiNiCo case [3], Most probably the carbonates cannot be formed as a con- 80 sequence of the evolution of CO instead of CO2. 90 However, impurities of carbon in the final spinel are observed (sample No. 3a), but, it must be pointed out, as to this respect that the presence of carbon signifi- 100 300 500 700 900 cantly enhances the cycling performances of lithium temperature, *C manganese oxide cathodes. We did not observe self- Fig.3. Thermal decomposition of the LiMn acetate ascorbate gel (—, Table 2, No. 1) and the gel with the addition of HNOj ignition exothermal features on the DTA traces. Worth (—No. 4). RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 83 200°C, 2h 270 °C after self-ignition Fig.4. XRD patterns and infrared spectra of LiMn gel No. 2. On the basis of the above results the following area At this stage of the overall reaction the thermal transformation mechanism for acetate ascor- crystalline LiMn2O4 is already formed. It seems bate Li-Mn systems can be proposed: that these phenomena are strongly affected by the « evaporation of water to form a very viscous sol; catalytic action of Mn species. • formation of melted gels at temperature between References 110-160°C; [I], Deptuia A., Lada W., Croce F., Appetecchi G.B,, Ciancia A., • (a) on a continuous heating (also at very slow Giorgi L., Brinocchi A., Di Bartolomeo A.: Synthesis and pre- heating rates - <0.5°C/min) intensive foaming is liminary electrochemical characterization of LixMn2O4 (x=0.55- observed, (b) foaming can be significantly limited 1.1) powders obtained by the complex sol gel process (CSGP). if both the very prolonged heating step is intro- in: Proceedings of new materials for fuel cell and modern battery systems II. Eds. O. Savadogo, P.R. Roberge. Montreal duced or nitric acid is added; 1997, p. 732. • further heating results in self-ignition of [2]. Sepulveda P.: Am. Ceram. Soc. Bull., 76,61 (1997). carbonaceous materials formed by the decomposi- [3]. Deptufa A., Lada W., Olczak T., Croce F., Ronci R., Ciancia A., tion of ascorbic acid. Self-ignition temperatures Giorgi L., Brignocchi A., Di Bartolomeo A.: Synthesis and preliminary electrochemical characterization of LiNio.5Coo.5O2 however do not depend on the content of powders obtained by the complex sol gel process (CSGP). In: carbonaceous compounds, but rather on its surface Proceeding of MRS Fall'97 Meeting, Boston, USA. Vol. 496. 84 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL Symposium Y: Materials for electrochemical energy storage [4]. Fumo D.A., MorelH M.R., Segades A.M.: Mat. Res. Bull., 31, and conversion II-batteries, capacitors and fuel cells. Pittsburgh 1243 (1996). 1998, pp. 237-242. [5], Kim W.J., Park J.Y., Kim Y.S., Kuk I.H.: Jf. Mat. Sci. Lett., 16, 719(1997). PREPARATION OF CALCIUM PHOSPHATE BIOMATERIALS (POWDERS, 2+ 3 + MONOLITHS, COATINGS AND FIBERS) FROM Ca -PO4 -NH4 -OH -ASCORBIC ACID-H2O BY COMPLEX SOL-GEL PROCESS (CSGP) Andrzej Deptuia, Wiesiawa Lada, Tadeusz Olczak, Bozena Sartowska, Racquel Z, LeGeros1', John P. LeGeros1' !/ College of Dentistry, New York University, New York, USA In a former paper [1] we described the preparation of crucial for the formation of coatings and significantly spherical calcium phosphate powders and coating [2] accelerates the formation of hydroxyapatite. Conse- on metallic supports by a sol-gel process, modified by quently, we decided to modify the process by sub- the addition of a very strong complexing agent - stituting calcium acetate solution with Ca2+-ASC ascorbic acid (ASC) - to calcium acetate and H3PO4 solution. This was done by dissolving CaCCh in solutions (CSGP). We found that this additive is concentrated aqueous solution of ASC. The starting CaCO3 ASC Dissolving II2O - AQ.CaASC,, H PO - 3 4 Blending NH4OH- - Vof - NHj - OH' - ASC sol PEO (polyethylene , oxide) Gelatin in ambient IChTJ IChTJ CSGP conditions Emulsion Process for process layers in partially (Patent covered recipient (Patent) pending) monolithic shard gel spherical gel layers viscous sol gel gel pwd >2000 cSt drying Fibres & thermal thermal thermal formation bv treatment treatment treatment putting out' heating? (will.De. ,. patented) thermal treatment 1 Irregular Spherical HA shaped HA HA coatings HA fibers powders powders Fig. 1. Flow-sheet for the experimental procedure for preparation of calcium phospate materials in different size and shapes. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 85 sols were obtained by the addition of H3PO4 to that Some photographs of product (also microscopic solution followed by alkalizing with aqueous and SEM) are shown in Figs. 3-6. ammonia. Because the sols were very stable (no precipitates observed) biomaterials of various physical shapes were prepared in the following routes: 1. spherical powders (diameter <100 urn) by the 2O'» **'••• IChTJ sol-gel process, similarly as in [1], 2. irregularly shaped powders (diameter <100 jam) by evaporation in ambient conditions to shard and calcination, 3. coatings (5-50 |im) by immersion of Ti plates utilizing the technique described in [1], 4. fibers (diameter 5-80 \xm, several meters long) by the addition of poly(ethylene oxide), ageing at 20 V elevated temperatures and pulling out of glass rod immersed in the obtained very viscous slip, 5. monolith (volume till tens of cm3) by slowly iv. evaporation of water in ambient conditions from partially covered recipients, 6. pumice like body by slowly evaporation of water te v in ambient conditions from open recipients. HA-24 200°C,66h lcm egzo DTA TG %Am \ 10 t \ 20 > \ 30 \ \ 40 \ \ 50 \ —^ 60 70 80 Fig.3. Photographs of HA monolithic ascorbate gels prepared by 90 slowly evaporation of water in ambient conditions from 100 300 500 700 900 partially covered recipients and products of theirs calcination. temperature, °C Fig.2. Thermal analysis of HA acetate-ascorbate (—) and ascorbate Drying and calcination of gel monoliths and fibers (---) gels dried at U0°C. to calcium phosphate solids is a very difficult process. The detailed flow chart for the preparation is As can be seen actually only small pieces (~1 cm) and shown in Fig. 1. Thermal analysis of ascorbate gels short fibers (several mm) were obtained. As can be shows (Fig.2) that the ascorbate gels contain more observed from SEM micrographs gel materials are volatilies than the acetate-ascorbate gels. However the amorphous. After calcination at 1200°C a crystalline final temperatures of decomposition (800°C) are structure is evident. Non destructive thermal treatment similar in both cases. of both monoliths and fibers are actually under study. 86 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL r -.- ^ • * j M»g= 500X WD = 6 mm Rioto No. = 2W timo :12:10 20°C, 7.5 months 1200°C,3 h Fig.4. SEM micrographs of HA monolithic ascorbate gel before and after sintering. ' '..->-• M ..*•..."•&-.•.• Fig.S. Photograph of HA gel fibers. EHT= 5.00kV aanaJA = at^ Date :13Hay 1938 7 mm Photo No. = 244 Time :11:44 gel fibres 1200°Cfor3h Fig.6. SEM micrographs of HA gel fibers and products of theirs calcination. References process (CSGP), Bioceramics, 9, 313 (1996). [1], Deptula A., Lada W., Olczak T., LeGeros R.Z., LeGeros J.P.: [2]. Deptuia A., Lada W., Olczak T., LeGeros R.Z., LeGeros J.P.: Preparation of calcium phosphate coatings by complex sol-gel Polish Patent Pending P.314453, 1996. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 87_ THE DYNAMICAL PATTERN OF THE 3-AMINO-2-PYRAZINE ACID MOLECULE BY INELASTIC NEUTRON SCATTERING, RAMAN SPECTROSCOPY AND AB INITIO CALCULATIONS Andrzej Pawlukoj£, Ireneusz Natkaniec", Zbigniew Malarski2', Janusz Leciejewicz u Frank Neutron Physics Laboratory, Joint Institute of Nuclear Research, Dubna, Russia :CM 21 Faculty of Chemistry, University of Wroclaw, Wroclaw, Poland IS The spectroscopy of inelastically and incoherently combined with Raman spectroscopy measurements IS scattered thermal neutrons (IINS) proved to be a useful and ab initio calculations on 3-aminopyrazine-2- tool for the studies of molecular motions in crystals. carboxylic acid (APZA). In crystal, the APZA mol- N(2a) O(2a) „ O(1a) Fig. I. Molecular sheets in the structure of APZA. Broken lines indicate hydrogen bonds. Continuing our studies of molecular dynamics of ecules form sheets (see Fig. 1) separated by a spacing amino acids we have performed an IINS experiment of 3.751 A [1], Within the sheet, the molecules are 100 3-aminopyrazine-2-carboxylic acid 3 •5- (3 0 100 200 300 400 500 600 700 BOO 900 1000 1100 1200 1300 1400 Energy transfer (cm'1) Fig.2. Phonon density of states vs. energy transfer plot for APZA. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL linked by weak hydrogen bonds, so that one may spectra. A comparison of the bond distances and expect that molecular model calculations performed angles obtained in the crystal structure study [1] with for an isolated APZA molecule will provide reason- the calculated values gave good agreement when the able agreement with the results of experiment. basis sets, which take into account the polarization IINS spectra were recorded at 10 K using the functions, were used. All characteristic frequencies inverted geometry time-of-flight spectrometer NERA- observed in experiment were identified when the 6- PR installed at the pulsed reactor IBR-2 at Dubna. 311G basis set was used to obtain the potential energy Fig.2 shows the phonon density of states vs. energy distribution. The calculations, which were done for transfer plot. The IINS spectra were supplemented by a "free" molecule did not permit to find the torsional Raman spectroscopy measurements. Semiempirical ab frequency of the OH moiety on the IINS and Raman initio calculations were carried out using the spectra. It was observed to be shifted towards lower GAUSSIAN 94 program on a SUN computer at frequencies due to the participation of this moiety in 1 Dubna. The molecular geometries were optimized and a hydrogen bond. subsequently adopted as equilibrium geometries for the calculations of harmonic force fields. Vibrational Reference frequencies were derived from these calculations and [1]. Ptasiewicz-Bajk H., Leciejewicz J.: Polish J. Chem., 71, 1350 assigned to the modes observed in IINS and Raman (1997). NEUTRON DIFFRACTION STUDY OF ANTIFERROMAGNETIC ORDERING IN HoPtSi, ErPtSi AND ErPtGe Stanisiaw Baran1', Michael Hofmann2', Janusz Leciejewicz, Boguslaw Penc1', Andrzej Szytula1' " Institute of Physics, Jagiellonian University, Krak6w, Poland = 00 11 5 CM Hahn-Meitner Institute, Berlin, Germany = C\J |O •CX> HoPtSi, ErPtSi and ErPtGe crystallize in the ortho- rhombic TiNiSi-type crystal structure and were reported to order antiferromagnetically at low tem- peratures. HoPtGe was found to be paramagnetic at 1.8 K. Neutron diffraction data were collected for polycrystalline samples of the first three compounds at a number of temperatures between 1.5 and 8 K. using an E6 diffractometer at the BER II reactor in Hahn- Meitner Institute, Berlin. Fig. I. Schematic representation of the magnetic structure of HoPtSi projected on the (010) crystallographic plane. The + and -*- b - signs symbolize the magnetic moments pointing upwards Fig.2. Schematic representation of two possible colinear magnetic and downwards in respect to the plane of the drawing. structures in ErPtSi and ErPtGe. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 89 HoPtSi shows a colinear antiferromagnetic struc- intensities do not permit to distiguish between two ture, characterized by the wave vector [1/2, 0, 1/2] and alternative ordering schemes displayed in Fig.2. Both stable between 1.5 K and the Neel point at 3.1 K. The models yield the same set of calculated magnetic magnetic moment localized on the Ho+3 ion amounts neutron intensities and values of magnetic moments at to 9.38(15) uB at 1.5 K and is aligned along the cry- 1.5 K. stallographic b-axis. This structure is shown schemati- In both compounds the colinear order transforms cally in Fig. 1. into a sine modulated structure with the wave vector ErPtSi and ErPtGe exhibit the same type of [0, ky, 0]. The transition occurs at 2.5 K (ErPtSi) and colinear antiferromagnetic order described by the wave 3.2 K (ErPtGe). The ky components are 0.416(1) and vector [0, 1/2, 0], The magnitudes of magnetic mo- 0.406(1) in ErPtSi and ErPtGe, respectively. The sine- ments at 1.5 K are: 7.60(11) uB in ErPtSi and of modulated structure vanishes at the respective Neel +3 7.79(8) uB in ErPtGe. They are localized on the Er points: 3.8 K (ErPtSi) and 4.1 K (ErPtGe). Neutron ions and aligned along the direction of the crystal- diffraction patterns of ErPtSi recorded at the tempera- lographic a-axis. The observed neutron magnetic tures below 8 K are shown in Fig.3. ErPtSi at 1.5, 3.0, 3.5, 8.0 K, Mon. 1E6, E615855. 59-61 T 3000 Vanadium Container, 21.11.1398, very sharp magnetic phase transition 2000 1000 -1000 20 40 80 Fig.3. Neutron diffraction patterns of ErPtSi recorded below 8 K. CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS OF HETEROCYCLIC CARBOXYLIC ACIDS. PART XXIII. THE CRYSTAL STRUCTURE OF NICKEL(II) COMPLEX WITH PYRAZINE-2,3-DICARBOXYLIC ACID Halina Ptasiewicz-B^k, Janusz Leciejewicz A new series of 3d metal complexes with pyrazine- contain monomeric molecules. The Ni(II) ion is 2,3-dicarboxyIate (2,3-PZDC) anions have been ob- coordinated by two molecules of 2,3-PZDC each tained by the reaction in warm acetone between the donating its heteroring nitrogen [Ni-N 2.048(2) A] relevant nitrates and the title ligand. In contrast to the and one oxygen atom belonging to the nearest mono- previously reported compounds, the new complexes dentate carboxylic group [Ni-0 2.020(1) A]. TWO exhibit the 1:2 stoichiometry and entirely different water molecules [Ni-0 2.091(2) A] complete crystal structures. The crystals of diaquobis(trans- octahedral environment of the central ion. Neither the hydrogen pyrazine-2,3-dicarboxylato-N,O)nickeI(II) second carboxylic group nor the second heteroring 90 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 03 H3 C3 Fig. 1. The molecule of Ni(2,3-PZDC)2 (H2O)2. nitrogen atom participate in chelating the Ni(II) ion. [3]. Part XVIII. Ptasiewicz-Bak H., Leciejewicz J.: Strontium ions Fig. 1 shows the molecule of the title complex. Strong bridged by pyrazine-2,5-dicarboxylic acid and water molecules intramolecular hydrogen bond of 2.41(5) A links the make a three-dimensional polymeric structure of triaquomono (l>pyrazine-2,5-dicarboxylato)strontium(Il) dihydrate crystals, carboxylic oxygen atoms inside the molecule [0(3)- J. Coord. Chem., 44,237 (1998). H(7)...O(2)]. The water molecules donate their hydro- [4]. Part XIX. Ptasiewicz-Bak H., Leciejewicz J.: X-ray diffraction gen atoms to the bonds which link them with the study of the crystal structures of pyrazine-2,5-dicarboxylic acid oxygen atoms of carboxylic groups in the adjacent dihydrate and its magnesium complex, J. Coord. Chem., 44, monomers. These bonds are characterized by longer 299(1998). distances of 2.82(7) A and 2.95(7) A indicating weak- [5]. Part XX. Leciejewicz }., Ptasiewicz-Bak R, Zachara J.: The crystal structure of strontium complex with 3-aminopyrazine-2- er interactions. carboxylic acid, Polish J. Chem, 72, 1994 (1998). X-ray diffraction data were collected using a KUMA [6], Part XXI. Ptasiewicz-Bak H., Ostrowski A., Leciejewicz J.: KM4 four circle diffractometer at this Institute. Struc- Monomerlc molecules in the isostructural calcium(II) and ture solution and refinement was performed using the strontiurn(II) complexes with pyrazine-2-carboxylic acid, Polish J. Chem, 72, 2014 (1998). SHELXL 93 program package. [7]. Part XXII. Paluchowska B, Lis T, Leciejewicz J.: Dimeric References molecules of cobalt(II) and zinc(II) complexes with furan-2- carboxylate ligands stabilized by the system of interconnected [1]. Part XVI. Ptasiewicz-Bak H, Leciejewicz J.: Polymeric crystal C - H ...Owafcr, OMer - H ... Ofuran and Ow»ier - H -jt hydrogen structure of trisaquo(|4-pyrazine-2,3-dicarboxylato)strontium(II), bonds, Polish J. Chem, 72, 2172 (1998). Polish J. Chem., 72, 627 (1998). [8]. Part XXIII. Ptasicwicz-Bajc H, Leciejewicz J.: The crystal and [2]. Part XVII. Paluchowska B., Maurin J.K., Leciejewicz J.: Di- molecular structures of nickel(II) complexes with pyraztne-2,3- nuclear copper(II) complexes with 3-furancarboxylic acid and dicarboxylic and 3-aminopyrazine-2-carboxylic acids, Polish J. 2-thiophencarboxylic acid, J. Coord. Chem., 44, 183 (1998). Chem, 73, 717 (1999). CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS OF HETEROCYCLIC CARBOXYLIC ACIDS. PART XXIV. THE CRYSTAL STRUCTURE OF Cu(II) COMPLEX WITH PYRAZINE-2,3-DICARBOXYLIC ACID Halina Pta\siewicz-B^k, Janusz Leciejewicz The reaction of copper nitrate with pyrazine-2,3- Cu ion and the rings of both pyrazinate ligands are dicarboxylic acid (2,3-PZCA), both dissolved i.n warm coplanar. In this plane, Cu-0 and Cu-N bonds are acetone gave a precipitate which was soluble in 1.958(2) A and 2.000(3) A, respectively. The second boiling water. Pale-blue single crystals were deposited carboxylic group of each ligand provides one oxygen after few days. In contrast to the previously reported atom for coordination the Cu ion in the adjacent compound Cu(2,3-PZCA)C1 [1], this new compJex moiety [Cu-0 2.414(3) A] forming molecular ribbons shows 1:2 stoichiometry. Its structure is also poly- in the crystal. The coordination polyhedron around the meric but the observed molecular pattern is different. Cu ion is an elongated octaehedron indicating strong The crystals of diaquobis((a-pyrazine-2,3-dicarboxylato- Jahn-Teller effect. Water molecules located in the N,O,O')copper(II) dihydrate contain Cu(2,3-PZDC)2 space between the ribbons are active in a network of moieties bridged by carboxylic oxygen atoms. Fig.l hydrogen bonds of 2.686(6) and 2.846(7) A respon- illustrates the way in which this bridging occurs. The sible for the cohesion of the crystal. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 91 04 Fig.l. A fragment of a molecular ribbon in the crystal of Cu(2,3-PZDC)2 • 2H2O. X-ray data collection was done using a KUMA KM4 Reference four circle diffractometer at this Institute. Structure [1]. O'Connor C.J., Klein C.L., Majeste R.J., Trefonas L.M.: Inorg. solution and refinement was carried out with the Chem.,21,64(1982). SHELXL 93 program package. CRYSTAL CHEMISTRY OF COORDINATION COMPOUDS WITH HETEROCYCLIC CARBOXYLIC ACIDS. PART XXV. THE CRYSTAL STRUCTURE OF CALCIUM(II) COMPLEX WITH 5-METHYLPYRAZINE-2-CARBOXYLIC ACID Halina Ptasiewicz-Bqk, Janusz Leciejewicz Monomeric molecules were detected in the crystals of bridging water oxygen atoms [Ca-0 2.627(1) A and calcium(II)complex with pyrazine-2-carboxylate ligand 2.495(1) A], the two bridging carboxylic oxygen [1], however the structure of calcium(II) compound atoms [Ca-0 2.457(1) and 2.461(1) A] and the the with 3-amino-2-pyrazine carboxylate ligand have been heteroring nitrogen atom of the bridging ligand [Ca-N found to be polymeric [2]. In the latter, the carboxylic 2.587(1) A ] make an approximately planar pentagon. oxygen atom acts both in chelating and bridging The planes of the pentagons around adjacent Ca ions manner. An X-ray diffraction study has been therefore are forming an almost flat chain. In addition, each undertaken in order to find out how the size of the Ca(II) ion is chelated by a second ligand molecule via ligand influences the molecular pattern in the crystals its N,0 bonding moiety [Ca-0 2.387(1) and Ca-N of some other calcium pyrazinates. Calcium complex 2.699(3) A]. The plane of this ligand is perpendicular with 5-metyl-2-pyrazinate ligand (5-MPZA) was to the plane of the pentagon. The coordination around chosen for this study. Its structure was found to be the central ion is completed by an oxygen atom of a polymeric. Fig.l shows a fragment of its molecular water molecule [Ca-0 2.366(1) A] situated on the pattern. Ca(II) ions are bridged alternatively by two other side of the pentagon. oxygen atoms donated by two water molecules and by X-ray diffraction data were collected at 293 K two oxygen atoms, each belonging to a monodentate using a KUMA KM4 four circle diffractometer at this carboxylic group of an acid ligand. The coordination Institute. Structure solution and refinement was per- around Ca ion is eightfold. The metal ion, the two formed using the SHELXL 93 program package. 92 RAPIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL N Fig.l. Molecular ribbon in the structure of Ca(5-MPZA)2(H2O)j. References Chem., 72,2014(1998). [2]. Leciejewicz J., Ptasiewicz-Bak H., Paluchowska B.: Polish J. [1]. Ptasiewicz-Bak H., Ostrowski A., Leciejewicz J.: Polish. J. Chem., 71, 1359(1997). CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLIC ACIDS. PART XXVI. THE CRYSTAL STRUCTURE OF MANGANESE(IH) COMPLEX WITH FURAN-3-CARBOXYLATE ANIONS Beata Paluchowska1', Jan K. Maurin1', Janusz Leciejewicz " Institute of Atomic Energy, Otwock-Swierk, Poland The crystals of diaquobis(jx-furan-3-carboxylato- 0,0')tetra(u-furan-3-carboxylato-0,0)(^-aquo)dimanga- nese(II) contain dinuclear structural units, in which two Mn(II) ions are bridged by oxygen atoms donated by two ligand molecules [Mn(l)-0(ll) 2.114(2); Mn(l)-O(22) 2.115(2); Mn(2)-O(12) 2.101(2); Mn(2)- 0(21) 2.121(2) A] and an oxygen atom belonging to the water molecules situated between the metal ions [Mn(l)-0(l) 2.250(1), Mn(2)-0(l) 2.264(2) A] - see Fig.l. Each Mn(ll) ion is also coordinated by two oxygen atoms belonging to carboxylic groups of two other ligand molecules [Mn(l)-O(32) 2.205(2) (twice), Mn(2)-O(42) 2.180(2) A (twice). These oxygen atoms are bidentate and bridge the Mn(l) and Mn(2) ions with the Mn ions in the adjacent structural units, forming molecular ribbons extending in the b direction of the crystal lattice. In addition, each Mn ion in a unit is linked to the oxygen atom of a water molecule [Mn(l)-0(3) 2.180(2); Mn(2)-O(3) 2.163(2) A.]. The coordination polyhedron around each Mn(II) ion is a distorted octahedron. Two octahedra share a common apex 0(1) and make an angle of 108.02 deg. The 033 ribbons are linked by C-H...Ofi,ran hydrogen bonds; the heteroring oxygen atoms do not directly participate in chelating the central ion but their electronodonor Fig.l. The molecule of Mnz(3Fu)4(H2O)j. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 93 abilities reveal themselves in hydrogen bonds which X-ray diffraction data were collected using a are essential for the stability of the crystal. The furan- KUMA KM-4 four circle diffractometer at this 3-carboxylate rings (Fu) are stacked by pairs (Fu2- Institute. Structure solution and refinemeent was done Fu4, Ful-Fu2) with the spacings between the ring using the SHELXL program package. planes of 3.46(1) and 3.49(1) A, respectively. SAXS STUDY OF THE INFLUENCE OF SOLVENTS ON THE STRUCTURE OF POLYURETHANE-BASED MEMBRANES Helena Grigoriew, Aleksandra WoMska-Grabczyk1', Andrzej G. Chmielewski, Jarostaw Domagata2' "institute of Coal Chemistry, Polish Academy of Sciences, Gliwice, Poland 21 Institute of Physics, Polish Academy of Sciences, Warszawa, Poland A study of the state of permeant in the membrane and materials: the membrane microstructure is one of the most 1. TDI PP/1000. An intense, broad diffraction maxi- important steps to understand membrane transport mum centered at 17 nm is visible after swelling the phenomena [1]. The results of such studies are of sample in benzene and much weaker one after special interest for pervaporation investigations. This swelling in ethanol. The intensity of the last maxi- membrane technique is expected to be an alternative mum decreases with raising temperature. technique for the separation of mixtures of close 2. 3(TDI PP)/1000. SAXS curve shows a very boiling liquids, azeotrops, structural isomers or heat- intense broad diffraction maximum centered at sensitive organics. In this work, our attention was 22 nm after swelling the sample in benzene and focused on the microstructure of the polyurethane- much weaker one at the same position after based membranes, the properties of which have been swelling it in ethanol. examined recently [2]. In general, segmented poly- urethanes are regarded as multiblock copolymers of 3. TDI PP/2000. The SAXS curves show no diffraction maximum after swelling the samples. (AB)n type in which A and B are the hard- and soft- segment repeat units. Due to thermodynamic The decrease in Rg is observed ranging from incompatibility, the segments undergo microphase 15 nm for the dry sample to 9.5 nm for the swollen separation and form impermeable hard-segment ones in benzene and to 8 nm for those swollen in domains dispersed in the ruberry soft-segment matrix. ethanol. It can be expected that permeability, like mechanical As can be seen from the existence of diffraction properties of these polymers, depends on the manner peaks on SAXS for the materials composed of shorter in which both the types of domains are organized and soft segments (1 and 2) there is some degree of how this organization changes in swollen membranes. ordering of the hard domains caused by swelling, The poiyurethanes studied are composed of poly(tetra- independently of the kind of solvent. Because of methylene oxide)-based soft segments and hard seg- smaller intensity of the peak after swelling in ethanol, ments composed of a 2,4-tolylene diisocyanate (TDI) the degree of this ordering is smaller for ethanol in chain extended with 4,4'-diphenylmetane diamine comparison with benzene which coresponds to a (PP). The structural variations within the series of the greater sorption value of benzene. investigated poiyurethanes come from the different Material 3, with longer soft segments, i.e. greater molar masses of the soft-segments (2000 or 1000) distance of the hard domains, has no tendency to and/or different length of the hard-segments (TDI PP structural ordering during swelling and raising tem- or 3(TDI PP) sequences). perature. Instead of it there is a change in Rg observed, SAXS experiment was performed on a synchrotron from 15 nm to 8 nm, i.e. the structure becomes more HASYLAB-DESY in Hamburg, Germany. We dispersed. worked on A2 beamline using a time-resolved mode References with raising temperature from room to 70°C and then cooling, for the dry membranes and membranes satu- [1]. Grigoriew H., Chmielewski A.G.: J. Membr. Sci., 142, 87-95 (1998). rated with benzene and ethanol. The following changes [2], Muszynski J., Wolinska-Grabczyk A., Penczak P.: J. Appl. were obtained on SAXS curves for subsequent Polym. Sci. (in press). 94 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL KINETICS OF STRUCTURAL CHANGES IN POLYMER MEMBRANES Helena Grigoriew, Andrzej G. Chmielewski, Heinz Amenitsch1', Sigrid Bernstorff2/, Jaroslaw Domagala3' ICO " Institute of Biophysics and X-Ray Structure Research, Austrian Academy of Sciences, Graz, Austria •CM 21 Sincrotrone ELETTRA, Trieste, Italy IS 3/ Institute of Physics, Polish Academy of Sciences, Warszawa, Poland IS As it was found in our Laboratory, in the process of First, the time interval of sol-gel type structural water sorption by cellulose membrane the volume of transition was estimated. After starting measurements absorbed water becomes equal to 1.5 volume of with dry cellulose the wet vapor was supplied to the cellulose. It is a kind of sol-gel transition. Also our sample. We found that the all structural change takes previous SAXS experiment showed creation of place in a very short time, about 1 sec, for both kinds heterogeneity after swelling cellulose with water [1,2]. of water. As it was found earlier by us, gyration radius At synchrotron ELETTRA, Italy, the structure of of particles generated during the change is about 8 nm the system cellulose-water has been studied on and a simultaneous decrease of chains order in WAX beamline SAXS, in a kinematic and thermal way. [1,2] is shown. SAXS and WAX measurements were performed Next, time-resolved measurements during in- simultaneously, in a time-resolved mode using linear creasing temperature of the system cellulose-water detectors. The samples were placed in a chamber built from room to 85°C were performed. They showed an in the INCT. The chamber makes it possible for emerging peak with a broad shoulder on the side of continuous supply of wet saturated penetrant vapor to greater angles in SAXS, and simultaneously a slight the sample, as well as rising its temperature, during increase of chains order in WAX, greater for D2O synchrotron experiment. The samples were made by (Fig.l) [3]. The peak position is about 27 nm. regenerated cellulose Tomophan I and light and heavy Existence of the peak is evidence of a diffraction water, because a difference in permeation rate for each phenomen, so in the material studied ordering occurs kind of water exists. of some great elements with increasing temperature. T°C T°C SAXS WAX Fig. 1. Temperature changes of SAXS and WAX for cellulose - H2O (bottom) and cellulose - D2O (top). RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 95 The only explanation is that it is the ordering of ordering is possible. particles formed during the first structural change at References room temperature. Our first presumption of the nature of particles [1]. Grigoriew H., Chmielewski A.G.: J. Mat. Sci. Lett., 16, 1945 formed in the first structural change was that they are (1997). [2]. Grigoriew H., Chmielewski A.G.: J. Membr. Sci., 142, 87 water particles [1,2]. But there is no reason for (1998). ordering water droplets in the structure. The particles [3]. Grigoriew H., Chmielewski A.G., Amenitsch H., Bernstorff S.: must be micelles of cellulose and only for them the EPDIC-6, Budapest 1998, pp. PO9-18. A STUDY ON ANION EXCHANGE THERMODYNAMICS AND THE EFFECT OF COLUMN TEMPERATURE ON THE QUALITY OF CHROMATOGRAPHIC SEPARATIONS IN ISOCRATIC ION CHROMATOGRAPHY Krzysztof Kulisa, Rajmund Dybczynski Establishing of conditions and parameters influencing carbonate-carbonate buffer (1.7 mM NaHCO3/1.8 mM the quality of chromatographic separations of mixtures Na2CO3) solutions (pH range 8.15-9.97) as well as of ionic species in aqueous solutions is essential for NaOH solutions (0.5, 1, 3, 5, 10, 20 and 30 mM, pH accurate and reliable chromatographic analysis. Column range 9.61-11.85) were used as a mobile phase. temperature is a valuable parameter for optimizing ion Changes of the above mentioned chromatographic chromatographic separations of inorganic anions. The parameters were established as a function of column influence of column temperature on the separation temperature in the range 10°C - 55°C for Ion Pac AS5 processes was investigated recently more widely than and AS9SC anion exchange columns and 5°C - 40°C up to now for several chromatographic techniques, for Ion Pac AS4A column for many inorganic anions 3 such as reversed phase chromatography as well as IEC such as: F\ Cr, IO3", BrO3\ Br\ NO/, NCV, I", PO4 ", 2 2 [1-8], ion-pair chromatography [10,11], normal-phase SO3 ' and SO4 ". The columns were maintained at HPLC [12] and occasionally for ion-exchange chro- a temperature chosen before elution process during the matography [13-16]. Comprehensive studies on the period of ca. 0.5 h to stabilize thermal conditions of thermodynamics of ion-exchange processes with the each experiment. use of special type of "agglomerated" ion exchange It was established that the chromatographic para- resins applied in ion chromatography, however, were meters investigated, such as column efficiency, capac- practically not carried out so far. ity factor, selectivity coefficient and the resolution for This study was carried out in order to evaluate the several anions may increase or decrease with increas- effect of column temperature on ion exchange equi- ing column temperature. Thermal resistance of the libria of low capacity "agglomerated" anion exchange investigated anion-exchange resin beds was evaluated resins of Dionex Ion Pac type, and to investigate the to be about 40°C. Above this limit, the symptoms of changes of basic chromatographic parameters such as partial ion-exchange bed degradation were observed retention time tR, column efficiency N (peak broaden- when applying Ion Pac AS5 and AS9S.C anion- ing), peak asymmetry T, capacity factor k, selectivity exchange columns. As a consequence, column ion coefficient K', separation factor a and resolution R exchange capacities rapidly decreased as well as according to column temperature changes. One can column efficiencies, which caused increasing of peak expect, that the "agglomerated" type ion exchangers of broadening and asymmetry (especially for multivalent low exchange capacity (10-30 (aeq/g) and short anions with greater values of capacity factor k, such as 3 2 2 diffusion paths for exchanging ions, which is applied PO4 ', SO3 " and SO4 ") and changes of retention times in ion chromatography, can be more strongly affected for several anions. Changes of chromatographic para- by changes of column temperature than the ion ex- meters caused by ion-exchange bed degradation were changers of greater ion exchange capacities used in irreversible. For the studies with the use of Ion Pac classical ion-exchange chromatography [17,18]. The AS4A column, the range of temperature 5°C - 40°C studies were carried out with the use of a commer- was applied as a column temperature with NaOH of cially available ion chromatograph Dionex 2000i/SP changeable concentration as a mobile phase. No symp- and three anion exchange columns of type Ion Pac toms of ion-exchange bed degradation were observed AS5, AS9SC and AS4A of different degree of hydro- during the experiments and the nominal ion-exchange phobicity of functional groups and different exchange capacity was maintained. Elevated column tempera- capacities (within the range of 10-30 (ieq/g). A hydro- ture up to 40°C caused the column efficiency to gen carbonate (1.5 and 10 mM NaHCO3), hydrogen increase for the majority of investigated anions (Fig.l). 96 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL AS4A AS4A Eluent 5 mM NaOH Eluent 10 mM NaOH oSO|- + logK' +Q- ABr' ONCK +SO? *I 4.50 4.00 3.50 3.00 1000 2.50 2.00 3.00 3.14 3.28 3.42 3.56 3.70 1/T (E-3) Fig. 1. Changes of number of theoretical plates as a function of Fig.2. Changes of selectivity coefficient as a function of column column temperature. temperature. 3 2 2 For several pairs of anions (e.g. PO4 '-SO4 ", SO4 '-I", [7]. Warren F.V., Bidlingmeyer B.A.: Anal. Chem., 60, 2821-2824 NCV-Cl') changes of column temperature induced an (1988). increase of selectivity (Fig.2) and resolution. [8]. Vigh G., Varga-Puchony Z.: J. Chromatogr., 196, 1-9 (1980). The values of standard thermodynamic functions [9]. Sander L.C., Wise S.A.: Anal. Chem., 61, 1749-1752 (1989). (AH, AS and AG) for ion-exchange reactions were [10]. Terweij-Groen C.P., Kraak J.C.: J. Chromatogr., 138, 245 (1977). calculated for the temperature range investigated. On [11]. Lammers N., Zeeman J., de Jong G.J.: J. High Res. this basis, the evaluation of energetic effects of ion- Chromatogr. and Chromatogr. Comm., 4,444 (1981). exchange reactions was possible for several inorganic [12]. Snyder L.R., Kirkland J.J.: Introduction to modern liquid anions at different column temperatures. chromatography. 2nd ed. Wiley Interscience, New York 1979, 390 p. References [13]. Baba Y., Yoza N., Ohashi S.: J. Chromatogr., 348,27-37 (1985). [1]. Snyder L.R.: J. Chromatogr., 179,167-172 (1979). [14]. Fortier E., Fritz J.S.: Talanta, 34,4,415-418 (1987). [2]. Melander W.R., Bor-Kuan C, Horvath C.J.: J. Chromatogr., [15]. Snyder L.R., Dolan J.W., Gant J.R.: J. Chromatogr., 165, 3 185,99-109(1979). (1979). [3]. Giod B., Alexander P.W., Zu L.C., Haddad P.R.: Anal. Chim. [16]. Henderson D.E., O'Connor D.J.: Adv. Chromatogr., 23, 65 Acta, 306, 267-272 (1995). (1984). [4]. Gennaro M.C. et a!.: J. Chromatogr. Sci., 33,360-364 (1995). [17]. Hamilton P.B., Bogue D.C., Anderson R.A.: Anal. Chem., 32, [5]. HerbutG., KowalczykJ.S.: J. High Res. Chromatogr., 4, 27-32 1782(1960). (1981). [18]. Pecina R., Bonn G., Burlscher E., Bobletter O.: J. Chromatogr., [6], Kowalczyk J.S., Herbut G.: J. Chromatogr., 196,11-20 (1980). 287,245(1984). SORPTION OF HEAVY METALS ON HYDROXYAPATITES Jadwiga Chwastowska, Elzbieta Sterlinska, Monika Sadowska-Bratek Hydroxyapatite (HA) has received much attention due [1,2]. In our work the sorption of heavy metals by to its potential using as a bioactive bone substitute. calcium phosphate powders, obtained by the sol-gel Owing to its crystal structure and chemical com- method of Deptula et al. [3] has been studied. position this material also shows a high capacity for The sorption of the following metals was ion exchange with heavy metal ions. For this reason investigated: Cu, Ni, Co, Cd, Pb and Zn. The influence HA can be applied to remove certain ions from of pH on the sorption of these metals by the bath aqueous solutions. method has been studied. The retention of metals was Few works have been publicated on this subject calculated from the amount of element determined by RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 97 1 1 i • i • lOO-i Cu 80- • eo- • / 40- • / 20- • () 1 J2 3 4 5 6 7 i • i .—,.. •—I 1 • i i—|— 1C0-- Zn .—•—' 80- r • 60 - «• // • 20- • / 1 f> 1 2 3 4 5 6 7 pH pH Fig.l Retention of elements from solutions of various pH. the absorption atomic spectrometry method in sol- (shaking time - 30 min, eluents 2M HC1), (Table 1) it utions after sorption. follows that the efficiency of desorption is not The results are shown in Fig.l. It can be seen that quantitative (59-90%). the elements are retained on the hydroxyapatite over From the data obtained it can be stated that HA is a a wide acidity range. In the most suitable acidity range useful sorbent material. The possibility of application (pH>3 or 4), the retention was about 100% (97-100%) of hydroxyapatite to the separation of heavy metals for all the metals studied. using the column method and the mechanism of The kinetic of sorption, for example, of two metals sorption deserve further investigations. - copper and nickel over a shaking time 5-30 min was Table 1 Desorption of elements by 2M HC1 examined. The results obtained show that the equi- librium of sorption for metals studied (Cu, Ni) was Element Desorption [%] attained in a few minutes. Cu 90.0 The retention capacity of HA estimated by the bath Cd 83.0 method for copper is 6 mg - 0.047 mmole per gram. Pb 79.0 The mole ratio of HA to the sorbed copper calculated Ni 61.0 on the basis of the above data is 20.8. Co 56.0 From the results of desorption in the bath conditions Zn 57.0 98 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL References [2]. Jeanjean I, Fedroff M., Faverjou F., Vincent U.: J. Mat. Sci., 31,6156-6160(1996). [1]. Reichert J, Binner J.G.D.: J. Mat.Sci.,31, 1231-1241 (1996). [3]. Deptula A., Lada W., Olczak T., Boreilo A., Alvani C, Di Bartolomeo A.: J. Noncryst. Solids, 147-148, 537 (1992). EFFECT OF GASEOUS CHLORINE AND HYDROCHLORIDE ON THE As-Pd AND Sb-Pd COMPOUNDS DURING THEIR ATOMISATION IN A GRAPHITE FURNACE Leon Pszonicki, Jakub Dudek The results of previous investigations [1] suggested 400°C, i.e. below the temperature of arsenic-palladium that palladium, proposed by some authors [2,3] as compound formation, when arsenic and palladium are a good modifier for the determination of arsenic by present as a mixture of oxides. Different behaviour of electrothermal atomic absorption spectrometry, works arsenic is observed in the presence of magnesium. correctly only in the nitric acid medium. In the Both elements form already during the drying process presence of some amounts of hydrochloric or per- a stable compound that is resistant against free chloric acids palladium is not able to save arsenic chlorine and hydrochloride in the total range of against its losses in the form of chloride during drying pyrolysis temperature up to 900°C. of the analytical sample in a graphite furnace. In this The above presented results confirm unambigu- phase of the process also some amount of palladium is ously our previous hypothesis [1] that, when some transformed in the chloride form. This palladium amount of hydrochloric acid is present in the analytic- chloride dissociates during the pyrolysis phase at a al sample, in the presence of palladium modifier the temperature of about 500°C evolving free chlorine that losses of arsenic can occur in two stages: during attacks the arsenic combined already with palladium drying process when arsenic is not yet protected by as intermetallic compounds and causes its additional palladium and at about 500°C when the excess of losses. The mentioned shortcomings of palladium palladium chloride dissociates and the evolved modifiers can be eliminated by using either mixed chlorine attacks the arsenic-palladium compounds. palladium-magnesium modifiers or only magnesium This results confirm also that in the recommended by nitrate. some authors [1,2] mixed palladium-magnesium The aims of the present investigation was to study modifier a dominant role is played by magnesium and the behaviour of arsenic and antimony compounds magnesium nitrate can replaced successfully this with palladium and magnesium in the presence of mixed modifier. gaseous chlorine and hydrochloride in the graphite A similar investigation was carried out for furnace during the pyrolysis phase in the temperature antimony. The obtained results were the same as for range from 200°C to 900°C. The investigated com- arsenic with one exception. Antimony is resistant pounds were obtained by the pyrolysis of arsenic or against the losses in the hydrochloride atmosphere also antimony together with palladium or magnesium (all when it was preliminary pyrolysed with palladium at in nitrate form) at the required temperature in an argon a temperature below 400°C. The losses in the chlorine atmosphere. Then the graphite tube was cooled, atmosphere are identical as for arsenic. This agrees purged with chlorine or a hydrochloride gas and the with a previous observation that antimony is not lost sample was pyrolysed again at 400°C. This second during the drying process in the presence of palladium pyrolysis was directly followed by the next stage of modifier in the sample containing hydrochloric acid. pyrolysis in the argon atmosphere at a standard Its losses occur only during the pyrolysis at a tempera- temperature of 900°C, by atomisation and by measure- ture higher than the dissociation temperature of ment of the analytical signal. palladium chloride. The obtained results indicated that free chlorine References causes the losses of arsenic in the presence of palladium in the total range of temperature to be investigated [1]. Pszonicki L, Dudek J.: INCT Annual Report 1997, p. 47. [2]. Wells B., Schlemer G., Mukadavit J.R.: J. Anal. Atom. Spectr., whereas the losses caused by gaseous hydrochloride 3,93-97(1988). are observed only in the temperature range up to [3]. idem: ibid, 3, 695-701 (1988). RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 99 DETERMINATION OF SILICON AND PHOSPHORUS BY FLAME AND ELECTROTHERMAL ATOMIC ABSORPTION SPECTROMETRY Witold Skwara, Leon Pszonicki From the point of view of chemical analysis silicon analytical signals and of the shape of the atomization and phosphorus belong to the troublesome elements, curves (peaks) the pyrolytically coated graphite tubes particularly, when present at a small concentration. without platform appeared to be optimum as atomizing Their determination is also difficult by spectral analy- furnace for both elements. The atomization tempera- sis because of the high excitation energy. Particularly ture was 2600°C and 10 ul of the sample was used. difficult is the determination of phosphorus since its Integrated absorbance was measured as analytical most intensive spectral lines are placed in the vacuum signal. The line broadening background correction ultraviolet region (167-179 nm) that requires the use (Smith-Heftje method) suppressed significantly the of a special equipment. Despite of this inconvenience, analytical signal of phosphorus and for silicon it was in the last years the spectral methods are applied for completely ineffective. Therefore, the deuterium-arc the determination of both these elements in various background correction was applied. materials as food, waters, biological and industrial For the determination of phosphorus the following materials, and petrol products [1-7]. For phosphorus, chemical modifiers were tested; calcium, magnesium, to avoid the use of vacuum equipment, its less nickel, palladium and lanthanum in the form of sensitive spectral line placed in the near ultraviolet nitrates and chlorides. Lanthanum nitrates added to the (213.6 nm) is applied. The detection limits of such sample solution at a concentration of 500 ug/ml was methods are comparable to the spectrophotometric found as optimum. In the presence of this modifier, methods and meet most of the analytical requirements. phosphorus is thermally stable up to 1200°C and no A significant advantage of the spectral method is a negative effects of nitric, hydrochloric and perchloric very simple preparation of the sample, usually, limited acids or their mixtures on the analytical signal were to its dissolution. found. The calibration curve is linear up to 50 ug P/ml The aim of the present work was to prepare a set of and the detection limit of the method is equal to flexible analytical procedures for the determination of 1 ug/ml. silicon and phosphorus. These procedures should be For silicon determination, magnesium and compatible with a Thermo-Jarrel Ash atomic absorp- palladium nitrates and their mixture were tested as tion spectrometer equipped with a furnace TJ 188 for modifiers. The mixture of 200 ug/ml Pd and 300 ug/ml electrothermal atomization and be easy applicable to Mg as nitrates appeared as optimum. In its presence various types of analytical samples and to large con- silicon is thermally stable up to 1200°C. No negative centration intervals of both analytes. effect of nitric, hydrochloric or perchloric acids was The procedure based on the flame atomization found. The calibration curve is linear up to 200 ng were prepared for the high concentration intervals: for Si/ml and the detection limit of the method is equal to silicon from 10 to 200 ug/ml and for phosphorus from 10 ng/ml. At the determination of silicon at a nano- 100 to 2000 ug/ml. For both elements the nearly gram level particular precaution should be taken stoichiometric (red feather 15-20 mm) nitrous oxide- because of the possible contamination of the sample acetylene flame with a 12 mm burner height was used by the laboratory environment. as optimum. For silicon determination potassium chloride was added to the sample and standard sol- References utions to avoid the ionization effect. Analytical [I]. Kobayashi R.: Anal. Sci., 13,17 (1997). samples may be dissolved in nitric, hydrochloric, [2]. Prewett W., Promphutha M.: Anal. Chim. Acta, 339,247 (1997). hydrofluoric and perchloric acids or in their mixture. [3]. NaterE.A., Burau R.G.: ibid, 220, 83 (1989). No interference effect in any of these media was [4], Chiricosta S., Saija Q., Calapaj R., Bruno E.: Atom. Spectrosc, found. Calibration curves were linear in the whole 10,183(1989). analytical intervals used. [5], Kharbade B.V., Agrawal K.C.: ibid, 18,130 (1997). For lower concentration of Si and P procedures [6]. Matsusaki K., Yamaguchi T., Sato T.: Anal. Sci., 12, 797 (1996). based on the electrothermal atomization were [7], Homung M., Krivan V.: J. Anal. Atom. Spectrom., 12, 1123 prepared. From the point of view of the height of (1997). PL9902232 _100 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL INVESTIGATION ON POSSIBILITIES OF DETERMINATION OF SOME PRECIOUS METALS IN GEOLOGICAL AND ENVIRONMENTAL SAMPLES BY NEUTRON ACTIVATION ANALYSIS Zbigniew Samczyriski, Bozena Danko, Rajmund Dybczynski Platinum, palladium and gold similarly like other Ion exchange behavior of about twenty elements precious metals are elements of very low abundance in including palladium, platinum and gold was investi- the earth's crust, still playing an important role in the gated by a batch equilibration technique using radio- modern technology. Constantly growing demand for active tracers in the following systems [8]: them is the reason that the great interest is addressed • hydrochloric acid solutions (0.01-12 mol I"1), to materials containing smaller and smaller amounts of • pH buffer solutions (pH 3-9), these metals. Therefore sensitive methods for the • ammonia solutions (0.01-10 mol I'1) at constant determination of low concentration of noble metals is concentration of NH4CI (0.1 moll"1). of great importance. It should be emphasized, that due In the range 0.1-1.0 molar hydrochloric acid, the to their complex chemistry, precious metals are anion exchange function of Chelex 100 starts to be classified as a group of the most difficult elements in active due to protonation of the iminodiacetic groups. analytical chemistry. Very few analytical methods are Palladium, platinum and gold, which form stable of sufficient sensitivity, accuracy and precision, which chloride complexes, exhibit in these conditions the assure reliable determination of these elements. highest affinity for the ion exchanger (Fig.l). This Neutron activation analysis (NAA) is quoted among situation enables to separate them from many elements them [1-5]. Despite the favourable detection limits, which do not form chloride complexes such as palladium and platinum cannot be determined directly alkaline metals, alkaline earth metals and metals by instrumental version of NAA. The reason for this I09 forming less stable chloride species, for example are short half-lives of the radionuclides Pd and 197Pt, as well as, low energies of their gamma-ray copper, iron, cobalt, zinc and cadmium. photopeaks, completely disturbed by a high radio- activity of a matrix. In case of gold, the indicator radionuclide 198Au is of longer half-life and higher energy, so even the instrumental version of neutron activation analysis is in many instances feasible. The above difficulties can be considerably elimin- ated by performing the isolation of noble metals before neutron activation. Despite of pre-irradiation isolation, some accompanying elements may interfere with gamma spectrometric measurement of precious metals. For this reason post-irradiation separation of them is also necessary. The possibility of application of an organic ion- 10 •• exchanger Chelex 100 in a hydrochloric acid medium for an effective isolation of Pd, Pt and Au from major constituents of a sample of geological and industrial origin has been examined at this stage of our study. 0.01 Ion exchange is one of the most often used separation mol L"1 methods in modern trace analysis [1,3,5-7], Chelex Fig.l. Mass distribution coefficients of Pd, Pt, Au and several 100, commonly regarded as a weakly acidic cation- selected elements for Chelex 100 ion exchanger (100-200 exchanger of chelating-type, has in fact an amphoteric mesh) as a function of concentration of HCI [8]. properties. Its ion exchange function is affected by The results of batch equilibration indicated poten- acidity of the external solution. As it is known, the tial possibility of separation of palladium, platinum nitrogen atom of the iminodiacetic group which has and gold from many accompanying elements and then a free electron pair is protonated in acidic medium. from each other. These assumptions were verified Hence, under these conditions, the functional groups performing a series of column experiments with the become weakly basic ammonium groups, capable of use of radioactive tracers, An ion exchange procedure retaining metal anionic complexes, which are present was devised with the goal to apply it for the separation in the solution. of Pd, Pt and Au, It is presented in Fig.2. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 101 1M NHj 0.5 M HCI 8M HCI O.1M 2.0-t* C 1.5- 3 alkali metals .2 1.0- u alkaline earth to metals rare earth elements £ 0.&- Cu, Co, Cd, Zn Cr, Fe, In, Ga, Ni, Pb, Mn, Br 0.0 T-r-r- J 100 200 1000 volume of effluent, drops {drop volume = 0.03? ml) Fig.2. Separation of Pd, Pt and Au from other elements by stepwise eluation using Chelex 100. Column: 9.5 x 0.0707 cm2. Chelex 100 (200- 400 mesh) [Na+ form], temperature 25°C, flow rate: 1.5 cm min"'. These metals together with other accompanying reason for this may probably be complexity of the elements in 0.5 molar hydrochloric acid are introduced chemical properties of this element. The main effort in onto the column with Chelex 100. The bed is then the next months will be focused on analyzing all eluted with this solution. Elements such as metals of potential sources of errors and modification of the the first and the second group of the Periodic Table, procedure in order to improve platinum recovery. rare earth elements and many transition elements, for example, copper, iron, zinc, cadmium and other are References washed out whereas the noble metals are fixed on the [1]. tobiriski R., Marczenko Z.: Spectrochetnicai trace analysis for resin. The next step is elution of Pd and Pt, which metals and metalloids. In: Wilson & Wilson's comprehensive exhibit rather low affinity for Chelex 100 in concen- analytical chemistry. Vol. XXX. Ed. S.G. Weber. Elsevier, 1 Amsterdam 1997. trated HCI solutions, with 8 mol I' hydrochloric acid. [2]. Beamish F.E., Van Loon J.C.: Analysis of noble metals. Gold, which is extremely strongly held by the ion Academic Press, New York 1977. exchanger in HCI medium, remains on the column [3]. Minczewski J., Chwastowska J., Dybczyriski R.: Separation while performing successive separation steps. It can be and preconcentration methods in inorganic trace analysis. 1 1 finally eluted with a 1 mol I' NH3 + 0.1 mol I" NH4C1 E. Horwood, Chichester 1982. solution. [4], Zmijewska W., Polkowska-Motrenko H.: Chemia Ana!., 38, 211 (1993). The elaborated ion exchange separation procedure [5]. Dybczynski R., Majchrzak J., Stokowska H.: Chemia Anal., 35, was tested determining Pd, Pt and Au, by NAA in two 60&(1990). certified reference materials SARM-7 and PTC-1 of [6]. Marhol M,; Ion exchangers in analytical chemistry. Academia, geological and industrial origin, respectively. The Prague 1982. analytical results for palladium and gold were gen- [7], Ion exchangers. Ed. K. Dorfner. W. de Gruyter, Berlin-New York 1991. erally in good agreement with the certified values. As [8]. Samczynski Z., Dybczynski R.: J. Chromatogr. A, 789 157 regards platinum, the results were not satisfactory. The (1997). RADIOBIOLOGY NEXT left BLAMK RADIOBIOLOGY 105 CERAMIDE IS NOT INVOLVED IN NUCLEAR TRANSLOCATION OF NF-KB IN L5178Y SUBLINES Barbara Sochanowicz, Irena Szumiel "pf9902233 Sphingolipids have emerged recently as regulators of NF-KB in this pair of sublines. We used two synthetic processes controlled by extracellular agents. It was ceramides, C2 (N-acetyl-D-sphingosine) and C6 (N- found that the stimulation of cell surface receptors, or hexanoyl-D-sphingosine), as well as PMA, phorbol oxidative stress, due to the production of reactive ester, which is an efficient activator of NF-KB in LY- oxygen species in cells exposed to ionizing radiation, R cells and a weaker activator - in LY-S cells (paper generate ceramide, a "death messenger", since it is submitted). Fig.l presents western blots of nuclear a signal for apoptotic death. extracts from LY sublines. As shown, only PMA gives A question of both practical and theoretical interest a clear activation of the transcription factor. The two is whether radiation-induced apoptosis is initiated by ceramides tested show no activatory effect. Therefore, a signal generated in the cell membrane or in the nucleus. other pathways are employed in LY cells for activa- Fragmentation of nuclear DNA could be produced by tion of NF-KB. A recent report indicates that in the a direct interaction with X rays or with the reactive irradiated cell the pathway is atm-dependent (ataxia oxygen intermediates generated within the cell by telaniectasia mutated) [8]. ionizing radiation. Primary DNA lesions have been A considered as signals that trigger the apoptotic f.Y-H l.Y-S response [1]; consistently, activation of ceramide synthase (another enzyme involved in ceramide gener- ation) is p53-dependent [2]. Other investigations provide evidence that the apoptotic signalling can also 1.0 2.0 i)* 8.3 1.6 2.1) be generated by an interaction of ionizing radiation with the plasma membrane. This interaction initiates B sphingomyelin hydrolysis to ceramide [3]. LVTt LY-S The use of cell permeable synthetic ceramides has shown that protein kinases stimulated by ceramides directly regulate the function of transcription factors, mainly the nuclear factor KB (NF-KB). These protein kinases are important for a coordinated regulation of gene expression in the stressed cell. NF-KB is in- 0 fl 2 * -0 2 2 volved in the transcriptional control of genes that II HI 1(1 il 10 10 (I regulate cell death, such as c-myc and p53 [4]. The Fig.l. Activation of NFKB in LY sublines, as judged form the predominant form of NF-KB in unstimulated cells nuclear translocation of the p65 subunit. Western blots occurs in the cytoplasm as a heterodimer of two shown: A - after treatment (1 h, 37°C) with various concen- proteins, p50 and p65, complexed to an inhibitory sub- trations of PMA alone (lane 1 - control, lane 2 - control with 0.3% acetone, solute used for PMA); B - after PMA and/or unit called I-KB; the latter prevents migration of the ceramide treatment; C2 or C6 ceramide (see text) applied at heterodimer to the nucleus and its binding to DNA. 10 uM concentration for 1 h at 37°C alone or preceding 1 h Upon cell stimulation (e.g. by cytokines or ionizing (37°C) incubation with PMA 2 uM (lane 1 - control; lane 2 - radiation) this inhibitory subunit becomes phos- ceramide alone; lane 3 - PMA followed by ceramide; lane 4 - PMA alone). All nuclear extract samples from correspon- phorylated and dissociates from the NF-KB hetero- dingly treated cells contained 30 ng of protein per lane. Note dimer. The released heterodimer (p50/p65) migrates to a more pronounced effect of PMA on nuclear translocation of the nucleus where it can bind to DNA and stimulate NFKB in LY-R than in LY-S cells and lack of effect of transcription. Interestingly, ceramide has been shown ceramide. to induce the translocation and activation of NF-KB. It This work was supported by the Polish State Committee possibly takes place through the phosphorylation of for Scientific Research, a statutory grant for the INCT. the cytosolic I-KB inhibitor by protein kinase CE, [5], thereby providing a link to integrate the sphingomyelin References cycle with NF-KB-dependent pathways. [1]. Eastman A., Barry M.A.: Cancer Invest., 10, 229-240 (1992). [2]. Dbaibo G.S., Pushkareva M.Y., Rachid R., Alter N., Smyth M. Differential activation of NF-KB reflects the anti- J., Obeid L.M.: J. Clin. Invest., 102, 329-339 (1998). oxidant defence efficiency in L5178Y (LY) murine [3]. Testi R.: Trends Biochem. Sci., 21, 468-471 (1996). lymphoma sublines, LY-R and LY-S, that differ in [4]. Wu H., Lozano G.: J. Biol. Chem., 269, 20067-20074 (1994). sensitivity to ionizing radiation and oxidants [6,7]. [5]. Hermann J.L., Bruckheimer E., McDonnell T.J.: Biochem. Soc. Transact., 24, 1059-1067(1996). Therefore, it has been of interest to examine, whether [6]. Beer J.Z., Budzicka E., Niepokojczycka E., Rosiek O., Szumiel ceramide is involved in translocation and activation of I., Walicka M.: Cancer Res., 336, 99-118 (1983). 106 RADIOBIOLOGY [7]. Kruszewski M., Green M.H.L., Lowe J.E., Szumiel I.: Mutat. [8). Lee S.J., Dimtchev A., Lavin M.F., Dritschilo A., Jung M.: Res., 326, 55-163(1994). Oncogene, 17,1821-1826 (1998). INDUCTION OF DNA BREAKAGE IN X-IRRADIATED NUCLEOIDS SELECTIVELY STRIPPED OF NUCLEAR PROTEINS IN TWO MOUSE LYMPHOMA CELL LINES DIFFERING IN RADIOSENSITIVITY IS Marcin Kruszewski, Teresa Iwanenko DNA in the nucleus of eukaryotic cells is tightly assay with LY cells. Another explanation of this associated with histones and other nuclear proteins phenomenon may be a different chromatin organis- and folded into a higher order chromatin structure that ation in LY sublines, previously proposed in view of is anchored to the nuclear matrix. Chromatin proteins the different supercoiling properties of nucleoids from are important not only for the maintenance of LY cells [5]. Nevertheless, the initial DNA damage chromatin structure but also may protect DNA against induced in unextracted chromatin with 1.5 Gy of X exogenous damage. Regions of chromatin of more radiation was similar in the two cell lines. A similar open conformation, like transcriptionally active DNA, level of initial DNA breakage was also found are more susceptible to ionizing radiation than inactive previously in non-exposed cells [6]. regions [1,2]. Proteins may also protect DNA against radiation-generated free radicals, or may serve as a source of reducing equivalents for chemical repair of DNA radicals. To examine the role of nuclear proteins in protection of DNA against ionizing radiation and their contribution to the radiation sensitivity, an alkaline version of comet assay, which detects overall DNA damage i.e. DNA breaks and alkali-labile sites, was used to estimate DNA damage [3]. The cellular model consisted of two L5178Y (LY) mouse lymphoma cell lines, LY-S and LY-R, differing in sensitivity to ionizing radiation; Do values of survival curves (the dose required to reduce the surviving fraction by the 1 factor e' ) are 0.5 Gy and 1 Gy, respectively. Sequen- 'V tial removal of nuclear proteins by an extraction with different concentrations of NaCl resulted in an in- crease of DNA damage in LY-R nucleoids. Removal Fig.l. DNA damage in protein-stripped nucleoids of L5178Y eel! of histone HI and a part of non-histone proteins lines expressed as a percentage of DNA in the comet "tail". (NHP's) (0.8 M NaCl) caused 1.1 fold increase in the Data represent mean values for 50 comets after subtraction of mean DNA content in the comet tails of the irradiated the mean value for 50 control comets. nucleoids, as compared to nucleoids treated with Although there is no doubt that the main cause of 0.14 M NaCl (p<0.01). Total removal of histones and LY-S cells' sensitivity to ionizing radiation is a defect NHP's (2.5 M NaCl) resulted in 1.25-fold increase in in the repair of DSB's, our data support the concept DNA damage of irradiated nucleoids (p<0.01, Fig.l). that chromatin organisation may contribute to the In contrast, in the radiation sensitive LY-S cell line, cellular susceptibility to DNA damaging agents. depletion of nuclear protein practically did not affect DNA damage (Fig.l). References In control (non-irradiated) cells the sequential [1]. Chiu S.M., Oleinick NX., Friedman L.R., StambrookP.J.: Bio- selective removal of chromatin proteins from the chem. Biophys. Acta, 699, 15-21 (1982). nucleoids did not result in any significant changes in [2]. Chiu S.M., Friedman L.R., Xue L.Y., Oleinick NX.: Int. J. Radiat. Oncol. Biol. Phys., 12, 1529-1532 (1986). DNA mobility. However, we found significantly more [3]. McKelvey-Martin V.J., Green M.R., Schmezer P., Pool-Zobel DNA in the comet tail of control LY-R cells than in B.L., De Meo M.P.C.: Mutat. Res., 288,47-63 (1993). LY-S cells (p<0.05). This phenomenon may reflect [4]. Szumiel !., Kapiszewska M., Kruszewski M., Iwanefiko T., a higher level of endogenously generated DNA Lange C.S.: Radiat. Environ. Biophys., 34,113-119 (1995). damage in LY-R cells due to the higher steady-state [5]. Kapiszewska M., Szumiel I., Lange C.S.: Radiat. Environ. transition metal ion content (for discussion see [4]) Biophys., 31, 311-322(1992). [6]. Kruszewski M, Green M.R.L., Lowe J., Szumiel I.: Mutat. and has repeatedly been observed by us in the comet Res., 326, 155-163(1995). RADIOBIOLOGY 107 CYTOSOLIC LABILE IRON POOL SIZE CORRESPONDS WITH THE SENSITIVITY OF L5178Y SUBLINES TO OXIDATIVE DAMAGE Pawel Lipinski1/, Hanna Retmanska1', Barbara Sochanowicz, Marcin Kruszewski "Department of Molecular Biology, Institute of Genetics and Animal Breeding, Polish Academy of Sciences, Mrokow, Poland Iron is present at active sites of a large number of expected, the low LIP level in H2O2-resistant LY-S enzymes and thus, actively participates in the aerobic cells was associated with a relatively high content of metabolism in eukaryotes. On the other hand, the same H-Ft. In contrast, H2O2-sensitive, iron-rich LY-R cells redox properties that allow iron to be a functional contained a small amount of H-Ft (Fig.2). enzymatic cofactor make this metal a key participant of oxygen-mediated toxicity. Intracellular iron homeo- stasis involves coordination of several processes such as iron uptake, utilization, storage and release [1]. All aspects of intracellular iron homeostasis are reflected in the so-called labile iron pool (LIP), a low molecular weight pool of weakly chelated iron that is rapidly in rL-Ft transit through the cell and constitutes a cross-road of metabolic pathways of iron-containing compounds. L-Ft LIP has been claimed to be a cellular source of iron participating in the Fenton reaction [2]. rH-Ft L5178Y (LY) mouse lymphoma cell lines that display unique inverse cross-sensitivity to ionizing H-Ft radiation (IR) and hydrogen peroxide (H2O2) [3,4] are a suitable model to study possible differences in the constitutive control of intracellular iron availability. Fig.2. Western blot analysis of ferritin subunit H in LY cells. Repre- sentative experimental results are shown (of 3 which gave similar results). 0,8 The relationship between the amount of H-Ft 0,7 (Fig.2) and the LIP level (Fig.l) in LY cells strongly ^0,6 suggests that low LIP in LY-S and high LIP in LY-R 5 2 0,5 cells are due to high and low, respectively, expression x: of H-Ft; this subunit has a ferroxidase activity which 1,0,4 increases the rate of iron uptake by the ferritin - molecule. This finding is consistent with the recently S-0,3 reported major role of H-Ft in regulation of the level 0,2 of LIP in mammalian cells [6]. L-Ft level was only 0,1 slightly higher in LY-S than in LY-R cells. Altogether, 0.0 these results imply a direct relationship between the LY-R LY-S resistance of cells to oxidative stress and high express- Fig.l. LIP levels in LY cells. LIP values are expressed as a mean ion of intracellular Ft and hence, with high capacity of ±S.E. and obtained from 5 independent measurements made cells to scavenge iron active in the Fenton reaction. on separate cultures. The results are significantly different, pO.Ol. This work was supported by the Polish State Committee To estimate LIP levels in resting LY cells we used for Scientific Research, a statutory grant for the INCT. a novel noninvasive method based on the fluorescent metallosensitive probe calcein which allows moni- References toring of the dynamic changes in cytosolic (chelat- [1]. Ponka P., Beaumont C, Richardson D.R.: Semin. Hematol., 35, able) iron [5]. Average steady-state LIP levels in 35-54 (1998). LY-R and LY-S cells were 0.57 and 0.18 ^M, [2]. Picard V., Renaudie F., Porcher C, Hentze M.W., Grandchamp respectively (Fig.l). This clearly shows that the B., Beaumont C: Blood, 87, 2057-2064 (1996). [3]. Beer J.Z., Budzicka E., Niepokojczycka E., Rosiek O., Szumiel amount of iron potentially active in the Fenton chem- I., Walicka M.: Cancer Res., 336, 99-118 (1983). istry is much higher in H2O2-sensitive LY-R cells. [4] Kruszewski M., Green M.H.L., Lowe J.E., Szumiel I.: Mutat. To determine whether different LIP levels in LY Res., 326, 55-163(1994). cells were related to the content of Ft subunits we [5]. Epsztejn S., Kakhlon O., Glickstein H., Breuer W., Cabantchik Z.I.: Anal. Biochem., 248,31-40 (1997). estimated H-Ft and L-Ft levels by immunoblotting [6]. Picard V., Epsztejn S., Santambrogio P., Cabantchik Z.I., using anti-mouse H-Ft and L-Ft antibodies. As Beaumont C.J.: Biol. Chem., 273, 15382-15386 (1998). PL9902235 108 RADIOBIOLOGY DIFFERENTIAL INACTIVATION OF DNA-DEPENDENT PROTEIN KINASE IN IRRADIATED REPAIR-COMPETENT AND REPAIR-DEFICIENT L5178Y SUBLINES Barbara Sochanowicz, Martin Kruszewski, Irena Szumiel DNA-dependent protein kinase (DNA-PK), a 3 sub- decrease in activity in LY-R cells (Fig.2) and a de- unit complex of high molecular weight, is activated,by DNA double strand breaks (DSB) [1]. The enzyme can t 250 initiate an alarm signal pathway by phosphorylation of transcription factors that are specific for the cellular response to DNA damaging agents. It also is indis- pensable for the DSB repair pathway termed non- homologous end rejoining, as well as for V(D)J re- combination. It acts together with DNA ligase IV and XRCC4 protein. Mutations in the two Ku subunits or in the catalytic subunit have been found responsible -M«uw80 for radiation sensitivity and deficient DSB repair. "MMIVSD Radiosensitive rodent xrs mutants from three comple- mentation groups (XRCC5, XRCC6 and XRCC7) CONTROL 1 2 A TIME AFTER GAMMA IRRADIATION (HOURS) defective in DNA-PK activity have been characterized Fig.2. Alterations in DNA-PK activity after y-irradiation (1 Gy) of in detail [2]. LY-R cells and subsequent incubation. The first rodent radiosensitive mutant described in 1961 [3], L5178Y-S (LY-S), still lacks such detailed definition. LY cells were originally isolated from a murine thymic tumour. LY-S cells appeared sponta- neously in the parental LY cell culture. The cells were subsequently called LY-R (radiation resistant, Do = 1.0 Gy) and LY-S (radiation sensitive, Do = 0.5 Gy). The high sensitivity of LY-S cells to X-rays was related to the impairment of DSB rejoining [4], We undertook examination of DNA-PK activity in : Mean«SD order to estimate the possible relation of LY-S cells to Mwt-SD xrs mutants of Chinese hamster ovary (CHO) cells. Mm 650 _ CONTROL 1 2 4 TIME AFTER IRRADIATION {HOURS) Fig.3. Alterations in DNA-PK activity after y-irradiation (1 Gy) of LY-S cells and subsequent incubation. layed but relatively more pronounced one, in LY-S cells (Fig.3). This is the first observation of this kind in the radiobiological literature. We expect, that when the non-homologous end rejoining is completed, DNA- PK becomes phosphorylated; hence, the enzyme loses the ability to bind DNA and, in. consequence, the catalyt- ic activity, as observed in vitro [6]. Thus, the repair- LY-R LY-S TK15 V3 S15 signaling machinery is switched off. Since DSB repair in CELLS LY-S cells is impaired, inactivation of DNA-PK after Fig. 1. DNA-PK activity in extracts from LY, CHO and xrs5 cells. irradiation is delayed. Examination of DNA-PK phos- As shown in Fig.l, in the presence of excess frag- phorylation is in progress. mented DNA, that is, under standard assay conditions This work was supported by the Polish State Committee [5], there is a comparable activity of DNA-PK in both for Scientific Research, a statutory grant for the INCT. LY sublines, about 50% lower than in CHO cells. As expected, there is no DNA-PK activity in xrs5 cells. References There is, however, a difference between LY sub- [1]. Anderson C.W., Lees-Miller S.P.: Crit. Rev. Eukaryot. Gene lines in DNA-PK activity levels after y-irradiation. Express., 2,283-314 (1992). Upon post-irradiaton incubation there is a marked [2]. Zdzienicka M.Z.: Cancer Surv., 28,281-293 (1996). RADI0B10L0GY 109 [3]. Alexander P., Mikulski Z.B.: Nature, 192, 572-573 (1961). [6]. Kharbanda S., Pandley P., Jin S., Inoue S;, Bharti A., Yuan Z., [4]. Wlodek D., Hittelman W.N.: Radiat. Res., 112, 146-155 (1987). Wiechselbaum R.R., Weaver D., Kufe D.: Nature, 386, 732-735 [5]. Finnie N.J., Gottlieb T.H., Blunt T., Jeggo P.A., Jackson S.P.: (1997). Proc. Nat. Acad. Sci. USA, 92, 320-324 (1995). LACK OF ADVERSE EFFECT OF SMOKING HABIT ON DNA STRAND BREAKAGE AND BASE DAMAGE Maria Wojew6dzka, Marcin Kruszewski, Teresa IwaneAko, Andrew R. Collins1', Irena Szumiel " Rowett Research Institute, Bucksburn, Aberdeen AB2 9SB, United Kingdom Various monitoring assays have been developed to habit in the control group and the hazard group, estimate the genotoxic risk connected with working including results obtained with base damage-specific conditions and the industrial environment. Develop- endonucleases. In the control group and the hazard ment of the comet assay (single cell gel electro- group neither the mean tail moment, tail length nor % phoresis) seemed to be an advantageous alternative to DNA in the comet tail was related to smoking habit. other tests, because of the considerable sensitivity and There was no relation of DNA damage, as expressed speed of the analysis. by the three comet parameters studied, to the Brinkman We have recently evaluated DNA breakage and index (cigarettes/day x years). The comparison was base damage with the use of the comet assay in a group of made for all individual smokers, for control and about 50 workers chronically exposed to low doses of hazard groups divided according to sex. ionizing radiation [1,2]. The control group, matched Although many studies report enhanced DNA for age and sex was chosen from administration damage related to the smoking habit, also a lack of such workers. Although there was a statistically significant relation has been found in several recent studies. An difference in the damage levels between the hazard increased resistance of smokers to DNA damage in- and control group, the high inter-individual variability duced by carcinogens has been described [6]. We offer of the results pointed to the need for methodology the following explanation to the reported results: the improvement before applying it as an individual applied method measures the DNA damage level that dosimeter. On the other hand, these reports, as well as is a result of equilibrium between damage infliction many others (reviewed in [3]) proved the applicability and repair. So, a low damage level assessed experi- of the assay in screening the occupationaliy exposed mentally in an individual may be the result of an populations. actual low number of lesions or of a high efficiency of In evaluations of the action of genotoxic agents the repair. It has been suggested that repair capacity is the smoking habit is a confounding factor. Its genotoxic best indicator of individual sensitivity to damaging effect, as well as its modifying effect on genome agents [7]. However, the repair capacity of smokers damage inflicted by other agents, have been firmly and non-smokers may not differ. established (for a recent summary, see [4]). Therefore, This work was supported by a Copernicus grant from it came as a surprise that no statistically significant European Community. effect of smoking was found in our study, either in the control or in the hazard group. A detailed description References of the DNA damage determinations, both direct (DNA [1], Wojewodzka M., Kruszewski M., Iwanenko T., Collins A.R., strand breakage and alkali-labile lesions) and enzyme- Szumiel I.: Mutat. Res., 416,21-35 (1998). combined (base damage) can be found in the previous [2], Kruszewski M., Wojewodzka M., Iwanenko T., Collins A.R., reports [1,2,5]. Szumiel I.: Mutat. Res., 416, 37-57 (1998). [3]. Collins A.R.,. Dobson V.L , Du5insk4 M., Kennedy G., Stetina Statistical analysis concerning the effect of the R.: Mutat. Res., 375,183-J93 (1997). smoking habit on various comet parameters, taken as [4]. Scherer G., Richter E.: Human Exp. Toxicol., 16, 449-459 damage indicators was made by three-way ANOVA. (1997). For all individuals grouped according to sex, risk of [5]. Kruszewski M., Green M.H., Lowe J.E., Szumiel I.: Mutat. exposure and smoking habit we found no statistically Res., 308,233-241(1994). significant differences between individuals as related [6]. Oesch R, Hengstler J.G., Fuchs J.: Mutat. Res., 321, 175-185 (1994). to smoking habit. Further, we examined the relation of [7]. Plappert U., Raddatz K., Roth S., Fliedner T.M.: Stem Cells, various DNA damage parameters to sex and smoking Suppl. 1,215-222(1995). PL9902236 no RADIOBIOLOGY POLY(ADP-RIBOSE) METABOLISM IN TWO L5178Y MURINE LYMPHOMA SUBLIMES EXPOSED TO X-RAYS Hanna £. Kleczkowska, Irena Szumiel, Felix R. Althaus17 ]/ Institute of Pharmacology and Toxicology, University of Zilrich, ZUrich, Switzerland The molecular mechanism of the involvement of resistant LY-R cells (Fig.l). On the other hand, in the poly(ADP-ribose) metabolism in DNA repair is not first 20 min after radiation exposure the content of well understood. The synthesis and subsequent degra- poly(ADP-ribose) in radioresistant LY-R cells transi- dation of poly(ADP-ribose) is stimulated in mammalian ently increased more than 3-fold (Fig.2). During the cells following induction of DNA damage [1,2]. same post-irradiation time poly(ADP-ribose) content The automodification reaction of poly(ADP-ribose) in radiosensitive LY-S cells was close to the control polymerase (PARP, EC 2.4.2.30) catalyses a temporary level in unirradiated cells (Fig.2). dissociation from and reassociation of proteins with DNA: a mechanism, which may guide specific proteins to sites of repair [3,4]. A role of poly (ADP- ribosyl)ation system in DNA damage signalling has recently been proposed [5]. We have analyzed poly(ADP-ribose) metabolism in two mouse lymphoma sublines which differ in their sensitivity to ionising radiation. L5178Y (LY) cells were originally isolated from a murine thymic tumour. LY-S cells appeared spontaneously in the parental LY-R cell culture and were primarily identified by their increased sensitivity to X-irradiation. LY sub- lines were subsequently called LY-R (radiation resis- tant, Do = 1.0 Gy) and LY-S (radiation sensitive, Do = 0.5 Gy) (rev. in [6]). They differ in efficiency of repair of double strand breaks. Time after irradiation, min Fig.2. Poly(ADP-ribose) content in LY-R and LY-S cells following 2 Gy of X-ray exposure. 120" In mammalian cells the level of chromatin-bound ADP-ribose polymers depends on the availability of i NAD+ [7]. In cells with extensively damaged DNA the 110" I X INHIBITION OF POLY(ADP-RIBOSYLATION) SIMILARLY AFFECTS CAMPTOTHECIN-TREATED LS178Y-R AND -S CELLS Iwona Grijdzka, Irena Szumiel It has been postulated, that poly(ADP-ribosylation) of poly(ADP-ribose) polymerase, can specifically displace chromatin proteins has a priming role in DNA repair: histones from DNA at the places with DNA strand ADP-ribose polymers, synthesized by an enzyme breaks, which lead to nucleosomal unfolding and give 8 10 12 14 IS 18 20 22 24 2.0 J 4 6 8 10 12 14 16 18 20 22 24 0.5 1.0 1.S j0 2 4 6 8 10 12 14 K 18 20 22 24 time after camptothecin removal, hours Fig.l. Time course of double-strand DNA break repair after 1-hour incubation with 2 j^M camptothecin (CPT), with or without benzamide (Bz) co-treatment (2 mM Bz was added for 24 hours before the experiment; during incubation with CPT its concentration was raised to 5 mM, and after CPT removal it "was lowered back to 2 mM). Double-strand breaks were measured in DNA synthesized during incubation with CPT, with the use of field inversion gel electrophoresis of DNA [6], The graphs were arranged to show the influence of Bz on the DNA repair rates after CPT treatment in LY-R (upper panel) and LY-S (middle panel) sublines separately, as well as to compare the course of the DNA repair between the two sublines, both treated with CPT and Bz (lower panel). 112 RADIOBIOLOGY murine lymphoma cell sublines. Camptothecin is an 100 anticancer drug, a topoisomerase I poison, which acts mainly in S-phase of the cell cycle [4], by generating double-strand breaks in DNA [5]. LY-S cells are more resistant to camptothecin than LY-R cells, and this is associated with faster DNA repair rate observed in this subline [6] (see also Fig.l, upper and middle panel). Benzamide slowed down double-strand DNA break 10 repair in both LY sublines treated with camptothecin (Fig.l). The cell growth was reduced in the cultures "O. LY-R+CPT treated with benzamide and camptothecin, compared "•. LY-R+CPT+Bi with the cultures treated with camptothecin alone, and 0.10 1.00 10.00 this effect was more pronounced in LY-R subline a (Fig-2). o Previously it was reported, that benzamide radio- sensitized LY-S cells only [7]. Also recovery from DNA damage was postulated to be less dependent on the ADP-ribose polymer synthesis in LY-R than in LY-S cells [8]. Thus, inhibition of poly(ADP-ribosylation) differ- 1 entially affects DNA repair in cells treated with o camptothecin or ionizing radiation. It may arise from different nature of DNA double strand breaks inflicted "A. LY-S+CPT by these two factors: after camptothecin treatment they LY-S+CPT+Bz appear specifically in newly synthesized DNA, at the 1.00 to.oo replication forks [5]; the breaks inflicted by ionizing radiation are heterogenous in nature, and may appear everywhere in the genome, independently of the cell cycle phase [9]. In consequence, it is assumed that the cells use mainly homologous recombination mechanism (active in S and G2 phases of the cell cycle) to repair double-strand breaks after camptothecin treatment, contrary to non-homologous recombination, which is active all over the cell cycle and is supposed to be engaged in double-strand break repair after ionizing radiation [6]. This work was supported by the Polish State Committee for Scientific Research under contract No. 0.10 .00 10.00 6PO4A 06010. camptothecin concentration, References [1]. Althaus F.R., Hofferer L., Kleczkowska H., Malanga M., Fig.2. 48-hour growth test after 1-hour incubation with different Naegeli H., Panzeter P.L., Realini C.A.: Mol. Cell Biochem., concentrations of camptothecin (CPT), with or without 138,1-2,53-59(1994). benzamide (Bz) co-treatment (see Fig.l for Bz treatment [2]. Althaus F.R., Bachmann S., Hofferer L., Kleczkowska H.E., protocol). The graphs were arranged to show the influence of Malanga M, Panzeter P.L., Realini C, Zweifel, B.: Biochimie, Bz on cell growth after CPT treatment in LY-R (upper panel) 77,6,423-432(1995). and LY-S (middle panel) sublines separately, as well as to [3]. Malanga M., Pleschke J.M., Kleczkowska H.E., Althaus F.R.: J. compare the cell growth between the two LY sublines, both Biol. Chem., 273,19,11839-11843 (1998). treated with CPT and Bz (lower panel). [4], Zhang H., D'Arpa P., Liu L.F.: Cancer Cells, 2,23-27 (1990). access to repair proteins ("histone shuttling" [1]). It [5]. Ryan A.J., Squires S., Strutt H.L., Johnson R.T.: Nucleic Acids was also documented, that the ADP-ribose polymers Res., 19, 3295-3300(1991). [6]. Gradzka I., Skierski J., Szumiel I.: Cell Biochem, Funct., 16, can interact non-covalently with other nuclear proteins 14,239-252(1998). and thereby modulate their function in DNA repair [7]. Johanson K.J., Sundell-Bergman S., Szumiel I., Wlodek D.: [2,3]. Acta Radiologica - Oncology, 24,451-457 (1985). Here we show an influence of benzamide, an [8], Szumiel 1., Wlodek D., Johanson K.J.: Acta Oncologica, 27, 851-855(1988). inhibitor of poly(ADP-ribose)-polymerase, on DNA [9]. Ahnstrom G., Bryant P.E.: Int. J. Radiat. Biol., 41, 671-676 repair after camptothecin treatment in two L5178Y (1982). RADIOBIOLOGY 113 TELOMERE SIGNALS IN TWO L5178Y MOUSE LYMPHOMA CELL LINES Andrzej Wojcik, Elzbieta Bouzyk, Irena Szumiel, Christian Streffer!/ " Institute of Radiation Biology, University Clinics, Essen, Germany Immortalized cells possess mechanisms for elonga- of the LY-S cells are very heterogeneous. In fact, on tion of their telomeres. The most common method of some chromosomes no signals are detectable at all. maintaining a stable telomere length is through Cells with active telomerase have distinct telomerase activity [1], However, approximately one telomeric signals on all chromosomes. In contrast, quarter of in vitro immortalized cell lines are telome- cells which extend their telomeres by alternative rase-negative and elongate their telomeres by alterna- mechanisms, like recombination, show highly hetero- tive mechanisms involving recombination or retro- geneous telomeric signals [3,4]. It has been suggested transposition [2]. These cell lines can be identified that this is so because telomere elongation takes place either biochemically by their lack of telomerase or by only when a telomere has shortened below a critical the fact that, in contrast to telomerase, elongation length [2]. of telomeres by alternative mechanisms generates Although our results are preliminary, they do telomeres of variable lengths [3,4]. indicate that during the conversion of the LY-R cells Using in situ hybridization we have analyzed into the S-form, the cells switch from telomerase telomere signals in the murine lymphoma cell lines mediated telomere elongation to an alternative mech- L5178Y-R (LY-R) and L5178Y-S (LY-S). The inter- anism. esting fact about these cells is that the LY-R cells This work was supported by a grant from Stifiungfur undergo conversion into the LY-S form as a result of Deutsch-Polnische Zusammenarbeit and by the Polish prolonged cultivation in vitro. The transformation State Committee for Scientific Research, a statutory affects a number of cellular features like cell cycle grant for the INCT. kinetics and sensitivity to ionizing radiation [5]. Our References aim was to identify any differences with respect to telomeres. [1]. Blackburn E.H.: Ann. Rev. Biochem., 61,113-129 (1992). [2], Reddel R.R., Bryan T.M., Murnane J.P.: Biochem. (Moscow), The conversion of the LY-R cells into LY-S form 62, 1172-1184(1997). is accompanied by major chromosomal rearrange- [3]. Henderson S., Allsopp R., Spector D., Wang S.-S., Harley C: J. ments. The FISH analysis reveals that the cell lines Cell Bio!., 134, 1-12 (1966). also have different telomeres: chromosomes of the [4]. Murnane J.P., Sabatier L., Marder B.A., Morgan, W.: EMBO, LY-R cells have bright, uniform telomeric signals 13,4953-4962 (1994). [5]. Beer J.Z., Budzicka E., Niepokojczycka E., Rosiek 0., Szumiel typical of a murine cell line. In contrast, the telomers I., Walicka M.: Cancer Res. 43,4736-4742 (1983). PREFERENTIAL SEGREGATION OF A MARKER CHROMOSOME 14 IN MOUSE RECOMBINANT INBRED STRAINS DERIVED FROM THE KE AND CBA/Kw STRAINS Malgorzata Lenartowicz1', Andrzej Wojcik Department of Genetics and Evolution, Institute of Zoology, Jagiellonian University, Krakow, Poland Murine inbred strains provide convenient models for a preferential inheritance of chromosome 9 with a understanding the regulation of gene expression. large heterochromatin block. Particularly, recombinant strains obtained from two The CBA/Kw (referred to as CBA) and KE inbred inbred strains allow the analysis of distribution strains [4] differ in several features associated with patterns of genes for which the progenitor strains are fertility: frequency of abnormal sperm, timing of polymorph. Polymorphisms are observed not only at meiotic maturation of oocytes, solubility of oocyte the level of genes, but with respect to chromosome investments and per cent of in vivo fertilization [5]. morphology. For example both human and murine Furthermore, they are polymorph with respect to the chromosomes have variable C-bands [1,2]. The influ- C-band of chromosome 14, which is much smaller in ence of this polymorphism on chromosome segrega- cells of the CBA strain [6]. In the present study we tion has not been studied extensively. While Robinson investigated the inheritance pattern of the marker et al. [1] found a Mendelian segregation of inversion chromosome 14 in recombinant strains obtained from and size polymorphisms, Carnevale et al. [3] observed crosses between the CBA and KE mice. The marker 114 RADIOBIOLOGY chromosome was identified both by banding and chro- Carnevale et al. [3] observed that chromosome 9 with mosome painting with a probe specific for mouse a large C-band showed preferential segregation. We chromosome 14. observed a preferential inheritance of a marker chro- Chromosome 14 with a small C-band was found in mosome with a reduced heterochromatin block. It 13 recombinant strains (number 2, 5, 6, 10, 12, 13, 15, appears therefore that factors other than C-band size 17, 20, 26, 28, 29, 32) indicating that the animals of govern the segregation pattern of chromosomes. these strains inherited the marker chromosome from KE parents. Chromosome 14 with a normal C-band References was detected in the mice of strains 21, 24 and 27. {lj. Robinson J.A., Buckton K.E., Spowart G., Newton M., Jacobs Statistical analysis using the chi-square test showed P.A., Evans H.J., Hill R.: Ann. Hum. Genet., 40, 113-121 that the preferential inheritance of the marker chromo- (1976). [2]. Akeson E.C., Davisson M.T.: Cytogenet. Cell. Genet., 57, 217- some is significant. 220(1991). It is not known whether the size of the hetero- [3], Camevale A., IbanezB.B., del Castillo V.: Am. J. Hum. Genet., chromatin block has an impact on chromosome segre- 28,412-416(1976). gation. Polymorphisms of C-bands have been reported [4]. Krzanowska H.: Mouse News Lett., 32, 54-56 (1965). both in humans [7] and in mice [2]. It can be assumed [5]. Krzanowska H.: Acta Biol. Cracoviensia, 19,79-85 (1976). [6]. Lenartowicz M., Koszut U., Wabik-Sliz B.: Genet. Polon., 29, that a preferentially inherited chromosome has an in- 161-170(1988). creased affinity for the mitotic spindle as compared to [7]. Ghosh P.K, Singh I.P.: Hum. Genet., 32,149-154 (1976). its counterpart. In the case of human chromosomes SISTER CHROMATID DIFFERENTIATION WITH BIOTIN-dUTP Elisabeth Bruckmann1', Andrzej Wojcik, Gttnter Obe1' " Institute of Genetics, University GH Essen, Essen, Germany I CM :O ! Sister chromatid exchanges (SCE) were described for The omitted, incompletely labelled chromosomes the first time by Taylor [1]. Although their nature is comprise approximately 12% of the total chromosome not known, SCE are regarded as a mechanism of DNA length. Assuming an equal participation of all chromo- repair [2]. SCE can only be detected in chromosomes somes in the formation of SCE the total genomic with differentially stained chromatids. Differential frequency of SCE is 7.14. Estimation of the sponta- labelling is achieved by incorporating either 3H- neous frequency of SCE in CHO cells analysed in ring thymidine or 5-bromodeoxyuridine (BrdU), followed chromosomes [8] or using very low concentrations of by autoradiography [1] or fluorescence plus Giemsa BrdU and detection with antibodies [9] revealed SCE staining [3] of cells in the second mitosis. Autoradio- frequencies of approximately 4 SCE per cell. This graphy does not permit a precise quantification of indicates that biotin-dUTP itself induces a few SCE. Incorporated BrdU may interact with mutagens additional SCE, possibly by steric hindrance of DNA such as ionising radiation and this may lead to an replication or due to an imbalance of the nucleotide enhanced SCE frequency. pool [10]. Alternatively, it cannot be ruled out that Biotinylated nucleotides have been widely used for electroporation has an effect on the SCE frequency. labelling isolated DNA. Hunting et al. [4] were the This, however, appears unlikely since electroporation first to incorporate biotin-dUTP into living cells. does not lead to chromosomal aberrations [11]. A Biotin-dUTP incorporated into DNA in intact cells direct proof of the role of electroporation (or other does not inhibit the replication rate significantly [5,6]. methods of permeabilisation) in combination with We labelled Chinese hamster ovary cells (CHO) with biotin-dUTP would be difficult because the nucleotide biotin-dUTP to investigate whether it can be applied to does not pass the cell membrane freely. visualise SCE. Biotin-dUTP was detected with Texas At. present it is not clear to what extent BrdU Red-conjugated avidin. Cells in the second mitoses enhances the ability of genotoxic agents, like ionising after exposure to the biotinylated nucleotides showed radiation, to induce SCE [10]. When human a clear differential staining of sister chromatids. Thus, lymphocytes are irradiated in Go prior to the addition substitution of thymidine with biotin-dUTP is another of BrdU no SCE are observed [12]. It is well known method to analyse SCE. that when cells are irradiated in Go or Gi phase of the We determined the SCE frequency in all chromo- cell cycle without BrdU only chromosome-type aber- somes excluding X and the marker chromosomes Z10, rations are observed. Natarajan et al. [13] reported that Z12 and Z13 (see [7] for a description of Z irradiation of cells following one round of replication chromosomes) and found 6.27 SCE per cell with a with BrdU also leads to chromatid-type aberrations. standard deviation of 2.28 (37 cells were analysed). This implies that the radiation-induced uracil radicals RAD10BI0L0GY 115 are the source of DNA damage which persists until [4], Hunting D.J., Dresler S.L., de Murcia G.: Biochemistry, 24, S-phase when both SCE and chromatid-type aberra- 5729-5734 (1985). tions are formed. The chemical structure of biotin- [5], Hiriyanna K.T., Varkey J., Beer M., Benbow R.M.: J. Cell dUTP suggests that it does not give rise to radicals. Bio]., 107, 33-44 (1988). Therefore it can be anticipated that its application in [6]. Banfalvi G., Wiegant J., Sarkar N., van Duijn P.: Histochemis- studies with mutagens like ionising radiation will try, 93, 81-86(1989). allow a more precise measure of the induced SCE [7]. Folle G.A., Boccardo E., Obe G.: Chromosoma, 106, 391-399 (1997). frequency. [8]. Sutou S.: Mutat. Res., 82, 331-341 (1981). This work was supported by a fellowship from [9]. Natarajan A.T., Rotteveel A.H.M., van Pieterson J., Schliermann Sparkasse Essen toAndrzej Wqjcik. M.G.: Mutat. Res., 163, 51-55 (1986). [10]. Morris S.M.: Mutat. Res.. 258,161-188(1991). References [11]. Johannes C, Obe G.: Int. J. Radiat. Biol., 59, 1379-1393 (1991). [1]. Taylor J.H.: Genetics, 43, 515-529 (1958). [12]. Littlefield L.G., Colyer S.P., Joiner E.J., DuFrain R.J.: Radiat. [2], WolffS.: Sister chromatid exchange. John Wiley & Sons, New Res., 78, 514-521 (1979). York 1982. [13]. Natarajan A.T., Kihlman B.A., Obe G.: Mutat. Res., 7, 307- [3]. Perry P., WolffS.: Nature, 251, 156-158 (1974). 317(1980). OXIDATIVE DAMAGE IN DIFFERENTIALLY HYDROGEN PEROXIDE SENSITIVE L5178Y SUBLINES CULTURED IN SELENIUM-SUPPLEMENTED MEDIUM Elzbieta Bouzyk Two sublines of L5187Y (LY) murine lymphoma unexplained. The micronuclei frequency in LY-R cells cells, differing in sensitivity to hydrogen peroxide 1.2 have been used as cellular model [1]. LY-R are more 1.1 oxidant sensitive than LY-S cells. Activity of catalase 1.0 o.e is twofold lower in LY-R than in LY-S cells, whereas o glutatione peroxidase (Gpx) is about two times higher 2 o.e in LY-R than in LY-S. z w 0.6 Both sublines were cultured in 100 nM Na2Se03 0.5 supplemented Fischer's medium in order to investi- O.4 gate how the G-Px activity, thus induced, affects the 0.3 sensitivity to hydrogen peroxide. We have previously 0.2 determined induction of G-Px with selenium; its O.I activity was increased 15.6 times in LY-R cells and H O 50.3 times in LY-S [2]. A sparing effect of selenium 2 2 pre-treatment was seen at the DNA damage level, as Fig.l. Relative cell numbers (Nt/Nc, where Nt is the number of cells shown by experiments caried out with the "comet" /ml in the treated cell culture, Nc - that in the control, both grown from the same initial cell density during 48 h) in assay [2]. hydrogen peroxide treated LY cell cultures previously grown Here, the relative cell numbers after a 48 h growth in Fischer's medium with or without selenium supplemen- period were measured in cell cultures kept for 5 days tation. in a selenium supplemented medium, and sub- sequently treated with hydrogen peroxide (0.1- 10 (iM). Fig.l shows the cytotoxic effect of hydrogen LY-S-Se I 1 LY-S-t-Se peroxide alone or combined with selenium pre- LY-R-Se treatment. The sparing effect was relatively larger in LY-K+Se LY-R than in LY-S cells. Further, we examined the cytogenetic damage with the use of micronuclei test. As shown in Fig.2, the frequencies of micronuclei caused by hydrogen peroxide (0.1-5 uM) in LY-S cells were similar, notwithstanding the selenium pre-treatment; however, 0.1 1.0 5.0 10.0 25.0 at hydrogen peroxide concentrations 10 pM and 25 \xM, H O pre-treatment with selenium caused an increase in 2 2 Fig.2, Micronuclei frequencies in hydrogen peroxide treated LY cell micronuclei frequency that was statistically signifi- cultures previously grown in Fischer's medium with or with- cant (Student's test). This observation remained out selenium supplementation. 116 RADIOBIOLOGY did not show statistically significant differences strand breaks into chromosomal damage that is related to selenium pre-treatment. This was observed revealed as micronuclei in the interphase cells. These in the whole concentration range of hydrogen peroxide factors may differ in LY sublines. (0.1-10 uM). So, these results point to a discrepancy between the amount of the initial DNA damage found References in LY cells with increased G-Px activity [2] and the [1]. Bouzyk E., Buraczewska I., Rosiek O., Sochanowicz B., final effect of the damage - micronuclei frequency. Szumiel L: Radiat. Environ. Biophys., 30,105-116 (1991). Probably, there are cellular factors that affect DNA [2]. Bouzyk E., Iwanenko T., Jarocewicz N., Kruszewski M., Sochanowicz B., Szumiel I.: Free Rad. Biol. Med., 22, 697-704 damage processing and efficiency of conversion of (1997). NUCLEAR TECHNOLOGIES AND METHODS NEXT MGE(S) left BLANK NUCLEAR TECHNOLOGIES AND METHODS 119 PROCESS ENGINEERING PL9902238 INTEGRATED CONTROL MONITORING SYSTEM FOR ELECTRON-BEAM INSTALLATION FOR FLUE GAS PURIFICATION FROM SO2 AND NOX AT THE ELECTRIC POWER STATION "POMORZANY" Andrzej G. Chmielewski, Edward IHer, Janusz Licki1/, Bogdan Tyminski " Institute of Atomic Energy, Otwock-Swierk, Poland A designed control monitoring system permits a proper The continuously operating automatic system will operation of electron-beam installation for a simulta- be composed of a few subsystems. Data from these neous removal of SO2 and NOX from flue gases. subsystems will be transmitted to a main computer The main tasks of the system are: located in a control room. The operator has a possibil- 1. continuous measurement of process parameters ity for the observation of actual status of the e-b instal- and automation of the flow of process media in lation operation on a synoptic scheme. dependency on the inlet concentrations of SO2, Beside the automatic control a monitoring system NOX and humidity of flue gasses. in selected points of installation sets, for manual 2. continuous monitoring of a SO2, NOX and NH3 emission level as well as a dust concentration in chemical analyzers of the gas composition, will be flue gases after treatment. installed. This system will be used occasionally for the 3. control of collection efficiency of a by-product in control of SO2, NOX, NH3 concentrations and gas ESP. humidity. 3 4. technical and economic optimization of e-b instal- The installation wil! be treating 270 000 m N/h of lation operation. flue gases. The removal efficiency of SO2 will be in Oyaib ESP s r"i— £SP flyajb ii ESP Ay sill <2) Fig. 1. Main components of control monitoring systems. 120 PROCESS ENGINEERING the range 70% - 95% (depending on operation the main registers are: conditions) while that of NOX will be reduced with an • recorder of gas temperature before ESP (TR-4.1), efficiency of 80%. • recorder of drop pressure (PDR-4.3). The by-product obtained during the e-b installation An internal control system of ESP will be respon- operation, which is a mixture of ammonium sulfate sible for its operation. and ammonium nitrate, is a useful fertilizer which has In the outlet stream concentrations of the following been confirmed by agriculture tests performed by the gases are measured: Institute of Cultivation, Fertilization and Soil Science - . SO (SO R-5.1), Putawy, Agricultural University of Warsaw and 2 2 recently by the Academy of Agriculture of Szczecin. • NOX (NOxR-5.2), The by-product could also be used as a component in • NH3 (NH3R-5J), NPK blended fertilizers. . O2(O2R-5.4). Main components of control monitoring systems After mixing of untreated and treated streams of are presented in Fig.l. flue gases the main determined parameter is the tem- In a stream of flue gases entering into the installa- perature of gases coming into stack, register TRC-6.0. tion (a set of registers 0.1-0.8) we measure: Some signals recordered in measurement points are • volumetric flow rate of gases (FR-0.2), transmitted to logic systems Xi, X2, X3, X4 in which, • gas pressure (PR-0.3), gas temperature (TR-0.4), according to algorithms, they are converted into • concentration of fly ash (AR-0.1), a command for the measurement - control system. • concentration of SO2 (SO2R-0.6), The signals from registers FR-0.2, SO2R-0.6, • concentration of NOX - NO+NO2 (NOXR-0.5), NOXR-0.5 are collected by logic system X] which is • concentration of oxygen (O2-O.8), sending the instruction to FRC-2.7. This register • humidity of gases (MR-0.7). controls the volumetric flow of gaseous ammonia. A recorder located in a conditioning unit, a set of System X2, depending on the indications of TRC- registers 1.0-1.7, is able to determine: 6.0 through FRC-3.1 and FRC-3.2, influences the • volumetric flow rate of water introduced to spray volumetric flow rate of gases passing into reactor nozzles (FRQ-1.1), chambers. • water pressure (PR-1.2), System X3, based on the indication of NOXR-0.5 as • volumetric flow of air introduced to spray nozzles well as on a given algorithm, sets up the power of (FRQ-1.4), accelerators. • air pressure (PRC-1.7), System X4 through TR-4.1 determines the value of • gas temperature after conditioning (TRC-1.5), temperature for controller TRC-1.5 depending on the • humidity contents in flue gas after humidification temperature of flue gases after a spray cooler. (MRC-1.6), Controller TRC-1.5 influences the amount of water • drop pressure on spray column (PDR-1.3). introduced into the conditioning unit. The amount of In an ammonia preparation and dosage unit the air added to nozzles is controlled by RPC-1.6. The main important regulator of ammonia flow is FRC-2.7. amount of water steam injected to the spray cooler is A set of registers 3.1-3.11, located in a reaction determined by MRC-1.6. unit allows to measure: • volumetric flow of gas entering into the reactor References (FRC-3.1, FRC-3.2), [1]. Chmielewski A.G., Mer £., Zimek Z., Romanowski M., Koper- • gas temperature (TR-3.9, TR-3.10), ski K.: Rad. Phys. Chem., 46, 4-6,1063-1066 (1995). • drop pressure (PDR-3.10, PDR-3.11). [2]. Licki }., Chmielewski A.G., liter E., Zakrzewska-TrHiadel G., Tokunaga O., Hashimoto S.: Rad. Phys. Chem., 52, 1-6, 351- In the collection and storage of by a product unit 354(1998). APPLICATION OF TRACER TECHNIQUES FOR INDUSTRIAL SUPPLY WATER AND WASTEWATER SYSTEM EXAMINATION iCD ICO Andrzej Owczarczyk, Jacek Paiige, Ryszard Wierzchnicki !CM ! TRACER INVESTIGATIONS OF SEDIMENTATION PROCESSES AFTER BIOLOGICAL TREATMENT OF WASTEWATFD Andrzej G. Chmielewski, Andrzej Owczarczyk, Jacek Palige PL9902240 In the petrochemical industry all the sewage It has been suggested that it is necessary to change contains organic compounds that are treated in the construction of the exit region of the settler to biological chambers with an activated sludge. The eliminate this unacceptable effect. sediment is removed after the process in settler tanks by sedimentation. The flow processes in a primary clarifier - equalizer [1] as well as in a biological reactor [2] and finally in a sedimentation basin [3,4] with the application of tracers were investigated •-V" •«•• ». recently. Based on these data it has been found that the purity of the discharged water strongly depends on the efficiency of a settler located directly after the biologi- cal chamber. It was also observed that the output of the total sediment contents of the effluent varies in a wide range 30-200 mg/l. These phenomena are con- nected with the nature of the sludge and the periodic character of a scraper work. \ '••-•-...Tube Modules Fig. 1. The scheme of model settler. Fig.2. The general view of model installation. 122 PROCESS ENGINEERING The application of a lamella plate settler was The suggestions about optimization of the indus- proposed. A simple model of a settler with a capicity trial installation are proposed. Also a design of a new of 2 m3 was constructed. The dependence of the settler construction with lamella application is pro- settling efficiency as a function of wastewater flow posed. rate, angle of lamella plate inclination and concentra- tion of flocculants was investigated. A scheme of the References model is presented in Fig. 1. [1], Chmielewski A.G., Owczarczyk A., Palige J.: Nukleonika, 43, The experiments were carried out under industrial 2,185-194(1998). conditions in a petrochemical- wastewater treatment [2]. Owczarczyk A., Palige J., Dobrowolski A., Strzelecki M: Ra- station (Fig.2). Fluoresceine was used as a tracer of porty IChTJ. Seria C nr 1/97 (in Polish). [3]. Owczarczyk A., Palige J.: CHISA'98, Praha, 23-28 August the sewage. The residence time distribution of water 1998. and the parameters of sludge sedimentation were [4]. Owczarczyk A., Paiige J., Chmielewski A.G.: Krajowe Symp. measured paralelly. Stabilization of the sediment Technika Ja.drowa w Przemys'le, Medycynie, Rolnictwie i contents at a level of 50-60 mg/1 was observed inde- Ochronie Srodowiska. Referaty, Krakow, Poland 16-18.09. pendently of the input sediment concentration. 1998, pp. 228-233. CONCENTRATION OF LIQUID LOW- AND MEDIUMACTIVE LEVEL RADIOACTIVE WASTES (LLRW AND MLRW) USING MEMBRANE METHODS = ^- Andrzej G. Chmielewski, Marian Harasimowicz, Bogdan Tyminski, Grazyna Zakrzewska-Trznadel !CN [CM I § Radioactive wastes create serious hazard to human life and HPRO - for high pressure reverse osmosis with ;O5 and environment. The process of decontamination 2RO modules for high saline solutions [3]. ; Q_ includes the elimination of radioisotopes from wastes, The separation process of radioactive model sol- | volume reduction of the concentrate and immobiliz- utions and original LLRW and MLRW has been | ation in asphalt, concrete or glass. Different methods examined on various RO modules with thin-film- and multistage processes are employed to reduce the composite (TFC) polymeric RO membranes. The concentration of radionuclides in regenerated water to membranes with a high value of the retention the level permitted by sanitary standards for commu- coefficient for NaCl (>99.5%) were tested on their nal sewage (below 10 Bq/dm3, total for p and y resistance to the irradiation using an external 60Co emitters). This process can be acomplished by source and by an immersion in a solution containing chemical precipitation, sedimentation, ion exchange, B7Cs. The results were positive for all the membrane thermal evaporation, as well as membrane permeation. sources; TFC RO membranes may be employed to This last method is applied by the INCT to nuclear separate LLRW with A < 3.7 x 1012 Bq/m3 [4]. technologies since 1985. During the 14 years the Retention coefficients for a 2-stage purification following membrane processes have been examined unit with 12 various RO modules produced by: [1,2]: ultrafiltration (UF), "seeded" ultrafiltration TriSep, TORAY and ROPUR (Japan) have been (SUF), nanofiltration (NF), reverse osmosis (RO) and calculated using a CAROL program. Best results were membrane distillation (MD). obtained for the modules SU-720R (TORAY). Using Since the end of 1997 the INCT has been the same program the calculations were carried out for participating in Strategic Governmental Programme 4 various LLRW and main operating parameters for SPR-4 "Treatment of radioactive wastes and burned the pilot plant (Im3/h) were calculated. On the basis of nuclear fuel". The part of SPR-4 carried out in the these calculations a technical project of the pilot plant INCT has the aim: investigations of a purification/ was prepared: on two RO modules (8-inch, SU-720R) concentration process on RO membranes and con- LLRW will be purified, and the retentate from the 1st struction of a pilot plant with an efficiency of purification stage will be concentrated on SU-810 regenerated water (permeate) 1 m3/h. This pilot plant (4-inch.) modules [5]. creates a part of the decontamination line of LLRW In November'98 all the main parts of the pilot plant and MLRW in the Institute of Atomic Energy (IEA) at were put together and the pilot plan construction Swierk and will be placed before an evaporator. began. At the end of March'99 the pilot plant should Some laboratory units were constructed and be set in operation. modernizated: MF/MD - for microfiltration and References membrane distillation, 5RO - with five various reverse osmosis modules, RO/DJ - for reverse osmosis + [1]. Chmielewski A.G., Harasimowicz M., Zakrzewska-Trznade! G.: Application of membrane processes to the treatment of radioac- deionization, F/UF - for pre-filtration and ultrafiltra- tive effluents. In: Towards hybrid membrane and biotechnology tion, NF/RO - for nanofiltration and reverse osmosis, solutions for Polish environmental problems. NUCLEAR TECHNOLOGIES AND METHODS 123 Technical University of Wroclaw, Wroclaw 1995, pp. 227-233. 21.05.1998, p.65. [2]. Chmielewski A.G., Harasimowicz M.: Application of ultrafil- [4], Chmielewski A.G., Harasimowicz ML: Influence of gamma and tration and complexation for the treatment of low-level radioac- electron irradiation on transport properties of nanofiltration tive effluents, Separ. Sci. Techn., 30, 7-9, 1779 (1995). (NF) and hyperfiltration (HF) membranes, Nukleonika, 42, 4, [3], Chmielewski A.G., Harasimowicz M., Zakrzewska-Trznadel 857-862(1997). G.: Zastosowanie ultrafiltracji i hiperfiltracji w procesach [5]. Chmielewski A.G., Harasimowicz M., Tyminski B., Zakrzews- zate.zania cieklych odpadow promieniotw6rczych. Krajowa ka-Trznadel G.: Zate.zanie cieklych odpadbw promieniotwor- Konf. Radiochemii i Chemii Jadrowej "W Stulecie Odkrycia czych (COP) nisko- i srednioaktywnych metodami membrano- Polonu i Radu". Streszczenia, Kazimierz Dolny, Poland, 18- wymi. Raporty IChTJ. Sena C nr 1/98. CONCENTRATION OF LIQUID LOW-LEVEL RADIOACTIVE WASTE BY MEMBRANE DISTILLATION - PILOT PLANT EXPERIMENTS iCN Grazyna Zakrzewska-Trznadel, Marian Harasimowicz, Andrzej G. Chmielewski IS The plant (Figure) can purify low-level radioactive distillate is additionally cooled down to the process wastes at a throughput -0.05 m3/h. The installation temperature in the heat exchanger 8. consists of a spiral-wound module (1), equipped with The experiments were conducted in the tempera- a PTFE membrane, an effective surface area of 4 m2, ture range 35-80°C at the feed inlet, and at 5-30°C at a distillate reservoir (2) (V = 80 dm3), a retentate the distillate inlet, the feed and distillate flow rates of reservoir (V = 80 dm3) (3), PRI 505M Ebara pumps up to 1500 dm3/h. Under these conditions the permeate (4,5), a heat Omega supplier (6), two heat exchangers stream was 10-50 dm3/h (60-300 dm3/m2/day). The (7,8) (JAD X-6/50 and JAD 6/50) and ceramic filters experiments have shown that the best conditions of (9,10) for pre-treatment. A cold distillate is pumped running the process are at higher inlet feed tempera- from the reservoir by the PRI 505M Ebara pump tures (70-80°C). In this temperature range the energy through the heat exchangers, pre-treatment units with consumption per unit of the product is less than for ceramic filters to the PTFE module. The retentate lower temperatures. (warm stream) is circulated from the reservoir by the The tests were performed with non-active solutions pump through the heat exchanger, the heater and pre- of inorganic salts and simulated or original radioactive treatment filters. Both streams - the cold (distillate) waste samples of a specific activity ranging from 2403 and the warm (retentate) are returned to the reservoirs. to4.7-504Bq/dm3. The flow rates in the module are set in such a way that Experiments with inorganic salts (sodium nitrate, the appropriate heat-transfer coefficients and the potassium chloride) showed that ions did not pass required permeate transport through the membrane are through the membrane, all of them being retained in obtained. The outlet temperature of the warm stream is the retentate. The conductivity of the distillate de- lower than that of the cold one and the recovery of the creased from 200 uS/cm at the beginning of experi- part of heat is possible in the heat exchanger 7. The ment, to 10 |J.S/cm after ca. 40 hours. tap water Fig. A diagram of the MD pilot plant. 1 - MD module, 2 - distillate reservoir, 3 - retentate reservoir, 4,5 - pump, 6 - heater, 7,8 - heat exchanger, 9,10 - ceramic filters. 124 PROCESS ENGINEERING An increase of concentration did not significantly Rererences influence the permeate flow rate and did not change [1], Chmielewski A.G., Harasimowicz M, Zakrzewska-Trznadel G.: the retention factor. Concentration of radioactive components in liquid low-level Similar results were obtained in the experiments radioactive wastes by membrane distillation. In: Preprints of with radioactive solutions. During the time of experi- International Conference on Membrane Science and Tech- nology (ICMST98), 9-13 June, 1998, Beijing, China, pp. 119- ment radioactivity of the distillate was at a level of 120. natural background and the concentration of radioac- [2]. Zakrzewska-Trznadel G.: Membrane distillation for radioactive tive compounds took place in the retentate. The waste treatment, Membrane Technol., Intern. Newslett., 103, 9- retention of radioactive ions in the retentate was 12(1998). complete (retention coefficient $ = 1). NUCLEAR TECHNOLOGIES AND METHODS 125 PL9902243 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS DOUBLE INTERFACIAL LAYERS FOR CERAMIC/METAL BRAZE JOINTS MADE BY HIGH INTENSITY PULSED PLASMA BEAMS AND ARC PVD TECHNIQUES Jerzy Piekoszewski, Jacek Stanislawski", Rainer Grotzschel2' " The Andrzej Sottan Institute for Nuclear Studies, Otwock-Swierk, Poland 2/ Institut fur Ionenstrahlphysik und Materialforschung, Forschungszentrum Rossendorf e.V,, Dresden, Germany Fabrication of ceramic joints is complicated by the parallel surfaces were exposed to processing. To each fact that most metals would not wet the ceramics sample a small witness sample v/as added for further unless certain conditions are met. The key concept of structural characterization of the metallized layer. our studies conducted over the past 3 years is to Preparation of samples in four different setups is metallize the ceramic surface prior to actual brazing outlined in Table 1. by alloying it with some chosen metal in the liquid The witness samples were characterized by the state using intense piasma pulses generated in the so- EDX, SEM and RBS techniques (the latter one at FZR called DPE regime (see our preceding contribution). Rossendorf)- The most important information emerg- Our experiments conducted with Mo and Ti [3] and ing from the characterization can be summarized as recently (1998) with Cu metals show that of these follows: three metals only Ti exhibits long range mixing with 1. Average thickness of Ti layers formed with the use AI2O3 substrates after the DPE processing. Therefore, of DPE process in the 1-46 and the IBIS facilities is we decided to fabricate double layers based on Ti 25 ug/cm2 and 50 ug/cm2, respectively. Thickness brought to an intimate contact with the ceramic of Cu layer formed with the use of DPE process in surface. Four experimental setups have been used on the IBIS facility equals to about 85 ug/cm2, and the two facilities: IONOTRON 46 (1-46) and IBIS. thickness of the layer deposited by ARC PVD The former one comprises of two sources: DPE technique in the 1-46 facility is about 1800 ug/cm2. plasma pulses (titanium electrodes) with energy 2. There is a substantial difference in appearance of 2 densities at the level of 3 J/cm , and an ARC PVD gun SEM micrographs taken on the Ti/Al2O3 samples capable of formation of Cu, Ti and TiN coatings. prepared by DPE in 1-46 with nitrogen as the Switching from the DPE to the PVD processing does working gas and that taken on samples prepared in not require breaking the vacuum in the facility. In the IBIS with argon as the working gas. The former latter (IBIS) facility the procedure of switching elec- one resembles the morphology observed earlier by trodes that serve as a metal source from one type to us on the same kind of samples processed in IBIS another needs breaking the vacuum. Energy densities with nitrogen, whereas the latter one exhibits a large 2 of pulses generated in IBIS were about 6 J/cm , The non-homogeneity of the thickness and craters. sintered A12O3 samples intended for vacuum sea! joints 3. There is definitely no mixing within the Ti-Al2O3 had the form of cylinders with 25 mm outer diameter, system processed in the 1-46 facility - in spite of 15 mm inner diameter, and 13 mm height. Both flat the fact that the surface layer melts. No unam- Table 1. Preparation of samples Series/ Way of preparation Sample No. DPE 1-46 ARC PVD 1-46 DPE IBIS ARC PVD 1-46 Remarks 1 2 3 4 5 6 5/1,2,3,4,5 Ti+N2 Cu - - Vacuum sustained between process 2 5 pulses 30 minutes and 3 6/1,2,3,4,5 Ti+Nz TiN - - Vacuum sustained between process 2 10 pulses 15 minutes and 3 7/1,2,3,4,5 - - Ti+Ar Cu Vacuum broken between process 4 and 5 5 pulses 30 minutes 8/1,2,3,4,5 - - Ti+Ar, Cu+Ar Vacuum broken during process 4 each 5 pulses for replacement of electrodes 126 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS biguous conclusion, in regard to the question of Some cylindrical samples of the 5th, 6th 7th and 8th mixing within the Ti-Al2O3 system processed in series (5 items in each batch) are still under brazing the IBIS facility with Ar working gas, can be experiments conducted at the Warsaw Technical Uni- drawn from the RBS spectra of the system. The versity. low energy tails may be accounted for either by Reference non-homogeneity of thickness of the surface layer, or by a long range mixing. Coexistence of both [1]. Piekoszewski J., Wieser E., Grbtzschel R., Reuther R., Werner mechanisms cannot be excluded. Z., Langner J.: Nucl. Instr. Melh. (in press). = FORMATION OF SURFACE Pd-Ti ALLOYS USING PULSED PLASMA BEAMS Jerzy Piekoszewski, Zbigniew Werner1', Egbert Wieser2', Jerzy Langner17, !3 Rainer GrStzschel2', Helmut Reuther2' " The Andrzej Soltan Institute for Nuclear Studies, Otwock-Swierk, Poland IS 21 :o Institute of Ion Beam Physics and Materials Research (FZR), Dresden, Germany Surface alloying of Pd into Ti is known as an effective substrate. The range of mixing for both nitrogen and way of achieving passivation against reducing acid argon working gases (as estimated from the spectra) environments. Thus far such alloys were formed by amounts to about 0.5 um for 5 pulses to over 1.3 um electroplating in combination with diffusion anneal- for 20 pulses. The pure Pd layer on top of the ing, ion implantation of Pd into Ti, and ion or laser processed substrate originates from the inherent beam mixing of Pd film pre-deposited on a substrate. features of the mechanisms governing the process. In the present work we demonstrate a new approach to During discharge, ions of the working gas are acceler- formation of Pd-Ti surface alloy using intense plasma ated to energy of the order of 1-10 keV. Hence they pulses containing Pd ions. The technique has some arrive to the substrate within a few microseconds, features of ion implantation (since mass transport takes where they heat and melt its near surface layer. The place) and some features of laser processing (since melted phase lasts several microseconds before solidi- melting of near-surface layer occurs). In our experi- fication takes place. On the other hand the evaporated ments Ti-foil substrates were exposed to irradiation by metallic atoms with kinetic energy of the order of 1 eV Pd-N and Pd-Ar plasma pulses of energy density 4- reach the surface with a delay much longer than 5 J/cm2 and duration in the microsecond range. Plasma duration of the liquid phase (>10 us). Therefore, the pulses were generated in the rod plasma injector metallic vapor only condenses on the re-solidified (IBIS) type of accelerator developed at the IPJ Swierk surface without mixing with the substrate. The Institute. The number of pulses was 5, 10, and 20. subsequent pulse melts both the metallic layer (pre- RBS spectra of irradiated samples show a substan- deposited by the former pulse) and the near surface tial mixing of Pd into Ti substrate. A sharp surface Pd region of the substrate, so an effective mixing via peak, accompanied by a tail in the low energy range, diffusion can occur. Each next pulse repeats the indicates that Pd has diffused quite far into the pattern outlined above. The remaining sample charac- Table 1. Results of sample characterization 2 2 2 Sample No. No. of pulses Am, [(Jg/cm ] Ampd Og/cm ] Vc [mV] Ic [mA/cm ] Mum] R*[um] Pd-N plasma: T = 170 |is, UB = 30 kV, L = 300 mm 010 5 47.5 - 0.17 0.92 013 5 37.5 36.3 672 0.37 0.25 1.17 08 10 70 75 0.16 0.88 09 10 87.5 - 660 0.93 - - 014 20 180 - 0.20 0.98 015 20 165 153 647 1.78 0.25 1.32 Pd-Ar plasma: T = 190 us, UB = 30 kV, L = 3 00 mm 06 5 97 - - - 0.28 1.66 07 5 92.5 97.5 679 0.36 0.20 1.30 05 10 197 196.5 703 1.05 0.21 1.37 016 20 307.5 307.8 682 0.31 0.25 1.77 017 20 285 - - - 0.23 2.01 Reference - - - 492 j 0.45 0.22 1.54 where: Am, is the total mass change; AmP Jerzy Piekoszewski, Jacek Stanislawski1', Rainer Grotzschel2', Egbert Wieser2/, Zbigniew Werner" "The Andrzej Sol tan Institute for Nuclear Studies, Otwock-Swierk, Poland 21 Institut fur lonenstrahlphysik und Materialforschung, Forschungszentrum Rossendorf e.V., Dresden, Germany Over the past several years we conducted a number of for Xd = 190-210 ms (for nitrogen as the working gas). experiments on modification of surface properties of For significantly shorter ij, when there is a steep materials using high intensity pulsed plasma beams. gradient of the gas concentration in the inter-electrode This technique has some features in common with ion space, effective erosion of the metallic electrodes implantation since mass transport takes place and occurs. This regime is referred to as deposition by some features of laser processing since heat transport pulsed erosion (DPE). In both regimes, the plasma and hence melting of the near surface layer occurs. carries a sufficient energy to melt the surface layer of High intensity short duration pulse of plasma deposits the substrate. DPE leads to the formation of well- its energy on the surface of the substrate; this energy is adhering metallic films and in some cases to a long transformed into heat. At a sufficiently high density of range mixing within the deposit-substrate systems. 6 2 the beam power, i.e. of the order of 10 W/cm or Until recently, we used to assume that in the PID more, a rapid temperature rise occurs in the irradiated regime the plasma pulses are rich in the ions of region, leading to its melting. Once the surface layer is working gas, whereas in the DPE regime the plasma molten, a rapid inward diffusion of pulse-delivered contains mostly the metal ions. Such belief was and/or pre-deposited atoms takes place. If the pulse is strongly supported by the results of Auger analysis of in the microsecond range, then the near surface layer the steel substrates processed with Cu-N beams [1] remains molten for a period of several microseconds since the PID-processed near surface layer was rich in In many cases it is enough to enable the deposited N atoms; on the other hand Cu dominated in the DPE- atoms to penetrate the substrate to a depth of urn processed layers. Although there are no doubts, as far range. The plasma pulses, capable of inducing such a as the PID case is concerned, the situation in the DPE process, are generated in a rod plasma injector, (RPI) case is not so clear. Our recent experiments were type, of generators described in details elsewhere [1]. conducted with Mo and Ti electrodes, sapphire Briefly, the plasma pulses are generated as a result of substrates, and nitrogen as the working gas. After 5 low-pressure, high current discharge between two pulses of the DPE treatment with Mo electrodes we concentric sets of electrodes. A high voltage pulse observed [2] that the resulting structure consisted of delayed some time -cd with respect to the moment of some Mo micro-droplets coexisting with a thin homo- injection of the working gas into the inter-electrode geneous film of the metal in-between. Formation of space ignites a discharge. droplets as a result of a large difference in surface If td is set long enough to allow the injected gas to tension between the metallic deposit and the sapphire expand over the whole inter-electrode space, the substrate was already observed and explained in [3]. plasma contains almost exclusively the elements of the In the case of Ti electrodes some mixing of Ti atoms working gas. This mode of operation is referred to as with, the substrate was observed apart from the surface pulse implantation doping (PID). Typically it occurs film of the metal. The simplest explanation of the 128 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS presence of the film is that metal ions or/and atoms enough time for the metal ions to get mixed with reach the surface when it is already solidified after the the substrate via diffusion mechanism in the liquid last pulse. state. The situation should be even more favorable Series of experiments performed in the present for mixing when Ar and Xe gases are used as the work were aimed at getting insight into the kinetics of working gases. The Tf of Xe ions is about 1.6 times the DPE process. The experimental conditions were as greater than that of Ti ions whereas Ar arrives follows: energy density about 6 J/cm2; 3 different practically in the same time as Ti ions do. working gases: N, Ar and Xe with optimized xd equal ii) Likely mechanism of ablation is bombardment of to 160, 190 and 240 \xs respectively; Ti electrodes; the ends of the electrodes by electrons yielding the AI2O3 substrates placed 30 cm away. The choice of the evaporation of particles with thermal energies. Ti-Al2O3 system was dictated by the fact that it is According to our numerical simulation of thermal miscible during the DPE process [2]. Samples were evolution of ceramic substrates their surface processed with 1, 2 and 3 pulses and subsequently remains hot (up 1000°C) for at least 100 ms. In analyzed using the RBS technique. Unexpectedly, addition, the surface is "fresh" after melting so it is mixing of Ti into the substrate was observed for quite comprehensible that a cloud of electrode neither of the working gases after a single pulse. On particles (in the vapor or/and of low energy ions the other hand the mixing was quite evident for 2 and state) reaching the surface forms a very well 3 pulses. Main conclusions emerging from these facts adhering film. The subsequent pulse melts both the are as follows: metallic film and the near surface layer leading to i) Metal atoms ablated during the discharge from mixing (as it is in the case of Ti/Al2O3 system). A electrodes do not undergo any acceleration along more detailed account of this work will be given in with the working gas atoms. If they were a separate publication. accelerated to the energy of about 1 kV, their time of flight Tf to the substrate would be about 5 us i.e. References only 2 us longer than that of nitrogen ions. [1]. Piekoszewski J., Langner J., WaliS L., Werner Z.: Surf. Coat. According to our numerical simulation of the Technol.,93,209(1997). thermal evolution of the ceramic substrates, molten [2]. Piekoszewski J., Wieser E., Gro'tzschel R., Reuther H., Werner Z., Langner J.: Nucl. Instr. Meth. (in press). phase of the near surface region of the substrate [3]. Popp D., Mehiing A., Wilzbark R., Langhoff H.: Appl. Phys. A, lasts about 10 us. This means that it would still be 85,561 (1992). SPECIAL ISOTOPE METHOD OF LEAKPROOF CONTROL OF TECHNOLOGICAL OBJECTS Janusz Kras, Stanisfaw Myczkowski PL9902246 The isotope method of leakproof control and localiz- connecting tubes (generally 3> = 5/3 mm); K - thin- ation of leaks in technological objects has been rou- walled measuring tube (1 = minimum 2 m), 0^. = tinely used by research groups of this Institute for max. 1.6 mm); A,B,C,D,E,F - cut-off valves of more than 20 years. Using this method it is possible to KW2MSP type or others of high quality; I,II,III,IV - detect and localize leaks of an output higher than radiometric probes e.g. of a DIDAC multichannel 30 cm3/h. The cost of such control is relatively high analyser. (though lower than in the case of traditional methods) because it is necessary to apply relatively high activity (approx. 37 MBq/m3), to fill the whole controlled object with a labelled medium and to carry out radi- ometric measurements of all the object. VI In some cases the customer is interested only in the tightness state of the object - the dimension of the leak V3 - without its localization. In order to meet such 1 requirement the method described in this paper was X A xB K K X elaborated. The principle of the method is illustrated in Iv IlI U 1 the diagram of the system for leakproof control pres- t t t I ented in Fig.l. The system consists of the following Scintillation probes elements: VI - object controlled; V2 - special tank Fig.l. A diagram of the system for leakproof control. containing gaseous radioisotope tracer (ClijBr82 or The above described method is based on the Kr85); V3 - compensation tank; 1,2,3 - thick-walled following phenomenon: if in the controlled object VI NUCLEAR TECHNOLOGIES AND METHODS 129 a loss of the controlled medium, AVI, takes place due results in displacement of the tracer in the measuring to a leak then at initially equal pressures in objects VI, tube by 80, 50, 20 or 10 cm depending on the internal V2 and V3, closed line "3" and opened line "l-k-2" of diameter of the tube (0.56, 0.76, 1.18, 1.6 mm). For the loss is proportionally compensated from objects scintillation probes with collimators a tracer displace- V2 and V3, AV2. As a result of this compensation the ment of 5 cm can be easily recorded. radioactive tracer is displaced in the measuring tube. Conditions of application of the method: The displacement is recorded during the control and if • volume ratio of VI to (V2+V3) not larger than suitable apparatus is available, e.g. a multichannel 5000:1; analyser operating in multiscaling mode, the rate of • control time of a single object not longer than tracer movement makes it possible to detect and 2 hours; estimate output of the leak. • temperature gradient inside the objects during the Assuming that : VI = 300 x 106cm3; AVI = 103; measurements not greater than 1 °C; V3+V2 = 6 x 104 cm3, AV2, in this case equal to 0.2 • specific activity of the tracer in tank V2 not less cm3, can be calculated from a generally known than 400 jj.Ci (15 MBq/m3) for Kr85 or 300 uCi formula. Such value of the compensation volume (UMBq/m3) forBr82. STUDIES ON NEW POLYMERIC COMPLEXES OF AMINOTRIAZOLE WITH MAGNESIUM Andrzej Lukasiewicz, Lech Walis, Luzja Rowiiiska Studies have been carried out in this Institute on dye (p-aminophenol-APh) and with Acid Black 24 polymeric complexes of aminotriazole with transition (AB24). The results are presented in Table 1. The colour metals of general formula MAnatr2 (p) (abbreviation intensity and colour shade (in the case of p-amino- MAXp), where M denotes the transition metal (Cu2+, phenol) is a measure of binding metal M' with the Ni2+, Co2+, Ag+) or two different metals, A stands for fibre in the complex. the acetic anion, n = 2 or n = 1 (for M = Ag+), atr(X) It follows from the obtained data that the binding denotes 3-amino-l,2,4-triazole and p is a complex with the fibre involves MgAXp + 4 M's complexes. poly condensed by means of formaldehyde [1]. The results are subject to a separate publication [2], in It has been found that similar complexes are which probable structures of the complexes have also formed with magnesium (M = Mg). It has also been been presented. found that in aqueous solutions MAXP, including By means of MgAXp + 4 M's complexes it is 1 MgAXp, attach magnesium acetate Mg(OAc)2 or possible to bind various metals (M ) with cellulose or magnesium acetate with an addition of another salt e.g. polyamide materials as well as with compounds Cu2+, Ni2+, Fe3+, Al3+, (M's) with the formation of new containing amine groups e.g. aminophenol or AB24. complexes of general formula MAXP + n M's, In this Therefore they can be used for modifying these formula n denotes the mole ratio M'/M. In MgAXp materials, among other things, for medical purposes M = magnesium. The binding of these complexes with (applicators of a new type). cellulose and polyamide fibres from aqueous solutions The ability of the complexes to bind nonabsorbable was examined. The binding degree was evaluated surgical sutures based on polyglycol acid (Dexan) was comparatively by dyeing the fibres with an oxidative examined. The results of preliminary experiments Table 1. Dyeing of cellulose and polyamide fibres treated with MgAXp + 4 M's complexes No M's n Dye Colour intensity 1 3/4 Mg (OAC)2 +1/4 Cu(OAc)2 r 4 APh, AB24 2 3/4 Mg (OAC)2 +1/4 Cu(OAc)2 2 APh, AB24 + 3 3/4 Mg (OAC)2 +1/4 Cu(OAc)2 6 APh, AB24 ++ 4 3/4 Mg (OAC)2 +1/4 Ni(OAc)2 4 APh, AB24 ++ 5 3/4 Mg (OAC)2 +1/4 Ni(OAc)2 2 APh 4- 6 3/4Mg(OAC)2+l/4FeCl3 4 APh ++ 7 3/4Mg(OAC)2+l/4FeCl, 2 APh + $ 3/4Mg(OAC)2+l/4AlCl3 4 AB24 + 9 Mg (OAC)2 4 AB24 + - Cotton wool or polyamide cloth was treated with a 10% aqueous solution of the complex for 1 h, washed with water and heated in a 0.2% dye solution at 90°C for S minutes; ** maximum colour intensity. 130 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS were promising. of the above mentioned materials e.g. for medical Polymeric complexes of aminotriazole with purposes. magnesium and with an addition of other metals have References been obtained. The complexes exhibit effective ability [1]. Lukasiewicz A., WaliS L., Michalik J., Sadlo J.: Mat. Lett., 29, to bind with cellulose and polyamide materials as well 149(1996). as with materials based on polyglycolic acid (surgical [2], Lukasiewicz A., WaliS L., Rowiftska L., Panasiewicz J.: Mat. sutures). The complexes can be used for modification Lett., 38,108(1999). THE 18TH CENTURY GLASSWARE FROM NALIBOKI AND URZECZE GLASSHOUSES. PHYSICO-CHEMICAL STUDIES 1 •CM Jerzy J. Kunicki-Goldfinger, Joachim Kierzek, Aleksandra J. Kasprzak ', Bozena Malozewska-Bulko is u National Museum, Warszawa, Poland 1. Introduction 3. Analytical methods During the period of May-July 1998, an exhibition The investigation consisted of three main parts: X-ray entitled "The Glasses from RadziwiH Family Factories. fluorescence analysis, fluorescence examination under Naliboki 1722-1862. Urzecze 1737-1846" was pres- ultraviolet light, inspection of the glass surfaces ented in The National Museum in Warszawa [1]. The (visual observation). exhibition showed more than 200 objects, thus making • X-ray fluorescence analysis. Energy dispersive an exhaustive representation of almost all items X-ray fluorescence analysis (EDXRF) is a well- attributed to these factories found in Polish collec- established analytical technique in the studies of tions. Collecting such a large and representative group th historical glass. X-ray spectra were measured using of vessels from one of the most important, 18 century an 80 mm2 Si(Li) detector (EG&G ORTEC) with a glass manufacturing centres in the Polish-Lithuanian 109 180 eV resolution for MnKa. A Cd radioisotope Commonwealth gave a scarce opportunity to conduct annular source (-200 MBq) was applied to excite a physico-chemical examination of the objects. the elements in the glass. The live-time of the The main goal of the study was to characterise the measurements was 1000 s. The obtained spectra glass formulation (metal) made by the Naliboki and were collected by a multichannel analyser and Urzecze factories in 18* century, on the basis of analysed by the AXIL-QXAS software, supplied chemical composition as well as on a few other by the International Atomic Energy Agency in qualities. The questions whether any specific chemical Vienna. The examined objects were placed directly composition could be associated with the products of on the source shield. The analysed area of glass these factories and whether the vessels from these surface was about 2 cm2. To correct the differences factories, differed as a group, from glasses originating in matrix absorption and measurement geometry, th from other 18 century Central European factories the coherently and incoherently scattered peaks constituted the elementary topics in the course of the were taken into account. 12 primary variables have research. been taken into account - they referred to the In this paper we present a part of preliminary following elements: K, Ca, Mn, Fe, Cu, Zn, Pb, results of a larger project - see a more comprehensive As, Rb, Zr, Sr, Y. report [2]. « Ultraviolet fluorescence. The vessels were 2. Examined objects examined using both long-wave (UV-A) and short- The project has covered a collection of colourless wave (UV-C) ultraviolet lamps. For the UV-A tableware items. It contained mostly engraved band, a high-pressure mercury discharge Black glassware, mainly goblets with and without covers, Light Blue (BLB) lamp was applied. It emits flutes, wineglasses, beakers, tumblers, flasks, bottles, radiation in the range of approximately 340-380 decanters and other types of vessels. Most of them nm with a peak at -365.5 nm. The HPW 125 W T (196 objects) were fabricated either at the Naliboki or lamp was used. For the UV-C band, a low-pressure in Urzecze glasshouses in 18th century. A limited mercury-vapour discharge lamp, which emits number (44 objects) of glassware originating from radiation peak at -253.7 nm, was applied. Two other glass centres were also examined, as a compa- TUV 15 W lamps, mounted in a specially con- rative group. These were the vessels from: Lubaczow, structed dark chamber, were used. Only the colour Dresden, Potsdam (Zechlin), Bohemia and England. of fluorescence was determined, and it was done Part of the examined objects have unquestioned by naked eye. attributes that have been taken as the basis for • Glass surface inspection - visual observation. The grouping of the remaining glasses. surfaces of the examined objects were carefully in- NUCLEAR TECHNOLOGIES AND METHODS 131 spected using an 8x magnification. The main chemical composition seems to be possible. It was also objective of the visual inspection was to identify possible to distinguish the Lubaczow factory formula- crizzled glass items. tion, which does not contain PbO. The main discrimi- nating features are concentrations and ratios of Sr, Zr, 4. Results and discussion Rb and Y, although other elements are also important. The EDXRF results have provided groupings of The long-wave ultraviolet light has not enabled any composition which, in some cases, turned out to be useful differentiating among the vessels; almost all characteristic of provenance. Moreover, two distinct glasses showed green fluorescence. The short-wave formulations of Central European glass have been ultraviolet light caused a distinctive ice-blue fluor- defined. It was apparent that the differences in compo- escence of many glasses. All of them contained lead, sition were barely sufficient to distinguish them. One including the English glass (-32% PbO) on one side of the formulations included lead and this was the and the Naliboki glass (-0.27% PbO) on the other side most surprising result in the entire study - see Fig.l. of this set of vessels. A difference of only about 0.1% of the PbO content divided all the glasses into two groups - compare Fig.3 (the English glass is not shown Lines A and B correspond to the same lines A and B in Figure 1 Fig.l. The PbO content in the glasses of the highest concentration of lead, o - Saxon, • - Brandenburg, Ci - Naliboki. The PbO content in this "crystalline" formulation Fig.3. Triangular diagram fot the variables Pb, Mn and Fe. reaches the range of approximately 7-9% (by weight) there). The first group may be identified by their blue in the case of part of the Saxon glasses and a level up fluorescence in UV-C, the second by the absence of to about 6% in several cases of the Naliboki and blue fluorescence (most of them show green fluor- Brandenburg glasses. The bottom limit of PbO content escence). The border of PbO content used in the dif- in the "crystalline" formula is not defined. Therefore, ferentiation of groups which show different colours of the knowledge of PbO content is not sufficient to fluorescence (line B) is not the same as the border of differentiate the formulations. Other characteristic PbO content dividing the set of glasses into the elements which have been identified in the course of "crystalline" and "not-crystalline" formulations (line A). the study seem to be sufficient to identify lead con- Moreover, in both cases the PbO content is not the taining "crystalline" formulation - Fig.2. In the case of only and sufficient feature of differentiation, in some Sr Rb instances it may be even deceiving. The contents of several other elements, which have been determined in the course of the study, are also important. Consider- ing the location of border line B in Fig.l, it is helpful to refer to a triangular representation of variables Pb, Fe, Mn - see Fig.3. It is evident from the Figure, that the blue fluorescence depends not only on the PbO content, but aiso on the relative contents of Fe and Mn. Among all the examined objects, 23 items were crizzled. All of them belong to the group of glasses that contain lead as one of their constituents. For Naliboki "crystalline" formulation crizzled objects make up about 44%. The EDXRF results have shown that the crizzling does not simply depend on the Ca content. The contents of Pb and K as well as the Fig.2. Square representation of the variables (Sr, Y, Zr, Rb}. "Crystalline" glass formulations: 3 - Naliboki, • - manufacturing processes seem to be no less important Brandenburg, A - Saxon. "Non-crystalline" glass formulation: factors. A - Lubaczow, + - remaining glasses. Multivariate analyses have given good results and this "crystalline" formula the characterisation of the allow grouping the objects on the basis of their products of a given factory on the basis of their chemical composition. Principal component analysis 132 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS 50 Ward's method Saxony 40 s Brandenburg Ji 30 to XJ v> CO Naliboki I 20 LU 10 I HTI P?* i ri Hs rfo nl nrVi m Fig.4. Cluster analysis - dendrogram for the "crystalline" glasses. with the use of 12 variables was performed. Five originating from Brandenburg and Saxon as well as groups of objects are separated. These are sets of from other Central European glass centres. Saxon "crystalline" glasses, Brandenburg "crystalline" A differentiation of the vessels under ultraviolet glasses, Naliboki "crystalline" glasses and glasses light does not cover the glass formulation distribution. from Lubacz6w that do not contain lead. Better results The absence of blue fluorescence (under UV-C) seems have been obtained with a cluster analysis. In Fig.4 to be a sign that the examined glass is not of a dendrogram for the "crystalline" glasses is shown. 10 a "crystalline" formulation, but blue fluorescence is variables were used: Ca, Fe, Mn, Cu, Pb, As, Sr, Zr, not a distinctive feature of only "crystalline" Rb, Y. This method has allowed us to group objects formulation. more accurately, also within the three sets of "crystal- The crizzling phenomenon does not depend on the line" glasses. Ca content only. In the case of "crystalline' formula- 5. Conclusions tion, the contents of Pb and K seem to be very The EDXRF seems to be a very valuable, non- important, too. destructive tool of differentiating of the 18th century Central European glass vessels. It allows discrimi- References nating the Central Europe "crystalline" formulation, as [1]. Kasprzak A.J.: 5zkla z hut radziwittowskich. T.l-2. Muzeum well as some other formulations, such as that charac- Narodowe, Warszawa 1998 (in Polish). teristic for Lubaczow. "Crystalline" formulations from [2]. Kunicki-Goldfinger J.J., Kierzek J., Kasprzak A.J., Matozew- ska-Bu6ko B.: XVIII-wieczne naczynia szklane z hut w Nalibo- different factories seem to be distinguishable from kach i Urzeczu. Badania fizykochemiczne. Instytut Chemii i each other, by the use of EDXRF. But it is necessary Techniki Ja.drowej, Warszawa 1999. Raporty IChTJ. Seria B nr to examine a larger quantity of well-attributed objects 2/99 (in Polish). DETERMINATION OF SURFACE CHARGE DENSITY FOR PARTICLE TRACK MEMBRANES iCO Danuta Wawszczak, Wojciech Starosta, Vladimir V. Berezkin1', Marek Buczkowski :•* iiCNsJ 11 Institute of Crystallography, Russian Academy of Sciences, Moscow, Russia Particle track membranes (PTM) can be applied in flow of liquid. The potential of this layer is called zeta many fields for microfiltration of different liquids [1]. potential (E,). Between the two surfaces of a membrane Electric properties of a membrane surface influence at the pressure difference Ap, the potential difference mass transport through pores in the process of micro- AE is created, which can be experimentally measured. filtration of electrolytes. Theory of this phenomenon Relation between the above parameters gives the is based on the concept of space charge in the area Helmholtz-Smoluchowski equation close to the wall of a micropore which shields the space charge of the wall. Close to the wall there is p=fl AE_ a layer of counter-ions stationary with respect to the ee0 Ap NUCLEAR TECHNOLOGIES AND METHODS 133 where: p - electric conductivity of solution, r\ - An experimental set-up for measurements of flow viscosity of solution, s - dielectric permeability of potential for membranes has been design and built. A solution, so- dielectric permeability of vacuum. scheme of this set-up is given in Fig.l. The examined The charge on the capillary wall {£) is connected membrane was placed in a measuring chamber (1) with zeta potential by the equation with KC1 solution at a given concentration. From both sides of the membrane silver electrodes were placed = zF (5,6). The pressure was supplied from a gas cylinder (8) and measured by a precise pressure gauge (9). For where: z - charge number, F - Faraday's constant, c - potential measurements a voltmeter as a computer card concentration of solution, R - universal gas constant, (Axiom firm, input resistance >10 Gfl at 3 V) was T - temperature of solution. used. Results of calculations for the PET track Results of measurements of the flow potential and membranes with pore size 0.16 and 0.40 um are given surface charge in the case of PTM with very small in Table 1. pores (in the range: 14-47 nm) at biochemical sol- Table 1. Flow potential (^) and charge density of pores (8) for PET utions are given in [3], particle track membranes 1 2 3 No. Pore Pore \ 5 diameter density [mV] [C/m2x 103] [Urn] [cm"2] 1 0.16 6xlO8 3.5 0.5 2 0.40 6x10' 4.2 0.6 The knowledge about the charge density of particle track membranes can be useful for some applications / \ of these membranes. The described methods give also the possibility of comparing the properties of track P C membranes after plasma or chemical surface treat- CARD of ment. | D1GI~TAL | |VOITMETER . References [1]. Proceeding of the 3rd Conference on Particle Track Membranes and Their Applications. Jachranka, Poland, 26-29 October 1993. Eds. W. Starosta, M. Buczkowski. INCT, Warszawa 1994, 123 p. [2]. Fridrichsberg D.A.: Kurs kolloidnoj chimii. Izd. Chimija, Fig.l. A scheme of measuring set-up for determination of flow Leningrad 1974, 351 p. (in Russian). potential of PTM. 1 - measuring chamber, 2 - solution, [3], Berezkin V.V. et al.: Track membranes as selective elements of 3 - precise pressure gauge, 4 - membrane, 5,6 - electrodes, electrochemical biosensors. Kolloid. Zh., 55, 6, 10-25 (1993). 7 - measuring vessel, 8 - gas cylinder. (in Russian). LABORATORY OF ISOTOPE RATIO MASS SPECTROMETRY Ryszard Wierzchnicki \ Fig. A general scheme of vacuum preparation line. • buffer vessel (2); will be the use of IRMS to hydrogen, oxygen and • pressure sensors (3a,3b); sulfur isotope analysis for: • diffusion vacuum pump (4); • water and air pollutants identification, • freezing pipe (5a,5b); • industrial application, • cold finger (6); • ground water origin determination, • manometer (7); • study of isotope effects in chemical reactions and • containers for gas samples (8); processes, • tube furnace (9). • food control. First vacuum experiments on the line were carried The Mass Spectrometer DELTAplus was purchased out recently. (in part) by means of the Polish State Committee for The next step of the activities in our laboratory Scientific Research. LABORATORY FOR POROUS MATERIALS EXAMINATION Marek Buczkowski, Helena Grigoriew, Bozena Sartowska, Danuta Wawszczak, Grazyna Zakrzewska-Trznadel IS For many years in this Institute work concerning For characterisation of the membranes the fol- I CM jo membrane technology has been conducted. A basic lowing methods were elaborated: research concerns the application of hydrophobic and • scanning electron microscopy, hydrophilic membranes for stable isotope separation in • gas-liquid porometry, a "bubble point method", 10. a process coupled with phase transition. The other • neutron scattering, field of interest is the application of some other • X-ray diffraction, membrane processes, as MD, RO, UF for concentra- • permeation methods. tion of liquid intermediate and low-level radioactive Structural investigations of polymer membranes wastes. Pressure driven membrane processes (RO, UF) were accomplished on a synchrotron in Triest and have been employed in some other industrial branches: Hamburg. On-line measurements during water per- for concentration of fruit juices, water purification for meation through cellulose membranes were done. electroplating plants, sorbent recovery in the process Such a technique with a short resolution time gives a of flue gas treatment. possibility of accurate description of the phenomena Work concerning the development of technology occurring in polymer membranes contacting different of track membranes manufacturing, characterisation solvents. and application is continued. These researches are Ait present the laboratory prepares membrane char- conducted in co-operation with the Joint Institute for acteristics for the INCT and for some external institu- Nuclear Research, Dubna. tions (Secura, Warsaw University of Technology). NUCLEAR TECHNOLOGIES AND METHODS 135 NUCLEONIC CONTROL SYSTEMS PL9902251 ACTIVITY OF RADON DECAY PRODUCTS SIMULATION AS THE BASIS FOR OPTIMIZATION OF RADON DAUGHTERS CONCENTRATION MONITOR IN AIR Bronislaw Machaj Employing relations describing variation of activity in k3c - number of simulated alpha disintegrations at time a series of decay of a radionuclide A into its daughters intervals ti, t2, t3 corresponding to 1 dis./min of >... [1]: nuclide C only at time t = 0; s - deposition and detection efficiency. Solving the set of equations (2) (1) with Cramer rules for ti = 1-7 min, t2 = 8-20 min, t3 = -\e A -e B 21-30 min and taking into account that to get the concentrations expressed in Bq/m3 the activity expressed in dis./min has to be multiplied by 1000/60/v one gets: _1 • _1 3 A = ~(2,0317nj-1.5548n2+1.179n3) [Bq/m ] (3) ve where: 3 B = —(0.4595nr1.1425n2+1.8065n3)[Bq/m ] h - ^ ^A ^B ve I T ^ 1 V. AD /Vp—A.T3 3 A D ^ D C = —(~0.61n,+1.1428n2-0.9450n3)[Bq/m ] •^A A-B ve where: v - air flow rate through the filter, L/min. Noting that deposition and detection efficiency E can A Bo C - number of atoms of nuclide A = Po-218, o> o be different for radon daughters, equ (3) can be B = Pb-214, C = Bi-214 at time t = 0; X = 0.693 - rewritten in a more general form: decay constant of the nuclide, Tl/2 - half life of the 3 nuclide, activities of radon daughters were computed A = -— (2.0317ni-1.5548n2+1.179n3) [Bq/m ] (3a) at 1/10 min intervals when only Po-218 or only Pb- ve, 214 or only Bi-214 was deposited on an air filter. To 3 simulate a continuous process of deposition of radon B = (0.4595n1-1.1425n2+1.8065n3) [Bq/m ] daughters on the air filter within 5 min, fifty activity ve2 spectra obtained in such a manner were summed with 3 C= (-0.61n1+1.1428n2-0.9450n3) [Bq/m ] 1/10 min delay each next with respect to the previous ve3 one [2]. These spectra, in turn, were used to compute Alpha potential energy concentration is equal to: the total alpha activity of Po-218 + Po-214 and a corresponding count rate at set deposition and E = —EA+—EB+—Ec= (5.8997 A + a detection efficiency of radon daughters. Employing XA A-B Xc simulated activities the following set of equations can +28.559B+21.2O2C)l0~4 [fiJ/m3j (4) be written: Simulations showed that measurement of total n, =k1AAe + k1BBe + kicCe (2) alpha activity at three time intervals makes the deter- n2 = k2AAe + k2BBe + k2CCs mination of radon daughters concentration indepen- n3 = k3AAs + k3BBe + k3CCe dent of radiation equilibrium between the decay where: n1; n2, n3 - number of counts registered at time products. Furthermore, measurement of alpha activity intervals ti, t2, t3; k!A, k2A, k3A - number of simulated at the intervals 1-7 min, 8-20 min, 21-30 min ensures alpha disintegrations at time intervals tj, t2, t3 a small statistic error due to the statistics of radiation corresponding to 1 dis./min of nuclide A only at time at a reasonable short measuring time. t = 0; k]A, k1B, k2B, k3B - number of simulated alpha Measurements of a model gauge in a radon disintegrations at time intervals ti, t2, t3 corresponding chamber showed that the deposition and detection to 1 dis./min of nuclide B only at time t = 0; kc, k2C, efficiency for radon daughters is different and is equal 136 NUCLEONIC CONTROL SYSTEMS p/min 18Q0 1600 A=95.6 Bq/m3 B=14.2 Bq/m3 C=13.9 Bq/m3 E=0,13uJ/m3 Q=1090Bq/m3 A=7897 Bq/m3 B=7043 Bq/m3 C=6045 Bq/m3 Q=7720 Bq/m3 E=37,6 uJ/m3 15 20 minutes Fig.l. Measured (broken line) and simulated (dotted line) count rates of three interval model gauge at low (left) and high (right) concentra- tion of radon daughters. Considerable counting statistics can be seen at low concentration of radon daughters. to et = 0.24, 62 = 1.24*8b E3 = 1.12*si. Deposition and Fig.l shows the measured and simulated count detection efficiency Sj for Po-218 was determined rates spectra at low and high concentrations of the from the concentration of Po-218 computed from radon short lived decay products. It was found that in equations (3) and from the known concentration of both cases (at low and high concentrations) the radon in the radon chamber (measured with Lucas number at counts at the intervals 1-7 min, 8-20 min cell) at radiation equilibrium of radon and Po-218 and and 21-30 min of the measured and simulated spectra at very high (saturating) smoke aerosols concentration are equal and a high accuracy (error <1%) is here in the radon chamber. The smoke aerosols concentra- worthy of mention. The only difference is the tion was so high that their further increase of concen- magnitude of the root mean square error (RMSE) of tration in the chamber did not result in increased counting that for the low concentration of radon deposition of Po-218 on the air filter determined from daughters is equal to 62.9%, 40.1% and 54% in equ. (3). Thus si is the effective deposition and relation to the three time intervals and for the high detection efficiency, including part of Po-218 concentration RMSE it is equal to 2.4%, 2.6% and deposited on the radon chamber walls and inside an air 2.5% in relation to the same intervals. This indicates duct to the air filter of the gauge and the efficiency of that the simulation procedure renders well the measured deposition of the nuclide on the air filter and the count rates. semiconductor detector efficiency of alpha radiation. On the basis of measurements carried out at low Efficiencies s2 and s3 were determined in such a way and high aerosol concentrations in the radon chamber as to get the same concentration of Pb-214 and Bi-214 and simulations for the same measurements, statistical as the concentration of Po-218. Concentration of the errors due to the counting statistics were computed daughters Pb-214 and Bi-214 cannot be higher than and are shown in Table 1. Relative RMSE of the = the concentration of the parent Po-218. At ei = e2 £3 concentration of radon daughters was computed in = 0.24 the concentration of Pb-214 and Bi-214 (Po- respect to the regression line of series of measure- 214) is higher than that of Po-218. The higher deposi- ments. Relative Root Square Error (RSE) was com- tion and detection efficiency of Pb-214 and Bi-214 can puted in the following way. The number of counts nl 2 be explained by a higher Po-214 radiation energy at the interval tj was replaced by nr(J ni)" where J, (7.69 MeV) as compared with that of Po-218 energy the coefficient responsible for an increased statistic (6.0 MeV) at a constant pulse discrimination level, but error, was selected J = 1.2 at a lower limit indicated in it not known why s2 is different from £3. [3] (J = 1.2-2.9). For such a count rate nl and un- Table 1. Relative errors due to the counting statistics Parameter Po-218 Pb-214 Bi-214 Rn-222 E Remarks (Po-214) Concentration 2991 1247 1110 9530 7.7 rgl2a-rgl2f RMSE (%) 10.6 7.0 14.9 7.4 low aerosols RSE (%) 10.5 15.5 16.1 4.9 concentration Concentration 4689 4693 4664 5280 26.1 rgl3a-rgl3g RMSE (%) 11.1 5.0 3.5 3.6 high aerosols RSE (%) 11.9 6.2 6.8 2.6 concentration concentration for Po-218, Pb-214, Bi-214 (Po-214) Rn-222 (average) is given in Bq/m3, for alpha potential energy E is given in uJ/m3. NUCLEAR TECHNOLOGIES AND METHODS 137_ changed counts n2 and n3 the concentration of decay measured statistic error of potential energy is approx. products was computed and the relative error of Po- higher by 50% than the error resulting from simu- 218, Pb-214, Bi-214 (Po-214) was computed too. The lations. 2 procedure was repeated replacing n2 by n2-(J n2)" and I/2 References n3 by n3 = n3-(J n3) . The computed, from such simulations, average RSE are given in Table 1. In both [1]. Evans R.D.: The atomic nucleous. McGraw-Hill Co., New York cases (low and high smoke concentrations) the 1970, pp. 470-502. measured RMSE of the decay product concentrations [2]. Machaj B., Bartak J.: Simulation of the activities of radon are comparable with the simulated RSE. Thus, to daughters on RGR monitor air filter, Nukleonika, 43, 2, 175- 184(1998). estimate the statistic error of radon daughter measure- [3}. Radiation monitoring in the mining and milling of radioactive ments a simulation procedure can be used. The ores. IAEA, Vienna 1989. Safety Series No. 95,25 p. A MEASUREMENT PROGRAMME FOR RADON DECAY PRODUCTS IN A RADON CHAMBER Tomasz Radoszewski PL9902252 1. Introduction EEDC is given by: Measurement of radon decay products in an air 2l8 204 3 EEDC = 0.106 x I ( Po) + 0.513 x I ( Pb) + 0.38 x sphere (in this case a radon chamber of 0.8 m I(2I4Bi) volume) to determine potential alpha energy concentra- 3 tion (PAEC) is usually done by deposition of the radon Where the concentration is given in Bq/m or in pCi/L. decay products on a filter paper and then by By tradition however, the total effect is usually given registering alpha activity with a semiconductor by a potential alpha energy concentration (PAEC). detector. The measuring process is based on the The relationship between these values is given by the assumption that a balance exists between radon and its relation: decay products in air, and that all the decay products PAEC = EEDC x 5.57 • 10~9 [J/Bq] (or 1287 MeV/pCi) are deposited and counted in the measuring arrange- PAEC is the basic unit for health effect caused by ment. In reality, these assumptions are not accomplished. radon decay products. Taking the real effect of the Firstly not all radon decay products stay in air, potential alpha energy on human system, the secondly not all decay products are deposited on the "unattached" and "attached" fraction should be given filter and consequently counted by the detector. There separately (in all cases where it is possible). It is are three factors that influence the measuring essential to give an equilibrium factor that is defined possibility of radon decay products in air: 1) humidity as the ratio of existing (measured) PAEC to the of air, 2) pollution of air (concentration and size of maximum PAEC at a radon concentration in radiation aerosols), 3) concentration of radon in air. equilibrium with radon daughters. It can be shown that The first factor influences the velocity of deposi- the equilibrium factor is given by: tion of decay products on the walls of a chamber that do react with the air particles as well as those that Fp = (0.106 Ai + 0.513 A2 + 0.381 A3)/Ao 218 214 form so called "unattached fraction". Apart of that, Where At, A2, A3, Ao - concentration of Po, Pb, humidity influences the size of aerosols that are 2!4Bi and 222Rn. At radiation equilibrium the created in air. The second factor is basically the most equilibrium factor Fp = 1. In real measuring conditions important one. The decay products react with aerosols the equilibrium factor varies in the range: 0.15-0.75. and form "attached fraction" which is absorbed on the The main reasons of that are: deposition (plate out) of air filter. The third factor has a not very clear influ- radon daughters on the surrounding walls and the fact ence on the measuring process. It causes an increase of that not all decay products are deposited on the air negative charge in air which, in turn, influences the filter and thus are not registered. decrease of the "attached fraction" formation and increases the velocity of deposition of "unattached 3. Programme of experiments fraction". 3.1. The purpose of experiment There are two main reasons to carry out the experi- 2. Potential alpha energy and equilibrium factor ments: determination of potential alpha energy con- A total effect of decay products can be expressed by centration (PAEC) and determination of equilibrium an equilibrium equivalent decay product concentration factor (Fp) in a radon chamber as a function of several (EEDC). Taking, as the basis, the energy of the factors such as: humidity, quantity and size of particles and the half life of radon decay products, the aerosols, radon concentration. 138 NUCLEONIC CONTROL SYSTEMS 3.2. Preparation of experiment measured as a function of aerosol concentration (using The experiments will be carried out in a radon laser aerosol spectrometer). The measurement should chamber of 0.8 m3 volume. The following equipment be carried out till the saturation effect is observed. is needed to fulfill the programme: Any higher humidity level during the experiment a) a radon source chamber with the arrangement to would be welcome. introduce radon to a radon chamber from the radon 3.5. Radon activity concentration experiments source chamber, Having any given humidity and aerosol concentration b) a Lucas cell with a proper electronic equipment for levels in the radon chamber radon activity in several radon concentration measurement, steps should be introduced into the chamber. PAEC c) a radiometer type RGR for PAEC measurement, (mainly) and aerosol concentration (additionally) d) a laser aerosol spectrometer with a high range of should be measured for all the steps. Radon concentra- aerosols concentration and aerosols diameter (0.1- tion should be measured by the Lucas cell. 7.5 urn), 3.6. Equilibrium equivalent (Fp) calibration e) barometer, hygrometer, thermometer, Having all the measurements done the values of f) arrangement to generate water vapor, arrangement equilibrium equivalent (Fp) should be calculated to to produce aerosols (burn out a cigarette), show its dependence from the main factors examined g) alpha radiation spectrometer. above. 5.3. Water vapor experiments References Experiments should be done for at least two radon 3 [I]. Gierdalski J., Bartak J., Urbanski P.: New generation of the concentration levels; low - about 10 Bq/dcm , and mining radiometers for determination of radon and its decay 3 high - more than 100 Bq/dcm . The PEAC and aerosol products in the air of underground mines, Nukleonika, 38, 4, concentration should be measured as a function of 27-32 (1993). humidity, starting from a normal room humidity level [2], Tien-Chi Chu, Ho-Ling Liu: Simulated equilibrium factor up to 100%. It would be interesting to repeat the studies in radon chamber, Appl. Radiat. Isot, 47, 5/6, 543-550 (1996). experiment for an increased level of aerosols, at least [3]. Ching-Tiang Chen, Chi-Chang Liu, Yu-Ming Lin: Measure- for a higher radon activity concentration. ment of equilibrium factor and unattached fraction of radon progeny in Kaohsiung, TAIWAN, Appl. Radiat. Isot., 49, 12, 3.4. Aerosol experiments 1613-1618(1998). Experiments should be done also for two radon [4]. Nazaroff W.W., Nero A.V.: Radon and its decay products in activity concentrations, as in p.3.3. PAEC should be indoor air. John Wiley & Sons 1988. RADIOMETRIC SCANNER FOR TITANIUM FOIL Piotr Urbanski, Ewa Kowalska Introduction than 0.52%. Since the main source of the measurement A titanium foil is often used as the material for exit error is statistics of the registered radiation, about windows in electron accelerators. Due to the inter- 37000 counts should be accumulated to get the root actions with electron beam structure of the foil can mean square error equal 1 um. change considerably during the exploitation of accel- Construction erator and some thinner areas on the foil surface can The basic principle and some sub-assemblies of an X- appear. A radiometric scanner was designed [1] for Y plotter were used for the mechanical design of the automatic determination of the thickness distribution instrument. The foil to be measured is fixed in a frame over the entire area of the measured foil sample. and can be moved in the gap between the source and Principle of operation detector. The width of the gap is about 1 mm. Elec- Thickness of the foil is measured using an X-ray tronic part of the instrument consists of analogue and absorption technique. Beam of the X-rays from a 100 digital blocks. The analogue block contains H.V. and MBq Cd-109 radioisotope source was collimated to L.V. power supplies, a charge sensitive preamplifier the diameter of 1.5 mm. An argon proportional counter and a discriminator. The high voltage can be con- was used for detection of the transmitted radiation. trolled from the keyboard within the range from 0 to A precise pulse amplitude discriminator allows to cut 1999 V with a 1 V step. The digital block contains a off pulses corresponding to the X-rays energy lower microprocessor assembly, counters, circuits for driving than 22.2 keV. Slope of the calibration curve at the step-motors, RAM, keyboard and display drivers. nominal thickness of 50 um was about 0.52%/l um. Performance This means that to obtain an error of 1 um the count Measurements can be performed on the foil of rate should be measured with a relative accuracy better maximal dimensions 400 x 150 mm with the steps NUCLEAR TECHNOLOGIES AND METHODS 139 ranging from 1 to 10 mm. The minimal acceptable dimensions of the foil are 40 x 40 mm. A measuring time at each point can be selected from 10 to 99 seconds. The results are stored in an internal memory and can be transmitted to a personal computer in the form of an ASCII file. It contains such information as date, time of start and end of the measurement, co- ordinates of the starting and ending points, counting time and the number of counts collected at each point. Thus, the collected results can be used for preparing a thickness map of the investigated foil sample. An 38 example of such a map for the titanium foil of dimen- sions 25 x 180 mm is presented in Fig.l. The distance between the contour lines is about 1 um, the measure- ment time 10 s and the step 4 mm. The map was prepared using a MATLAB software [2] and the data Lenght [mm] was smoothed using regression splines [3,4]. Conclusions The automatic scanner for testing titanium foil was designed and constructed. It allows imaging of the foils of nominal thickness from 20 to 50 um. The accuracy of thickness measurements is about 2 u.m at 50 urn and the spatial resolution is not worse than 2 mm. It can be also used for imaging thickness of the foils made from other materials, provided that their dimensions do not exceed 400 x 150 mm. References [I]. Urbariski P., Kowalska E., Strzalkowski I, Swistowski E.: Radiometryczny skaner folii tytanowej. Krajowe Sympozjum Technika JEtdrowa w Przemysle, Medycynie, Rolnictwie i Ochronie Srodowiska, Krakow, Poland, 16-18.09.1998, pp. 348-352. [2]. Using MATLAB Graphics. Ver.5. The MathWorks, December 1996. [3]. Urbanski P.: Aproksymacja za pomoca. wielomianowych regre- syjnych funkcji sklejanych. Instytut Chemii i Techniki Ja_dro- wej, Warszawa 1998. Raporty IChTJ. Seria B nr 10/96. [4]. Antoniak W., Urbanski P.: Wygladzanie widm promieniowania 20 X metodami regresyjnych funkcji sklejanych i szybkiej transfo- rmaty Fouriera. Instytut Chemii i Techniki Ja.drowej, Warszawa Fig.l. An example of thickness distribution on a titanium foil 1998. Raporty IChTJ. Seria B nr 9/96. (in Polish). measured by a scanner, (a) - 3d plot, (b) - contour plot. APPLICATION OF HEXAGONAL WELL DETECTOR FOR DETERMINATION OF MASS AND SPATIAL DISTRIBUTION OF NEUTRON RADIATION SOURCES INSIDE BULK SAMPLES Malgorzata Swiderska-Kowalczyk, Wojciech Starosta, Tadeusz Zoltowski : = CVI :O Thanks to financial support a neutron coincidence inputs operate for the 22 cm diameter volumes, and detector constructed in this Institute [ 1 ] was equipped 24 - for the 22-65 cm diameter volumes). 13 with: The correlator unit - connected with a PC - • six additional 3He tubes that increased the absolute registers time and place (i.e., the 3He counter number) and coincidence detection efficiency up to 65 cm of the pulse (neutron) appearance. Each channel diameter volumes (volume height is equal to consists of a 3He tube, a preamplifier, an amplifier, 50 cm); and a discriminator circuit. Inputs of the correlator are • a new correlator with 36 independent inputs (18 checked with frequency in the range from 0.5 to 32 us, 140 NUCLEONIC CONTROL SYSTEMS determined by the user. The pulse train obtained in discrete positions along the main perpendicular axis of such a way is then processed by means of the chosen the detector). For further data processing the two- correlation technique implemented in software. dimensional discrete Fourier transformation for all the The basic features of the device determined using matrices was performed (each matrix corresponds to a small 252Cf source (~0.05 j^Ci, with emission of 244 one given system of the plutonium sources, and is neutrons per second in the period of measurements) called as "count profile" of the system). Amplitudes are the following: - . and phases of the transformation coefficients for the • for 22 cm diameter volumes: particular count profile were treated as the input - absolute detection efficiency-10.9%, ; parameters for hierarchical clustering with the use of - coincidence counting efficiency - 4.0%, the statistical package STATISTICA. Results of such - mean die-away time - 38.3 \xs, a clustering can be presented graphically in the form • for 65 cm diameter volumes: of a dendrogram, as shown in Fig. 1. - absolute detection efficiency - 5.0%, Five clustering methods were considered, namely: - coincidence counting efficiency - 0.7%, single linkage, complete linkage, unweighted pair- - mean die-away time - 49.3 \xs. group average, weighted pair-group average, and the For coincidence measurements the above characte- Ward method. For each of the above methods the four ristics are fairly typical for this class of well counters. special cases of Minkowski metric measure (Euclidean The total plutonium mass contained in the distance and its square, Manhattan, and Chebychev) examined volume, determined as Pu effective mass, were applied. can be evaluated from the dependence (for non- Systems of neutron sources under consideration multiplying samples this dependence is expected to be were consisted of one, two or three sources. linear): coincidence counting rate vs. 240Pu effective Hierarchical clustering was carried out for the mass, performed for standard plutonium samples. following data sets: Assessment of the spatial distribution! of neutron » for 44 source systems taken as standard systems emitters inside the big volume was verified for the (S-type objects in Fig.l); 22 cm well diameter. The metod, similar to that • for 44 standard systems and 14 test systems proposed in [2], was applied. Various systems of, (X-type objects in Fig.l); every test system was roughly speaking, plutonium "point" sources as obtained from the particular standard systems by neutron emitters, were scanned by the detection head. changing the total mass and/or distances between Results of measurements were collected in the form of sources. two-dimensional (6 x 7) matrices (where number 6 The following regularities can be observed: 3 concerns six He counters sections, number 7 - seven 1. The main criterion of clustering was the total mass Diagram for 56 cases Complete linkage Euclidean distances 5000 4000 3000 2000 CD 1000 Fig. 1. Dendrogram for 44 standard systems (S-type objects) and for 14 test systems (X-type objects). NUCLEAR TECHNOLOGIES AND METHODS Kl of all sources in the system. In the case of every small (non-multiplying) samples containing plutom'um method and every distance measure objects form isotopes. Recently, the INCT took part in the inter- two groups: of small masses (the right cluster in laboratory Round-Robin Test organised by the Inter- Fig. 1, systems from AI to S24), and big masses national Technical Working Group under the auspices (the left cluster in Fig.l, objects from S28 to S21). of the Non-Proliferation Experts Group. The results 2. Within the groups of objects of the same mass the obtained with the use of the presented device seem to dominant role in the further division into sub- be satisfactory. clusters plays the angle coordinate, while perpen- The work was supported by the Foundation for Polish dicular distances between sources are of secondary Science (SUBIN'96 Programme, Contract No. 10/96) importance. and by the Polish State Committee for Scientific 3. In the majority of cases the test systems are recog- Research, Grant No. 8 T10B 008 13). nised correctly as more "similar" to their respective References standards than to whichever else in the set (in Fig.l [1]. Mtowski T., Starosta W., Swiderska-Kowalczyk M,: INCT pairs X1-S1,X5-S5, etc.). Annual Report 1994, p. 110. Up to now this coincidence detector was tested for [2], Mtowski T., Ksiaikiewicz B.: Raport IBJ, 152/XXII/78. MATHEMATICAL MODEL OF THE MOSSBAUER SPECTRUM IN THE TRANSMISSION GEOMETRY Wojciech Starosta PL9902255 Commonly used representation of the Mossbauer i-th line of absorber and source, respectively; tj - spectrum as a sum of spectrum lines of the shape effective thickness of the i-th line (tj = f; c ns d). decribed by the Lorentz profile has a limited Calculating the integral using the residual method application and is reasonable only in the case of a one can obtain: "thin absorber" and isolated spectrum lines. In the general case, especially in the case of overlapping lines, the proper spectrum pattern can be obtained by where the sum in brackets means the sum of residual calculation of the transmission integral. Numerical of the G(E) function given by the expression presented calculation of the transmission integral is a time- below at the points E = Ej + i/2T at the upper half- consuming process, even with the use of the newest plane: laboratory computers. For this reason an analytical G(E)= exp(a-as+b-bs)-l approximation of the transmission integral is proposed, enabling performing of calculations with the desired fE-E.--r. accuracy. Solution of the problem is based on the method of the complex argument function residual L >0tk i i> calculations. "Sr~ T~" " 7 Experimental Mossbauer spectrum for the S7Fe E-Ek—r isotope can be described by the following formula: a = —, bs = as* (complex conju- •E,-Ek-i(r,+ra) where TI - transmission integral equal to: gate of as). After expanding into Taylor series and application of Newton binomial formula, and after rejection of exp terms with zero contribution, function G can be represented in the following form: TI = -i dE . . ^^^(aj^bbj" G E =ab \ Y~ n=2k=l -k ' and where I , I14 - intensities of gamma radiation and Mossbauer r ~2ii i ' ak~ radiation (14.4 keV), respectively; Ts, Ta - half-widths E -E -i(r rj' E-Ek--r. s k s+ of source line and absorber, respectively; fr - recoilless fraction of Mossbauer source; Ej, Es - energy of the 142 NUCLEONIC CONTROL SYSTEMS Depending on term number of the sum considered imperfect collimation of the incident beam and the real in residual calculations one obtains approximations of energetic distribution of source emission. different degree of accuracy. In the case of taking Application of this method increases the accuracy terms with at least one of powers is less or equal to 2, of the obtained information concerning the physical and for a single spectrum line, an accuracy of the nature of the absorber. approximation better than 1% is obtained for the Fig.l presents the Mossbauer spectrum of the effective absorber thickness t < 3.6. mineral substances in coal and the results of spectrum Precise form of the function describing the treatment with the use of the presented method. spectrum shape enables the determination of charac- i 1 teristic parameters of a radiation source, basing on the spectrum of the absorber of known parameters (in the studies foils of natural iron ARMCO of thickness of 6 um were used). 760000 Different models describing energetic distribution of source emission were taken into account. The first one assumes existing of the single broadened line. Instead, the second model assumes a homogeneous distribution of the Mossbauer isotope in the source and presence of the resonance - as well as non- resonance - absorptions modifying energy distribution of the source emission. A computer program calculating the MSssbauer spectra, based on the described approximation, was prepared. In calculations the influeunce of divergence of radiation emitted from the source on the spectrum shape was also considered. The obtained analytical approximation for the 710 000 transmission integral made it possible elaboration of 0 40 80 120 160 200 240 Channel Number the new mathematical model of the MQssbauer Fig.l. The Mossbauer spectrum of coal sample decomposed to four spectrum. Such a model introduces corrections due to doublets. APPLICATION OF PARTICLE TRACK MEMBRANES FOR DETERMINATION OF MICROIMPURITIES DISTRIBUTION IN ENVIRONMENTAL WATER SAMPLES CO Marek Buczkowski, Danuta Wawszczak, Wojciech Starosta, Bozena Sartowska JO ICO Particle track membranes (PTM) manufactured by supplied to the set-up by a syringe. Introductory means of heavy ions beam accelerated in a cyclotron cleaning of water samples was performed by a metallic represent a product of advanced technology [1]. Such grid at a 50 um mesh value. membranes have been practically applied in works Using the above set-up measurements of four carried out with the participation of the INCT. These samples of environmental water from the Institute area examples are: disposable syringe filters, multilayer after rain and snow precipitation were carried out. For medical dressings and a dynamic filtration device for comparison a sample of tap water was taken. pH biotechnological solutions [2]. Some attempts at the values of the samples were determinated and then evaluation of microfiltration effectiveness of water microfiltration through individual stages of the set-up and biomedical solutions samples have been under- was carried out up to a high level of flow resistance. taken [3]. After drying of the membrane discs, an increase of In the work, introductory results of PTM applica- impurities was determined by the weighing method. tion for the determination of microimpurities distribu- Some results are given in Table 1. It is seen that most tion in environmental water samples are presented. To of the impurities in the water sample came from snow this end a cascade filtration set-up with PTM at de- and were in the range: 0.2-0.45 um and 0.45-1.2 um. creasing pore size: 2.3; 1.2; 0.45 and 0.2 urn have In case of rain and tap water the quantity of impurities been applied. PTM discs were mounted in plastic was one or two orders of magnitude lower than in the holders clamped by metal rings. That tested water was previous case. For tap water most impurities were in NUCLEAR TECHNOLOGIES AND METHODS 143 Table I. Distribution of impurities on different PTMs after microfiltration in case of tap and environmental water samples Tap water Water from rainfall Water from snowfall No. Pore size Amount Sediment Impurities Amount Sediment impurities Amount Sediment Impurities of PTM of filtrated mass on concentra- of filtrated mass on concentra- of filtrated mass on concentra- [urn] water [ml] PTM tion [mg/1] water [ml] PTM tion [mg/1] water [ml] PTM tion [mg/1] surface after surface after surface after filtrat. [mg] filtrat. fmgl filtrat. [mg]_ 1. 2.3 969 0.3 0.31 260 0.1 0.38 103 0.2 1.94 2. 1.2 720 0.1 0.14 212 - - 80 0.1 1.25 3. 0.45 147 0.1 0.68 142 0.2 1.4 17 0.2 11.76 4. 0.2 100 0.1 1.00 88 - - 10 0.2 20.00 I:-. Fig.l. Impurities on the PTM surface (pore size - 2.3 jim) after Fig.2. Impurities on ihe PTM surface (pore size - 1.2 fim) after filtration of rainfall water. filtration of rainfall water. the range 0.2-1.2 urn. Observations of the membrane for the monitoring of environmental water pollution as surfaces after microfiltration by the scanning electron well as for the evaluation of tap water quality. microscopy method was done. Some results are shown References in Figs. 1 and 2. [1]. Proc. of 3rd Conference on Particle Track Membranes and Their Particle track membranes because of their unique Applications, Jachranka, Poland, 26-29 October, 1993. Eds. W. features such as: precisely determinable pore size, Starosta., M. Buczkowski. INCT, Warszawa 1994, 123 p. smooth surface, chemical stability, are a proper tool [2]. Buczkowski M., Starosta W., Wawszczak D., Zoltowski T.; Application of particle track track membranes - Polish for the determination of microimpurities distribution experiences. In: Proc. of VI International School - Seminar on in water samples. In the Department of Structural Heavy Ion Physics, Dubna, Russia, 22-27 September, 1997. Research of the Institute current research enables the World Scientific Publishing Co. 1998, pp. 761-769. determination of changes in element distribution in [3], Buczkowski M, Starosta W., Wawszczak D., ZoJtowski T.: water samples after individual stages of micro- Membrany trekowe oraz ich zastosowanie. II Ogolnopolska Konferencja Naukowa: Membrany i Procesy Membranowe w filtration, using the total-reflection X-ray fluorescence Ochronie Srodowiska, Ustroii-Jaszowiec, 23-25.10.1997, pp. 15- analysis. The described investigations can be useful 23 (in Polish). DETERMINATION OF CARBON CONTENT IN COAL AND ASH BY XRF g| Jozef Parus, Joachim Kierzek, Bozena Maiozewska-Bucko == = C\| The layered synthetic microstructures or the synthetic possible [3]. For efficient analysis of these elements : O multilayer crystals (MLC) became commercially a number of factors plays a very important role, e.g., available in the early eighties [1,2]. Their introduction the X-ray tube geometry, target, current and window to X-ray spectrometers has made possible the determi- thickness, the reflectivity and resolution of the MLC, nation of very light elements with atomic numbers in the X-ray collimation and the counter window the range from 5 (boron) to 9 (fluorine). In the last few thickness and material. The RhL X-rays are very well years the analysis of beryllium (Z=4) became also suited to excite these elements. The element of this 144 NUCLEONIC CONTROL SYSTEMS group determined most often is carbon in steels [4,5]. scattered radiation intensity as a second variable to the We have not found any attempts to determine the carbon content in coals. CKa (kcps) The measurements were performed using a Phillips sequential spectrometer equipped with a Rh side window, X-ray tube operated at 40 kV and 70 mA. A PX4 MLC with 12.2 nm 2d spacing was used as an analyzing crystal. A 2Q angle for CKa X-rays was 42.8° and the background was measured on both sides at ±5.0°. Additionally, RhLa scattered radiation was also measured. The measurement time was 50 sec. for all measurement channels. A flow proportional counter 0 0 10.S ZJ.O M.5 CO 52.5 63.0 735 M.O M.5 105.0 with a 1 um polypropylene window and a coarse Fig.2. CKa line intensity vs. carbon content for coal samples. collimator were used. 6.000 CKa The samples for measurement were prepared as (kcps) pellets, in majority of cases in duplicate, on a boric 4.500- acid support. The powdered samples of coal and ash, in which the carbon content was determined by com- bustion, were additionally ground during 5 minutes in a Retsch mixer mill using a 25 ml stainless steel cup and balls. One gram of a very fine powder so obtained was pressed as a uniform disk of 28 mm diameter onto Carbon content, % 6 g of boric acid powder in a 40 mm diameter, 0.000 vacuumed die. A number of coal samples and all ash O.O 10.5 Z1.0 31.5 *Z.O SZ.5 63.0 73.5 M.O 9».S ID5.0 samples were ground with the addition of 20% of Fig.3. CKa line intensity vs. carbon content for coal samples diluted with 20% of boric acid. boric acid. regression analysis does not improve the CV value. As can be seen in Fig.l, the CKa partially overlaps Fig.4 shows a relationship for the carbon content in with the second order OKa line (2Q, 42.8 vs. 44.7°). ash. In this case a multiple regression using CKa and kcps scattered RhLa as a second variable decreased significantly the value of CV from 22.6 to 15%. The presented results clearly show that XRF can be an alternative method for rapid determination of the carbon concentration in coals and ashes. The final assessment of the precision and accuracy will require a set of the reference materials with well-defined confidence limits for the carbon concentration. .2000 .0000 •-.-n-.^.. o'oo 10.00 20:00 3o'.oo 4o'.oo s'o'ioo "eioibo "70T06 so.bo 20, degrees Fig.l. X-ray spectrum of ash sample containing 9.3% of carbon. In the case of coal this interference is negligible because of a low oxygen content, but for ashes where oxygen content is rather high it can introduce some bias. Fig.2 shows the relationship between CKa -0.5O O.6S I.IHJ Z.95 4.10 5.25 6.40 7.95 B. 70 3.BS 11.00 intensity and the carbon content determined by Fig.4. CKa and RhLa intensities in multiple regression vs. carbon combustion for 26 measurements. Fig.3 shows the content in ash samples diluted with 20% of boric acid. same relationship for coal with 20%, by weight, References addition of boric acid for 13 measurements. It should [!]. Nicolosi J.A., Groven J.P., Merlo D.: Advan. X-Ray Anal., 30, be noted that the point corresponding to pure graphite 183 (1987). (100% of carbon) fits very well to a straight line. The [2]. Anzelmo J.A., Boyer B.W.: Advan. X-Ray Ana!., 30, 193 coefficients of variation (CV) calculated from the (1987). linear regression analysis of Fig.2 and Fig.3 have the [3]. Toda K., Kohno H., Aral T., Araki Y., Hamill G.: Advan. X- values of 2.35 and 1.56 relative per cent, respectively. Ray Anal., 37,629 (1994). The CV value for samples diluted with boric acid is [4]. Wariwoda L.,, Mantler M., Weber F.: Advan. X-Ray Anal., 36, 35 (1993). significantly lower. The introduction of the RhLa [5]. Mantler M.: Advan. X-Ray Anal., 36,27 (1993). THE INCT PUBLICATIONS IN 1998 145 THE INCT PUBLICATIONS IN 1998 1. Ambroż H.B., Kemp T.J., Kornacka E.M., Kraszewski M., Przybytniak G.K. Studies of the direct and indirect effects in the y-radiolysis of DNA. 31st Annual International Meeting: "ESR Spectroscopy of Paramagnetic Species in Inorganic and Bio- Inorganic Systems", Manchester, England, 29.03. - 2.04.1998, p. 1. 2. Ambroż H.B., Kemp T.J., Kornacka E., Przybytniak G. SSB and DSB generated in plasma DNA in presence of the transition metal ions upon gamma irradiation. 4th Symposium Free Radicals in Biology and Medicine. Abstracts, Łódź, Poland, 8-10.06.1998, p. 194. 3. Ambroż H.B., Kemp T.J., Kornacka E.M., Przybytniak G.K. The role of copper and iron ions in the y-radiolysis of DNA. 31st Annual International Meeting: "ESR Spectroscopy of Paramagnetic Species in Inorganic and Bio- Inorganic Systems", Manchester, England, 29.03.-2.04.1998, p. 1. 4. Ambroż H.B., Kemp T.J., Kornacka E.M., Przybytniak G.K. The role of copper and iron ions in the y-radiolysis of DNA. Part I. EPR studies at cryogenic temperatures. Radiation Physics and Chemistry, 53, 491-499 (1998). 5. Ambroż H.B., Kornacka E.M., Przybytniak G.K. Rola jonów Cu(II) i Fe(III) w indukowanych radiacyjnie pęknięciach pasm DNA (The role of Cu(II) and Fe(III) ions in radiation-induced DNA lesions). XI Zjazd PTBR, Siedlce, Poland, 15-17.04.1998, p. 68. 6. Ambroż H.B., Przybytniak G.K. Paramagnetyczne produkty niskotemperaturowej radiolizy nukleotydów DCMP, TMP i DGMP (Paramagnetic products of low-temperature radiolysis of nucleotides DCMP, TMP and DGMP). XI Zjazd PTBR, Siedlce, Poland, 15-17.04.1998, p. 32 7. Baran S., Hofmann M., Leciejewicz J.s Penc B., Starawicz P., Stusser N., Szytuta A., Zygmunt A, Magnetic phase diagram, of the HoRh2-xRuxSi2 solid solution. Journal of Physics: Condensed Matter, 10, 6367-6379 (1998). 8. Baran S., Hofmann M., Leciejewicz J., Penc B., Śląski M„ Szytuła A. Magnetic order in RAgGe (R=Gd-Er) intermetallic compounds. Journal of Alloys and Compounds, 281, 92-98 (1998). 9. Baran S., Hofmann M., Leciejewicz J., Śląski M., Szytuta A. Antiferromagnetic ordering in PrCuSn and NdCuSn. Journal of Physics: Condensed Matter, 10,2107-2114 (1998). 10. Baran S., Leciejewicz J., Śląski M., Hofmann P., Szytuła A. Magnetic properties of RAuSn compounds. Journal of Alloys and Compounds, 275-277, 541-544 (1998). 11. Bartak J., Pieńkos J.P. Urządzenie do ciągłego pomiaru radonu w kopalniach (Measuring probe for radon concentration monitoring). Krajowe Sympozjum Technika Jądrowa w Przemyśle, Medycynie, Rolnictwie i Ochronie Środowiska. Referaty, Kraków, Poland, 16-18.09.1998, pp. 344-347. 146 THE INCT PUBLICATIONS IN 1998 12. BilewiczA. Wpływ efektu relatywistycznego na liczbę koordynacyjną rutherfordu (The influence of relativistic effect on coordination number of rutherfordium). Krajowa Konferencja Radiochemii i Chemii Jądrowej "W Stulecie Odkrycia Polonu i Radu". Streszczenia, Kazimierz Dolny, Poland, 18-21.05.1998, p. 15 13. Biłewicz A., Narbutt J., Satyanarayana J. Sorpcja radionuklidów długożyciowych z modelowych odpadów promieniotwórczych na oc-krystalicznym kwasie poliantymonowym (The sorption of long-lived radionuclides from modelling radioactive wastes on a-crystalline polyantimonic acid). Krajowa Konferencja Radiochemii i Chemii Jądrowej "W Stulecie Odkrycia Polonu i Radu". Streszczenia, Kazimierz Dolny, Poland, 18-21.05.1998, p. 69. 14. Bobrowski K., Hug G.L., Marciniak B., Schoneich C, Wiśniowski P. Intramolecular hydrogen transfer during oxidation of (3-hydroxysulfides and a-(methyl)thio-acatamide. Pulse radiolysis and flash photolysis studies. Proceedings of Trombay Symposium on Radiation and Photochemistry. TRSP-98. Part I. Abstracts of the invited talks, Trombay, Mumbai, India, 14-19,01.1998, p. 13. 15. Bobrowski K., Pogocki D., Schoneich Cfa. Oxidation of (carboxyalkyl)thiopropionic acid derivatives by hydroxyl radicals. Mechanisms and kinetics of competitive inter- and intramolecular formation of a' and o*-type sulfuranyl radicals. Journal of Physical Chemistry, 102, 10512-105521 (1998). 16. Bobrowski K., Poznański J., Holcman J., Wierzchowski K.L. Long-range electron transfer between proline-bridged aromatic amino acids. In: Photochemistry and radiation chemistry. Complementary methods for the study of electron transfer. Eds. J.F. Wishart, D.G. Nocera. Advances in Chemistry Series no. 254. American Chemical Society, Washington 1998, pp. 131-143. 17. Bobrowski K., Wiśniowski P., Pogocki D. Wewnątrzcząsteczkowe przeniesienie wodoru podczas indukowanego rodnikami wodorotlenowymi utleniania podstawionych tioeterów (Intramolecular hydrogen transfer during hydroxyl radical induced oxidation of substituted tioethers). XLI Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i Techników Przemysłu Chemicznego. Streszczenia, Wrocław, Poland, 14-18.09.1998 r., p. 42. 18. Borkowski M., Lis S., Siekierski S. Complexation of f-electron (3+) ions with pseudohalide ligands. Journal of Alloys and Compounds, 275-277, 754-758 (1998). 19. Boużyk E., Kraszewski M. Różnica w uszkodzeniach początkowych DNA wywołanych przez jony Cr(VI) w dwóch podliniach komórek L5178Y (The difference in DNA strand breakage induced by ions Cr(VI) in two L5178Y sublines). XI Zjazd PTBR. Streszczenia, Siedlce, Poland, 15-17.04.1998, p. 105. 20. Brenscheidt R., Piekoszewski J., Wieser E., Langner J., Grotzschel R., Reuther H. Modification of silicon nitride ceramics with high intensity pulsed ion beams. Materials Science and Engineering, A253, 86-93 (1998). 21. Buczkowski M., Starosta W., Wawszczak D., Żółtowski T. Application of particle track membranes - Polish experiences. VI International School-Seminar "Heavy Ion Physics". Proceedings, Dubna, Russia, 22-27.09.1997. JINR, Dubna 1998, pp. 761-769. THE INCT PUBLICATIONS IN 1998 _1I 22. Cebulska-Wasilewska A., Niedźwiedź W., Nowak D., Kasper E., Wierzewska A., Wójcik A., Bouiyk E. DNA and chromosomal damage estimate in blood od people suspected of exposure to radiation. Nukleonika, 43, 1, 65-72 (1998). 23. Chmielewski A.G. Electron beams for power plant flue gas treatment. In: Radiation technology for conservation of the environment. Proceedings, Zakopane, Poland, 8- 12.09.1997. IAEA-TECDOC-1023. IAEA, Vienna 1998, pp. 3-29. 24. Chmielewski A.G. Radiation induced sulphur dioxide removal. Workshop on Reactive Intermediates in Sulfur Chemistry. Dedicated to Professor K.-D. Asmus on his 60th birthday. Book of abstracts, Poznań, Poland, 23-26.08.1998, L-3. 25. Chmielewski A.G. Zastosowanie technologii wykorzystujących wiązkę elektronów w ochronie środowiska (Application of technologies using electron beam in environment protection). XLI Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i Techników , Przemysłu Chemicznego. Mikrosympozjum 2-5. Sekcja 1-16. Streszczenia, Wrocław, Poland, 14-18.09. 1998, p. 181. 26. Chmielewski A,G. Zintegrowany system do jednoczesnego usuwania tlenków siarki i azotu z gazów elektrownianych (Integrated system for simultaneous removal of SO2 and NOX from flue gases). Sympozjum "Doświadczenia Polskiej Energetyki w Modernizacji Bloków Opalanych Węglem". Wystąpie- nia, Referaty, Ankara, Turkey, 20-21.10.1998, [10 p.] 27. Chmielewski A.G., Harasimowicz M., Zakrzewska-Trznadel G. Concentration of liquid low level radioactive wastes by membrane distillation. 2nd International Yugoslav Nuclear Society Conference. Book of Abstracts, Belgrade, Yugoslavia, 28.09.- 1.10.1998, p. 65. 28. Chmielewski A.G., Harasimowicz M., Zakrzewska-Trznadel G. Concentration of radioactive components in liquid low-level radioactive wastes by membrane distillation. Preprints of International Conference on Membrane Science and Technology. Book of Abstracts, Beijing, China, 9-13.06,1998, pp. 119-120. 29. Chmielewski A.G., Harasimowicz M., Zakrzewska-Trznadel G. Membrane technologies for liquid radioactive waste treatment. 13th Radiochemical Conference. Book of Abstracts, Marianske Laznie - Jachymov, Czech Republic, 19- 24.04.1998, p. 380. 30. Chmielewski A.G., Harasimowicz M., Zakrzewska-Trznadel G. Zastosowanie ultrafiltracji i hiperfiltracji w procesach zatężania ciekłych odpadów promieniotwórczych (Application of ultrafiltration and hyperfiltration processes for concentration of liquid radioactive wastes). Krajowa Konferencja Radiochemii i Chemii Jądrowej "W Stulecie Odkrycia Polonu i Radu". Streszczenia, Kazimierz Dolny, Poland, 18-21.05.1998, p. 65. 31. Chmielewski A.G., Harasimowicz M., Zakrzewska-Trznadel G. Zatężanie roztworów radioaktywnych metodami membranowymi (Concentration of radioactive solutions by membrane methods). XLI Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i Techników Przemysłu Chemicznego. Mikrosympozjum 2-5. Sekcja 1-16. Streszczenia, Wrocław, Poland, 14-18.09. 1998, p. 324. 32. Chmielewski A.G., Harasimowicz M., Zakrzewska-Trznadel G. Zatężanie ścieków niskoaktywnych w procesie destylacji membranowej (Concentration of liquid low-level radioactive wastes in membrane distillation process). 148 THE INCT PUBLICATIONS IN 1998 Krajowa Konferencja Radiochemii i Chemii Jądrowej "W Stulecie Odkrycia Polonu i Radu". Streszczenia, Kazimierz Dolny, Poland, 18-21,05.1998, p. 64. 33. Chmielewski A.G., Wer E. Demonstracyjna przemysłowa instalacja jednoczesnego usuwania SO2 i NOX z gazów odlotowych przy użyciu wiązki elektronów w Elektrowni Pomorzany (Demonstration industrial installation for simultaneous removal of SO2 and NOX from flue gases using electron beam in Power Station Plant Pomorzany). Krajowe Sympozjum Technika Jądrowa w Przemyśle, Medycynie, Rolnictwie i Ochronie Środowiska. Referaty, Kraków, Poland, 16-18.09.1998, pp. 45-51. 34. Chmielewski A.G., IHer E. Demonstracyjna przemysłowa instalacja jednoczesnego usuwania SO2 i NOX z gazów odlotowych przy użyciu wiązki elektronów w elektrowni Pomorzany (Demonstration industrial installation for simultaneous removal of SO2 and NOX from flue gases using electron beam in Power Station Plant Pomorzany). Postępy Techniki Jądrowej, 41, 3, 37-41 (1998). 35. Chmielewski A.G., Iller E., Frank N. Technical and economic aspects of electron beam installations for treatment of flue gases from power plants. In: Radiation technology for conservation of the environment. Proceedings, Zakopane, Poland, 8- 12.09.1997. IAEA-TECDOC-1023. IAEA, Vienna 1998, pp. 133-143. 36. Chmielewski A.G., Iller E., Licki J., Ty miński B., Sowiński M., Pawlowski K., Kostrzewski R., Mazurek J. Zintegrowany system kontrolno-pomiarowy dla instalacji oczyszczania gazów odlotowych z SO2 i NOX w Elektrowni Pomorzany (The control-monitoring system of e-b installation for flue gas purification from SO2 and NOX of EPS Pomorzany). 6th Integrated Approach to Pollution Prevention and to Avoidance, Minimalization and Disposal of Waste, Szczecin, Poland, 5-7.05.1998, pp.269-276. 37. Chmielewski A.G., Iller E., Licki J., Tymiński B., Sowiński M., Pawłowski K., Kostrzewski R., Mazurek J. Zintegrowany system kontrolno-pomiarowy dla instalacji oczyszczania gazów odlotowych z SO2 i NOX w Elektrowni Pomorzany (The control-monitoring system of e-b installation for flue gas purification from SO2 andNOx of EPS Pomorzany). Zeszyty Naukowe Politechniki Łódzkiej, Inżynieria Chemiczna i Procesowa, 23,1-11 (1998). 38. Chmielewski A.G., IHer E., Tymiński B. Możliwości rolniczego zastosowania produktu oczyszczania spalin przy użyciu technologii wykorzystującej wiązkę elektronów (Agriculture application of by-product from electron beam process of flue gas purification). II International Scientific Conference "Air Protection in Theory & Applications". Proceedings, Szczyrk, Poland, 2-4.06.1998, pp. 377-378. 39. Chmielewski A.G., Iller E., Tymiński B. Technical and economical aspects of electron beam installations for treatment of flue gases from power plant. The 1998 European Workshop on Water and Air Treatment by Advanced Oxidation Technologies: Innovative and Commercial Applications. Abstracts, Lausanne, Switzerland, 11-14.10.1998, p. 15. 40. Chmielewski A.G., Owczarczyk A., Palige J. Radiotracer investigations of industrial waste water equailizer-clarifiers. Nukleonika, 43, 2,185-194 (1998). 41. Chmielewski A.G., Tymiński B. Badania procesu radiacyjnego usuwania zanieczyszczeń z gazów spalinowych w skali pilotowej (Investigation of electron beam process of flue gas purification in pilot plant scale). THE INCT PUBLICATIONS IN 1998 149_ Krajowe Sympozjum Technika Jądrowa w Przemyśle, Medycynie, Rolnictwie i Ochronie Środowiska. Referaty, Kraków, Poland, 16-18.09.1998, pp. 39-44. 42. Chmiełewski A.G., Tymiński B., Dobrowolski A., Licki J. Wyznaczanie modeli empirycznych efektywności usuwania NOX i SO2 dla dwustopniowego systemu napromieniania spalin w oparciu o wyniki uzyskane w pilotowej stacji w EC Kawęczyn (Empirical models of NOX and SO2 removal for two stage irradiation of flue gas based on results of experiments in pilot plant scale in EPS Kawęczyn). Krajowe Sympozjum Technika Jądrowa w Przemyśle, Medycynie, Rolnictwie i Ochronie Środowiska. Referaty, Kraków, Poland, 16-18.09.1998, pp. 52-57. 43. Chmiełewski A.G., Tymióski B., Dobrowolski A., Licki J., Sato S., Tokunaga O., Machi S. Influence of dose distribution and flow pattern between irradiation stages on removal of NOX. In: Radiation technology for conservation of the environment. Proceedings, Zakopane, Poland, 8-12.09. 1997. IAEA-TECDOC-I023. IAEA, Vienna 1998, pp. 145-156. 44. Chmiełewski A.G., Tymiński B., Dobrowolski A., Sato S., Tokunaga O., Machi S. Influence of gas flow patterns on NOX removal efficiency. Radiation Physics and Chemistry, 52, 1-6, 339-343 (1998). 45. Chmiełewski A.G., Tymiński B., Mer E., Zimek Z., Licki J. Electron-beam flue-gas treatment process upscaling. In: Environmental application of ionizing radiation. Eds. WJ. Cooper, R.D. Curry, K.E. O'Shea. John Wiley & Sons, New York 1998, pp. 197-216. 46. Chmiełewski A.G., Tymiński B., Zakrzewska-Trznadel G,, Tokunaga O., Machi S. Collection and application of by-product formed in e-beam flue gas treatment process. In: Radiation technology for conservation of the environment. Proceedings, Zakopane, Poland, 8-12.09. 1997. IAEA-TECDOC-1023. IAEA, Vienna 1998, pp. 31-41. 47. Chmiełewski A.G., Zakrzewska-Trznadel, G., Harasimowkz M., Tymiński B. Zastosowanie procesów membranowych do zatężania ciekłych odpadów promieniotwórczych (Application of membrane processes for concentration of liquid radioactive wastes). Postępy Techniki Jądrowej, 41,4,42-52 (1998). 48. Chwastowska J., Polkowska-Motrenko H., Kulisa K., Dybczyński R. Analiza produktu z pilotowej stacji usuwania SO2 i NOX z gazów odlotowych w EC Kawęczyn (Analysis of product from pilot plant of removing SO2 and NOX from flue gases in EPS Kawęczyn). XLI Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i Techników Przemysłu Chemicznego. Mikrosympozjum 2-5. Sekcja 1-16. Streszczenia, Wrocław, Poland, 14-18.09. 1998 r., p. 191. 49. Chwastowska J., Skwara W., Sterlińska E., Dudek J., Pszonicki L. Determination of inorganic and alkylmercury in natural waters using chelating sorbent and cold vapour AAS. Chemia Analityczna, 43, 6, 995-1002 (1998). 50. Ciesielski B., Stuglik Z., Wielopolski L., Zvara I. The effect of high let radiation on the dynamics of microwave power saturation of EPR signal in alaninę. International Conference on Biodosimetry and 5th International Symposium on ESR Dosimetry and Applications. Book of Abstracts (GO-I), Moscow/Obninsk Russia, 22-26.06.1998, p. 147. 51. Ciesielski B., Stuglik Z., Wiełopołski L., Zvara I. The effect of high-linear energy transfer ions on the electron paramagnetic resonance signal induced in alaninę. Radiation Research, 150,469-474 (1998). 150 THE INCT PUBLICATIONS IN 1998 52. Danko B., Dybczyński R. Dokładna metoda oznaczania śladowych zawartości uranu w materiałach biologicznych (Accurate method for the determination of trace amounts of uranium in biological materials). Nowoczesne Metody Przygotowania Próbek i Oznaczania Śladowych Ilości Pierwiastków. Materiały VII Poznańskiego Konwersatorium Analitycznego, Poznań, Poland, 16-17.04.1998, p. 28. 53. Danko B., Dybczyński R. Uniwersalna metoda oznaczania śladowych zawartości molibdenu w materiałach biologicznych za pomocą RNAA (The universal method for the determination of trace amounts of molybdenum in biological materials by RNAA). Krajowa Konferencja Radiochemii i Chemii Jądrowej "W Stulecie Odkrycia Polonu i Radu". Streszczenia, Kazimierz Dolny, Poland, 18-21.05.1998, p. 80. 54. Danko B., Połkowska-Motrenko H., Dybczyński R. Wpływ sposobu mineralizacji próbki na wyniki oznaczania kobaltu w materiałach roślinnych metodą radiochemicznej neutronowej analizy aktywacyjnej (The influence of mineralization on the results of the detennination of cobalt in plant materials by radiochemical neutron activation analysis). XLI Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i Techników Przemysłu Chemicznego. Mikrosympozjum 2-5. Sekcja 1-16. Streszczenia, Wrocław, Poland, 14-18.09. 1998, p. 253. 55. Dąbek J., Dźwigalski Z. Projektowanie wyrzutni do liniowego akceleratora elektronów (Designing of electron gun to linear electron accelerator). Kongres Polskiego Towarzystwa Próżniowego. Książka streszczeń, Kraków, Poland, 25-30.05.1998, p. P.I.9. 56. Dąbek J., Dźwigalski Z. Projektowanie wyrzutni do liniowego akceleratora elektronów (Designing of electron gun to linear electron accelerator). In: Materiały I Kongresu Polskiego Towarzystwa Próżniowego (w setną rocznicę urodzin Prof. Janusza Groszkowskiego), Kraków, Poland, 25-27 maja 1998. Wydaw. Uniwersytetu Jagiellońskiego, Kraków 1998, pp. 120-125. 57. Degueldre C, Fuks L., Schenker E. In-line measurement of the oxide layer build-up on Zircaloy under boiling water reactor (BWR) conditions using diffuse reflection spectroscopy. Measurement Science and Technology, 9, 809-815 (1998). 58. Degueldre C, Fuks L., Schenker E. Pre-oxidation of stainless steel: a study by diffuse reflection spectroscopy. Applied Surface Science, 134,254-262 (1998). 59. Dembiński W. Rynek uranu oraz produkcji i przerobu paliw reaktorowych (The market of uranium, nuclear fuel production and reprocessing). Postępy Techniki Jądrowej, 41, 1, 22-28 (1998). 60. Dembiński W., Janiszewski Z., Fiedler R. + 2 Fractionation of europium isotopes in extraction systems: Eu(III), HDEHP/Eu(III), H (Cl\ NO3", SO "4). Ligand isotope effect. Journal of Radioanalytical and Nuclear Chemistry, 228, 1-2, 89-93 (1998). 61. Dembiński W., Poniński M., Fiedler R. Efekt "even-odd" w separacji izotopów metodami chemicznymi (Effect "even-odd" in separation of isotopes by chemical methods). Krajowa Konferencja Radiochemii i Chemii Jądrowej "W Stulecie Odkrycia Polonu i Radu". Streszczenia, Kazimierz Dolny, Poland, 18-21.05.1998, p. 33. THE INCT PUBLICATIONS IN 1998 1S1 62. Dembiński W., Poniński M., Fiedler R. Preliminary results of the studies on fractionation of ytterbium isotopes in Yb(III)-acetate/Yb-amalgam system. Separation Science and Technology, 33, 11, 1693-1701 (1998). 63. Dembiński W., Poniński M., Fiedler R. Rozdzielanie izotopów iterbu metodą amałgamowania (Separation of iterbium isotopes using amalgamation method). Krajowa Konferencja Radiochemii i Chemii Jądrowej "W Stulecie Odkrycia Polonu i Radu". Streszczenia, Kazimierz Dolny, Poland, 18-21.05.1998, p. 40. 64. Deptuta A., Lada W., Olczak T,, Croce F., Ronci F., Cianria A., Giorgi L., Brignocchi A,, Bartolomeo di A. Synthesis and preliminary electrochemical characterization of LiNio.5Coo.5O2 powders obtained by the complex sol-gel process (CSGP). Materials Research Society Symposium Proceedings: Materials for Electrochemical Energy Storage and Conversion II-Batteries, Capacitors and Fuel Cells, 496, 347-352 (1998). 65. Deptuła A., Lada W., Olczak T., Sartowska B., Ciancia A., Giorgi L., Bartolomeo di A. Preparation of P1/WO3 powders and thin coatings on carbon black and metal supports by the complex sol- gel process (CSGP). Materials Research Society Symposium Proceedings: Materials for Electrochemical Energy Storage and Conversion II-Batteries, Capacitors and Fuel Cells, 496,237-242 (1998). 66. Deptuła A., Lada W., Olczak T., Sartowska B., Le Geros R.Z., LeGeros J.P. Complex sol-gel process (CSGP) preparation of calcium phosphate biomaterials (powders, monoliths, fibers). Bioceramics, 11, 743-746 (1998). 67. Drzewicz P., Trojanowicz M., Głuszewski W., Panta P. Zastosowanie promieniowania y do rozkładu 2,4-dichlorofenolu dla potrzeb ochrony środowiska (The use of y-radiation for degradation of 2,4-dichlorophenol as a contribution to environment protection). Krajowe Sympozjum Technika Jądrowa w Przemyśle, Medycynie. Rolnictwie i Ochronie Środowiska. Referaty, Kraków, Poland, 16-18.09.1998, pp. 148-154. 68. Dudek J., Pszonicki L. Ocena działania różnych modyfikatorów przy oznaczaniu arsenu za pomocą ASA z atomizacją elektroter- miczną (Behaviour of various modifiers of arsenic during atomization of arsenic in the graphite furnace atomic absorption spectrometry). Nowoczesne Metody Przygotowania Próbek i Oznaczania Śladowych Ilości Pierwiastków. Materiały VII Poznańskiego Konwersatorium Analitycznego, Poznań, Poland, 16-17.04.1998, p. 24. 69. Dybczyński R. A general approach to the construction of "very accurate" or "definitive" methods by radiochemical NAA and the role of these methods in quality assurance. 13th Radiochemical Conference. Book of Abstracts. Marianske Laznie - Jachymov, Czech Republic, 19- 24.04.1998, p. 26. 70. Dybczyński R. Idea "definitywnych" i "bardzo dokładnych" metod oznaczania pierwiastków śladowych za pomocą radiochemicznego wariantu NAA i znaczenie tych metod dla zapewnienia jakości wyników analitycznych (The idea of "definitive" and "very accurate" methods for the determination of trace elements by radiochemical NAA and significance of these methods for quality assurance in analytical chemistry). Krajowa Konferencja Radiochemii i Chemii Jądrowej "W Stulecie Odkrycia Polonu i Radu". Streszczenia, Kazimierz Dolny, Poland, 18-21.05.1998, p. 70. 71. Dybczyński R. Materiały odniesienia i ich rola w zapewnieniu jakości w nieorganicznej analizie śladowej (Reference materials and their role in quality assurance in inorganic trace analysis). 152 THE INCT PUBLICATIONS IN 1998 In: Problemy jakości analizy śladowej w badaniach środowiska przyrodniczego (Quality problems in trace analysis in environmental studies). Eds. A. Kabata-Pendias, B. Szteke. Wyd. II. rozsz.; Wydaw. Edukacyjne Z. Dobkowskiej, Warszawa 1998, pp. 41-78. 72. Dybczyński R., Kulisa K., Połkowska-Motrenko H., Samczyński Z., Szopa Z,, WasekM. Neutronowa analiza aktywacyjna jako narzędzie do badania jednorodności materiałów odniesienia (Neutron activation analysis as a tool for studying homogeneity of certified reference materials). Nowoczesne Metody Przygotowania Próbek i Oznaczania Śladowych Ilości Pierwiastków. Materiały VII Poznańskiego Konwersatorium Analitycznego, Poznań, Poland, 16-17.04.1998, p. 22. 73. Dybczyński R., Połkowska-Motrenko H., Samczyński Z., Szopa Z. Virginia tobacco leaves (CTA-VTL-2) - new Polish certified reference materials for inorganic trace analysis including microanalysis. Fresenius' Journal of Analytical Chemistry, 360, 384-387 (1998). 74. Fessas D., Cieśla K., Schiraldi A. y-radiation effects on the thermal stability of bovine y-globulin. Journal of Thermal Analysis, 52, 745-751 (1998). 75. Głuszewski W., Bieliński J. Badania procesu bezprądowego osadzania warstw dyspersyjnych NiP-SiC (Investigation of electroless process codeposition particles SiC in NiP matrix). XLI Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i Techników Przemysłu Chemicznego. Mikrosympozjum 2-5. Sekcja 1-16. Streszczenia, Wrocław, Poland, 14-18.09. 1998, p. 164. 76. Gniazdowska E., Narbutt J. Hydration of dioxaalkanes in aqueous solutions. VII International Conference "The Problems of Solvation and Complex Formation in Solutions". Abstracts, Ivanovo, Russia, 29.06.-2.07.1998, p. 33. 77. Górecki P., Kedzia B., Migdał W., Owczarczyk H.B. Irradiation as an alternative environment friendly method for microbiological decontamination of herbal raw material. In: Radiation technology for conservation of the environment. Proceedings, Zakopane, Poland, 8- 12.09.1997. IAEA-TECDOC-1023. IAEA, Vienna 1998, pp. 397-402, 78. Grądzka I., Jaworska A., Wójcik A. Zastosowanie elektroforezy pulsowej w badaniach naprawy podwójnoniciowych pęknięć DNA po subletalnych dawkach promieniowania X (Application of pulse field gel electrophoresis (PFGE) in investigation of DNA double-strand breaks formation after sublethal doses of X-radiation). XI Zjazd PTBR. Streszczenia, Siedlce, Poland, 15-17.04.1998, p. 106. 79. Grądzka I., Skierski J., Szumiel I. DNA repair, cell cycle progression and cell death following camptothecin treatment in two murine lymphoma L5178Y sublines. Cell Biochemistry and Function, 16, 239-252 (1998). 80. Grigoriew H., Chmielewski A.G. Capabilities of X-ray methods in studies of processes of permeation through dense membranes. Journal of Membrane Science, 142, 87-95 (1998). 81. Hołderna-Kfdzia E., Kędzia B., Migdał W., Madajczyk D., Owczarczyk B. Ionizing radiation in decreasing of microbiological contamination of honey. 8th International Symposium on Apitherapy. Book of the Symposium, Portoroz, Slovenia, 17-19.09.1998, p. 101. THE INCT PUBLICATIONS IN 1998 153 82. Honkonen V., Ruuskanen J., Aatamila M., MSkelS J., Lehtomaki J., Svarfvar B., Chmielewski A.G., Zimek Z., Ostapczuk A. VOC removal by simultaneous electron beam and biofilter application. In: Radiation technology for conservation of the environment. Proceedings, Zakopane, Poland, 8-12.09. 1997. IAEA-TECDOC-1023. IAEA, Vienna 1998, pp. 87-95. 83. Hug G.L., Bobrowski K., Kozubek H., Marciniak B. Photooxidation of methionine derivatives by the 4-carboxybenzophenone triplet state in aqueous solution. Intracomplex proton transfer involving the amino group. Photochemistry and Photobiology, 68, 6, 785-796 (1998). 84. Hug G., Bobrowski K., Kozubek H., Marciniak B. Photooxidation of methionine derivatives by the 4-carboxybenzophenone triplet state in aqueous solution. Intra-complex proton transfer involving the aminó group. Workshop on Reactive Intermediates in Sulfur Chemistry. Dedicated to Professor K.-D. Asmus on his 60th birthday. Book of abstracts, Poznań, Poland, 23-26.08.1998, L-15. 85. Jackowski Z., Chmielewski A.G., Zimek Z. Optimization of irradiation chamber for electron-beam flue-gas treatment in application for large steam boilers. In: Environmental applications of ionizing radiation. John Wiley & Sons, New York 1998, pp. 167-195. 86. Kaczmarek S., Jabłoński R., Kwaśny M., Warchoł S., Kisieiewski J., Moroz Z., Łukasiewicz T,, Wojtkowska J. Otrzymywanie i właściwości optyczne monokryształów granatu itrowo-aluminiowego domieszkowanych cerem i magnezem (Growth and optical properties of yttrium-aluminium garnet single crystals doped with cerium and magnesium). Biuletyn WAT, 47, 7-8, 113-139 (1998). 87. Kaczmarek S.M., Jabłoński R., Pracka I., Boulon G., Łukasiewicz T., Moroz Z., Warchoł S. Radiation defects in SrLaGa3O7 crystals doped with rare-earth elements. Nuclear Instruments and Methods in Physics Research B, 142, 515-522 (1998). 88. Kaczmarek S.M., Koepke Cz., Grinberg ML, Dominiak-Dzik G., Łuczyński Z., Jabłoński R., Moroz Z., Rzewuski H. Change of optical properties of Ce.YAG single crystals due to codoping and ionizing radiation treatment. International Conference on Solid State Crystals - Materials Science and Applications. Abstracts, Zakopane, Poland, 12-16.10.1998, p. 165. 89. Kaczmarek S.M., Kwaśny M., Łukasiewicz T., Moroz Z., Kopczyóski K., Piramidowicz R., Wojtkowska J., Warchoł S., Stępka K., Matkovskii A. Defekty radiacyjne w kryształach Nd:YAG i ich wpływ na właściwości optyczne i charakterystyki generacyjne lasera (Radiation defects in Nd:YAG single crystals and their influence on optical output of a laser). Materiały Elektroniczne, 26, 1, 56-77 (1998). 90. Kaczmarek S.M., Łukasiewicz T., Pracka I., Jabłoński R., Boulon G., Kaczmarek B., Warchoł S. 3+ Influence of y-radiation on Dy doped LiNbO3 single crystals. Biuletyn WAT, 47, 7-8, 101-112 (1998). 91 Kaczmarek S.M., Łukasiewicz T., Pracka I., Jabłoński JR., Boulon G., Kaczmarek B., Warchoł S. 3+ Radiation defects in Dy doped LiNbO3 single crystals. Journal of Alloys and Compounds, 275-277, 105-108 (199'8). 92. Kaczmarek S.M., Żendzian W., Łukasiewicz T., Stfpka K., Moroz Z., Warchol S. Effects of gamma irradiation and annealing treatments on the performance of Cr;Tm;Ho: YAG lasers. Spectrochimica Acta: Part A 54, 2109-2116 (1998). 154 THE INCT PUBLICATIONS IN 1998 93. Kędzia B., Migdal W., Madajczyk D., Holderna-Kfdzia E., Qwczarczyk B. Badania nad zmniejszaniem zanieczyszczeń mikrobiologicznych w miodzie przy użyciu promieniowania jonizującego (Investigations on decrease of microbiological contamination of honey by ionising radiation). Krajowe Sympozjum Technika Jądrowa w Przemyśle, Medycynie, Rolnictwie i Ochronie Środowiska. Referaty, Kraków, Poland, 16-18.09.1998, pp. 297-301. 94. Kordyasz A.J., Bilewicz A. A novel fast method for radium determination in low radioactive aqueous solutions by radon emanation from radium adsorbent. Nukleonika, 43,4, 489-498 (1998). 95. Kordyasz A., Bilewicz A. Określenie śladowych aktywności Ra-226 poprzez pomiar emanacji Rn-222 (Determination of trace activities of Ra-226 by measurement of Rn-222 emanation). Krajowa Konferencja Radiochemii i Chemii Jądrowej "W Stulecie Odkrycia Polonu i Radu". Streszczenia, Kazimierz Dolny, Poland, 18-21.05.1998, p. 76. 96. Kowalak S., Jankowska A., Stuglik Z. Zastosowanie sit molekularnych w dozymetrii (Application of molecular sieves in dosymetry). V Forum Zeolitowe "Zeolity - Synteza, Adsorpcja, Kataliza". Abstrakty, Kraków, Poland, 7-9.05.1998, pp. 1-2. 97. Kowalak S., Stuglik Z., Kraszona K,, Jankowska A. Application of alaninę adsorbed on the molecular sieves for the dosimetric measurements. 12th International Zeolite Conference. Proceedings, Baltimore Maryland, USA,5-10.07.1998, [p. 8], 98. Kowalska E., Urbański P. Zastosowanie matematycznej standaryzacji widm promieniowania X w aparaturze radiometrycznej (Application of mathematical standardization of X-ray spectra in radiometrie instruments). Krajowe Sympozjum Technika Jądrowa w Przemyśle, Medycynie, Rolnictwie i Ochronie Środowiska. Referaty, Kraków, Poland, 16-18.09.1998, pp. 265-270. 99. Kowalska-Loth B., Bubko I., Komorowska B., Szumie! I., Staroń K. Contribution of topoisomerase I to conversion of single-strand into double-strand DNA breaks. Molecular Biology Reports, 25, 21-26 (1998). 100. Krajewski K.J., Łukasiewicz A., Ważny J. A new wood preservative based on polymerized complexes of aminotriazole with copper acetate. 29th Annual Meeting of the International Research Group on Wood Preservation, Maastricht, Netherlands, 14-19.06.1998, Section 3, 10 p. 101. Krajewski K.J., Łukasiewicz A., Ważny J. Współdziałanie czwartorzędowych związków amoniowych i kompleksów poliaminotriazolu z miedzią w fungicydach (Interaction of quarternary ammonium compounds and polymerized aminotriazole complexes with copper in fungicides). "Czwartorzędowe Sole Amoniowe i Obszary ich Zastosowania w Gospodarce". IV Sympozjum Komisji Nauk Chemicznych PAN i ITD, Poznań, Poland, 2-3.06.1998, pp. 33-40. 102. KrejzlerJ.,NarbuttJ. High coordination numbers of central metal ions in tropolonates of scandium, indium and thalium(III) and selectivity of solvent extraction separations. Proceedings of International Solvent Extraction Symposia "Solvent Extraction", Moscow, Russia, 21- 27.06.1998, p. 202. 103. Kraszewski M. Mutanty komórek ssaków wrażliwe na promieniowanie jonizujące (Mammalian cell mutant sensitive to ionizing radiation). Postępy Techniki Jądrowej, 41, 3, 31-36 (1998). THE INCT PUBLICATIONS IN 1998 155 104. Kruszewski M., Iwaneńko T. Induction of DNA breakage in X-irradiated nucleoids selectively stripped of nuclear proteins in two mouse lymphoma cell lines differing in radiosensitivity. Acta Biochimica Polonica, 45, 3, 701-704 (1998). 105. Kruszewski M., Kruszewska H., Szutniel I. Rekombinacja homologiczna w komórkach ssaków upośledzonych w naprawie DNA (Homologous recombination in mammalian cells deficient in DNA repair). XI Zjazd PTBR. Streszczenia, Siedlce, Poland, 15-17.04.1998, p. 90. 106. Kruszewski M., Malec-Czecfaowska K., Dancewicz A.M., Iwaneóko T., Szot Z., Wojewódzka M. Application of the DNA comet assay for detection of irradiated meat. Nukleonika, 43, 2, 147-160 (1998). 107. Kruszewski M., Wojewódzka M., Iwaneńko T., Collins A.R., Szumiel I. Application of the comet assay for monitoring DNA damage in workers exposed to chronic low-dose irradiation. II. Base damage. Mutation Research, 416, 37-57 (1998). 108. Kruszewski M., Wojewódzka M., Iwaneńko T., Szumiel I. Differential inhibitory effect of DNA-PK inhibitor - OK-1035 on DNA repair in L5178Y cell lines. The 29th Meeting of the European Society for Radiation Biology and the 9th Meeting of the Italian Society for Radiation Research. Programme and Abstracts, Capri, Italy, 3-7.10.1998, p. 55. 109. Kruszewski M., Wojewódzka M., Iwaneńko T., Szumiel I., Okuyama A. Differential inhibitory effect of OK-1035 on DNA repair in L5178Y murine lymphoma sublines with functional or defective repair of double strand breaks. Mutation Research, 409, 31-36 (1998). 110. Kunicki-Goldfmger J.J., Kiereek J. Nondestructive analysis of potassium in ancient glass on the base of its natural gamma activity. Glass, Science and Technology (Glasstechnische Berichte), 71,11, 332-335 (1998). 111. Kunicki-Goldfinger J.J., Kierzek J., Sartowska B. Oznaczanie potasu w zabytkowych szkłach metodami radiometrycznymi (Potassium determination in ancient glasses by detection of its natural gamma ray activity). Krajowe Sympozjum Technika Jądrowa w Przemyśle, Medycynie, Rolnictwie i Ochronie Środowiska. Referaty, Kraków, Poland, 36-18.09.1998, pp. 308-313. 112. Kunicki-Goldfinger J.J., Urbański P. Wykorzystanie niektórych metod radiometrycznych do identyfikacji zabytkowych szkieł i szkliw ceramicznych (Application od some radiometrie methods for identification of antique glasses and ceramics). Krajowe Sympozjum Technika Jądrowa w Przemyśle, Medycynie, Rolnictwie i Ochronie Środowiska. Referaty, Kraków, Poland, 16-18.09.1998, pp. 283-288. 113. Leciejewicz J., Ptasiewicz-Bąk H., Zachara J. The crystal structure of strontium complex with 3-ami.nopyrazine-2-carboxylic acid. Polish Journal of Chemistry, 72,1994-1998 (1998). 114. Legocka I., Mirkowski K., Ku!ka B., Łukaszewska E., .Bujnowska E., Kurcwska U. Specjalne kleje termoplastyczne do wyrobów termokurczliwych (Special thermoplastic adhesives to thermoshrinkable products). Prace Naukowe Katedry Budowy Maszyn Politechniki Śląskiej. 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System monitoringu dla przemysłowo-demonstracyjnej instalacji odsiarczania i odazotowania spalin przy wykorzystaniu wiązki elektronów z akceleratorów w elektrowni "Pomorzany" w Szczecinie (Monitoring system for demonstrative-industrial installation dersulphurization and denutrification of flue gases in EPS "Pomorzany" in Szczecin). Monitoring Środowiska. II Forum Inżynierii Ekologicznej. Referaty. Nałęczów, Poland, 23-26.10.1998, pp. 249-256. 118. Licki J., Chmieiewski A.G., Iller E., Tymiński B. System monitoringu i sterowania dla przemysłowo-demonstracyjnej instalacji odsiarczania i odazotowania spalin przy wykorzystaniu wiązki elektronów z akceleratorów w Elektrowni "Pomorzany" w Szczecinie (Monitoring and control system for demonstrative-industrial installation desulphurization and denutrification of flue gases in EPS "Pomorzany" in Szczecin). Krajowe Sympozjum Technika Jądrowa w Przemyśle, Medycynie, Rolnictwie i Ochronie Środowiska. Referaty, Kraków, Poland, 16-18.09.1998, pp. 338-343. 119. Licki J., Chmieiewski A.G., Iller E., Zakrzewska-Trznadel G., Tokunaga O. Analytical methods and monitoring system for electron-beam flue-gas treatment. In: Environmental application of ionizing radiation. Eds. W.J. Cooper, R.D. Curry, K.E. O'Shea. John Wiley & Sons, New York 1998, pp. 217-230. 120. Licki J., Chmieiewski A.G., Iller E., Zakrzewska-Trznadel G., Tokunaga O., Hashimoto S. Analytical methods and monitoring system for e-beam flue gas treatment process. Radiation Physics and Chemistry, 52, 1-6, 351-354 (1998). 121. Machaj B., Bartak J. Simulation of the activities of radon daughters on RGR monitor air filter. Nukleonika, 43, 2, 175-184 (1998). 122. Machaj B., StugHk Z., Panta P., Kaluska I., Bryl-Sandelewska T., Strzałkowski J., Malicki W. Computerized PVC absorbance reader as the device for quick detection of dose distribution on, under and inside the electron irradiated object. 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THE INCT PUBLICATIONS IN 1998 157_ 126. Malec-Czechowska K., Stachowicz W., Dancewicz A.M., Szot Z. Zastosowanie spektrometrii EPR, termoluminescericji oraz metod badania uszkodzeń DNA i zdolności kiełkowania do identyfikacji napromieniowania żywności (Application of EPR spectroscopy, thermo- luminescence, analysis of DNA damage and germination power for identification irradiation food). Krajowe Sympozjum Technika Jądrowa w Przemyśle, Medycynie, Rolnictwie i Ochronie Środowiska. Referaty, Kraków, Poland, 16-18.09.1998, pp. 90-96. 127MaIickiW.,StuglikZ. Szybka metoda oszacowania energii elektronów w zakresie 5+10 MęV dla przemysłowego akceleratora z wiązką szeroką (Quick method of electron energy evaluation for industrial accelerator with wide beam of 5-10 MeV electrons). XI Zjazd PTBR. Streszczenia, Siedlce, Poland, 15-17.04.1998, p. 30. 128. Michalik J., Sadło J., Kodaira T., Shimomura S., Yamada H. ESR and opticals studies of cationic silver clusters in zeolite rho. Journal of Radioanałytical and Nuclear Chemistry, 232,1-2,135-137 (1998). 129. Michalik J., Sadło J., Kodaira T., Shimomura S., Yamada H. ESR and optical studies on silver clusters in sodalites and zeolites rho. Sixth Meeting of the Benelux EPR Society. Book of Abstracts, Antwerp, Belgium, 24.04.1998, p. I. 130. Michalik J., Yu J.S., Kim J,Y., Sadło J., Kevan L. Paramagnetic silver clusters in ZK-4 zeolites. Symposium on "Application of Magnetic Resonance in Chemistry and Related Areas". Book of Abstracts, Warszawa, Poland, 24-26.06.1998, p. P30. 131. Migdal W., Owczarczyk B., Kędzia B., Hołderna-Kfdzia E„, Segiet-Kujawa E. The effect of ionizing radiation on microbiological decontamination of medical herbs and biologically active compounds. Radiation Physics and Chemistry, 52, 1-6, 91-94 (1998). 132. Migdał W., Owczarczyk B., Malec-Czechowska K. Radiacyjna dekontaminacja surowców zielarskich i fitopreparatów (Decontamination of herbal raw materials and medicinal herbs by irradiation). Krajowe Sympozjum Technika Jądrowa w Przemyśle, Medycynie, Rolnictwie i Ochronie Środowiska. Referaty, Kraków, Poland, 16-18.09.1998, pp. 61-66. 133.MioduskiT. AQUO ion stoichiometries of radium(II), actimdes(II) and of some similar cations. 13th Radiochemical Conference. Book of Abstracts, Marianske Lazne-Jachymov, Slovakia, 19-24.04.1998, p. 1. 134. MioduskiT. Identification of saturating solid phases in aqueous solutions of lanthanide(III) sulfates from the solubility data. Chemia Analityczna, 43,457-462 (1998). 135. Mioduski T. On the discovery of polonium and radium. Nukleonika, 43, 1, 15-22 (1998). 136. Mirkowski J., Grodkowski J., Gajewski K. Wspomagające oprogramowanie analityczne na stanowisku do radiolizy impulsowej przy akceleratorze elektronów LAE 13/9 Żerań (Supporting analytical software for the pulse radiolysis set-up at the electron accelerator LAE 13/9 Żerań). XI Zjazd PTBR, Siedlce, Poland, 15-17.04.1998, p. 70. 158 THE INCT PUBLICATIONS IN 1998 137. NarbuttJ. Hydration/solvation of metal cheiates and selectivity in solvent extraction of metal ions. Proceedings of International Solvent Extraction Symposia "Solvent Extraction", Moscow, Russia, 21- 27.06.1998, p. 201. 138. NarbuttJ. Radiochemia u progu drugiego stulecia (Radiochemistry on the verge of its second century). Krajowa Konferencja Radiochemii i Chemii Jądrowej "W Stulecie Odkrycia Polonu i Radu". Streszczenia, Kazimierz Dolny, Poland, 18-21.05.1998, p. 11. 139. Narbutt J., Bilewicz A. Gamma emitting radiotracers 224Ra, 212Pb and212 Bi from natural thorium. Applied Radiation and Isotopes, 49, 1-2, 89-91 (1998). 140. Narbutt J., Czewiński M. Density functional calculations on hydrogen-bonded hydrates of metal acetylacetonates. VII International Conference "The Problems of Solvation and Complex Formation in Solutions". Abstracts, Ivanovo, Russia, 29.06.-2.07.1998, p. 17. 141. NarbuttJ., Fuks L. Interlaboratory comparison of the determination of 226Ra and228 Ra in samples simulating coal mine water. Nukleonika, 43, 4, 469-480 (1998). 142. NarbuttJ., Fuks L. Międzylaboratoryjny eksperyment porównawczy pomiarów zawartości radu w wodach kopalnianych (Interlaboratory comparision of the determination 226Ra and 228Ra in samples simulating coal mine water). Krajowa Konferencja Radiochemii i Chemii Jądrowej "W Stulecie Odkrycia Polonu i Radu". Streszczenia, Kazimierz Dolny, Poland, 18-21.05.1998, p. 72. 143. Narbutt J., Krejzler J., Czerwiński M. High coordination numbers of metal ions in chelate complexes. XXXIII International Conference on Coordination Chemistry "The Chemistry of Metal Ions in Everyday Life". Book of Abstracts, Florence, Italy, 30.08.-4.09.1998, p. 605. 144. Nichipor H., Dashouk E., Chmielewski A.G., Zimek Z., Bulka S. CC14 removal from dry air under influence of electron beam. Ninth National Conference on Applied of Charged Particle Accelerators in Medicine and Industry. Abstracts, Saint-Petersburg, Russia, 22-24.09.1998., pp. 52-53. 145. Nichipor H., Dashouk E., Chmielewski A.G., Zimek Z., Bułka S. Theoretical study on decomposition of carbon tetrachloride and trichloroethylene in dry air under influence of electron beam. The 1998 European Workshop on Water and Air Treatment by Advanced Oxidation Technologies: Innovative and Commercial Applications. Abstracts, Lausanne, Switzerland, 11-14.10.1998, pp. 12-13. 146. Nichipor H., Radjuk E., Chmielewski A.G., Zimek Z. Energy consumption of SO2 removal from humid air under electron beam and electric field influence. In: Radiation technology for conservation of the environment. Proceedings, Zakopane, Poland, 8-12.09. 1997. IAEA-TECDOC-1023. IAEA, Vienna 1998, pp. 157-165. 147. Owczarczyk A., Palige J., Chmielewski A.G. Badanie procesu sedymentacji cząstek osadu biologicznego w przemysłowym zbiorniku prostokątnym (Study of precipitation process of biological sediment particles in industrial tank). Krajowe Sympozjum Technika Jądrowa w Przemyśle, Medycynie, Rolnictwie i Ochronie Środowiska. Referaty, Kraków, Poland, 16-18.09.1998, pp. 228-233. 148. Owczarczyk A., Pruszak Z., Wierzchnicki R. Bed-load movement processes in marine near-shore zone. THE INCT PUBLICATIONS IN 1998 112. Nukleonika, 43,2, 195-202 (1998). 149. Paluchowska B., Lis T., Leciejewicz J. Dimeric molecules of Co(II) and Zn(II) complexes with furan-2-carboxylate ligands stabilized by the system of interconnected C-H"Owater ,Owater-H..O&ran and OTOter-H'-r: hydrogen bonds. Polish Journal of Chemistry, 72,2172-2180 (1998). 150. Paluchowska B., Maurin J.K., Leciejewkz J. 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Krajowe Sympozjum Technika Jądrowa w Przemyśle, Medycynie, Rolnictwie i Ochronie Środowiska. Referaty, Kraków, Poland, 36-28.09.1998, pp. 334-339. 157. PawłukojćA. The IINS spectroscopy of hydrogen bonds dynamics in amino acids. International Workshop on Deuteration of Biological Molecules for Structural and Dynamic Studies, Application to Neutron Scattering and NMR. Abstracts, Dubna, Russia, 19-25.05.1998, [p. 1]. 358. Pawlukojć A., Natkaniec I., Grech E., Baran J., Malarski Z., Sobczyk L. Incoherent inelastic neutron scattering, Raman and IR absorption studies on 3,8~bis(dimethyl- amino)naphthalene and its protonated forms. Spectrochimica Acta. Part A, 54,439-448 (1998). 159. Piekoszewski J., Werner Z., Langner J., Waliś L. Modification of the surface properties of materials by pulsed plasma beams. Surface and Coating Technology, 106, 228-233 (1998). 160 THE INCT PUBLICATIONS IN 1998 160. Pogocki D., Bobrowski K., Hug G.L., Schoneich C. 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Baran S., Ivanov V., Leciejewicz J., Stusser N., Szytuła A„ Zygmunt A., Yong Fan Ding Magnetism of ternary stannides RCuSn (R=Gd-Er). Journal of Alloys and Compounds, 257, 5-13 (1997). 239. Cfamielewski A.G., Hler E., Frank N. Technical and economical aspects of e-b installations for treatment of flue gases from power plant. THE INCT PUBLICATIONS IN 1998 167_ Ósma Międzynarodowa Konferencja "Elektryczny Łuk Łączeniowy" oraz Sympozjum "Elektrotechnologie Ochrony Środowiska". Materiały Konferencyjne. Część II, Łódź, Poland, 3-6.09.1997, pp. 145-149. 240. Chwastowska J., Skalmowski K. Speciątion of heavy metals in municipal composts. International Journal of Environmental Analytical Chemistry, 68, 13-24 (1997). 241. Dźwigalski Z., Zimek Z. The electron gun of LAE 10 linear electron accelerator. Electron Technology, 30,4, 331-334 (1997). 242. Góral A.B., Panta P.P., Maciak J., Pogorzelska J. Further premises for the existence of the helen. Bulletin of the Polish Academy of Sciences. Technical Sciences, 45, 1, 97-107 (1997). 243. Ignatowicz S., Migdał W. Disinfestation of polypropylene bags with electron beam radiation generated by a linear electron accelerator. Polish Agricultural Annual, Series E, 26, 1/2,19-24 (1997). 244. Krajewski K.J., Łukasiewicz A., Ważny J, Kompleksowe związki poliaminotriazoli z miedzią jako biocydy w ochronie drewna (Polymerized complexes of aminotriazoie with copper as biocides in the wood preservation). IV Sympozjum PSMB "Ochrona Obiektów przed Korozją Biologiczną i Ogniem". Referaty, Szklarska Poręba, Poland, I3-15.11.1997, pp. 97-107. 245. Kruszewski M., Kruszewska H., Inaba H., Jeggo P., Szumiel I. Homologous recombination in CHO cell lines defective in DNA damage processing. 7th International Conference on Environmental Mutagens. Abstracts, Toulouse, France, 7-12.09.1997, p. SS7. Mutation Research, 379, Suppl. 1, S65 (1997). 246. Michalik J., Wąsowicz T., Sadło J., Jong-Sung Yu., Kevan L. Tetrameric silver clusters in zeolite rho. Symposium on "Application of Magnetic Resonance in Chemistry and Related Areas", Warszawa, Poland, 25-27.06.1997, p. C-9. 247. Najer A., Parnowska W., Łukasiewicz A. New polymerized complexes of amino-triazole with transition metals as potential fungicidal drugs. Acta Poloniae Pharmaceutica - Drug Research, 54, 3,203-205 (1997). 248. Pawłukojć A. The IINS spectroscopy of hydrogen bonds dynamic in amino acids. International Conference on Neutron Scattering. Conference Program and Abstracts, Toronto, Canada, 17- 21.08.1997, p. 229. 249. Pawłukojć A., Natkaniec I., Grech E., Baran J., Malarski Z., Sobczyk L. Incoherent inelastic neutron scattering, Raman and IR absorption studies on 1,8- bis(dimethylamino)naphthalene and its protonated forms. XHth Conference-Workshop Horizons in Hydrogen Bond Research, Styria, Austria, 21-26.09.1997, pp. 1-2. 250. Ptasiewicz-Bąk H., Olovsson I., Mclntyre G.J. Charge density in orthorhombic NiSO4 • 7 H2O at room temperature and 25 K. Acta Crystallographica B, 53, 325-336 (1997). 251. Świderska-Kowalczyk M., Gomez F.J., Martin M. Particle generation methods applied in large-scale experiments on aerosol behaviour and source term studies. 168 THE INCT PUBLICATIONS IN 1998 Informed Tecnicos CIEMAT, Madrid 1997, Report no. 819,100 p. 252. Zimek Z., Chmielewski A.G., Bułka S., Lysov G.W. Flue gases treatment by simultaneous use of electron beam and streams of microwave energy. Ósma Międzynarodowa Konferencja "Elektryczny Łuk Łączeniowy" oraz Sympozjum "Elektrotechnologie Ochrony Środowiska". Materiały Konferencyjne. Część II, Łódź, Poland, 3-6.09.1997, pp. 150-157. 253. Zimek Z., Genuario R.D. High power electron accelerators for ecological applications. Ósma Międzynarodowa Konferencja "Elektryczny Łuk Łączeniowy" oraz Sympozjum "Elektrotechnologie Ochrony Środowiska". Materiały Konferencyjne. Część II, Łódź, Poland, 3-6.09.1997, pp. 170-175. SUPPLEMENT LIST OF THE INCT PUBLICATIONS IN 1996 254. Chmielewski A.G., Zimek Z., Bulka S., Licki J., Piderit G., Villanueva L., Ahumada L. Electron beam treatment of flue gas with high content of SO2. Journal of Advanced Oxidation Technologies , 1, 2, 142-149 (1996). 255. Nichipor, H., Radouk E., Chmielewski A.G., Zimek Z. SO2 oxidation by simultaneous application of electron beam and electric field in humid air. Journal of Advanced Oxidation Technologies, 1, 2, 150-153 (1996). THE INCT REPORTS IN 1998 169 THE INCT REPORTS IN 1998 1. Annual Report 1997. IChTJ, Warszawa 1998, 167 p. 2. Skwara W., Dudek J., Sterlińska E., Chwastowska J., Pszonicki L. Investigation of ionic mercury and alkylmercury stability in natural waters and modification of the method for its determination. IChTJ, Warszawa 1998. Raporty IChTJ. Seria A nr 1/98, 15 p. 3. Urbański P. Application, manufacturing and trends in development of nucleonic gauges in Poland. IChTJ, Warszawa 1998. Raporty IChTJ. Seria A nr 2/98, 35 p. 4. Migdał W., Owczarczyk H.B., Malec-Czechowska K. Badanie wpływu promieniowania jonizującego na stopień czystości mikrobiologicznej i wartość użytkową wybranych mieszanek przyprawowych (Investigation the effect of ionizing radiation on the level of microbiai contamination and usefulness of selected blends and seasoning). IChTJ, Warszawa 1998. Raporty IChTJ. Seria B nr 15/97, 18 p. 5. Do HoangCuong Low noise amplifier for ZnS(Ag) acintillation chamber. IChTJ, Warszawa 1998. Raporty IChTJ. Seria B nr 1/98, 14 p. 6. Machaj B. Badania miernika produktów rozpadu radonu RGR-30 w komorze radonowej (Investigations of radon decay products monitor RGR-30 in radon chamber). IChTJ, Warszawa 1998. Raporty IChTJ. Seria B nr 2/98, 32 p. 7. Mirkowski J., Grodkowski J. Oprogramowanie do obsługi stanowiska radiolizy impulsowej. Program RADIO96 (Programminig for controlling of pulse radiolysis setup. Program RADIO96). IChTJ, Warszawa 1998. Raporty IChTJ. Seria B nr 3/98,28 p. 8. Mirkowski J. Program do analizy zdjęć elektroforezy DNAnaiyser (Program for analysis of electrophoresis pictures DNAanalyser). IChTJ, Warszawa 1998. Raporty IChTJ. Seria B nr 4/98, 16 p. 9. Chmielewski A.G. Solid waste electron beam treatment. IChTJ, Warszawa 1998. Raporty IChTJ. Seria B nr 5/98, 52 p. 10. Chmielewski A.G., Dobrowolski A., Tymiński B. Dose distribution effect on optimal geometry for industrial flue gas treatment system. IChTJ, Warszawa 1998. Raporty IChTJ. Seria B nr 6/98, 32 p. 11. Machaj B. Modyfikacja radiometru górniczego typu RGR do pomiaru stężenia produktów rozpadu radonu w powietrzu (Modifications of mining radiometer type RGR for measurement of radon daughters concentration in air). IChTJ, Warszawa 1998. Raporty IChTJ. Seria B nr 7/98,24 p. 12.ZimekZ. Electron accelerators for environmental protection, IChTJ, Warszawa 1998. Raporty IChTJ. Seria B nr 8/98, 92 p. 170 THE INCT REPORTS IN 1998 13. StuglikZ., Bryl-Sandelewska T. Optymalizacja parametrów roboczych dozymetru EPR/D,L-ct-alaninowego (Optimization of measuring parameters of EPR/DL-a-alanine dosimeter). IChTJ, Warszawa 1998. Raporty IChTJ. Seria B nr 9/98, 16 p. 14. Antoniak W., Urbański P., Kowalska E. Badanie wpływu wygładzania widm na parametry modelu kalibracyjnego (Influence of smoothing of X-ray spectra on parameters of calibration model). IChTJ, Warszawa 1998. Raporty IChTJ. Seria B nr 10/98, 16 p. 15. Kowalska E., Urbański P. Wielowymiarowe metody statystyczne standaryzacji widm promieniowania X (Multivariate statistic methods for standardization of X-ray spectra). IChTJ, Warszawa 1998. Raporty IChTJ. Seria B nr 11/98, 26 p. NUKLE0N1KA NUKLEONIKA THE INTERNATIONAL JOURNAL OF NUCLEAR RESEARCH EDITORIAL BOARD Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. (Editor-in-Chief); Krzysztof Andrzejewski, Ph.D. (physical sciences); Prof. Bohdan Dziunikowski, Ph.D., D.Sc. (technical physics, nuclear physics); Prof. Zbigniew Jaworowski, Ph.D., D.Sc. (radiation protection); Stanisław Latek, Ph.D. (reactor physics and engineering); Prof. Jacek Michalik, Ph.D., D.Sc. (radiation chemistry); Assoc. Prof. Tomasz Mioduski, Ph.D., D.Sc. (chemical sciences); Prof. Irena Szumiel, Ph.D., D.Sc. (medical biology, cellular radiobiology); Prof. Piotr Urbański, Ph.D., D.Sc. (measuring instruments, nucleonic control systems) INTERNATIONAL ADVISORY BOARD Prof. Janusz Z. Beer (USA), Prof. Gregory R. Choppin (USA), Prof. Andrei Gagarinsky (Russia), Prof. Alexander van Hook (USA), Prof. Larry Kevan (USA), Prof. Evgeni A. Krasavin (JINR-Dubna, Russia), Prof. Samuel H. Levine (USA), Dr Sueo Machi (Austria), Dr James D. Navratil (USA), Dr Shoichi Sato (Japan), Prof. Robert H. Schuler (USA) CONTENTS OF No. 1/98 1. Editor At the centenary of the discovery of polonium and radium. 2. T. Mioduski On the discovery of polonium and radium, 3. S. Warchol, H. Rzewuski lonization-induced damage increase in As-implanted GaAs. 4. F. Premti, P. Fuga Trend in (n, p) reaction cross-sections at 14.5 MeV neutron energy. 5. P. Fuga AGE of Am-Be neutrons in water. 6. M. Zieliński, A. Zielińska, H. Papiernik-Zielińska A contribution to studies of carbon-13 kinetic isotope effect of the decarbonylation of liquid formic acid in the presence of phosphoric acids. I. I3C KIE in the decarbonyiation of HCOOH in the presence of phosphoric acids and P2OS. 7. M. Zieliński, A. Zielińska, H. Paul, H. Papiernik-Zieiińska Carbon-13 isotope effects in the decarbonylation of liquid formic acid in the presence of pyrophosphoric 13 acid. II. C KIE in the decarbonylation of HCOOH in the presence of H4P2O7. 8. M. Zieliński, A. Zielińska III. Carbon-13 fractionation in the decomposition of formic acid initiated by phosphoric anhydride. 13C fractionation in the decomposition of HCOOH initiated by P2O5. 9. A. Cebulska-Wasilewska, W. Niedźwiedź, D. Nowak, E. Kasper, A. Wierzewska, A. Wójcik, E. Boużyk DNA and chromosomal damage estimate in blood of people suspected of exposure to radiation. 10. A.J. Niemi, K. Zenger, J. Thereska, J.G. Martinez Tracer testing of processes under variable flow and volume. 172 NUKLEONIKA 11. J. Thyn, Jin Joon Ha, P. Strasak, R. Żitny RTD prediction, modelling and measurement of gas flow in reactor. 12. A.E. Stewart, J.D. Navratil Treatment of waste sodium/NaK; decommissioning hardware and facilities. CONTENTS OF No. 2/98 1. I. Szumiel, B. Sochanowicz Signal transfer in the cellular response to ionizing radiation. 2. M. Kraszewski, K. Malec-Czechowska, A.M. Dancewicz, T. Iwaneńko, Z. Szot, M. Wojewódzka Application of the DNA comet assay for detection of irradiated meat. 3. R. Ludwig, S. Tachimori, T. Yamato New macrocyclic extractants for the processing of inorganic waste. 4. B. Machaj, J. Bartak Simulation of the activities of radon daughters on RGR monitor air filter. 5. A.G. Chmielewski, A. Owczarczyk, J. Palige Radiotracer investigations of industrial waste water equalizer-clarifiers. 6. A. Owczarczyk, Z. Pruszak, R. Wierzchnicki Bed-load movement processes in marine near-shore zone. CONTENTS OF No. 3/98 1. F. Hanappe, L. Stuttge DEMON: a Thermometer and a clock for fusion-fission dynamics studies: an introduction. 2. 0. Dorvaux, F. Hanappe, L. Stuttge Dynamics of binary collisions in 86Kr + 165Ho at 60 MeV/u with DEMON. 3. E. de Goes Brennand Fusion-fission dynamics in a medium mass nucleus: I26Ba. A progress report. 4. B. Benoit Entrance channel effects on the dynamics of fusion-fission reactions leading to Z = 110. A progress report. 5. C. Badimont Fusion-fission time-scales and dynamics in the platinum region: a progress report. 6. L. Donadille, P. Desesquelles, E. Liatard Determination of the correlation between the thermal energy and the neutron multiplicity using the backtracing technique. 7. G.Rudolf Pre- and post-scission neutron multiplicities in the frame of the Bass model. 8. S. Jokić, D. Vorkapic, B. Ivanisevic, A. Kelić, Ż. Todorovic, S. Savovic, B. Botchev, M. Zamani, F. Fernandez Letter of intent: investigation of the fission before K-equilibration. 9. K, Yuasa-Nakagawa, T. Nakagawa, K. Yoshida, X. Liu, S.M. Lee, D.X. Jiang, Y. Aoki, J. Kasagi, K. Furutaka Reaction mechanism study using total kinetic energy and prescission. particle multiplicity in medium mass nuclei. 10. W.H. Trzaska, V.A. Rubchenya, J. Aysto, Z. Radivojevic, D.N. Vakhtine, I.D. Alkhazov, A. Evsenin, S.V. Khlebnikov, A.V. Kuznetsov, V.G. Lyapin, O.I. Ossetrov, G.P. Tiourine, A.A. Alexandrov, Yu.E. Penionzhkevich, Yu.V. Pyatkov, Yu.G. Sobolev, M. Mutterer, K. Brinkmann, V. Makarenko Current research at HENDES. U.K. Siwek- Wilczyńska, J. Wilczyński Systematics of the dissipation coefficient deduced from pre-scission neutron multiplicities in fusion-fission reactions. NUKLEONIKA _____ 12. Z. Szefliński, M. Popkiewicz, R. Zagańczyk Neutron emission from 101Rh produced via 12C + 89Y reaction. Progress report. 13. J. Pluta, F. Hanappe, J.C. Angelique, M. Assenard, B. Benoit, E. de Goes Brennand, G. Bizard, J. Colin, P. Desesquelles, A. Długosz, E. Doroshkevich, O. Dorvaux, P. Duda, D. Durand, B. Erazmus, Ph. Eudes, F. Haddad, T. Kirchner, S. Kuleshov, C. Lebrun, R. Lednicky, P. Leszczyński, M. Marques, L. Martin, K. Mikhailov, K. Miller, T. Pawlak, M. Przewłocki, A. Stavinsky, L. Stuttgć, B. Tamain, A. Vlasov, L. Vorobyev, K. Wosińska Nuclear interferometry for two-nucleon systems (experiment E286 at GANIL). 14. Z. Basrak Dynamical Landau-Vlasov model as a source generator for Hanbury-Brown-Twiss correlations. 15. R. Lednicky New possibilities of interferometry in particle physics. 16. Yu.M. Sinyukov, S.V. Akkelin, A.Yu. Tolstykh The analysis of hedron matter properties in heavy ion collisions. 17. S. Mrówczyński Two-particle correlation and bound state formation - two sides of the same medal. CONTENTS OF No. 4/98 1. J. Sobkowski Application of radiometrie methods to the study of electrosorption and electrode reaction on solid electrodes. 2. A. Płonka Kinetic isotope effects of atomic hydrogen in condensed phases. 3. J. Szydłowski Influence of the deuterium substitution on miscibility of water with methyl derivatives of pyridine. 4. B. Petelenz, E. Ochab, R. Misiak, E. Bakewicz Possibilities for production of medical radiotracers on the AIC-144 cyclotron in the Cracow Institute of Nuclear Physics. 5. K. Samochocka, A. Rysińska, I. Kozłowicz-Gudzińska The use of electronic autoradiography in nuclear medicine. 6. B. Mysłek-Laurikainen, M. Biernacka, M. Bysiek, E. Droste, M. Matul Radionuclides in the ground-level air in Poland. 7. J.W. Mietelski Transuranic elements and strontium-90 in samples from forests in Poland. 8. H. Bem, E.M. Bern, I. Majchrzak Comparison of two methods for 226Ra determination in mineral water. 9. J. Narbutt, L. Fuks Interlaboratory comparison of the determination of 226Ra and 228Ra in samples simulating coal mine water. 10. A. Hetman, J. Dorda, W. Zipper Determination of radium isotopes concentrations in mineral waters by liquid scintillation method. 11. A.J. Kordyasz, A. Bilewicz A novel fast method for radium determination in low radioactive aqueous solutions by radon emanation from radium adsorbent. 12. E. Ochab, R. Misiak Ether extraction of carrier-free 139Ce as a method of separation of cerium from lanthanum target. 13. R. Bojanowski, R. Piękoś, S. Pasławska Leachability of radionuclides from fly ash and phosphogypsum. 14. J. Ogłaza, Z. Nowak Attempts to solidify some selected liquid radioactive organic wastes. 174 NUKLEQN1KA 15. J. Satyanarayana, A. Bilewicz, J. Narbutt Sorption of iong-lived radionuclides from model liquid radioactive wastes on a-crystalline polyantimonic acid. Information and subscription 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; telex: 813027 ichtj pi; fax: (+48-22) 811-15-32; e-mail: [email protected] THE INCT PATENTS AND PATENT APPLICATIONS IN 1998 175 THE INCT PATENTS AND PATENT APPLICATIONS IN 1998 PATENTS 1. Urządzenie wprowadzające wiązkę elektronów do komory reakcyjnej w procesie radiacyjnego usuwania SO2 i NOX ze strumienia przemysłowych gazów odlotowych (Facility introducing electron beam into a reaction chamber in the process of radiation induced removal of SO2 and NOX from a stream of industrial gases). A.G. Chmielewski, Z. Zimek Polish Patent 174442 PATENT APPLICATIONS 1. Nowe środki do barwienia drewna i innych materiałów celulozowych o własnościach grzybobójczych (New fungicidal agents for colouring wood and other cellulose materials). A. Łukasiewicz, L. Waliś, B. Sartowska P.325106 2. Sposób usuwania tlenków azotu z przemysłowych gazów odlotowych (Method for removal of nitrogen oxides from industrial flue gases). A.G. Chmielewski, Z. Zimek, J. Licki P.325107 UTILITY MODELS 1. Nasadka filtracyjna (Filtration attachment). J. Kiełkiewicz, M. Buczkowski, W. Starosta, P. Olczyk, T. Żółtowski, E. Meinhardt, H. Frydrych, A. Fiderkiewicz P.302895 176 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1998 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1998 1. KRAJOWA KONFERENCJA RADIOCHEMIII CHEMII JĄDROWEJ "W STU- LECIE ODKRYCIA POLONU I RADU" (NATIONAL CONFERENCE ON RADIOCHEMISTRY AND NUCLEAR CHEMISTRY "ON THE CENTENARY OF THE DISCOVERY OF POLONIUM AND RADIUM"), 18-21 MAY 1998, KAZIMIERZ DOLNY, POLAND Organized by Department of Radiochemistry, Institute of Nuclear Chemistry and Technology; Committee for Nuclear and Radiation Chemistry; Council for Nuclear Problems Organizing Committee: Assoc.Prof. Jerzy Narbutt, Ph.D., D.Sc. (Chairman), Jadwiga Krejzler, Ph.D. (Secretary), Leon Fuks, Ph.D., Aleksander Bilewicz, Ph.D., D.Sc. Wykłady plenarne (Plenary lectures) Chairman: A. Hrynkiewicz (Institute of Nuclear Physics) • Własności i synteza najcięższych pierwiastków (Properties and synthesis of the heaviest elements). A. Sobiczewski (Institute for Nuclear Studies, Warszawa, Poland) • Medycyna nuklearna, fakty i fikcje (Nuclear medicine - facts and fiction) L. Królicki (Medical Academy, Warszawa, Poland) • Naturalne i sztuczne skażenia atmosfery globu (Natural and anthropogenic pollution of the Earth atmosphere). Z. Jaworowski (Central Laboratory for Radiological Protection, Warszawa, Poland) Chairmen: W. Reimschussel (Łódź Technical University), A.G. Chmielewski (Institute of Nuclear Chemistry and Technology • Radiochemia u progu drugiego stulecia (Radiochemistry on the verge of its second century). J. Narbutt (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Elementy chemii jądrowej w programach nauczania chemii w szkołach średnich i uczelniach wyższych - czy wiedza ta jest potrzebna? (Elements of nuclear chemistry in secondary school and university programmes - is this kind of information necessary?). A. Czerwińska, A. Czerwiński (University of Warsaw, Warszawa, Poland) Chemia pierwiastków promieniotwórczych i zastosowanie radionuklidów do badań fizykochemicznych (Chemistry of radioelements and radionuclides in physicochemical research) Chairmen: S. Siekierski (Institute of Nuclear Chemistry and Technology), J. Sobkowski (University of Warsaw) • Przewidywanie własności chemicznych pierwiastków transaktynowcowych (Forecasting of chemical properties of transactinide elements). S. Siekierski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Chemiczne badania pierwiastków 104, 105 i 106 w roztworach wodnych w modelowych układach z ich homologami Hf, Ta i W (Chemical investigation of the 105 and 106 elements in aqueous solutions in model systems with their homologous Hf, Ta and W). Z. Szeglowski (Institute of Nuclear Physics, Kraków, Poland) CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1998 177 • Wpływ efektu relatywistycznego na liczbę koordynacyjną rutherfordu (Relativistic effect and the coordina- tion number of rutherfordium). A. Bilewicz (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Zastosowanie metod radiochemicznych do badania adsorpcji i reakcji elektrochemicznych na metalach stałych (Application of radiochemical methods in studies on adsorption and electrochemical reactions on solid metals). J. Sobkowski (University of Warsaw, Warszawa, Poland) • Otrzymywanie i własności kompleksowych halogenków uranu(III) (Synthesis and properties of uranium(III) halide complexes). J. Drożdżyński, M. Karbowiak, K. Kossowski (University of Wrocław, Wrocław, Poland) • Sorpcja Hf, Zr i Nb na żywicach jonowymiennych z roztworów kwasów nieorganicznych (Sorption of Hf, Zr and Nb from mineral acid solutions on ion exchange resins). B. Kubica, M. Tuteja-Krysa, Z. Szeglowski (Institute of Nuclear Physics, Kraków, Poland) • Adsorpcja jonów siarczanowych na monokrystalicznych elektrodach srebrnych i miedzianych (Adsorption of sulphate ions on single-crystal silver and copper electrodes). S. Smoliński (University of Warsaw, Warszawa, Poland) • Radiometryczne badanie podpotencjałowego osadzania talu na monokrystalicznych elektrodach srebrnych (Radiometrie study on sub-potential precipitation of thallium on single-crystal silver electrodes). P. Waszczuk (University of Warsaw, Warszawa, Poland) Radionuklidy w medycynie nuklearnej, radiofarmaceutyki i związki znakowane (Radionuclides in nuclear medicine, radiopharmaceutical and labelled compounds) Chairpersons: Cz. Deptuła (Radioisotope Production and Reactor Centre), K. Samochocka (University of Warsaw) • Kompleks metalu jako łącznik pomiędzy przeciwciałem a radionuklidem (Metal complex as a spacer between antibody and radionuclide). K. Samochocka (University of Warsaw, Warszawa, Poland) • Zastosowanie związków znaczonych jodem-125 w radioimmunodiagnostyce medycznej in vitro (Application of compounds labelled with iodine-125 in medical radioimmunodiagnosis in vitro). E. Byszewska-Szpocińska (Radioisotope Production and Reactor Centre, Otwock-Świerk, Poland) • Enzymatyczne i chemiczne syntezy znakowanych nC i 18F związków organicznych stosowanych w tomografii pozytonowej (PET) (Enzymatic and chemical syntheses of organie compounds labelled with nC and I8F, applied in positron emission tomography (PET)). . M. Kańska (University of Warsaw, Warszawa, Poland) • Elektroosadzanie 105Ru i 241Am jako sposób wytwarzania zamkniętych źródeł promieniowania (Electro- deposition of 106Ru and 241Am as a method for producing sealed radiation sources). M. Mielcarski, A. Piasecki, E. Molenda (Radioisotope Production and Reactor Centre, Otwock-Świerk, Poland) « Zastosowanie szybkiej, bezkliszowej autoradiografii w medycynie nuklearnej (The use of fast plateless electronic autoradiography in nuclear medicine). K. Samochocka, A. Rysińska, I. Kozłowicz-Gudzińska (University of Warsaw and Oncology Centre, Warszawa, Poland) • Zastosowanie chromatografii ekstrakcyjnej w procesie otrzymywania niektórych radiofarmaceutyków S9 9O ( SrCi2, YC13) (Application of extraction chromatography in the process of obtaining some radio- 89 9O pharmaceutical ( SrCl2, YC13)) Cz. Deptuła, T. Kempisty, A. Markiewicz, R. Mikołajczak, S. Stefańczyk, T. Terlikowska, W. Zulczyk (Radioisotope Production and Reactor Centre, Otwock-Świerk, Poland) 178 CONFERENCES ORGANIZED AND CO-ORGANIZEP BY THE INCT IN 1998 • Perspektywy otrzymywania izotopów dla medycyny nuklearnej w cyklotronie AIC-144 w Instytucie Fizyki Jądrowej (Perspectives for production of radionuclides for nuclear medicine using an AIC-144 cyclotron in the Cracow Institute of Nuclear Physics). B. Petelenz, R. Misiak, E. Ochab (Institute of Nuclear Physics, Kraków, Poland) • Synteza i znakowanie radionuklidami kompleksu bipirymidinometioninoplatynowego (Synthesis and radionuclide labelling of bipyrimidinemethionine platinum complex). K. Samochocka, M. Paszewski (University of Warsaw, Warszawa, Poland) • Stereoselektywna, enzymatyczna synteza aminokwasów aromatycznych znakowanych trytem i węglem C-14 (Stereoselective, enzymatic synthesis of aromatic aminoacids labelled with tritium and carbon C-14). J. Jemielity, M. Kańska, R. Kański (University of Warsaw, Warszawa, Poland) • Chemiczna i enzymatyczna synteza znakowanych węglem C-14 prekursorów kwasu cynamonowego (Chemical and enzymatic synthesis of cinnamic acid precursors labelled with C-14). J. Bukowski, M. Kańska, R. Kański (University of Warsaw, Warszawa, Poland) Efekty izotopowe (Isotope effects) Chairmen: A. Płonka, (Łódź Technical University), J. Szydłowski (University of Warsaw) • Efekty izotopowe w równowagach fazowych (Isotope effects in phase equilibria). J. Szydłowski (University of Warsaw, Warszawa, Poland) • Efekty izotopowe wodoru atomowego (Isotope effects of atomic hydrogen). A. Płonka (Institute of Applied Radiation Chemistry, Łódź Technical University, Łódź, Poland) • Efekt "even-odd" w separacji izotopów metodami chemicznymi ("Even-odd" effect in the separation of isotopes by chemical methods). W. Dembiński, M. Poniński (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), R. Fiedler (International of Atomic Energy Agency, Seiberdorf, Austria) • Efekty izotopowe w procesach permeacji wody naturalnej przez membrany polimerowe (Isotope effects in processes of permeation of natural water across polymer membranes). G. Zakrzewska-Trznadel, A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) » Wpływ podstawienia izotopowego na mieszalność metylowych pochodnych pirydyny i wody (Effect of deuterium substitution on miscibility of water with methyl derivatives of pyridine). J. Szydłowski (University of Warsaw, Warszawa, Poland) • Wpływ podstawienia izotopowego H/D na właściwości fizykochemiczne wodnych roztworów prostych amidów (Effect of isotopic substitution H/D on physico-chemical properties of aqueous solutions of simple amides). M. Jelińska-Kazimierczuk, J. Szydłowski (University of Warsaw, Warszawa, Poland) • Wpływ podstawienia izotopowego na lepkość roztworów o ograniczonej mieszalności (Effect of isotopic substitution on viscosity of solutions of limited mixibility). A. Milewska, J. Szydłowski (University of Warsaw, Warszawa, Poland) • Efekty izotopowe reakcji katalizowanej przez karbamoilotransferazę asparaginianową (Isotope effects in reaction catalysed by asparginate carbamyltransferase). J. Pawlak (Institute of Applied Radiation Chemistry, Łódź Technical University, Łódź, Poland), M.H. O'Leary, P. Paneth (California State University, Sacramento, USA) • Nowa metoda oznaczania składu izotopowego chloru (New method for determination of isotopic composition of chlorine). J. Rudziński (Institute of Applied Radiation Chemistry, Łódź Technical University, Łódź, Poland) • Rozdzielanie izotopów iterbu metodą amalgamowam'a (Separation of iterbium isotopes using amalgamation method). CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1998 179_ W. Dembiński, M. Poniński (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), R. Fiedler (International of Atomic Energy Agency, Seiberdorf, Austria) Radionuklidy w środowisku naturalnym (Radionuclides in the environment) Chairpersons: Z. Pietrzak-FHs, (Central Laboratory for Radiological Protection), H. Bem (Łódź Technical University) • Izotopy pochodzenia naturalnego w atmosferze (Isotopes of natural origin in the atmosphere). L. Kownacka (Central Laboratory for Radiological Protection, Warszawa, Poland) • Radionuklidy w przyziemnej warstwie powietrza (Radionuclides in the ground-level air in Poland). B. Mysłek-Laurikainen (Institute for Nuclear Studies, Otwock-Świerk, Poland), M. Biernacka, M. Bysiek (Central Laboratory for Radiological Protection, Warszawa, Poland), E. Droste, M. Matul (Institute for Nuclear Studies, Otwock-Świerk, Poland) • Pierwiastki transuranowe i Sr-90 w próbkach z ekosystemów leśnych Polski (Transuranic elements and Sr-90 in samples from forests in Poland). J.W. Mietelski (Institute of Nuclear Physics, Kraków, Poland) • Rozmieszczenie i nagromadzenie polonu, uranu i plutonu w ekosystemie Morza Bałtyckiego (Distribution and accumulation of polonium, uranium and plutonium in the Baltic Sea ecosystem). B. Skwarzec (Institute of Oceanology, Polish Academy of Sciences, Sopot, Poland) • Skażenia promieniotwórcze wód Bałtyku: stan do 1986 r. i następstwa awarii reaktora w Czarnobylu (Radioactive contamination of Baltic Sea waters: condition by 1986 year and the consequence of Chernobyl disaster). J. Tomczak, R. Bojanowski (Institute of Meteorology and Water Management, Gdynia, Poland) • Zachowanie się w środowisku naturalnym radu odprowadzonego z kopalń węgla z wodami i osadami (Environmental behaviour of radium removed from coal mines with waters and deposits). M. Wysocka, A. Mielnikow, S. Chałupnik, K. Skubacz, J. Lebecka (Central Mining Institute, Katowice, Poland) • Naturalne izotopy promieniotwórcze w pożywieniu ludności Polski (Natural radionuclides in food of the population of Poland). Z. Pietrzak-Flis (Central Laboratory for Radiological Protection, Warszawa, Poland) • Rad, radon oraz produkty jego rozpadu w brzeżnej części granitu karkonoskiego (Radium, radon and its decay products in the border zone of Karkonosze granite). T.A. Przylibski (Wrocław Technical University, Wrocław, Poland) • Badanie nierównowagi pomiędzy Ra-226 i Po-210 w osadach dennych i roślinności na terenie GZW (Studies on non-equilibrium between Ra-226 and Po-210 in bortom deposits and flora of the Silesian Coal District). S. Chałupnik, A. Mielnikow, M. Wysocka, B. Michalik, J. Lebecka, K. Skubacz (Central Mining Institute, Katowice, Poland) • Określenie wielkości promieniowania naturalnego w otoczeniu kopalń rud miedzi (Determination of the magnitude of natural radiation in the surroundings of copper ore mines). J. Olszewski (Institute of Occupational Medicine, Łódź, Poland) • 137Cs i pluton w osadach dennych Morza Bałtyckiego w latach 1994-1996 (Cesium-137 and plutonium in bottom deposits of Baltic Sea in the years 1994-1996). M. Suplińska, D. Grzybowska (Central Laboratory for Radiological Protection, Warszawa, Poland) • Cs-137 wmleku konsekwencją skażenia środowiska (Cs-137 in milk as a result of environmental pollution). D. Grabowski, B. Rubel, J. Świętochowska, W. Muszyński (Central Laboratory for Radiological Protection, Warszawa, Poland) • Zawartość radu w butelkowanych wodach mineralnych w Polsce (Content of radium in bottled Polish mineral waters). 180 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1998 E.M. Bem, H. Bern, I. Majchrzak (Institute of Applied Radiation Chemistry, Łódź Technical University, Łódź, Poland) • Polon 210Po i ołów 210Pb w bezkręgowcach Morza Bałtyckiego (The 210Po and 2!0Pb content in invertebrates of the Baltic Sea). P. Stępnowski, B. Skwarzec (Institute of Oceanology, Polish Academy of Sciences, Sopot, Poland) • Czy powódź miała wpływ na poziom I37Cs i 226Ra w wodzie i w osadach dennych dorzecza Wisły i Odry? (Did the recent flood have any influence on the 137Cs and 226Ra content in the bottom deposits of the Vistula and Odra basin rivers?). I. Radwan, T. Wardaszko, Z. Pietrzak-Flis (Central Laboratory for Radiological Protection, Warszawa, Poland) • Migracja Cs-137 w różnych typach gleb okolic Lublina (Migration of the Cs-137 in various types of soil of the Lublin surroundings). S. Chibowski, J. Zygmunt (M. Curie-Skłodowska University, Lublin, Poland) • Migracja izotopów plutonu w glebie leśnej z okolic Lublina (Migration of plutonium isotopes in forest soil of the Lublin surroundings). A. Komosa (M. Curie-Skłodowska University, Lublin, Poland) • Radon w żłobkach, przedszkolach i szkołach województwa łódzkiego (Radon concentrations in creches, nurcery schools and schools of the Łódź district). H. Bem, E.M. Bem, M. Ostrowska (Łódź Technical University, Łódź, Poland) • Porównanie depozycji radiocezu (I37Cs) w Zatoce Pomorskiej przed i po powodzi w lipcu 1997 r. (Comparison of the 137Cs deposition in the Pomeranian Bay prior to and after the flood of June 1997). D. Knapińska-Skiba, R. Bojanowski, W. Chomka (Institute of Oceanology, Polish Academy of Sciences, Sopot, Poland) • Promieniotwórczość mleka po wielokrotnych skażeniach kóz radiocezem - dekontaminacyjna skuteczność bentonitu (Radioactivity of milk obtained from goats contamined with radiocesium - decontamination efficiency of bentonite). A. Dziura, B. Kowalski, J. Rachubik (National Institute of Veterinary Medicine, Puławy, Poland) Chemia odpadów promieniotwórczych (Chemistry of nuclear wastes) Chairmen: S. Chwaszczewski, W. Tomczak (Institute of Atomic Energy) • Program postępowania z odpadami promieniotwórczymi i wypalonym paliwem jądrowym z reaktorów badawczych (Programme of treatment of radioactive wastes and spent nuclear fuel from research reactors). J. Włodarski (National Atomic Energy Agency, Warszawa, Poland) • Gospodarka wypalonym paliwem z reaktorów badawczych w Polsce (Management with spent nuclear fuel from research reactors in Poland). S. Chwaszczewski (Institute of Atomic Energy, Otwock-Świerk, Poland) • Sztuczne i naturalne bariery przeciwdziałające rozprzestrzenianiu się radionuklidów w środowisku naturalnym w okresie długotrwałego składowania odpadów promieniotwórczych (Engineered and natural barriers preventing migration of radionuclides in the environement during long-term storage of radioactive wastes). W. Tomczak, A. Cholerzyński, Z. Frankowski, J. Mitręga (Institute of Atomic Energy, Otwock-Świerk, Poland) • Zatężanie ścieków niskoaktywnych w procesie destylacji membranowej (Preconcentration of liquid low-level radioactive wastes in membrane distillation process). A.G. Chmielewski, M. Harasimowicz, G. Zakrzewska-Trznadel (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) » Zastosowanie ultrafiltracji i hiperfiltracji w procesach zatężania ciekłych odpadów promieniotwórczych (Application of ultrafiltration and hyperfiltration processes for preconcentration of the radioactive liquid wastes). CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1998 181_ M. Harasimowicz, A.G. Chmielewski G. Zakrzewska-Trznadel (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Próby zastosowania różnych sorbentów w badaniach laboratoryjnych nad oczyszczaniem wód radowych (Applications of various sorbents in studies on purification of radium containing waters). S. Chałupnik, A. Mielnikow, M. Wysocka, B. Michalik, J. Lebecka (Central Mining Institute, Katowice, Poland) • Ruchliwość radionuklidów zawartych w odpadach przemysłowych (Leachability of radionuclides from industrial wastes). R. Bojanowski, R. Piekoś, S. Pasławska (Institute of Oceanology, Polish Academy of Sciences, Sopot, Poland) • Próby zestalania wybranych ciekłych odpadów organicznych (Attempts to solidify some selected liquid radioactive organic wastes). J. Ogłaza, Z. Nowak (Institute of Atomic Energy, Otwock-Świerk, Poland) • Sorpcja radionuklidów długożyciowych z modelowych odpadów promieniotwórczych na oc-krystalicznym kwasie poiiantymonowym (Sorption of long-lived radionuclides from model radioactive wastes on ct- crystalline polyantimonic acid). A. Bilewicz, J. Narbutt, J. Satyanarayana (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Metody radioanalityczne (Radioanalytical methods) Chairmen: R. Dybczyński (Institute of Nuclear Chemistry and Technology), J. Drożdżyński (University of Wrocław) • Idea "definitywnych" i "bardzo dokładnych" metod oznaczania pierwiastków śladowych za pomocą radiochemicznego wariantu NAA i znaczenie tych metod dla zapewnienia jakości wyników analitycznych (The idea of "definitive" and "very accurate" methods for the determination of trace elements by radiochemical NAA and significance of these methods for quality assurance in analytical chemistry). R. Dybczyński (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Jakość pomiarów w analizach radiochemicznych i sposoby jej poprawy (Quality in radiochemical analysis; ways of improvement). R. Bojanowski (Institute of Oceanology, Polish Academy of Sciences, Sopot, Poland) • Międzylaboratoryjny eksperyment porównawczy - oznaczanie radu w wodach kopalnianych (Interlaboratory comparison of the determination of 226Ra and228 Ra in samples simulating coal mine water). J. Narbutt, L. Fuks (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Oznaczanie zawartości radu w próbkach środowiskowych (Determination of radium content in environmental samples). J.W. Mieteiski, B. Wąs (Institute of Nuclear Physics, Kraków, Poland) » Oznaczanie izotopów radu w wodzie mineralnej metodą ciekłych scyntylatorów (Determination of radium isotopes in mineral waters by liquid scintillation method). A. Hetman, J. Dorda, W. Zipper (Silesian University, Katowice, Poland) • Szybka metoda oznaczania Ra-226 w wodach z wykorzystaniem techniki spektrometrii promieniowania alfa (Rapid aifa-spectrometric method for Ra-226 determination in waters). A. Mielnikow, A. Śmieszek, S. Chałupnik (Central Mining Institute, Katowice, Poland) • Określenie śladowych aktywności Ra-226 poprzez pomiar emanacji Rn-222 (Determination of trace activities of Ra-226 by measurement of Rn-222 emanation). A. Kordyasz (University of Warsaw, Warszawa, Poland), A. Bilewicz (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Przykłady wykorzystania jonitu Chelex-100 do rozdzieleń radiochemicznych (Examples of the use of CheIex-100 ion exchanger for radiochemical separations). Z. Samczyński, R. Dybczyński (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) 182 ... CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1998 • Badanie nad rozdziałem 90Y od izotopów radu i toru przy oznaczaniu 90Sr w próbkach gleby (Studies on separation of 90Y from radium and thorium isotopes for the determination of 90Sr in some soil samples). J. Sołecki (M. Curie-Skłodowska University, Lublin, Poland) » Oznaczanie zawartości izotopów promieniotwórczych w materiałach budowlanych metodą wielokanałowej spektrometrii promieniowania gamma (Determination of radionuclide content in building materials using multichannel gamma spectrometry). W. Walkowiak, A. Żebrowski, W. Charewicz, B. Borek (Wrocław Technical University, Wrocław, Poland) • Uniwersalna metoda oznaczania śladowych zawartości molibdenu w materiałach biologicznych za pomocą RNAA (The universal method for determination of trace amounts of molybdenum in biological materials using RNAA method). B. Danko, R. Dybczyński (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Bardzo dokładne równoczesne oznaczanie śladowych ilości Co i Ni w materiałach biologicznych metodą RNAA (Very accurate simultaneous determination of trace amounts of Co and Ni in biological materials using RNAA method). H. Polkowska-Motrenko, R. Dybczyński, B. Danko (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), D.A. Becker (National Institute of Standards and Technology, Gaithersburg, USA) • Uran w wodach kopalni kaolinu w Żarowie (Dolny Śląsk) - metodyka oznaczania i przesłanki genetyczne (Uranium content in waters of the kaolin mine at Żarów (Lower Silesia) - methodology of determination and genetic premises). N. Dinh Chau, P. Wyszomirski, E. Chruściel, A. Ochoński (Academy of Mining and Metallurgy, Kraków, Poland) • Ekstrakcja Ce-139 w układzie eter etylowy - HNO3 w aspekcie zastosowania do wydzielania ceru z tarcz lantanowych (Etheral extraction of carrier-free Ce-139 as a method for the separation of cerium from lanthanum target). E. Ochab, R. Misiak (Institute of Nuclear Physics, Kraków, Poland) 2. KRAJOWE SYMPOZJUM "TECHNIKA JĄDROWA W PRZEMYŚLE, MEDYCY- NIE, ROLNICTWIE I OCHRONIE ŚRODOWISKA (NATIONAL SYMPOSIUM ON NUCLEAR TECHNOLOGY IN INDUSTRY, MEDICINE, AGRICULTURE AND ENVIRONMENTAL PROTECTION), 16-18 SEPTEMBER 1998, KRAKÓW, POLAND Organized by Council for Nuclear Problems; Polish Nucleonic Society; Faculty of Physics and Nuclear Technology, Academy of Mining and Metallurgy; Institute of Nuclear Chemistry and Technology; Foundation for Radiation Research Organizing Committee: Prof. Tadeusz Florkowski, Ph.D., D.Sc. (Chairman), Zdzisław Stfgowski, Ph.D. (Secretary), Prof. Andrzej G. Chmielewski, Ph.D., D.Sc, Stanisław Galant, Ph.D., Prof. Andrzej Kreft, Ph.D., D.Sc, Andrzej Owczarczyk, Ph.D., Jacek Siwiński, M.Sc, Stanisław Szpilowski, Ph.D., Prof. Piotr Urbański, Ph.D., D.Sc, Mirosław Zimnoch, M.Sc. Sesja ogólna (General session) • Belgian experience with radiation technologies for sterilization. H. Bonet, P. Dardenne (National Institute for Radioisotopes, Belgium), A. Herer (Ion Beam Application S.A., Belgium) • Non power applications of nuclear technology: the case of Belgium. A.L. Jaumotte (Belgium) CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1998 __ • The main activities of SCK-CEN, the Belgian Nuclear Research Centre. P. Govaerts (Belgian Nuclear Research Centre, Belgium) • NIRAS/ONDRAF and radioactice waste management in Belgium. F. Decamps (NIRAS/ONDRAF, Belgium) • Fleurus site - the isotope valley created by the National Institute for Radioisotope (IRE). H. Bonet (National Institute for Radioisotope, Belgium) • AVN: its regulatory activities. P. Govaerts (AVN, Belgium) • Ion Beam Aplications S.A., Chemin du Cyclotron 3, Louvain-la-Neuve, Belgium. Radiacyjne technologie oczyszczania spalin (Radiation technologies for the purification of flue gas) • Badania procesu radiacyjnego usuwania zanieczyszczen z gazow spalinowych w skali pilotowej (Investigation of electron beam process of flue gas purification on a pilot plant scale). A.G. Chmielewski, B. Tyminski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Demonstracyjna przemyslowa instalacja jednoczesnego usuwania SO2 i NOX z gazow odlotovvych przy uzyciu wia_zki elektronow w Elektrowni Pomorzany (Demonstration of industrial installation for a simultaneous removal of SO2 and NOX from flue gases using electron beam in the Power Station Plant Pomorzany). A.G. Chmieiewski, E. IHer (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Wyznaczanie modeli empirycznych efektywnosci usuwania NOX i SO2 dla dwustopniowego systemu napromieniania spalin w oparciu 0 wyniki uzyskane w pilotowej stacji w EC Kaw?czyn (Empirical models of NOX and SO2 removal for two stage irradiation of flue gas based on the results of experiments on a pilot plant scale in the EPS Kawe.czyn). Chmielewski A.G., Tyminski B., Dobrowolski A. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), Licki J. (Institute of Atomic Energy, Otwock-Swierk, Poland) Technologie radiacyjne w przemysle zywnosciowym i kosmetycznym (Radiation technologies in the food and cosmetic industries) • Radiacyjna dekontaminacja surowc6w zielarskich i fitopreparatow (Decontamination of herbal raw materials and medicinal herbs by irradiation). W. Migdai, H.B. Owczarczyk, K. Malec-Czechowska (Pilot Plant for Food Irradiation, Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Radiacyjna dekontaminacja (higienizacja) surowc6w i wyrobbw kosmetycznych (Decontamination (hygienisation) of cosmetics and raw materials by radiation). K. Malec-Czechowska, W. Migdai, H.B. Owczarczyk (Pilot Plant for Food Irradiation, Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Napromienianie zywnosci jako zabieg kwarantannowy (Food irradiation as quarantine treatment). S. Ignatowicz (Agricultural University of Warsaw, Warszawa, Poland) • Opracowania w Instytucie Problemow Jajdrowych akceleratorow elektronow dla technologii radiacyjnej (Development of accelerators for radiation technology in the Institute for Nuclear Studies). J. Bigolas, S. Kulinski, M. Pachan, E. Plawski (Institute for Nuclear Studies, Otwock-Swierk, Poland) • Zastosowanie akceleratorowej techniki w.cz. w agrotechnice (Application of high frequency accelerator technique in agrotechnique). J. Sura (Institute for Nuclear Studies, Otwock-Swierk, Poland) • Zastosowanie spektrometrii EPR, termoluminescencji oraz metod badania uszkodzen DNA i zdolnos"ci kielkowania do identyfikacji napromieniowania zywnos"ci (Application of EPR spectroscopy, thermoluminescence, analysis of DNA damage and germination power for identification irradiation food). 184 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1998 K. Malec-Czechowska, W. Stachowicz, A.M. Dancewicz, Z. Szot (Laboratory for Detection of Irradiated Foodstuffs, Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Zastosowanie technik jqdrowych w badaniach srodowiska i naukach o Ziemi (Application of nuclear techniques in studies of the environment and Earth sciences) • Izotopowa identyfikacja antropogenicznego CO2 w aglomeracji krakowskiej (Isotopic identification of anthropogenic CO2 in the Krakow agglomeration). T. Kuc, H. Mr6z {Academy of Mining and Metallurgy, Krakow, Poland) • Opracowanie metody prognozy wzdluzbrzegowego nate_zenia ruchu osadow morskich przy zastosowaniu radioznacznikow (Prediction of longshore sediment transport rate by the use of radiotracers). Z. Pruszak (Institute of Hydroengineering, Polish Academy of Sciences, Gdansk, Poland), R. Wierzchnicki (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Badania dynamiki Morza Kaspijskiego z wykorzystaniern izotop6w Srodowiska (Studies of dynamics of the Caspian Sea with the use of environmental isotopes). K. Rozanski (Academy of Mining and Metallurgy, Krakow, Poland), K. Froehlich (International Atomic Energy Agency, Vienna, Austria), R. Kipfer (Swiss Federal Institute of Technology ETH/EWAG, Dilbendorf, Switzerland) • Dyfuzyjne parametry dla neutrondw termicznych w os"rodkach o zmiennej ge_stosci nasypowej (Thermal neutron diffusion parameters for media of variable bulk density). J. Dabrowska, K. Drozdowicz, B. Gabanska, M. Kosik, E. Krynicka, U. Woznicka (Institute of Nuclear Physics, Krakow, Poland) • Stanowisko do pomiaru niestacjonarnych pol neutronowych przy impulsowym generatorze neutron6w pre,dkich IFJ w Krakowie (Time-dependent neutron field experimental set-up at pulsed neutron generator in the INP, Krakow). J. Burda, A. Igielski, W. Janik, M. Kosik, A. Kurowski, U. Woznicka, T. Zaleski (Institute of Nuclear Physics, Krakow, Poland) • Niektore zastosowania spektrometrii gamma w odwiertach naftowych i we.glowych (Some application of spectrometric gamma-ray loging in prospection of oil and hard-coal deposits). E. Chrus'ciel, K.W. Palka, T. Zaorski (Academy of Mining and Metallurgy, Krakow, Poland), T. Massalski, J. Puchacewicz (Geophysics, Krak6w, Base of Drilling Geophysics, Zielona Gora, Poland) • Oznaczanie izotopow uranu i radu w wodach metoda. pomiarow niezaleznych promieniowania alfa i beta za pomoca. spektrometru z cieklym scyntylatorem (Determination of uranium and radium isotopes in water by alpha- and beta-liquid scintillation spectrometry). Nguyen Dinh Chau, E. Chrusciel, J. Niewodniczanski, A. Ochonski (Academy of Mining and Metallurgy, Krakow, Poland) • Zmiany ste.zen metali cie_zkich w torfie z Puscizny Rejcowianskiej (Changes in the concentration of heavy metals in peat from Puscizna Re.kowianska). B. Holyhska, B. Ostachowicz, J. Ostachowicz, L. Samek, P. Wachniew, D. W?grzynek (Academy of Mining and Metallurgy, Krakow, Poland), K. Stroeli, D. Wobrauschek (Technical University, Atominstitute, Vienna, Austria) » Badania izotopowe pochodzenia w6d w kopalniach soli w Polsce (Isotope studies of the orgine of waters in salt mines in Poland). M. Duliriski, A. Garlicki, J. Grabczak (Academy of Mining and Metallurgy, Krakow, Poland), A. Zuber (Institute of Nuclear Physics, Krakow, Poland) • Zastosowanie promieniowania y do rozkladu 2,4-dichlorofenolu dla potrzeb ochrony srodowiska (The use of y-radiation for degradation of 2,4-dichlorophenol as a contribution to environmental protection). P. Drzewicz, M. Trojanowicz, W. Gluszewski, P. Panta (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1998 185_ Metody radiometryczne w badaniach materialowych (Radiometric methods for materials testing) • Technika radiometryczna w badaniach ge.stosci i wytrzymalosciowej jakos"ci iglastej tarcicy budowlano- konstrukcyjnej (Radiometric technique in studies of the density and quality strenght of coniferous timber in construction - building engineering). W. Dzbehski, S. Krzosek (Agricultural University of Warsaw, Warszawa, Poland) • O pomiarze ge.stos"ci drewna za pomoca. promieniowania gamma (Measurement of wood density by means of Y-radiation). E. Gierlik, M. Muchorowska (Agricultural University of Warsaw, Warszawa, Poland) • Oznaczanie zawartosci naturalnych pierwiastkdw promieniotworczych w surowcach i materialach budowlanych - opis i por6wnanie stosowanych metod (Determination of concentration of natural radioisotopes in some raw and building materials - description and comparison of used methods). P. Jodtowski, SJ. Kalita (Academy of Mining and Metallurgy, Krakow, Poland) Znaczniki izotopowe w badaniach biologicznych i diagnostyce medycznej (Radiotracers in biological studies and in medical diagnosis) • Wpiyw dolistnego nawozenia mocznikiem i stosowania chlorku chlorochliny na akumulacje. Cs-137 w plonach pszenicy jarej (The influence of nitrogen - urea fertilization to leaves and chloride chlorocholine on the accumulation of Cs-137 in spring wheat crops). B. Hrynczuk, R. Weber (Institute of Soil Science and Plant Cultivation, Jelcz-Laskowice, Poland) • Wpryw skazen dolistnych i doglebowych na zawartos"c metali cie.zkich w plonie pszenicy (The effect of contamination through leaves and soil on the content of heavy metals in spring wheat yield). B. Hrynczuk, R. Weber (Institute of Soil Science and Plant Cultivation, Jelcz-Laskowice, Poland) • Wejiel 14C w diagnozowaniu zakazenia przewodu pokarmowego - Helicobacter pylori (14C in the diagnosis of infection of alimentary canal - Helicobacter pylori). M. Wasilewska-Radwanska, A. Jung, T. Kuc (Academy of Mining and Metallurgy, Krak6w, Poland), Z. Kopanski, A. Cienciaia, B. Witkowska (Military Hospital, Krakow, Poland) • Sonda Modelo-2 do radioimmunodetekcji nowotworow dla kontroli srodoperacyjnej - perspektywy zastosowan w Polsce (Modelo-2 probe to radioimmunodetection of tumors for intraoperative control - application prospects in Poland). J.-F. Chatal, Ch. Curtet (Institut Nationale de la Sante et dela Recheche Medicale, Nantes, France), G. Daniel (Commissariat a 1'Energie Atomic, Gif-sur-Yvette, France), J. Kulka, M. Wasilewska-Radwanska, P. Strozik (Academy of Mining and Metallurgy, Krakow, Poland) • "Igla fotonowa" do radioterapii ("Photon needle" for radiotherapy). M. Slapa, S. Pszona, W. Stas, M. Traczyk (Institute for Nuclear Studies, Otwock-Swierk, Poland), J. Dora (Dora Power System, Wroclaw, Poland), R. Gutowski (Uniquant, Warszawa, Poland) • Niektore elementy narazenia radiologicznego mieszkancow wojewodztwa lodzkiego (Some aspects of radiological hazard of the inhabitants of the £<5dz province). H. Bern, P. Wieczorkowski, M. Ostrowska (Institute of Applied Radiation Chemistry, Lodz Technical University, Lodz, Poland) Radioizotopowa aparatura przemysiowa (Industrial radioisotope apparatus) • Kinetyczny efekt izotopowy we.gla-13 w reakcji dekarboksylacji kwasu fenylopropiolowego w bezwodnym kwasie mrowkowym (Kinetic effect of !3C in the decarboxylation reaction of phenylpropiolonic acid in anhydrous formic acid). M. Zielihski, A. Zielinska, H. Papiernik-Zielinska (Faculty of Chemistry, Jagiellonian University, Krakow, Poland), H. Paul (Laboratory of Stable Isotopes, Swiss Federal Institute of Technology, Zurich, Switzerland) • Wykorzystanie zamkniejych zr6del promiemotw6rczych do precyzyjnych pomiarow pre_dkosci przeplywow dwufazowych (Sealed sources application for precise velocity measurements in two phase flows). L. Petryka (Academy of Mining and Metallurgy, Krak6w, Poland) 186 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1998 35 35 • Dyfiizja siarki S w P-Ni3S2 (Diffusion of the sulfur S nuclide in (3-Ni3S2). J. Gilewicz-Wolter, A. Ochonski (Academy of Mining and Metallurgy, Krakow, Poland), Z. Zurek (Cracow Technical University, Krakow, Poland) • Badanie procesu sedymentacji czajstek osadu biologicznego w przemyslowym zbiorniku prostokajtnym (Study of precipitation process of biological sediment particles in industrial tank). A. Owczarczyk, J. Palige, A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Zastosowanie techniki jajdrowej w urzajdzeniach i systemach kontrolno-pomiarowych w gornictwie (Application of nuclear technique in facilities and control-measuring systems in the mining industry). T. Sikora, B. Czerw (Research and Development Centre for Electrical Engineering and Automation in Mining EMAG, Katowice, Poland) Detektory promieniowania i aparatura (Radiation detectors and apparatus) • Nowa generacja wzorc6w radionuklidow (New generation of radionuclide standards). A. Chylinski, T. Radoszewski, T. Terlikowska-Drozdziel (Radioisotope Production and Reactor Centre, Otwock-Swierk, Poland) • Postej? w dziedzinie gazowych detektor6w promieniowania (Progress in the field of gaseous detectors of radiation). K. Jeleri, T. Kowalski, E. Rulikowska-Zare.bska (Academy of Mining and Metallurgy, Krak6w, Poland) • Ciaj*fy pomiar radonu w powietrzu za pomoca. komory Lucasa (Continuous measurement of radon concentration in air with Lucas cell). B. Machaj, P. Urbanski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Zastosowanie matematycznej standaryzacji widm promieniowania X w aparaturze radiometrycznej (Application of mathematical standardization of X-ray spectra in radiometric instruments). E. Kowalska, P. Urbahski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Uniwersalny, mikroskopowy uktad zbierania i przetwarzania danych radiometrycznych (Versatile PC-logger for radioisotope measurements). L. Furman, K. Przewiocki, L. Petryka, Z. Ste.gowski, A. Wierzbicki (Academy of Mining and Metallurgy, Krakow, Poland) Technologie jqdrowe w badaniach zabytkow kultury materialnej (Nuclear technologies in studies of monuments of material culture) • Proba wykorzystania kamery CCD do obrazowania rozkladu ste,zen emiterow niskoenergetycznego promieniowania p~ (A trial to use a CCD camera to illustrate the distribution of emiters of soft p-radiation). Z. Gorski (Poznan Technical University, Poznan, Poland) • Wykorzystanie niektorych metod radiometrycznych do identyfikacji zabytkowych szkiei i szkliw ceramicznych (Application of some radiometric methods for identification of antique glasses and ceramics). JJ. Kunicki-Goldfinger (Institute of Preservation and Conservation of Works of Art, Nicholas Copernicus University of Torun, Torun, Poland), P. Urbariski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Postery (Posters) • Nowe rozwia^zania systemu przyspieszaja^cego w medycznym akceleratorze CO-LINE/1000 - 4 MeV (New solution of an accelerating system of the medical accelerator CO-LINE/1000 - 4 MeV). J. Bigolas, S. Gietka, S. Kuliriski, J. Olszewski, M. Pachan, E. Plawski, J. Pszona (Institute for Nuclear Studies, Otwock-Swierk, Poland) • Badania nad zmiejszaniem zanieczyszczen mikrobiologicznych w miodzie przy uzyciu promieniowania jonizuJQcego (Studies on the reduction of microbiological impurities in honey by means of ionizing radiation). CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1998 J87_ B. Ke.dzia, E. Holderna-Ke.dzia (Institute of Medicinal Plants, Poznan, Poland), W. Migdal, B. Owczarczyk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), D. Madajczyk (Qkre.gowa SpoWzielnia Pszczelarska, Poznan, Poland) • Standardowe i specjalne gazowe detektory promieniowania jonizujaj:ego opracowane i wykonywane w AGH (Standard and special gaseous detectors for ionizing radiation developed and produced in the Academy of Mining and Metallurgy). B. Bednarek, K. Jelen, T. Kowalski, K. Ostrowski, E. Rulikowska-Zare>ska (Academy of Mining and Metallurgy, Krakow, Poland) • Oznaczanie potasu w zabytkowych szkiach metodami radiometrycznymi (Potassium determination in ancient glasses by detection of its natural gamma ray activity). J.J. Kunicki-Goldfinger (Institute of Preservation and Conservation of Works of Art, Nicholas Copernicus University of Torun, Torun, Poland), J. Kierzek, B. Sartowska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Analiza aktywacyjna jako przyczynek do ustalenia pochodzenia rzezby (Contribution of activation analysis to determination of sculpture provenance). E. Panczyk, L. Rowinska, L. Walis, B. Sartowska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), M. Lige.za (Academy of Fine Arts, Warszawa, Poland) • Rozwoj zastosowan membran trekowych w Polsce (Development of particle track membranes application in Poland). W. Starosta, M. Buczkowski, D. Wawszczak (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Wpryw Ti na kinetyke. tworzenia sig fazy a w ukiadzie Fe-Cr (Influence of Ti on the formation of c phase in the Fe-Cr system). A. Biachowski, J. Cieslak, S.M. Dubiel (Academy of Mining and Metallurgy, Krakow, Poland), B. Sepioi (Institute of Material Physics, Vienna University, Vienna, Austria) • Wielolicznikowy detektor neutronow do badania zawartosci i rozktadu przestrzennego materialow rozszczepialnych w probkach o duzej objetosci (Multicounter neutron detector for content and spatial distribution of fissile materials in large volume samples). M. Swiderska-Kowalczyk, W. Starosta, T. Zoltowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • System monitoringu i sterowania dla przemyslowo-demonstracyjnej instalacji odsiarczania i odazotowania spalin przy wykorzystaniu wiajzki elektronow z akceleratordw w Elektrowni "Pomorzany" w Szczecinie (Monitoring and control system for demonstrative-industrial installation desulphurization and denutrification of flue gases in the EPS "Pomorzany" in Szczecin). J. Licki (Institute of Atomic Energy, Otwock-Swierk, Poland), A.G. Chmielewski, E. Iller, B. Tyminski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Urzajdzenie do ciajjtego pomiaru radonu w kopalniach (Measuring probe for radon concentration monitoring). J. Bartak, J.P. Pieiikos (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Radiometryczny skaner folii tytanowej (Radiometric scanner for titanium foil). P. Urbanski, E. Kowalska, J. Strzalkowski, E. Swistowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • MozliwoSc przystosowania cyklotronu C-30 do wspoJpracy z PET (Adaptation possibilities of a cyclotron C- 30 to cooperate with PET). S. Kulinski, J Lorkiewicz, M. Pachan, E. Plawski, Z. Sujkowski, J. Sura (Institute for Nuclear Studies, Otwock-Swierk, Poland), L. Krolicki (Department of Nuclear Medicine, Joint Hospital Brodno, Warszawa, Poland) • Zastosowanie sieci neutronowych do radiometrycznego wyznaczania ge.stosci drewna (Neural network application to radiometric wood density determination). Z. St^gowski, M. Micuta (Academy of Mining and Metallurgy, Krakow, Poland) 188 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1998 • Pomiary nate_zenia przeplywu sciek6w w Krakowskiej Fabryce Kabli S.A. (Flow measurements sewers of Cracow Cable Factory). Z. Stejowski, L. Furman, L. Petryka, K. Przewlocki, M. Wojcik (Academy of Mining and Metallurgy, Krakow, Poland) • Mie.dzynarodowy system informacji nukleonicznej INIS - baza danych i mozliwosci jej wykorzystania (International system of nucleonic information INIS - data base and possibilities its use). T. Urbanski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) 3. WORKSHOP ON REACTIVE INTERMEDIATES IN SULFUR CHEMISTRY (DEDICATED TO PROFESSOR K.-D. ASMUS ON HIS 60th BIRTHDAY), 23-26 AUGUST 1998, POZNAN, POLAND Organized by Faculty of Chemistry, Adam Mkkiewicz University, Poznan and Institute of Nuclear Chemistry and Technology, Warszawa Organizing Committee: Prof. Bronislaw Marciniak, Ph.D., D.Sc. (Chairman), Prof. Krzysztof Bobrowski, Ph.D., D.Sc. (Co-Chairman), Jarogniew Bartoszewkz, M.Sc. (Secretary), Janina Brzezinska, Piotr Filipiak, M.Sc., Edyta Janeba, M.Sc., Halina Kozubek, Ph.D., Prof. Stefan Paszyc, Ph.D., D.Sc., Tomasz Pedzinski, M.Sc., Dariusz Pogocki, Ph.D., Grazyna Strzelczak, Ph.D., Pawel Wisniowski, M.Sc. Scientific session I Chairman: C. von Sonntag (Germany) • Sulfur- and selenium-centered radical ions as studied by radiation chemical methods K.-D. Asmus (University of Notre Dame, Notre Dame, USA) Chairman: D.A. Amstrong (Canada) • Role of adduct formation in the atmospheric oxidation of DMS A.R. Ravishankara (National Oceanic and Atmospheric Administration Aeronomy Laboratory (NOAA) & University of Colorado, Boulder, USA) • Radiation induced sulphur dioxide removal A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Chairman: J. Paczkowski (Poland) • Mass spectrometry of thio analogs of pyrimidine bases: [M-*SH] ions and the differentiation of isomeric benzylthiouracils and alkylthiouracils E. Wyrzykiewicz, Z. Nowakowska, G. Bartkowiak (A. Mickiewicz University, Poznan, Poland) » Atmospherically relevant reactions of SH radical S.C. Herndon, A.R. Ravishankara (NOAA & University of Colorado, Boulder, USA) Scientific session II Chairman: A.R. Ravishankara (USA) • Theoretical studies on radicals of some thiols of biological interest within quantum chemical method S. Chhun, J. Berges (P. and M. Curie University, Paris, France), Z. Abedinzadeh (R. Descartes University, Paris, France), C. Houee-Levin (Paris-Sud University, Orsay, France) • Theoretical studies on sulfur-containing radical ions I. Carmichael (University of Notre Dame, Notre Dame, USA) CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1998 Chairman: Ch. Houee-Levin (Fiance) • Equilibria in thiyl and disulfide anion radicals S.P. Mezyk (Atomic Energy of Canada Ltd., Chalk River, Canada), D.A. Amstrong (University of Calgary, Calgary, Canada) • Intermediates during one-electron reduction of sulfonium, selenonium and telluronium cations P. Erikson, L. Engman, J. Lind, G. Merenyi (Uppsala University, Uppsala & Royal Institute of Technology, Stockholm, Sweden) • Radiation chemistry of solid thiosulfate Z.P. Zagorski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Scientific session III Chairman: K.-D. Asmus (USA) • Free radical induced oxidation of thiourea C. von Sonntag (Max-Planck Institute fur Strahlenchemie, Mulheim an der Rohr, Germany) • Adsorption and transformation of sulfur compounds on zeolites M. Ziofek, P. Decyk (A. Mickiewicz University, Poznari, Poland) Chairman: M. Bonifafcic (Croatia) • Mechanisms of reactions of sulfide radical cation complexes with superoxide and oxygen Ch. Schoneich, B.L. Miller, J. Hong (University of Kansas, Lawrence, USA), G.L. Hug, M. Bonifa&c (University of Notre Dame, Notre Dame, USA), K. Bobrowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Fragmentation reactions of aromatic sulfide cation radicals as mechanistic tool to distinguish electron transfer processes in enzymatic and biomimetic oxidations E. Baciocchi, 0. Lanzalunga (University di Roma "La Sapienza", Roma, Italy), S. Steenken (Max-Planck Institut fiir Strahlenchemie, Mulheim, Germany) Chairman: G.L. Hug (USA) « Oxidation of organic sulfur compounds by peroxyl radicals M. Bonifacic (Ruder Boskovic Institute, Zagreb, Croatia) • Radiolytically induced reductive degradation of halothane in air-saturated aqueous solutions in presence of methione and dimethyl sulfide R. Fliount, O. Makogon (Institute of Physico-Chemistry, Academy of Sciences of the Ukraine, Lvov, Ukraine), Ch. Schoneich (University of Kansas, Lawrence, USA), K.-D. Asmus (University of Notre Dame, Notre Dame, USA) Scientific session IV Chairman: Ch. Schoneich (USA) • One-electron reduction of disulfide bonds in proteins free properties modulated by the peptidic environment Ch. Houee-Levin (University of Paris XI, Orsay, France) • Hydroxyl-radical induced oxidation of thiaproline derivatives D. Pogocki, A. Sciejosz, K. Bobrowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Poster session • Mass spectrometry of some derivatives of thiostilbenols W. Prukala (A. Mickiewicz University, Poznan, Poland) 190 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1998 • Mass spectrometry of bromo substituted derivatives of 2-alkoxycarbonylalkylthio-6-methyluracils J. Wybieralska (A. Mickiewicz University, Poznan, Poland) • Time-correlated background elimination and optical calibration of the time scale of TCSPC measurements of picosecond deactivation of aromatic thiones K. Dobek, J. Karolczak, D. Komar, J. Kubicki, M, Szymanski, T. Wr6zowa, M, Zi61ek Jr., A. Maciejewski (A. Mickiewicz University, Poznari, Poland) • Picosecond deactivation of benzopyranthione S2 state in reactive solvents J. Karolczak, D. Komar, J. Kubicki, M. Szymanski, T. Wr6zowa, W. Augustyniak, A. Maciejewski, M. Milewski (A. Mickiewicz University, Poznan, Poland) • The time-resolved study of Ti-excimer formation and its characteristic for xanthione in benzene solution P. Antkowiak, J. Baksalary, M. Binkowski, M. Szymanski, A. Maciejewski (A. Mickiewicz University, Poznan, Poland) • Direct spectroscopic characterization of benzopinacole radical cation J. Rogowski, A. Marcinek, P. Bednarski, J. G?bicki (Technical University of L6dz, Lodz, Poland), J.H. Penn (West Virginia University, Morgantown, USA) • Polymerization of acrylamide in aqueous mediem initiated by a redox system of 4-carboxybenzophenone and sulfur-containing amino acids A. Wrzyszczynski, F. Scigalski, J. P^czkowski (Technical and Agricultural University, Bydgoszcz, Poland) • Phenylthiocetic, S-benylthioglycolic and 2,2'-thiodiglycolic acids, as the coinitiators of the polymerization A. Wrzyszczynski, F. Scigalski, J. P^czkowski (Technical and Agricultural University, Bydgoszcz, Poland) • ESR study of polycrystalline tripeptides G. Strzelczak, K. Bobrowski, J. Michalik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • *OH induced oxidation of a-(methylthio)acetamide P. Wisniowski, K. Bobrowski (Institute of Nuclear Chemsitry and Technology, Warszawa, Poland) • Photochemical reactions of trithianes in solution E. Janeba, H. Kozubek, W. Urjasz, B. Marciniak (A. Mickiewicz University, Poznan, Poland), G.L. Hug (University of Notre Dame, Notre Dame, USA) • Interaction of the excited singlet state of acridine deratives with sulfur-containing organic compounds in aqueous solution T. Pe_dziriski, B. Marciniak (A. Mickiewicz University, Poznan, Poland) Scientific session V Chairman: G. MerGnyi (Sweden) • Sulfur-containing organic compounds as initiators and contiators of free radical polymerization F. Scigalski, A. Wrzyszczynski, J. Paczkowski (Technical and Agricultural University, Bydgoszcz, Poland) • Cyclic sulfides as coinitiators in benzophenone induced photopolymerization E. Andrzejewska, M. Andrzejewski (Poznan University of Technology, Poznan, Poland), G.L. Hug (University of Notre Dame, Notre Dame, USA), B. Marciniak (A. Mickiewicz University, Poznan, Poland) • Photooxidation of methionine derivatives by the 4-carboxybenzophenone triplet state in aqueous solution. Intra-complex proton transfer involving the amino group G.L. Hug (University of Notre Dame, Notre Dame, USA), K. Bobrowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), H. Kozubek, B. Marciniak (A. Mickiewicz University, Poznan, Poland) Chairman: S. Paszyc (Poland) • The role of reactive intermediates in deactivation of aromatic thioketones from S2 and T, -states CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 1998 19j_ A. Maciejewski, M. Szymanski (A. Mickiewicz University, Poznan, Poland) • Femtosecond transient absorption spectrometer for investigation of reactive intermediates of aromatic thiones in solution M. Lorenc (A. Mickiewicz University, Poznan, Poland) 192 Ph.D./D.Sc. THESES D.Sc. THESES 1. Aleksander Bilewicz, Ph.D. Wpływ efektu relatywistycznego na własności chemiczne pierwiastka 104 (Influence of relativistic effect on chemical properties of element 104). Institute of Nuclear Chemistry and Technology Ph.D. THESES 1. Bożena Danko, M.Sc. Studia nad konstruowaniem bardzo dokładnych metod oznaczania wybranych pierwiastków śladowych w materiałach biologicznych za pomocą radiochemicznego wariantu neutronowej analizy aktywacyjnej (Studies on the development of very accurate methods for the determination of selected trace elements in biological materials by a radiochemical variation of activation analysis). supervisor: Prof. Rajmund Dybczyński, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, 30.04.1998 2. Iwona Grądzka, M.Sc. Wpływ kamtotecyny na komórki L5178Y (The influence of camptothecin on LS178Y cells). supervisor: Prof. Irena Szumiel, Ph.D., D.Sc. University of Warsaw, Faculty of Biology, 7.11.1998 Ph.D. PROGRAMME IN CHEMISTRY The Institute of Nuclear Chemistry and Technology offers a four year Ph.D. degree programme to: graduates from chemical, physical and biological faculties of universities, engineers of chemical technology and material science, graduates from medical universities. 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. Besides of the employement for candidates accepted for the forementioned programme, the Institute offers an opportunity of application for supplemental doctoral scholarship. During the programme each participant takes part in a 45 h course of lectures of fundamental physical chemistry, a 30 h specialization course and is obliged to give an annual seminar on a topic of his/her dissertation area. The final requirements for the Ph.D. programme graduates, consistent with the Ministry of the National Education rules, are: • submission of a formal dissertation, summarizing original research contributions suitable for publication; • final examination and public defense of the thesis. Applicants for the Ph.D. degree programme are accepted all around the year. Detailed information can be obtained from Admission Secretary, Dr. Jadwiga Krejzler (phone (+48-22) 811-27-35). RESEARCH PROJECTS AND CONTRACTS 193 RESEARCH PROJECTS AND CONTRACTS RESEARCH PROJECTS GRANTED BY THE POLISH STATE COMMITTEE FOR SCIENTIFIC RESEARCH IN 1998 AND IN PREVIOUS YEARS 1. New wood preservatives based on polymerized aminotriazole complexes with copper. supervisor: Prof. Andrzej Lukasiewicz, P.D., D.Sc. 2. Application of a multi-counter neutron detector for fissionable isotopes identification and determination of their spatial distribution in bulk samples. supervisor: Assoc.Prof. Tadeusz Zoitowski, Ph.D., D.Sc. 3. Differential scaning 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. 4. Multivariate statistical methods for analysis in radiometric measurements. supervisor: Prof. Piotr Urbanski, Ph.D., D.Sc. 5. Influence of relativistic effect on chemical properties of the heaviest elements. supervisor: Assoc.Prof. Aleksander Bilewicz, Ph.D., D.Sc. 6. Even odd effect in separation of the isotopes of f-electron elements in the three electron exchange reactions. supervisor: Wojciech Dembinski, Ph.D. 7. Hydration of oxaalkanes in aqueous solutions. supervisor: Assoc.Prof. Jerzy Narbutt, Ph.D., D.Sc. 8. High coordination number of metal ions in chelate complexes. supervisor: Assoc.Prof. Jerzy Narbutt, Ph.D., D.Sc. 9. Concentration of radioactive wastes using the membrane distillation (MD) process. supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. 10. Polypropylene composites with thermoplasic elastomers modified by radiation processing. supervisor: Prof. Jacek Michalik, Ph.D., D.Sc. 11. Polymer materials with adhesive properties modified by fast electron beams. supervisor: Przemysfaw P. Panta, Ph.D. 12. Optical spectra of free radicals in polypropylene at room temperature. supervisor: Prof. Zbigniew P. Zagorski, Ph.D., D.Sc. 13. Separation analytical application of amphoteric ion exchange resin retardion 11 A 8. supervisor: Prof. Rajmund Dybczynski, Ph.D., D.Sc. 14. 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. 15. Studying of the significance of DNA double-strand break repair in the adaptive response of human lymphocytes. supervisor: Maria Wojew6dzka, Ph.D. 16. Analysis of centromeres in micronuclei by fish for biological dosimetry. supervisor: Andrzej Wojcik, Ph.D. 194 _^ RESEARCH PROJECTS AND CONTRACTS 17. Optimization of radiation removal process of SO2 and NOX from flue gases containing high concentration of SO2 (supervision of IEA PhD fellow). supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. 18. The transport and activation of the corrosion products in the nuclear reactor eguipped with independent multi-loop cooling (supervision of IEA PhD fellow). supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. IMPLEMENTATION PROJECTS GRANTED BY THE POLISH STATE COMMITTEE FOR SCIENTIFIC RESEARCH IN 1998 1. Thermo-melt glue polymer composites with adhesive properties for heat-shrinkable products. 3T09B544 96C/2871 2. Irradiation method for microbiological decontamination of herbal raw materials. 5P O6G 004 96 C/2870 3. Serenissima. Investigation and restauration of XV-XVIII century Venice paintings from National Museum Collection in Warsaw. Elaboration of model of physical-chemical and restauration researches of XV-XVIII century Venice paintings from National Museum Collection in Warsaw. 1H01E00196C/3009 4. Instruments for measurements of radon concentration. 8T10C 016 97C/3615 5. Small dimensions universal eiectrofilter for inorganic hygroscopic salts capture. 8T10A 083 98 GOVERNMENTAL 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: Assoc.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 1998 1. Complexation and distribution of ecologically important metals in heterogenous systems. POL/7377/RB principal investigator: Assoc.Prof. Jerzy Narbutt, Ph.D., D.Sc. 2. Synthesis and studies of new selective absorbents for beryllium, strontium and radium radionuclides. POL/7216/RB principal investigator: Assoc.Prof. Aleksander Bilewicz, Ph.D., D.Sc. 3. 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. 4. Materials for in-situ monitoring of light water reactor (LWR) water chemistry by optical methods. 8426/RB principal investigator: Leon Fuks, Ph.D. RESEARCH PROJECTS AND CONTRACTS 195 5. Thin layer alanine dosimeter with optical spectrophotometric evaluation. 8533/RB principal investigator: Prof. Zbigniew P. Zagorski, Ph.D., D.Sc. 6. Decontamination of herbal raw materials and herbal drugs by irradiation. 10355/Regular Budget Fund principal investigator: Wojciech Migdai, Ph.D. 7. 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 1998 1. Electron beam flue gas treatment. POL/8/013 2. Industrial scale demonstration plant for electron beam purification of flue gases. POL/8/014 3. Control laboratories for radiation processing. POL/8/16 4. Repair of ionization detector chamber. IRA 8012-108G EUROPEAN COMMISSION RESEARCH PROJECTS IN 1998 1. The comet assay: application in gentoxicity testing and as a screening method for assessing the exposure of human populations to genotoxins. CIPA-CT94-0129 supervisor: Marcin Kruszewski, Ph.D. 2. Establishment of an Eastern European Network of Laboratories for Identification of Irradiated Foodstuffs. a) ERB CIPA CT 940134-2 supervisor: Wactaw Stachowicz, Ph.D. b) ERB CIPA CT 940134-3 supervisor: Wojciech Migdai, Pd.D. 3. 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. 4. Accreditation for high dose measurement. IC15-CT96-0824 supervisor: Zofia Stuglik, Ph.D. OTHER FOREIGN CONTRACTS IN 1998 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 Deptuia, Ph.D. 196 RESEARCH PROJECTS AND CONTRACTS 2. Validation of an immunochemical assay for the detection of DNA damage as a tool for biological desimetry of human exposure to ionizing radiation. Contract with TNO Prins Maurits, Laboratory, Rijswijk, Holland principal investigator: Marcin Kruszewski, Ph.D. 3. Preparation of HTS (BSCCO) dopped by strontium zirconate and barium zirconate. 81240033 Contract with Argonne National Laboratory, USA 4. Know-how and thermoshrinkable tubes technology by application of Electron Beam Accelerator. PL/000144058/57-5073 Contract with Atomic Energy Organization, Iran 5. Know-how and technology of thermoshrinkable tubes radiation crosslinking in the range of extrusion. PW/HO/119/97 Contract with KNM ENTERPRISE, Malaysia 6. Decomposition of organic volatile compounds by electron beam treatment. Contract with University of Kuopio, Finland principal investigator: Anna Ostapczuk, M.Sc. LIST OF VISITORS TO THE INCT IN 1998 197 LIST OF VISITORS TO THE INCT IN 1998 Name Institution Country Period 1. Angelo Alberti Institute for Carbon and Heteroatom Containing Italy 18.02-27.02 Compounds and Application 2. Jacqueline Belloni Universite Paris-Sud France 14.04-16.04 3. Jacqueline Berges Universite Paris-Sud France 20.08-27.08 4. Brian Broznick Center for Organ Recovery and Education USA 27.06-28.06 5. John Burgess University of Leicester Great r 23.11-25.11 Britain 6. Dora de Castro Rubio Institute of Energy and Nuclear Research, IPEN Brazil 13.05-22.05 Poli 7. Zhifang Chai Chinese Academy of Sciences, Institute of High China 09.05-17.05 Energy Physics 8. Andrew Collins Rowett Research Institute Great 02.09 Britain 9. Nicolas Confuorto Research Cottrell USA 03.03-05.03 10. Anatolije Czalych Institute of Physical Chemistry, Russian Academy of Russia 01.12-03.12 Sciences 11. Xiongxin Daj Chinese Academy of Sciences, Institute of High China 09.05-17.05 Energy Physics 12. Henry Delincee Institute of Nutritional Physiology Germany 03.05-15.05 13. Robert Delmas CEA/CNR Laboratoire Pierre Sue France 21.09-25.09 14. Ann-Charlotte University of Lund, Department of Food Technology, Sweden 09.06-14.06 Eliasson Chemical Centre 15. Alireza Farahmand Atomic Energy Organization of Iran, Nuclear Research Iran 02.07-23.12 Center 16. Norman Frank International Business Consultants USA 29.06-04.07 22.11-09.12 17. Ralph Genuario Virginia Accelerators Corporation USA 28.02-05.03 27.06-28.06 18. Julius Glaser Royal Institute of Technology Sweden 15.05 19. Maija Harkonen Virginia Accelerator Corporation USA 28-02-05.03 20. Darleane Hoffman University of California USA 25.09 21. Veijo Honkonen School of Engineering Finland 08.06-27.06 22. Chantal Houee-Levin Universite Paris-Sud France 20.08-27.08 23. Gordon L. Hug University of Notre Dame, Radiation Laboratoiy USA 06.02. 198 LIST OF VISITORS TO THE INCT IN 1998 24. Tetsuya Kodaira National Institute of Materials and Chemical Research, Japan 06.09-10.09 Department of Surface Chemistry 25. Valentyna Kotusova Institute "Energostall" Ukraine 01.10-03.11 26. David Lewis DRL Group, Inc. USA 16.03 27. Wanderley de Lima Institute of Energy and Nuclear Research IPEN Brazil 13.05-22.05 28. Johan Lind Royal Institute of Technology, Department of Nuclear Sweden 17.08-23.08 Chemistry 29. Xueying Mao Chinese Academy of Sciences, Institute of High China 09.05-17.05 Energy Physics 30. Yann Martin Ecole des Mines Nantes France 04.05-04.08 31. Juan Menguala University Complutense, Department of Applied Spain 31.10-07.11 Physics 32. Gabor Merenyj Royal Institute of Technology, Department of Nuclear Sweden 22.08-28.08 Chemistry 33. Ame Miller Ris0 National Laboratory Denmark 11.10-16.10 34. Henrieta Nichipor Institute of Radiation Physical and Chemical Belarus 01.02-14.02 Problems, Academy of Sciences of Belarus 28.06-12.07 35. Dioko Slamet Yogyakarta Nuclear Research Centre, BATAN Indonesia 01.04-30.06 Pudjorahardjo 36. Pekka Pyykko University of Helsinki Finland 24.01 37. Omer Salah Harraga Tajoura Nuclear Research Centre Libya 07.09-31.12 38. Christian Schoneich University of Kansas USA 11.09-14.09 39. Shuichi Shimomura National Institute for Research in Inorganic Materials Japan 02.09-10.09 40. Masaru Shiotani Hiroshima University, Department of Applied Physics Japan 22.06-27.06 41. Rostislav Silber Czech Technical University Czech 16.09 Republic 42. Ulrich Waldschlager Institute of Environmental Technologies Germany 05.07-10.07 43. Hirohisa Yamada National Institute for Research in Inorganic Materials Japan 02.09-10.09 44. Ajji Zaki Radiation Technology Department AECS Syria 14.09-19.09 45. Sergei P. Institute of Nuclear Physics Russia 17.02-24.02 Zakovriachin THE INCT SEMINARS IN 1998 199 THE INCT SEMINARS IN 1998 1. Dr John Burgess (University of Leicester, Great Britain) Slow substitution at labile metal ions. 2. Prof. Zhifang Chai, Prof. Xueying Mao (Academie Sinica, Beijng, China) Iridium anomaly and dinosaur extinction. 3. Prof. Zhifang Chai (Academie Sinica, Beijng, China) Chemical speciation study by molecular activation analysis. 4. Dr Andrew Collins (Rowett Research Institute, Bucksburn, Aberdeen, Great Britain) Antioxidants and human health. 5. Dr Henry Delincee (Federal Research Centre for Nutrition, Karlsruhe, Germany) Detection of irradiation foods. 6. Prof. Ann-Charlotte Eliasson (University of Lund, Sweden) Understand the behaviour of starch in cereal products. 7. Dr Julius Glaser (Royal University of Technology, KTH, Stockholm, Sweden) Compounds for light-induced electron transfer: metal-metal bonds between main group and transition metals. 8. Dr Edward Iller (Institute of Nuclear Chemistry and Technology) Model dyspersyjny w radioznacznikowych badaniach transportu medi6w w reaktorach chemicznych (Dispersion model in radiotracer investigations of transport media in chemical reactors). 9. Prof. Juan Menguala (Universidad Complutense de Madrid, Madrid, Spain) Membrane distillation. 10. Dr Andrzej Pawlukojc (Joint Institute of Nuclear Research, Dubna, Russia; Institute of Nuclear Chemistry and Technology, Warszawa, Poland) Zastosowanie spektroskopii neutronowej we wspokzesnej chemii (Application of neutron spectroscopy in contemporaneous chemistry). 11. Prof. Christian Schb'neich (University of Kansas, Lawrence, USA) Reactive oxygen species in aging: mechanistic investigation using radiation and photochemistry. 12. Prof. Masaru Shiotani (Hiroshima University, Japan) Generation, structure and dynamics of radicals in zeolites: EPR study. 200 SEMINARS DELIVERED OUT OF THE INCT IN 1998 SEMINARS DELIVERED OUT OF THE INCT IN 1998 1. Aleksander Bilewicz Synteza i wiasnos"ci chemiczne nowych pierwiastkow (Synthesis and chemical properties of new elements). Faculty of Chemistry, University ofWarsaw, Warszawa, Poland, 03.02.1998 2. KrzysztofBobrowski Intramolecular hydrogen transfer during OH-induced oxidation of substituted thioethers. Laboratoire Chimie-Physique des Rayonnements, Universite Paris Sud (XI), Orsay, France, 07.05.1998 3. KrzysztofBobrowski Intramolecular hydrogen transfer in a-(metylthio)acetamide. Pulse radiolysis and flash photolysis studies. Department of Chemistry, Brookhaven National Laboratory, Upton, NY, USA, 13.07.1998 4. KrzysztofBobrowski Intramolecular hydrogen transfer in p-hydroxy sulfides and thioamides. Department of Chemistry and Nuclear Chemistry, Royal Institute of Standards and Technology, Stockholm, Sweden, 25.03.1998 5. KrzysztofBobrowski Metody chemii radiacyjnej w badaniach mechanizm6w reakcji fotochemicznych zwiazkow organicznych (Methods of radiation chemistry in the investigations of mechanisms of photochemical reactions of organic compounds). Wydzial Technologii i Inzynierii Chemicznej, Akademia Techniczno-Rolnicza (Department of Technology and Chemical Engineering, Technical and Agricultural University), Bydgoszcz, Poland, 08.12.1998 6. Andrzej G. Chmielewski Application of radiotracers in research and optimization of waste-water treatment stations. International Atomic Energy Agency, Vienna, Austria, 20.04.1998 7. Andrzej G. Chmielewski Co zawdzie_czamy odkryciom Marii Sktodowskiej-Curie i Piotra Curie w technice i technologii (What we owe to the discoveries of Maria Sklodowska-Curie and Pierre Curie in technique and technology). Seminarium "Atom i spokczenstwo. W stulecie odkrycia polonu i radu" (Seminar on "Atom and society. Hundred years after the discovery of polonium and radium"). Paristwowa Agencja Atomistyki (National Atomic Energy Agency), Warszawa, Poland, 15.06.1998 8. Andrzej G. Chmielewski 1). Conventional technologies for air pollution control. 2). EB for flue gas treatment. 3). Overview of air pollution. Seminar on Electron Beam Technology for Environmental Protection, Malaysian Institute of Nuclear Technology, Bangi, Malaysia, 30.11.1998 9. Andrzej G. Chmielewski Nuclear methods for science and technology - the main areas of activities of the Institute of Nuclear Chemistry and Technology. Universidad Complutense de Madrid, Facultad de Ciencias Fisicas, Departamento de Fisica Aplicada 1, Madrid, Spain, 7.10.1998 10. Andrzej G. Chmielewski (co-author: Zbigniew Zimek) Nuclear technology cleans coal emissions. Example of international cooperation that led to the application of a nuclear technology in a civilian sector. Environmental Challenges of Nuclear Disarmament. Workshop NATO, Krak6w, Poland, 10.11.1998 11. Edward Iller (co-authors: Andrzej G. Chmielewski, B. Tyminski, Z. Zimek, J. Licki) SEMINARS DELIVERED OUT OF THE INCT IN 1998 201 Electron beam flue gases treatment in Poland. NATO Advanced Research Workshop: The Modern Problems of Electrostatics with Applications in Environment Protection, Bucharest, Rumunia, 10.11.1998 12. Marcin Kruszewski Mutanty kom6rek gryzoni wrazliwe na promieniowanie jonizujaj;e (Mutants in cells from rodents sensitive to ionizing radiation). Komisja Ochrony Radiologicznej i Radiobiologii PAN (Commission for Radiological Protection and Radiobiology, Polish Academy of Sciences), Warszawa, Poland, 17.03.1998 13. Marcin Kruszewski :. . . Oksydacyjne uszkodzenia DNA w linii komorkowej L5178Y - stymulacja metabolizmu jon6w metali przejsciowych, ochronnego systemu antyoksydacyjnego (Oxidative damage of DNA in L5178Y cell lines - stimulation of the metabolism of ions of transient metals, an oxidative defence system). Akademia Medyczna (Medical Academy), Bydgoszcz, Poland, 10.02.1998 14. Jacek Michalik Conduction Electron Spin Resonance of metallic particles in mezoporous materials. National Institute for Research in Inorganic Materials, Tsukuba, Japan, 17,03.1998 15. JerzyNarbutt Inorganic ion exchangers as selective adsorbents and potential primary barrier for radionuclides. Environmental Challenges of Nuclear Disarmament. Workshop NATO, Krakow, Poland, 11.11.1998 16. JerzyNarbutt Inorganic ion exchangers for waste management with special reference to nuclear wastes. Department of Chemistry, Andhra University, Visakhapatnam, India, 17.03.1998 17. JerzyNarbutt Ion exchange and its applications. College of Engineering, Ghandi Institute of Technology and Management (GITAM), Visakhapatnam, India, 12.03.1998 18. JerzyNarbutt Outer sphere hydration of metal (3-diketonates. Regional Research Laboratory (CSIR), Bhubaneshwar, India, 19.03.1998 19. JerzyNarbutt Outer sphere hydration of metal chelates and its role in solvent extraction. Radiochemistry Division, Bhabha Atomic Research Centre (BARC), Mumbai-Bombay, India, 23.03.1998 20. JerzyNarbutt Solute-solvent interactions of metal complexes and their role in solvent extraction. Department of Chemistry, Utkal University, Bhubaneshwar, India, 18.03.1998 21. Slawomir Siekierski Chemia pierwiastkow (Chemistry of elements). Cykl wykladow dla studentow Studium Doktoranckiego Uniwersytetu Warszawskiego (A series of lectures for postgraduate students of Warsaw University). University of Warsaw, Warszawa, Poland, October-December 1998. 22. Zygmunt Szopa A proposal for the general certification scheme as applied to the results of two IAEA intercomparisons IAEA-085 and IAEA-086. International Atomic Energy Agency, Vienna, 02.09.1998 23. Zygmunt Szopa SSQC package as a tool at the certification of a candidate reference material. PCI Laboratories, International Atomic Energy Agency, Seibersdorf, 28.08.1998 24. Irena Szumiel Sygnalizacja komorkowa w odpowiedzi na promieniowanie jonizuj^ce (Cell signalling in the respons to ionizing radiation). Centrum Onkologii (Oncology Centre), Warszawa, Poland, 02.12.2998 202 SEMINARS DELIVERED OUT OF THE INCT IN 1998 25. Piotr Urbański, Ewa Kowalska Radiometryczne metody pomiaru grubości powłok (Radiometrie methods of coating thickness gauges). Wykłady i ćwiczenia na kursie: Metody pomiaru grubości powłok metalowych i niemetalowych na różnych rodzajach podłoża (Lectures and classes on: Methods of coatings thickness gauges on metallic and non- metallic substrates). Instytut Mechaniki Precyzyjnej (Institute of Precision Mechanics), Warszawa, Poland, 18-22.05.1998 26. Andrzej Wójcik Kuenstlische menschlische Chromosomen (Artificial human chromosomes). Essen University, Essen, Germany, 25.11.1998 27. Andrzej Wójcik Radiation-induced aberration frequencies in chromosomes 1 and 2 of two human donors. University of Leiden, Leiden, Holland, 28.10.1998 28. Andrzej Wójcik Risiko niedriger Strahlendoses (Risk of low radiation doses). Essen University, Essen, Germany, 11.11.1998 29. Andrzej Wójcik Telomere, Telomerase und Krebs (Telomere, telomerase and cancer). Essen University, Essen, Germany, 18.11.1998 30. Grażyna Zakrzewska-Trznadel Membrane technology for radioactive effluents treatment and isotope separation. Universidad Complutense de Madrid, Facultad de Ciencias Fisicas, Departamento de Fisica Aplicada 1, Madrid, Spain, 6.10.1998 31. Zbigniew Zimek Industrial applications of electron beam accelerators. National Center for Radiation Research Research and Technology, Cairo, Egypt, 17.12.1998 32. Zbigniew Zimek Perspektywy zastosowań techniki radiacyjnej na skalę przemysłową (Prospects of radiation processing application on industrial scale). Zebranie Polskiego Towarzystwa Nukleonicznego (Meeting of the Polish Nucleonic Society), Warszawa, Poland, 16.04.1998 33. Zbigniew Zimek Sterylizacja radiacyjna sprzętu medycznego jednorazowego użytku przy wykorzystaniu przyśpieszonych elektronów (Radiation sterilization of disposable medical devices by accelerated electrons). Nowoczesne technologie radiacyjne w 100 lat od odkrycia polonu i radu (Modern Radiation Technologies 100 Years after the Discovery of Polonium and Radium), Salon Medyczny (Medical Chamber), Poznań, Poland, 03.04.1998 COMPUTER NETWORK IN THE INCT 203 COMPUTER NETWORK IN THE INCT A subnet for scientific, administrative and management purposes have been put in operation in the Institute. The network in its physical layer is based on the 10 Base-T technology. This is a multistar type of network. The network links computers localized in different buildings of the Institute with a net hub miniMMAC (Cabletron). The interior of the buildings is wired UTP with cables, joining the particular terminals with the buildings hub. Transfer of the data in the network amounts to 10 MB/s. All the computers attached to the network are of PC type. They are equipped with network cards made by 3 Com (EtherLink III - 3C 509). The server from this internal network is working under the Windows NT 4.0 system, in the PDC mode. Data files located in the server are commonly used by the different research departments and administrative divisions of the Institute. A security system of the availability of the files allows to use the data only by the authorized users. The subnet is protected from an external access to both the hardware and software. 204 INDEX OF THE AUTHORS INDEX OF THE AUTHORS A FIEDLER R. 70 ACTIDA L. 52 FUKS L. 54,79 ALTHAUSF.R. 110 AMBROŻ H.B. 26,27 G AMENITSCH H. 94 GŁUSZEWSKI W. 30 GRĄDZKA I. 111 B GRIGORIEW H. 93,94,134 BARAN S. 88 GRÓTZSCHEL R. 125, 126, 127 BARTOŚ B. 70 H BEREZKIN V.V. 132 BERNSTORFF S. 94 HARASIMOWICZ M. 122, 123 BILEWICZ A. 70 HOFMANN M. 88 BOBROWSKIK. 19,20,24 HUG G.L. 19 BOUŻYK E. 113,115 •j BRUCKMANN E. 114 1 BRYL-SANDELEWSKA T. 50 ILLER E. 119 BUCZKOWSKIM. 132, 134, 142 IWANEŃKO T. 106,109 BUŁKA S. 28 BURZYŃSKA-SZYSZKO M. 52 K KACZMAREK S.M. 43 C KASPRZAK A.J. 130 CHMIELEWSKI A.G. 28,93,94, 119, KIERZEK J. 67, 130, 143 121, 122, 123 KLECZKOWSKA H.E. 110 CHWASTOWSKA J. 96 KORNACKA E.M. 26,27 CIEŚLA K. 56, 57, 59 KOWALSKA E. 138 COLLINS A.R. 109 KRAŚJ. 128 CROCE F. 80 KREJZLER J. 73 CZERWIŃSKI M. 73 KRUSZEWSKI M. 106, 107, 108, 109 KRYNICKI J. 45 TV D KULISA K. 95 DANKO B. 100 KUNICKI-GOLDFINGER J.J. 67, 130 DASHOUK E. 28 DEGUELDRE C. 54 L DEMBIŃSKI W. 70 LANGNERJ. 126 DEPTUŁA A. 80,84 LECIEJEWICZ J. 87,88,89,90,91, DINDUNE A. 52 92 DOMAGAŁA J. 93,94 LeGEROS J.P. 84 DRZEWICZ P. 30 LeGEROS R.Z. 84 DUDEK J. 98 LEGRAS R. 59 DYBCZYŃSKI R. 95, 100 LENARTOWICZ M. 123 LfCKI J. 119 F L1GĘZA M. 63 FERAIN E. 59 L1PIŃSKI P. 107 INDEX OF THE AUTHORS 205 Ł RETMAŃSKA H. 107 LADA W. 80,84 REUTHER H. 126 ŁUKASIEWICZ A. 129 RIBEIRO M. 56 ŁUKASIEWICZ T. 43 ROWIŃSKA L. 63, 64, 129 RZEWUSKI H. 45 M s MACHAJ B. 135 MALARSKI Z. 87 SADŁO J. 21 SADOWSKA-BRATEK M. 96 MALICKI W. 53 MAŁOŻEWSKA-BUĆKO B. 130, 143 SAMCZYŃSKI Z. 100 MARCIN1AK B. 19 SARTOWSKA B. 67, 84, 134, 142 SEHESTED K. 36 MARCINIEC B. 26 MAURIN J.K. 92 SKWARA W. 99 SOCHANOWICZ B. 105, 107, 108 MICHALIK J. 21,24 STANISŁAWSKI J. 125, 127 MIODUSKI T. 77 MOROZZ. 43 STAROSTA W. 59,132, 139, 141, 142 MYCZKOWSKI S. 128 STERLIŃSKA E. 96 N STĘPKA K. 43 STREFFER Ch. 113 NALEPA B. 63 STRZELCZAK G. 24 NARBUTT J. 71,73,79 STUGLIK Z. 49,50,51,52,53 NATKANIEC I. 87 SZUMIEL I. 105, 108,109, 110, NICHIPOR H. 28 111, 113 SZYTUŁA A. 88 O OBEG. 114 Ś OLCZAK T. 80,84 ŚWIDERSKA-KOWALCZYK M. 139 OLENIAK J. 45 OLSZEWSKA J. 64 T OWCZARCZYK A. 120, 121 TROJANOWICZ M. 30 TYMIŃSKI B. 119, 122 P PALIGE J. 120, 121 U PALUCHOWSKA B. 92 URBAŃSKI P. 138 PANTA P.P. 30 PAŃCZYK E. 63,64 W PARUS J. 143 WALIŚ L. 63, 64, 129 PAWLUKOJĆ A. 87 WARCHOŁ S. 43,45 PENC B. 88 WAWSZCZAK D. 132, 134, 142 PIEKOSZEWSKI J. 325, 126, 127 WERNER Z. 126, 127 PONIŃSKI M. 70 WIERZCHNICKI R. 120, 133 PRZYBYTNIAK G. 26, 27, 34 WIESERE. 126, 127 PSZONICKI L. 98,99 WJ.ŚNIOWSKI P. 20 PTASIEWICZ-BĄK H. 89,90,91 WOJEWÓDZKA M. 109 PUTON J. 45 WOLIŃSKA-GRABCZYK A. 93 WÓJCIK A. 113, 114 R RADOSZEWSKI T. 137 Y RAFALSKI A. 38,41,46,47 YU J-S. 21 206 INDEX OF THE AUTHORS z ZAGORSKI Z.P. 33,34,36,38,46, 47 ZAKRZEWSKA-TRZNADEL G. 122, 123, 134 ZIMEK Z. 28 Z ZENDZIAN W. 43 ZOLTOWSKI T. 139 ZUCHOWSKA D. 34 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]