PL9702079 ISSN 1425-ZU4A
IN/&~PL- 003
INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY m DO /? WMEM\ 1996 OF NUCLEI AND TECHNOLOGY
1996 EDITORIAL BOARD
Wiktor Smuiek, Ph.D. Ewa Godlewska Sylwester Wojtas
© Copyright by the Institute of Nuclear Chemistry and Technology, Warszawa 1997 All rights reserved CONTENTS
GENERAL INFORMATION 7
MANAGEMENT OF THE INSTITUTE 9 MANAGING STAFF OF THE INSTITUTE 9 HEADS OF THE INCT DEPARTMENTS 9
PROFESSORS AND SCIENTIFIC COUNCIL 10 PROFESSORS 10 ASSOCIATE PROFESSORS 10 ASSISTANT PROFESSORS (Ph.D.) 11 SCIENTIFIC COUNCIL (1995-1999) 13 HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (1995-1999) 14
RADIATION CHEMISTRY AND PHYSICS 15 ONE-ELECTRON OXIDATION OF METALLOPORPHYCENES AS STUDIED BY RADIOLYTIC METHODS D M. Guldi, J. Field, J. Grodkowski, P. Neta, E. Vogel 17 IRON-PORPHYRIN CATALYZED REDUCTION OF CO& PHOTOCHEMICAL AND RADIATION CHEMICAL STUDIES J. Grodkowski, D. Behar, P. Neta, P. Hambright 17 RATE CONSTANTS FOR REACTIONS OF ALIPHATIC CARBON-CENTERED RADICALS IN AQUEOUS SOLUTION P. Neta, J. Grodkowski, A.B. Ross 19 TETRABENZOPORPHYRINS: METAL INCORPORATION AND EXCHANGE KINETICS, LIGATIONAL EQUILIBRIA AND PULSE RADIOLYSIS STUDY S. Cromer, P. Hambright, J. Grodkowski, P. Neta 19 REDUCTION AND ALKYLATION OF RHODIUM PORPHYRINS IN ALCOHOL SOLUTIONS. RADIATION CHEMICAL AND PHOTOCHEMICAL STUDIES J. Grodkowski, P. Neta, Y. Abdallach, P. Hambright 20 •OH RADICAL INDUCED OXIDATION OF S-METHYLCYSTEINE AND ITS DERIVATIVES FRAGMENTATION OF a-AMINOALKYL RADICALS D. Pogocki, K. Bobrowski, K.-D. Asmus 21 Trp ' -* iyrO RADICAL TRANSFOMATION IN HEN-EGG WHITE LYSOZYME K. Bobrowski, J. Holcman, J. Poznafiski, K.L. Wierzchowski 24 SENSITIZED PHOTOOXIDATION OF METHIONINE-CONTAINING PEPTIDES IN AQUEOUS SOLUTION K. Bobrowski, B. Marciniak, G.L. Hug 25 GENERATION OF SULFUR RADICALS IN ZEOLITES BY MEANS OF IONIZING RADIATION S. Kowalak, Z. Stuglik, M. Strtiiyk, AB. Wiqckowski 28 ESR STUDY OF RADIATION INDUCED RADICALS IN POLYCRYSTALLINE METHIONINE AND ITS HOMOPEPTIDES G. Strzelczak-Burlitiska, K. Bobrowski, D. Pogocki, J. Michalik 28 ENDOR OF HUMAN TOOTH ENAMEL HEATED AT 400°C J. Sadto, F. Callens, J. Michalik, W. Stachowicz, P. Mattys, E. Boesman 30 DAMAGE BUILDUP AND AMORPHIZATION IN ION - IMPLANTED GaAsi-xPx S. Warchol, J. Krynicki, H. Rzewuski, R. Groetzschel 31 DOSIMETRIC RESPONSE OF MICROCRYSTALLINE L-a- ALANINE AND STANDARD BONE POWDER TO HIGH-LET RADIATIONS Z. Stuglik, J. Sadto 33 DOSIMETRIC PROPERTIES OF CDP-F2 FOILS Z. Stuglik, T. Bryl-Sandelewska 34 THE FORMATION OFdCMP RADICALS FOLLOWING RADIOLYSIS, THE EFFECT OF CYSTEAMINE G. Przybytniak, J, Hiittermann, H. Ambroz, B. Weiland 35 UV-Vis ABSORPTION SPECTRUM OF THE RADICAL ANION DERIVED FROM e-ALANINE BY DEAMINATION ZP. Zagdrski, G.K, Przybytniak 36 EXAFS STUDY OF SILVER CLUSTERS IN ZEOLITE H. Grigoriew, J. Michalik 38 RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 41
SOLVENT EXTRACTION OF GROUP 4 AND 14 METAL CHELATE COMPLEXES. MODEL EXPERIMENTS FOR CHEMICAL STUDIES ON COORDINATION NUMBER OF ELEMENT 104 A Bilewicz 43 FRACTIONATION OF EUROPIUM ISOTOPES IN THE EXTRACTION SYSTEMS. Eu(HI), HDEHPZEu(IlI), H+ (Cl-, NOJ, SO* -). LIGAND ISOTOPE EFFECT W. Dembitiski, R. Fiedler, Z. Janiszewski 43 FRACTIONATION OF YTTERBIUM ISOTOPES IN Yb(III)-ACETATE/Yb-AMALGAM SYSTEM. EVEN-ODD EFFECT W. Dembitiski, M. Poniliski, R. Fiedler 45 SEPARATION OF PROTIUM/DEUTERIUM AND OXYGEN-16/OXYGEN-18 BY MEMBRANE DISTILLATION G. Zakrzewska-Trznadcl, A.G. Chmielewski 46 PRECONCENTRATION OF RADIUM FROM SALINE COAL-MINE WATER ON SELECTIVE ION EXCHANGER - a-CRYSTALLINE MANGANIC ACID J. Narbutt, A Bilewicz, B. Bart06, R. Postek 47 SYNTHESIS AND ION EXCHANGE PROPERTIES OF VARIOUS FORMS OF MANGANESE DIOXIDE FOR CATIONS OF I AND II GROUPS B. BartoA, A Bilewicz, R. Delmas, C. Loos-Neskovid 48 HYDRATION AND COVALENCE OF THE Ln2+ AND An2+ IONS vs. ALKALINE EARTH IONS AS REFLECTED IN SOLUBILITY AND COCRYSTALLIZATION OF THEIR SULFATES T. Mioduski SO LIQUID-LIQUID PARTITION AND HYDRATION OF STRAIGHT-CHAIN OXAALKANES E. Gniazdowska, J. Narbutt 51 BEHAVIOUR OF THE SYSTEM: ARSENIC-PALLADIUM-MAGNESIUM DURING ATOMIZATION IN GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROMETRY L. Pszonicki, J. Dudek 53 DETERMINATION AND SPECIATION OF MERCURY IN NATURAL WATERS J. Chwastowska, W. Skwara, E. Sterlirtska, J. Dudek, L. Pszonicki 54 PREPARATION OF GEL PRECURSORS FOR SYNTHESIS OF MERCURY - BASED SUPERCONDUCTING CUPRATES FROM ACIDIC ACETATE-AMMONIA SYSTEMS A Deptuta, T. Olczak, W. Lada, A Di Bartolomeo 54 A STUDY OF SUITABILITY OF THE ION CHORMATOGRAPHY EQUIPMENT OF DIONEX 2000i/SP FOR THE DETERMINATION OF ALKALI METALS AND OTHER INORGANIC CATIONS IN AQUEOUS SOLUTIONS K. Kulisa, R. Dybczyliski, H. Polkowska-Motrenko 55 IINS SPECTROSCOPY OF AMINOACIDS. PART IV. SULFOGLYCINE A Pawlukojd, J. Tomkinson, S.F. Parker 58 IINS SPECTROSCOPY OF AMINOACIDS. PART V. L-SERINE A Pawlukojd, S.F. Parker 58 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLIC ACIDS. PART XV. THE CRYSTAL AND MOLECULAR STRUCTURES OF DIAQUABIS (3-AMIN0PYRAZINE-2-CARB0XYLAT0-N,0)MAGNESIUM(II) MONOHYDRATE AND 3-AMINOPYRAZINE-2-CARBOXYLIC ACID DIHYDRATE H. Ptasiewicz-Bqk, J. Leciejewicz 59 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLIC ACIDS. PART XVI. THE CRYSTAL AND MOLECULAR STRUCTURE OF CALCIUM AMINOPYRAZINATE J. Leciejewicz, H. Ptasiewicz-Bqk, B. Paluchowska 60 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLIC ACIDS. PART XVII. THE CRYSTAL AND MOLECULAR STRUCTURES OF PYRAZINE-2.5-DICARBOXYLIC ACID DIHYDRATE AND ITS MAGNESIUM COMPOUND H. Ptasiewicz-Bqk, J. Leciejewicz 61 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLIC ACIDS. PART XVIII. THE CRYSTAL STRUCTURE OF DIAQUABIS(THIOPHENE-2-CARBOXYLATE)ZINC(II) B. Paluchowska, IK. Maurin, J. Leciejewicz 62 MAGNETIC ORDERING IN LANTHANIDE INTERMETALLIC PHASES J. Leciejewicz, A Szytula 62 X-RAY STUDY OF WATER INFLUENCE ON CELLULOSE MEMBRANE STRUCTURE H. Grigoriew, AG. Chmielewski 64
RADIOBIOLOGY 67 OXIDATIVE BASE DAMAGE IN DNA FROM L5178Y SUBLINES M. Kruszewski, T. Zastawny, T. Wrortska, R. Oliliski 69 EFFECT OF COPPER CHELATOR, NEOCUPREINE, ON L5178Y CELLS E. BouZyk, T. Iwancliko, M. Kruszewski 70 ION CHELATOR, DESFERAL, DIFFERENTIALLY AFFECTS NULEOID DNA IN TWO SUBLINES OF L5178Y MURINE LYMPHOMA E. Bouiyk, T. Iwaneliko, M. Kruszewski 70 DETERMINATION OF DNA DAMAGE REPAIR IN CAMPTOTHECIN - TREATED MURINE LYMPHOMA CELLS BY THREE METHODS I. Grqdzka, I. Szumiel 71 INDUCTION OF DNA-PROTEIN CROSS LINKS BY GAMMA RAYS IN CELLS OF THREE MURINE LYMPHOMAS N. Jarocewicz, I. Szumiel 72 LACK OF CORRELATION BETWEEN DNA REPAIR KINETICS, RESIDUAL DAMAGE AND MICRONUCLEI FREQUENCY IN RADIOADAPTBD HUMAN LYMPHOCYTES M. Wojew6dzka, M Kruszewski, I. Szumiel 73 APPLICATION OF THE COMET ASSAY FOR DETECTION OF DNA DAMAGE IN LYMPHOCYTES OF WORKERS EXPOSED TO LOW-DOSES OF IONIZING RADIATION M. Wojewddzka, T. Iwaneliko. M. Kruszewski 73 LOVASTATIN TREATMENT DIFFERENTIALLY ALTERS ACTIVATION OF TRANSCRIPTION FACTOR, NF*B AND SENSITIVITY TO HYDROGEN PEROXIDE B. Sochanowicz, I. Szumiel 74 INITIAL DNA DAMAGE AND LETHALITY IN BLEOMYCIN - TREATED L5178Y CELLS J. Zaim, I. Szumiel 75
NUCLEAR TECHNOLOGIES AND METHODS 77 PROCESS ENGINEERING 79 CONCEPTUAL DESIGN OF THE DEMO-INDUSTRIAL INSTALLATION FOR ELECTRON-BEAM FLUE GAS TREATMENT AG. Chmielewski, E. Iller, B. Tymiliski, Z Zimek 79 FILTRATION OF AEROSOLS FORMED IN EB FLUE GAS TREATMENT PROCESS AG. Chmielewski, B. Tymiliski, G. Zakrzewska-Trznadel, O. Tokunaga, S. Machi 82 RADIOTRACERS IN ROTARY KILNS INVESTIGATION J. Palige, A Owczarczyk 83 TRACER INVESTIGATION OF THE SEDIMENT AND SEWAGE FLOW DYNAMICS THROUGH AERATION TANK A Owczarczyk, J. Palige, M. Strzelecki, AG. Chmielewski 84 MEMBRANE DISTILLATION EMPLOYED FOR CONCENTRATION OF LIQUID RADIOACTIVE WASTE AG. Chmielewski, M. Harasimowicz, G. Zakrzewska-Trznadel 86 METAL RECOVERY FROM DILUTE STREAMS M. Harasimowicz, J. Palige 86 APPLICATION OF PARTICLE TRACK MEMBRANES IN A DYNAMIC FILTRATION DEVICE W. Starosta, M. Buczkowski, S. Wroliski, A Adach 87 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS 89 NEW APPARATUS FOR PREPARATION OF GASEOUS METHYL BROMIDE AND RECORDING LEAKS IN UNDERGROUND PIPELINES J. KraS, S. Myczkowski 89 INTENSE PLASMA PULSES; TWO MODES OF THE USE FOR SURFACE PROCESSING PURPOSES J. Piekoszewski, J. Langner, L. WaliS, Z. Werner 89 USE OF HIGH INTENSITY PULSED PLASMA BEAMS IN FORMATION CERAMIC/MBTAL JOINTS J. Piekoszewski, J. Langner, A Krajewski, L. WaliS, W. Wiosiliski 90 THE PLASMA DISCHARGE DEVICE FOR MODIFICATION OF SURFACE PROPERTIES OF PARTICLE TRACK MEMBRANES W. Starosta, M. Buczkowski, D. Wawszczak, T. Z6ttowski 91 PREPARATION OF HIGH PURITY BORON ON A LARGE LABORATORY SCALE A. Nowicki 92 ORGANIC FIBRES IMPREGNATED WITH POLYMERIC COMPLEXES OF AMINOTRIAZOLE WITH METALS AS NEW FILTERS AND SORBENTS A. Lukasiewicz, L. WaliS 93 PREPARATION OF CALCIUM PHOSPHATE SPHERICAL POWDERS AND COATINGS BY COMPLEX SOL-GEL PROCESS (CSGP) A Deptula, W. Lada, T. Olczak, R Z LeGeros, J.P. LeGeros 94 DETERMINATION OF TRACE ELEMENTS IN LEAD WHITE FROM LANCKORONA PAINTING COLLECTION BY INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS E. Paliczyk, P. Rudniewski, L. WaliS 96 APPLICATION OF X-RAY FLUORESCENCE ANALYSIS FOR EXAMINATION OF THE AUTHENTICITY OF THAI CERAMICS A. Kalicki, E. Paliczyk, L. WaliS 100 STUDIES OF MILLINGABILITY OF COAL COMBUSTED IN HEAT POWER STATIONS P J. Bukowski 101 TOTAL-REFLECTION X-RAY FLUORESCENCE ANALYSIS FOR EFFECTIVENESS OF MICROFILTRATION MEASUREMENTS M Buczkowski, J. Kierzek, D. Wawszczak, U. Waldschlager 102 RADIATION TECHNOLOGIES 104 RADIATION STERILIZATION OF MEDICAL DEVICES I. Kaluska, Z. Stuglik 104 GERMINATION TEST APPLIED TO IRRADIATED GRAIN AND CORN K. Malec-Czechowska, AM. Dancewicz, Z. Szot 104 SPATIAL DOSE DISTRIBUTION IN REACTION VESSEL MEASUREMENTS USING PVC AND CTA FILMS P. Panta, S. Bulka, W. Ghiszewski 106 INVESTIGATIONS OF STRUCTURAL CHANGES IN HEAVY ION IRRADIATED POLYESTER FILMS K. CieSIa, E. Ferain, K. Grzebieniak, R. Legras, H. Frydiych 108 POSSIBILITIES OF INSTRUMENTAL NAA APPLICATION FOR MULTIELEMENT LARGE-SCALE ANALYSIS OF MATERIALS IMPORTANT FOR ECOLOGY AND GEOLOGY M. Wasek, Z. Szopa, R. Dybczyliskl 109 NUCLEONIC CONTROL SYSTEMS 111 RADON MEASUREMENTS IN AIR B.Machaj 111 APPLICATION OF ANN FOR CALIBRATION OF SOME RADIOMETRIC GAUGES E. Kowalska, P. Urbaflski 113 DOSE READER B. Machaj, J. Strzalkowski, K. Smofko 114 NANOSECOND GENERATOR FOR THREE ELECTRODE ELECTRON GUN Z. DZwigalski, Z. Zimek 116 80 kV/100 ns ELECTRON GUN MODULATOR OF LAE 10 ACCELERATOR Z. Diwigalski, Z. Zimek 117
THE INCT PUBLICATIONS IN 1996 119
THE INCT REPORTS IN 1996 137
NUKLEONIKA 139
THE INCT PATENTS AND PATENT APPLICATIONS IN 1996 142 PATENTS 142 PATENT APPLICATIONS 142 CONFERENCES ORGANIZED BY THE INCT IN 1996 143
PhD THESES 150
RESEARCH PROJECTS AND CONTRACTS 151 RESEARCH PROJECTS GRANTED BY THE POLISH STATE COMMITTEE FOR SCIENTIFIC RESEARCH IN 1996 AND IN PREVIOUS YEARS 151 IMPLEMENTATION PROJECTS GRANTED BY THE POLISH STATE COMMITTEE FOR SCIENTIFIC RESEARCH IN 1996 152 RESEARCH PROJECTS OF MARIA SKLODOWSKA-CURIE JOINT FUND II IN 1996 152 IAEA RESEARCH CONTRACTS IN 1996 152 IAEA TECHNICAL CONTRACTS IN 1996 153 EUROPEAN COMMISSION RESEARCH PROJECTS IN 1996 153 OTHER FOREIGN CONTRACTS IN 1996 153 LIST OF VISITORS TO THE INCT IN 1996 154 GENERAL INFORMATION 7
GENERAL INFORMATION
The Institute of Nuclear Chemistry and Technology (INCT) is one of the successors of the Institute of Nuclear Research (INR) which was established in 1955. The latter Institute, once the biggest Institute in Poland, has exerted a great influence on the scientific and intelectual life in this country. The INCT came into being as one of the independent units established after the dissolution of the INR in 1983. The fundamental research on radiobiology, radio- and coordination chemistry and radiation chemistry is continued. Two outstanding scientists representing these fields - Professors Siawomir Siekierski and Zbigniew P. Zagdrski celebrated their 70-ieth birthday in 1996. To acknowledge their attainments during nearly half a century of scientific work President of Poland awarded them the Officer’s Cross of Polonia Restituta. The Institute offers academic and research programmes for Ph.D. and D.Sc. thesis in chemistry. Institute is one of the most advanced innovation centres working on development of technologies and methods in the field of: • radiation chemistry and technology, • application of nuclear methods in material and process engineering, • design and manufacturing of instruments based on nuclear techniques, • trace analysis and radioanalytical techniques, e 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: e experimental pilot plant for food irradiation, • pilot plant for radiation sterilization of medical devices and transplantations, • pilot plant for radiation modification of polymers, • pilot plant for removal of SO2 and NO% from flue gases. In 1996 the Institute organized a large conference on "Electron paramagnetic resonance of radicals and metal complexes" and an annual coordination meeting on the flue gas treatment between the International Atomic Energy Agency (IAEA), the Japan Atomic Energy Research Institute (JAERI) and the Institute of Nuclear Chemistry and Technology. Common research projects were performed in the frames of: • grants from the European Union: - The comet assay: application in genotoxicity testing and as a screening method for assessing the exposure of human populations to genotoxins, - Decontamination of aqueous waste streams, - Examination of homological recombination in mammalian cell mutants defective in DNA double strand break repair, - Establishment of an Esteam European Network of Laboratories for Identification of Irradiated Foodstuffs; • under contract with the National Commission for Nuclear and Alternative Energy Sources (ENEA, Italy) - Preparation of cathodic materials precursors for fabrication 8 GENERAL INFORMATION of rechargeable Li batteries (Li manganates, LiCoOz, LiNio.5Coo.5O2) by sol-gel process; • via a three-parties agreement with the IAEA and JAERI - Electron beam purification of flue gases. In 1996 several students and specialists from Finland, India, Iran and Cuba completed their longer research trainings in the Institute. The INCT participates in IAEA technical cooperation programmes and organizes training courses. The employees of the Institute undertake many expert missions for the IAEA. The Polish Section of the International Nuclear Information System is situated in the INCT. The Institute is the editor of NUKLEONIKA - world wide recognized journal for nuclear research. MANAGEMENT OF THE INSTITUTE 9
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 Radiation Chemistry and Engineering Technology Assoc.Prof. Lech WaliS, Ph.D. Zbigniew Zimek, Ph.D.
• Department of Structural Research • Department of Analytical Chemistry Wojciech Starosta, M.Sc. Prof. Rajmund Dybczyriski, Ph.D., D.Sc.
• Department of Radioisotope Instruments and • Department of Radiobiology and Health Methods Protection Assoc.Prof. Piotr Urbahskl, Ph.D., D.Sc. Prof. Irena Sznmiel, Ph.D., D.Sc.
• Department of Radiochemistry • Pilot Plant for Food Irradiation AssocProf. Jerzy Narbutt, Ph.D., D.Sc. • Wojciech Migdal, Ph.D.
• Department of Nuclear Methods of Process • Laboratory for Detection of Irradiated Engineering Foodstuffs Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. Wadaw Stachowicz, PhD. 10 PROFESSORS AND SCIENTIFIC COUNCIL
PROFESSORS AND SCIENTIFIC COUNCIL
PROFESSORS
1. Chmielewskl Andrzej G. chemical and process engineering, nuclear chemical engineering, isotope chemistry 2. Dancewicz Antoni biochemistry, radiobiology 3. Dybczynski Rajmund analytical chemistry 4. Fidelis Irena physical chemistry, coordination chemistry of lanthanides and actinides 5. Leciejewicz Janusz crystallography, solid state physics, material science 6. Lukasiewicz Andrzej material science 7. Piekoszewski Jerzy solid state physics 8. Pszonicki Leon analytical chemistry 9. Radoszewski Tomasz radiometry 10. Rzewuski Henryk solid state physics 11. Slekierski Stawomir physical chemistry, inorganic chemistry 12. Szot Zbigniew radiobiology 13. Szumiel Irena cellular radiobiology 14. Trojanowicz Marek analytical chemistry 15. Zagdrski Zbigniew physical chemistry, radiation chemistry, electrochemistry
ASSOCIATE PROFESSORS
1. Ambroi Hanna physical and radiation chemistry, photochemistry 2. Bobrowski Krzysztof radiation chemistry, photochemistry, biophysics 3. Chwastowska Jadwiga analytical chemistry 4. Grigoriew Helena solid state physics, diffraction research of non-crystalline matter 5. Michalik Jacek radiation chemistry PROFESSORS AND SCIENTIFIC COUNCIL 11 6. Milner Ewa radiation chemistry 7. Mioduski Tomasz lanthanide and actinide chemistry 8. Narbutt Jerzy radiochemistry 9. Paros J6zef analytical chemistry 10. Urbanski Piotr radiometric methods, industrial measurement equipment, metrology 11. WaliS Lech material science, material engineering 12. ifcdftowski Tadeusz nuclear physics
ASSISTANT PROFESSORS (Ph.D.)
1. Bilewicz Aleksander chemistry 2. Borkowski Marian chemistry 3. Bouzyk Elzbieta biology 4. Bryl-Sandelewska Teresa radiation chemistry 5. Buczkowski Marek physics 6. Bukowski Piotr mechanics 7. Burzyriska-Szyszko Maja dosimetry 8. CieSla Krystyna chemistry 9. Dembinski Wojciech chemistry 10. Deptuta Andrzej chemistry 11. Dobrowolski Andrzej chemistry 12. Dzwigalski Zygmunt high voltage electronics, electron injectors, gas lasers 13. Fiderkiewicz Alfred physics 14. Fuks Leon chemistry 15. Grodkowski Jan radiation chemistry 16. Harasimowicz Marian technical nuclear physics, theory of elementary particles 12 PROFESSORS AND SCIENTIFIC COUNCIL 17. Iller Edward chemical and process engineering 18. J a wo rska Alicja biology 19. Kierzek Joachim physics 20. Kleczkowska Hanna biology 21. Krejzler Jadwiga chemistry 22. Kruszewski Marcln biology 23. Krynicki Janusz solid state physics 24. Mach^j Bronislaw electricity 25. Migdat Wojciech chemistry 26. Mirkowski Jacek nuclear and medical electronics 27. Nowicki Andrzej organic chemistry and technology, high-temperature technology 28. Owczarczyk Andrzej chemistry 29. Owczarczyk Hanna biology 30. Palige Jacek metallurgy 31. Panta Przemyslaw nuclear chemistry 32. Pogocki Dariusz radiation chemistry, pulse radiolysis 33. Polkowska-Motrenko Halina analytical chemistry 34. Przybytniak Grazyna radiation chemistry 35. Ptosiewicz-Bqk Halina physics 36. Skwara Witold analytical chemistry 37. Smulek Wiktor radiochemistry 38. Sochanowicz Barbara biology 39. Stochowicz Waclaw radiation chemistry, EPR spectroscopy 40. Stuglik Zofia radiation chemistry 41. Szpilowski Stonislaw chemistry PROFESSORS AND SCIENTIFIC COUNCIL 13 42. Tymitiski Bogdan chemistry 43. Urbariski Tadeusz chemistry 44. Walicka Maigorzata biology 45. Warchoi Stanisiaw solid state physics 46. Wasek Marek nuclear physics 47. Wqsowicz Tomasz radiation chemistry, molecular spectroscopy 48. Wdjcik Andrzej cytogenetics 49. Wronska Teresa chemistry 50. Zimek Zbigniew electronics, accelerator techniques 51. Zmijewska Wanda analytical chemistry
SCIENTIFIC COUNCIL (1995-1999)
1. AssocProf. Hanna Ambroz, Ph D., D.Sc. 9. Prof. Janusz Jurczak, PhD., D.Sc. Institute of Nuclear Chemistry and Technology Polish Academy of Sciences, Institute of Organic physical and radiation chemistry, photochemistry Chemistry, University of Warsaw organic chemistry, stereochemistry 2. AssocProf. Krzysztof Bobrowski, Ph D., D.Sc. Institute of Nuclear Chemistry and Technology 10. Antoni Kalicki, M.Sc. radiation chemistry, photochemistry, biophysics Institute of Nuclear Chemistry and Technology radiometric methods, industrial measurement 3. Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. equipment, metrology Institute of Nuclear Chemistry and Technology chemical and process engineering, nuclear che 11. Iwona Kaluska, M.Sc. mical engineering, isotope chemistry Institute of Nuclear Chemistry and Technology 4. AssocProf. Jadwiga Chwastowska, PhD., D.Sc. radiation chemistry Institute of Nuclear Chemistry and Technology 12. Barbara Kazmirska analytical chemistry Institute of Nuclear Chemistry and Technology 5. Prof. Rajmund Dybczynski, Ph.D., D.Sc. staff representative Institute of Nuclear Chemistry and Technology 13. Prof. Kazimierz Korbel, Ph D., D.Sc. analytical chemistry Stanisiaw Staszic Academy of Mining and Me 6. Zyta Gl^bowicz tallurgy Institute of Nuclear Chemistry and Technology nuclear electronics, nuclear technical physics staff representative 14. Janusz KraS, M.Sc. 7. Ewa Gniazdowska, M.Sc. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology radioisotope diagnostic methods for engines physical chemistry of solutions and industrial installations 8. Edward Iller, Ph.D. 15. Gabriel Kuc, M.Sc. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology chemical and process engineering radiation chemistry 14 PROFESSORS AND SCIENTIFIC COUNCIL
16. Prof. Janusz Lipkowski, PhD., D.Sc. 27. Michat Strzelecki, M.Sc. Polish Academy of Sciences, Institute of Physical Institute of Nuclear Chemistry and Technology Chemistry chemical and process engineering physico-chemical methods of analysis 28. Prof. Irena Szumiel, Ph.D., D.Sc. 17. Prof. Andrzej Lukasiewicz, Ph D., D.Sc. (Co-chairman) Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology material science cellular radiobiology 18. Prof. J6zef Mayer, PhD., D.Sc. L6di Technical University 29. Prof. Jan Tacikowski, Ph.D. physical and radiation chemistry Insitute of Precision Mechanics physical metallurgy and heat treatment of me 19. Assoc.Prof. Jacek Michalik, Ph.D., D.Sc. tals (Co-chairman) Institute of Nuclear Chemistry and Technology 30. Prof. Marek Trojanowicz, Ph.D., D.Sc. radiation chemistry Institute of Nuclear Chemistty and Technology analytical chemistry * 20. Assoc.Prof. Jerzy Narbutt, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology 31. Assoc. Prof. Piotr Urbanski, Ph D., D.Sc. radiochemistry Institute of Nuclear Chemistry and Technology 21. Dariusz Pogockl, Ph.D. radiometric methods, industrial measurement Institute of Nuclear Chemistry and Technology equipment, metrology radiation chemistry, pulse radiolysis 32. Assoc.Prof. Lech WaiiS, Ph.D. 22. Prof. Jan Przytuski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Warsaw University of Technology material science, material engineering chemistry, solid state technology 33. Prof. Stanislaw Wrotiski, Ph.D., D.Sc. 23. Prof. Leon Pszonicki, Ph D., D.Sc. Warsaw University of Technology (Chairman) chemical engineering Institute of Nuclear Chemistry and Technology analytical chemistry 34. Prof. Zbigniew Zagdrski, Ph.D., D.Sc. 24. Prof. Henryk Rzewuski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology physical chemistry, radiation chemistry, electro chemistry solid state physics 25. Prof. Stawomir Siekierski, Ph.D. 35. Wieslaw Zielitiski, M.Sc. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology physical chemistry, inorganic chemistry staff representative 26. Jan Skajster 36. Wanda 2mijewska, Ph.D. Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology chemical technology analytical chemistry
HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (1995-1999)
1. Prof. Maria Koped, Ph.D., D.Sc. 2. Prof. Antoni Dancewicz, Ph D., D.Sc. Institute of Haematology and Blood Transfusion Institute of Nuclear Chemistry and Technology haematology, radiobiology biochemistry, radiobiology RADIATION CHEMISTRY
AND
PHYSICS
NEXT PA0E13) i left BLANK | PL9702080 RADIATION CHEMISTRY AND PHYSICS 17 ONE-ELECTRON OXIDATION OF METALLOPORPHYCENES AS STUDIED BY RADIOLYTIC METHODS D.M Guldi17, J. Field2/, J. Grodkowski, P. Neta3/, E. VogeI 4/ 11 University of Notre Dame, USA ^University of Waterloo, Ontario, Canada 3/ National Institute of Standards and Technology, Gaithersburg, USA 4/ Universitat zu KOln, Germany
Porphycenes, one of several classes of porphyrin of the porphycene peaks, and, similar to the free isomers, have evoked considerable interest in their base, a formation of broad absorption in the red. electron transfer properties and their application in The results indicate the formation of ^-radical biological processes. Little information is available cation. Prolonged radiolysis in an air saturated on their reactions with oxidizing radicals. In the CH2CI2 led to the formation of dications. Similar present study we utilized radiolytic techniques to results were observed in the case of Fe^^TPrPc. study the oxidation of metalloporphycenes under Qj(ii)Tprpc is oxidized by radiation to Co( ln)TPrPc. various conditions. The spectral changes observed in pulse and y-ra- The free base porphycene, 2,7,12,17-tetrapropyl- diolysis are in good agreement and confirm the porphycene (HzTPrPc) and its complexes of Fe(Iff), stability of the tervalent complex. Pulse radiolysis of Co(II), Ni(II), Cu(II), and Sn(IV) were radiolytically Co< In)TPrPc showed the formation of stable ^-radi oxidized in several solvents and solvent mixtures. In cal cations. Stationary radiolysis also indicated the aerated CH2CI2 the porphycenes are oxidized mainly same changes. Ni^^TPrPc is effectively oxidized to by the CH2CIO2 and CHCI2O2 radicals, in CCI4 and Ni(ni)rprpc in both pulse and steady-state radio in 2-propanol/CCl4 solutions by the CCI3O2 radi lysis. The stability of the metal oxidized nickel por cals. phycene is remarkable, since the oxidation of Ni(n) Spectral changes observed in pulse radiolysis of porphyrins by radiolysis resulted in the formation of HzTPrPc in the aerated CH2Q2 or 2-propanol/CCLi jr-radical cations of Ni'11). (9:1) indicate one-electron oxidation to its ^-radical Most of the oxidized species observed with por cation, by comparison with porphyrins and results phycenes were more stable than those reported for from oxidative electrolysis. The spectral features ob porphyrins. This is in line with the oxidation poten served in y-radiolysis are different from those at short tials of the porphycenes, slightly lower than those of time after the pulse. The stable, in minutes in CH2CI2, the corresponding porphyrins. product is probably dication formed through the disproportionation of the ^-radical cations. This research was supported by the Division of A Sn(rv)TPrPc oxidation yield was veiy low and Chemical Sciences, Office of Basic Energy Sciences, no stable radical cation or anion were observed. U S. Department of Energy. Cu(I1>TPrPc in the pulse radiolysis exhibit bleaching
PL970208 IRON-PORPHYRIN CATALYZED REDUCTION OF CO% PHOTOCHEMICAL AND RADIATION CHEMICAL STUDIES J. Grodkowski, D. Behar1/, P. Neta2/, P. Hambright 3/ lzSoreq Nuclear Research Center, Yavne, Israel 21 National Institute of Standards and Technology, Gaithersburg, USA ^Howard University, Washington D C., USA
Catalyzed reduction of CO2 has been studied ex kis(N-methyI-3-pyridyl)porphyrin (TM3PyP), tetra- tensively as a means of energy storage. A number of kis(N-methyl-4-pyridyl)porphyrin (TM4PyP), and transition metal complexes have been utilized as tetrakis(4-sulphonatophenyI)porphyrin (TSPP). electron transfer mediators to achieve electrochem Fe(III) porphyrins undergo photoreduction to the ical or photochemical reduction of CO2. In the pre Fe(II) state by excitation at the ligand-to-metal charge sent study we utilized photochemical and radiation transfer band. We carried out photoreduction of chemical techniques to examine several iron por Qpe(lli)rpp in dimethylformamide (DMF) and in phyrins (FeP) in terms of their one-electron reduc several other solvents and found that the process is tion steps and their possible role as catalysts for the greatly accelerated by the addition of triethylamine photoreduction of CO2 Most photochemical ex (TEA). Excitation at the Soret band does not lead to periments were carried out with tetraphenylporphy- the reduction and the process is most likely an rin (TPP) and most radiolysis experiments were intramolecular transfer from the axially bound TEA carried out with water soluble porphyrins: tetra- to the iron centre. The quantum yield of approxi kis(N-methyl-2-pyridyl)porphyrin (TM2PyP), tetra- mately 0.05 was estimated from a comparison with the 18 RADIATION CHEMISTRY AND PHYSICS photoreduction of ClFe(ni)TPP in alkaline ethanol containing HCOf, as OH scavenger, led to the for solution. Further illumination of Fe(II^TPP in DMF mation of Fe(0TM2PyP along with small amounts resulted in the reduction of this species to Fe(^TPP of the phlorin anion and chlorin. In neutral solu but the process was less efficient. tion, the yield of Fe^)TM2PyP was about half of Photoreduction in most cases did not lead to that in alkaline solutions and was accompanied quantitative conversion into Fe^^TPP. Upon con by a considerable yield of chlorin. Radiolytic re tinued photolysis additional products were seen: duction of Fe^TMSPyP did not yield a stable (CO)FeWTPP, the chlorin, and the isobacterio- Fe(^TM3PyP under any conditions. chlorin. Under CO2, however, a steady-state con To observe the short-lived species that con centration of Fe^bTPP was achieved within a short tribute to the above products, we utilized pulse time and most of the porphyrin was converted to radiolysis. For these experiments Fe(m)p were first (CO)Fe(^TPP. Photolysis of (CO)Fe(^TPP is reduced to Fe(")p by H2 on Pd and then pulse known to decompose this complex to CO and irradiated. The transient spectra obtained with Fe^^IPP with a high quantum yield. Continued Fe(n>TM2PyP, Fe^TMSPyP, Fe
Alkyl radicals and substituted alkyl radicals are droxy groups. Table 26 contains data for the radical important reactive intermediates formed in certain from formate (carboxyl radical, carbon dioxide ra reductions and oxidations of organic and biological dical anion). Reactions of other substituted alkyl materials. Because of their importance in biological radicals have been collected in Table 27. Benzyl and systems, in atmospheric reactions, and in industrial ketyl radicals, having an aromatic moiety adjacent processes, they have been the topic of numerous to the radical site, are collected in Tables 28-30. investigations. Earlier studies have been discussed The compilation is published in [5]. The data are in several reviews [1,2] and the kinetic results were also included in the NDRL/NIST Solution Kinetics summarized in several compilations [3, 4], Many Database [6]. direct measurements of absolute rate constants for This research was supported by the Division of reactions of carbon-centered radicals in solution Chemical Sciences, Office of Basic Energy Sciences, have been reported. The present compilation is U.S. Department of Energy. intended to evaluate the available rate constants in aqueous solution and to present them in a concise References and readily accessible form. The radicals were gene [1] . Neta P.: Adv. Phys. Org. Chem., 12,223 (1976). rated by radiolysis, photolysis, or other techniques, [2] . Swallow A.J.: Prog. React. Kinet., 2,195 (1978). and their rate constants were determined generally [3] . Ross A.B., Neta P : Natl. Ref. Data Ser., Natl. Bur. Stand. by kinetic spectrophotometry. The tables include (U.S.), 26(1982). over 2500 reactions of 373 radicals, compiled from [4] , Beckwith A.L.J., Griller D., Lorand J.P.: Landolt-Boemstein 740 literature references. Tables 1-6 cover unsubsti Numerical Data and Functional Relationship in Science and tuted alkyl radicals containing only carbon and hy Technology. New Ser., Group II, 13a (1984); Asmus K.-D., drogen. Tables 7-11 cover halogen substituted alkyl Bonifacio M.: ibid., 13b (1984); ibid., 18a and 18b (1995). radicals. Tables 12-17 contain reactions of mono- [5] . J. Phys. Chem. Ref. Data, 25,3,709-1050 (1996). [6] . Ross A.B., Mallard W.G., Helman W.P., Buxton G.V., Huie hydroxyalkyl radicals; other hydroxyalkyl radicals R.E., Neta P.: NDRL/NIST Solution Kinetics Database: Ver. are collected in Table 27. Tables 18-25 include alkyl 3.0. National Institute of Standards and Technology, Gaithers radicals substituted with alkoxy, carboxy and hy burg, USA.
TETRABENZOPORPHYRINS: METAL INCORPORATION AND EXCHANGE KINETICS, LIGATIONAL EQUILIBRIA AND PULSE RADIOLYSIS STUDY milli
S. Cromer 1^ P. Hambright 1^ J. Grodkowski, P. Neta2' PL9702083 lz Howard University, Washington D C., USA 21 National Institute of Standards and Technology, Gaithersburg, USA We explored aspects of the solution chemistry of with a decrease in porphyrin basicity. We measured the tetrabenzoporphyrin (TBP) which, while a porphy formation constants of Cd^1), Zn^O, VCK11), Mg( ir), rin, mimics the phtalocyanines in such a way that and Ni^11) tetrabenzoporphyrins with pyridine (py) each of the two adjacent beta-pyrrole carbon atoms spectrophotometrically in benzene, NiWTBP was are fused into benzene rings. We report work, com studied in DMF. Two equilibria were noticed: paring the metal incorporation and exchange kine M(n)TBP + py = (py)-M(">TBP tics, and the pyridine ligation properties of tetra- (py)-M
REDUCTION AND ALKYLATION OF RHODIUM PORPHYRINS IN ALCOHOL SOLUTIONS. RADIATION CHEMICAL AND PHOTOCHEMICAL STUDIES J. Grodkowski, P. Neta% Y. Abdallach2'', P. Hambright 2/ 11 National Institute of Standards and Technology, Gaithersburg, USA L9702084 21 Howard University, Washington, D C., USA
In a recent study [11, it was found that radiolytic Methyl radicals do not reduce porphyrins but reduction of ClRhlirP to Rh’P" in alkaline 2-pro react by addition to RhnP. panol solutions involved a chain reaction. In the RhnP+ CH3 -» CH3-RhmP. present study we examined the reactions of H+ react with some of the solvated electrons to ClRhmP in neutral and acidic 2-propanol solutions. form hydrogen atoms which are transformed to the Most experiments were carried out with chloro- (CHs)2C OH radicals. Furthermore H+ will affect rhodium(III)5,10,15,20-tetramesitylporphyri (mesi the fate of RhnP. tyl = 2.4.6-trimethylphenyl) to prevent dimeriza 2Rh"P + H+ - RhmP+ + HRhluP tion of the RhnP state. HRhmP + H+ - H2 + RhmP+. Radiolysis of 2-propanol results in the formation of several species: solvated electrons (e^iy), hydro Addition of triethylamine (TEA) makes the solu gen atoms, (CH3)2C'OH radicals, CH3 radicals, tion basic and promotes the formation of Rh1?" as H+ and some molecular products. CRhmP is reduc the main product of radiolytic reduction. When both ed by solvated electrons (k ~1010 Lmol V1) and triethylamine and acetic acid are added radiolytic re more slowly by (CHs^C OH radicals (k - lOVo 8 duction led to the formation of the mixture of Rh*P~ Lmol V1) which may also react by the addition to and HRhmP. the metal center. Radiolytic reduction in the presence of C02 CRhmP + efoiv -» Cl + RhnP progressed more effectively than in argon-bubbled solutions. In the absence of CO2 some electrons CRhinP + (CH3)2COH - may be lost with reactions with H+, but in the pre Cl + RhuP + (CH3)2CO + H+ sence of CO2 they are converted to the reducing RhuP + (CH3)2C OH - HO(CH3)2C-RhIIIP. radicals "CO2, which lead to effective reduction of The formation of HO(CH3)2C-RhIUP was demon RhmP+. When CO2 was bubbled into the solution strated also by UV photolysis of 2-propanol solu containing both TEA and acetic acid the. formation tions containing acetone where (CH3)2C' OH radi of a mixture of Rh*P" and HRhInP was observed cal was the sole intermediate. during radiolysis. Both these products were unreac- RADIATION CHEMISTRY AND PHYSICS 21 live toward CO% for several hours. To examine the ing 0.35 molL' 1 triethylamine for a period 10 times possibility that the products of rhodium porphyrins longer than that required for complete reduction of reduction may catalyze the reduction of CO2 we ClRhUIP resulted in the formation of very little H2 examined the products from gamma radiolysis of (less than concentration of porphyrin). TTie photo solutions with and without the porphyrins and CO* chemical yield was similar when the solutions were This system may effect some radiolytic reduction of saturated with Ar or CO2. The CO concentration CO2, but with a very low efficiency and with no was below detection limit of our system at least 500 catalytic activity toward CO2. times less than the yield of H* Since the radiolysis experiment failed to show In summary, although rhodium porphyrins cata significant reduction of CO2, we carried out photo lyze the photochemical formation of H2, they ap chemical experiments. Photolysis of ClRhinP in the pear to be ineffective as homogeneous catalysts for presence of triethylamine in 2-propanol/benzene the reduction of CO2 under ambient conditions. solutions led to the formation of RhrP* and HRhmP+ in a proportion which depends on the This research was supported by the Division of concentration of triethylamine and on the presence Chemical Sciences, Office of Basic Energy Sciences, of acetic acid. Photochemical reduction of ClRhniP U.S. Department of Energy. to Rh1?" and HRhraP+ was also achieved in solu tion with CO2 Both reaction products were stable References and did not react with CO2 for hours. Photolysis of [1], Grodkowski J., Neta P., Hambright P.: J. Phys. Chem., 22, ClRhIJIP in 2-propanol/benzene solutions contain 6019 (1995).
OH RADICAL INDUCED OXIDATION OF S-METHYLCYSTEINE AND ITS DERIVATIVES. FRAGMENTATION OF a-AMINOALKYL RADICALS* D. Pogocki, K. Bobrowski, K.-D. Asmus1/ 11 University of Notre Dame, USA PL9702085 The reaction of hydroxyl radicals with sulphur-con nine, thiaproline) in high yields ot p-mtroaceto- taining amino acids proceeds via an initial forma phenone radicals (PNAP'_) (Fig.l). tion of a hydroxy sulphuranyl radical >S -OH. The interaction of these hydroxy sulphuranyl radical with the amino functional groups NH2/NHL that ■ Jo ■ are present in the amino acids, leads ultimately to the formation of a-aminoalkyl radicals (aN) with parallel elimination of CO2 [1-3]. Decarboxylation is enhanced by this carbon-centered radical stabili zation which is provided by the resonance between the unpaired electron at the a-carbon atom and the free electron pair at the nitrogen atom (see E$ in Table 1). a-Aminoalkyl radicals are strong reduc- tants (see IP in Table 1) and can be probed by one-electron reduction of a moderately good elec tron acceptor such as p-nitroacetophenone (PNAP) __ b; ! [2] and methyl viologen (MV). Table 1. AM 1 calculated stabilization energies (E$) and ioniza tion potentials (IP) of a-aminoalkyl radicals. Amino acids Es(aN)a [kcal/mol] IP(aN)a Methionine 21 6.9 a-methylmethionine 26 6.5 Homomethionine 22 6.6 Thiaproline 53 8.7 10 12 14 S-methylcysteine 23 6.9 S-ethylcysteine 23 6.7 pH Thiaisoleucine 23 6.7 Fig.l. Radiation chemical yields (G-values) of CO2 and PNAP a when amino groups in radicals are deprotonated. vs. pH of the N20-saturated solution containing (A) thiaproline (Thz): a -10 mM Thz, b - 2 mM Thz, c - 5 mM Hydroxyl radical induced oxidation of amino Thz + 30 ftM PNAP; (B) - S-methyl-L-cysteine (Cys(Me)): acids containing sulphur atom in the /3-position to a -10 mM Cys(Me), b - 2 mM Cys(Me), c - 5 mM Cys(Me) Ca leads to efficient decarboxylation. This is not + 30ftM PNAP. reflected, however, contrary to other sulphur-con The aim of the present study was to explain why taining amino acids (i.e. methionine, homomethio a-aminoalkyl radicals formed in amino acids con- 22 RADIATION CHEMISTRY AND PHYSICS taining sulphur in the /3-position to Ca are not able (S-substituted cysteine derivatives) leads to efficient to reduce PNAP efficiently. decarboxylation (Fig.l, curves Aab, Bab), accom Employing various S-substituted cysteine deriva panied by a simultaneous formation of a-amino tives (Chart 1) together with thiaproline and alkyl radicals (Figs. 2 and 3), according to the methionine has several advantages for this type of mechanism presented in Scheme 1.
8000- COD ch 3-s-ch 2-ch S-methyl-L-cysteine NH,4 6000-
COD CH,-CH2-S-CH2-ck S-ethyl-L-cystehe
NH,4 2000-
COO CH 3-S-CH-C h D,L-4-thiaisoleucine NH,4 Fig.3. Absorption spectra of transient species derived from 50 COD mM thiaproline: (a) - 20 ns, (b) - 40 fts after the pulse %N-----CH L-lhiazolidine-4-carboxylic acid obtained in the pulse radiolysis of N20-saturated aqueous HzC^CH, (Thiaprolne) solution at pH - 5.7. Inserts: kinetic traces recorded at 330 nm (A) and 260 nm (B). .COD a-Aminoalkyl radicals derived from these amino %N--- 96 q_CH 3 L-5,5-dimethyIthiazolidme-4-caiboxylic acid acids decay exponentially by a clean first-order "S ' process (Fig.2 insert) in the microsecond time CH, region with the rate constants (1-5 x 106 s'1) (Table 2), contrary to a-aminoalkyl radicals derived from COD HOOC-CH2-S-CH2-CH S-carboxymethyl-L-cysteine thiaproline and methionine that do not decay in the W same time domain (Fig.3, insert B). The high yields of a-aminoalkyl radicals in COD S-substituted cysteine derivatives are not reflected HOOC-CH2-CH2-S-CH2-ck S-carboxyethyl-L-cystetne by the corresponding high yields of p-nitroaceto- W4 phenone radical anions (PNAP'") contrary to methionine and thiaproline (compare Fig.l, curves OOC COD hl-CH2-S-CH2-CH D,L-(meso>lanthionine TljN ■ W - /NH, Chart 1. spontaneous H Vk intramolecular dissociation proton transfer mechanistic study. Thiaproline is the cyclic deriva tive of S-methylcysteine, and methionine contains / CH- •HjO sulphur in the y-position to Ca. ,co, OjC^CH^s—CH, Hydroxyl radical induced oxidation of the amino -L),C-CH,-S-CH,-CH H,N-CH acids containing sulphur atom in /3-position to Ca NH,' CO,-
8000- electron transfer
6000- CO, H,C-S-CH,-cfo -0,C'CH,-S—(jM, NH,' -/CH H,N CO, 4000- CO, electron 2000- transfer
•0,C-CH,-s— CH, ZCH 4 CO, H,N Fig.2. Absorption spectra of a-aminoalkyl radicals (aN) derived from 5 mM S-methylcysteine: (a) -120 ns, (b) - 3 jts after Scheme 1. the pulse; and 50 mM S-methylcysteine: (c) -120 ns after the pulse, obtained in the pulse radiolysis of NgO-saturated aqueous solution at pH = 5.7. Insert: kinetic trace re Be and Ac). The reason is a competing ^-frag corded at 260 nm. mentation process of the a-aminoalkyl radicals. RADIATION CHEMISTRY AND PHYSICS 23
Table 2. Radiation chemical yields of CO2 and aldehydes, and rates contents of fragmentation of a-aminoalkyl radicals.
Amino acids (pH 5.8) Cone. [mM] G(C02) G(AcH) G(AH ‘ -)a kf 10-&[s-l] Thiaproline 50 3.2 0 2.99 0.07 S-methylcysteine 50 3.8 3.7 3.96 2.4 S-ethykysteine 50 3.7 3.5 3.92 2.8
Thiaisoleucine 50 - 33s - 4.7 S-carboxymethylcysteine 30 3.9 2.5 3.28 1.3 S-carboxyethylcysteine 30 4.1 2.9 3.74 3.3 Lanthionine 35 3.9 3.7 3.94 c 1.2 G(C02) - radiation yield of CO2 G(AcH) - radiation yield of acetaldehyde. G(AH'_) - radiation yield of ascorbic acid oxidation. kf - rate constants of fragmentation, calculated fron. kinetic traces recorded at 260 nm. a amino acid concentration SO mM, ascorbic acid concentration 2 mM. k radiation yield of propionaldehyde. c lanthionine concentration 5 mM. The rate constants of the fragmentation can be Vinyl amine tautomerises to the respective imines calculated assuming the competition of PNAP for that subsequently undergo hydrolysis to the respec a-aminoalkyl radicals (Scheme 2). They are in a tive aldehyde (Table 2): acetaldehyde or propion very good agreement with those measured directly aldehyde (for thiaisoleucine) and ammonia (Scheme from the decay of a-aminoalkyl radicals at X=260 2). The thiyl radicals (R-CH2S ) are relatively nm (Table 2). strong oxidants and were easily probed by one-elec ______kt G(CQ2) - G(PNAP -) tron oxidation of ascorbic acid (AH'). kf + k(aN+PN AP)[P NAP] G( c62) PNAP PNAP" Hjtp-S-^H-CH - NHj where: R1 R2 k(a N+PNAPJ imine kf - rate constant of fragmentation, k(oN+PNAP) - rate constant of reaction PNAP + a-aminoalkyl radicals, [PNAP] - p-nitroacetophenone concentration [M]. tautomerization When [PNAP]=3 x l"5 M, k(aN+PNAP) — 2.4 x 109 + 01=CH-NH2 ------CHj-CH-NH MV1 (for methionine) and for S-methylcysteine: Ri R2 G(C02)=5.9 G(PNAP ‘ ~)=0.16 thus: kf «2.4xl06s'1. HjO In the presence of ascorbic add (AH) high yields Ascorbic Acid of the ascorbic acid radical (Amax = 360 nm, e = 3300 AH- M^cm"1) have been observed (Table 2, Fig.4). AH" (Xjnax - 360 nm) ^ ^ NH, R2 H 8000. *
6000- detected by puke radiolysis detected by GC 4000- Scheme 2 Cyclization of amino acid chain (thiaproline and 2000- its derivatives) effectively slows fragmentation since the main driving force of /8-fragmentation is an increase of entropy resulting from the formation of two entities from one. a-Aminoalkyl radicals, derived from methionine, Fig.4. Absorption spectra of anion radicals (AH") derived from which contain an extra methylene group compared the pulse radiolysis of NzO-saturated aqueous solution to the S-substituted cysteine derivatives, cannot containing 30 mM S-carboxymethylcysteine and 2 mM undergo this kind of fragmentation. ascorbic acid at pH = 5.8 6 after the pulse. Insert: kinetic trace recorded at 360 nm. References In steady-state y-radiolysis experiments high [1] . Pogocki D., Bobrowski. K., Grodkowski. J.: INCT Annual yields of acetaldehyde and propionaldehyde (thia- Report 1993, p. 15. isoleucine) have been detected in aqueous solution [2] , Pogocki D., Bobrowski. K.: INCT Annual Report 1994, p. 23. of S-substituted cysteine derivatives (Table 2). [3] , Pogocki D., Bobrowski. K.: INCT Annual Report 1995, p. 20. * a-Aminoalkyl radicals undergo /3-cleavage of the C-S bond, characteristic for the carbon centred * Part of this work was presented during VII International Symposium on Organic Free Radicals, Bardolino (Lake Garda), radicals containing sulphur atom in /3 position, which Italy, 16-21 June 1995, and on Radiation Chemistry Gordon leads to the formation of thiyl radicals (iV-CHaS) Research Conference, Newport, Rhode Island, USA, 7-12 July and corresponding vinyl amine (R2-CH=CH-NH2). 1996. PL9702086 24 RADIATION CHEMISTRY AND PHYSICS Trp - I>rO RADICAL TRANSFORMATION IN HEN-EGG WHITE LYSOZYME K. Bobrowskl, J. Holcman 1/, J. Poznafiski 2/, KL. WlerzchowskI 2/ 1Z Risd National Laboratory, Denmark 21 Institute of Biochemistry and Biophysics, Polish Academy of Sciences, Warszawa, Poland
Efficient intramolecular radical transformation LRET pathways between various Trp /Tyr redox Trp -» TyrO', involving long range electron pairs in HEWL, calculated with help of the transfer (LRET) between the phenol side chain of PATHWAYS model [11]. Tyr and the Trp ' indolyl radical, has been observed Intramolecular long range electron transfer in a number of proteins [1], including hen egg-white (LRET) in hen egg-white lysozyme (HEWL), ac lysozyme (HEWL) [1-3] and in model systems made companying Trp" -» TyrO radical transformation, of a single Trp/Tyr pair separated by a peptide was investigated in aqueous solution by pulse radio bridge [4-9]. There is also accumulating evidence lysis as a function of pH (S.2-7.4) and temperature that tyrosine and tryptophan radicals are involved (283-328 K). The reaction was induced by higly in electron transfer associated with physiological selective oxidation of Trp with Nj radicals under redox reactions. So that further studies on LRET in HEWL, as model protein system for Trp -» TyrO' transformation, are worth of continuing. Our pre liminary pulse radiolysis study on temperature dependence of LRET in HEWL [2] showed a close similarity between the Arrhenius plots for the kinetics of this process and the specific enzymatic reaction of HEWL, suggesting that similar thermal ly induced conformational fluctuations are involved in the activation of the two processes in lysozyme. So far it proved impossible, however, to identify T = 296 K which of the potential Trp /Tyr redox pairs, formed by six tryptophan and three tyrosine residues pre sent in HEWL, and which of the associated mole cular pathways were actually involved in the ob served LRET. To identify which of the potential Trp /Tyr red Fig.2. Dependence of the rate constant for reaction ket on pH in native HEWL, and in H-Trp-(Pro); iyr-OH peptide (in ox pairs are actually involved in the Nj-induced set: ket vs. pH; Bobrowskl et al., unpublished results). Trp' -* TyrO transformation in HEWL, we per formed further pulse radiolysis studies of this reac low concentration of the reactants but with a high tion in: (i) the native enzyme, (ii) the complex of HEWL/Nj molar ratio so that more than 99 per HEWL with an oligosaccharide inhibitor, triacetyl- cent of the oxidized protein molecules contained chitotriose, and (iii) HEWL selectively oxidized by only a single tryptophyl radical. Synchronous decay ozone to the NFKyn62 derivative (Fig.l). Both tem of Trp and build up of TyrO conformed satisfac- perature and pH perturbations of the HEWL Nattve HEWL structure were employed [10]. The results obtained E « 56 Old mol-' are interpreted in terms of the most probable E » 7 .6 U mol-' pH 5.20 E - 37.6 kj mol* 1
E - 10.5 Id mol ' Native HEWL pH 6.30
0.4 - E * 35.0 Id mol-' pH 7.43
103 t-1 (K-1) Fig.3. Arrhenius plots for the temperature dependence of the rate constant, ket for native HEWL at pH values indicated: Ea - corresponding energies of activation, derived from the slopes of the plots. Fig.l. Spectrophotometric control of oxidation of Trp62 indole side chain to N’-formylkynurenine in HEWL, by ozone; the torily to first-order kinetics indicating that LRET difference between the spectra of native HEWL and NFKyn62-HEWL corresponds to 1:1 conversion of 1 mole involved either one or more Trp /Tyr redox pairs of Trp into NFKyn; in the inset a part of the absorption characterized by similar rate constants. The rate spectrum due to O-formylaminobenzoale group of NFKyn. constant of LRET, ket, increased monotonically RADIATION CHEMISTRY AND PHYSICS 25 with decreasing pH (Fig.2) in the manner charac pH 5.2 (Fig.4), were again somewhat different than terized by: (i) in the pH range 7.4-S.2 the plot of h# in HEWL alone. Considering known solvent ac vs. pH was sigmoidal in shape reflecting pro cessibilities of tryptophans in the complex, the tonation of Glu35 (pKa « 6) and indicating in observed LRET process in HEWL(GlcNAc)3 was volvement of a conformational control of the assigned to Trp 123. kinetics of LRET, below pH 5.2 a sharp increase in Theoretical evaluation of the electronic coupling ket was observed due to the protonation of Trp to for the dominant LRET pathways between all the form TrpH' + which is known to oxidize tyrosine potential Trp '/Tyr redox couples in HEWL, with help faster. Arrhenius plots of the temperature depen of the PATHWAYS model, allowed Trp62/Tyr53, dence of ket showed that activation energy of LRET Trp63/Tyr53 and Trpl23/Tyr23 to be identified as the varies both with the state of protonation of the pairs involved in the electron transfer observed enzyme and the temperature (Fig.3). The activation experimentally [10]. energies are in the range 7.6-56.0 kJ mol" 1 and are similar to those for activation of amide hydrogen References exchange in native HEWL below its denaturation [1] . Butler Land E.J., Prfltz W.A., Swallow A.J.: Charge temperature. Selective oxidation by ozone of the transfer between tryptophan and tyrosine in proteins. Trp62 indole side chain in HEWL to N’-formyl- Biochim. Biophys. Acta, 705.150 (1982). [2] , Bobrowski K., Holcman J., Wierzchowski K.L.: Tem kynurenine caused a large drop in the initial of Trp ' perature dependence of intramolecular electron transfer as a probe for predenaturational changes in lysozyme. Free Rad. Res. Comms. 6,235 (1989). Native HEWL E » S6.0 kJ mol-' [3] . Weinstein M., Alfassi Z.B., DeFelippis M R., Klapper M.H., Faraggi M.: Long range electron transfer between tyrosine and tryptophan in hen egg-white lysozyme. Biochim. Bio E * 7.6 kJ moN phys. Acta, 11126,173 (1991). [4] . Prfltz W.A., Land E.J., Sloper R.W.: Charge transfer in peptides. J.C.S. Faraday Trans. I., 22,281 (1981). [5] . Faraggi M., DeFelippis M R., Klapper M.H.: Long-range electron transfer between tyrosine and tryptophan in pep tides. J. Am. Chem. Soc., Ill, 5141 (1989). [6] , Bobrowski K., Wierzchowski K.L., Holcman J., Ciurak M.: Intramolecular charge transfer between tryptophan and - pH 5.2 tyrosine in peptides with bridging prolines. Stud. Biophys., 122,23(1987). ]7]. Bobrowski K., Wierzchowski K.L., Holcman J., Ciurak M.: Intramolecular electron transfer in peptides containing methionine, tryptophan and tyrosine. A pulse radiolysis Fig.4. Arrhenius plots for the temperature dependence of the study. Ini. J. Radial. Biol., 52,919 (1990). rate constant, ket at pH 5.2 for NFKyn62-HEWL and [8) . Bobrowski K., Holcman J., Poznaiiski J., Ciurak M., Wierz HEWL(G1cNA c)3 complex. Eg - corresponding energies chowski K.L.: Pulse radiotysis studies of intramolecular of activation; the Arrhenius plot for the same reaction at electron transfer in model peptides and proteins. 5. Trp " -» pH 5.2 in native HEWL (from Fig.3) shown for com TyrO' radical transformation in H-Trp-(Pro) n-Tyr-OH parison purposes. series of peptides. J. Phys. Chem., 26,10036 (1992). [9] , Bobrowski K., Poznaiiski J., Holcman J., Wierzhowski K.L.: radicals, G(Trp ),. This was accompanied by a Long range electron transfer between proline-bridged relatively small decrease in ket but selective oxida aromatic amino acids. Ed. J. Wishart, D. Nocera. Advances tion by ozone had a profound change in its tem in Chem. Ser. (1997), in print. perature dependence (Fig.4). Taken together these [10] . Bobrowski K-, Holcman J., Poznaiiski J., Wierzchowski K.L: Pulse radiolysis studies of intramolecular electron observations indicate that of the six tryptophans transfer in model peptides and proteins. 7. Trp -» TyrO present in HEWL Trp62 contributes about 50% to radical transformation in hen egg-white lysozyme. Biophys. the yield of the observed LRET. In the enzyme-in Chem. (1997), in print. hibitor complex, HEWL(GlcNAc)3, where Trp62 [11] , Betts J.N., Beratan D.N., Onuchic J.N.: Mapping electron and Trp63 are completely shielded from the solvent tunnelling pathways. An algoritm that finds the "Minimum LengthTMaximum coupling pathway between electron by the bound triacetylchitriose, G(Trp'),, was lower donors and acceptors in proteins. J. Am. Chem. Soc., Hi, than in NFKyn62-HEWL, and both the kinetic and 4043(1992). energetic characteristics of LRET, observed only at
PL9702087 SENSITIZED PHOTOOXIDATION OF METHIONINE-CONTAINING PEPTIDES IN AQUEOUS SOLUTION K, Bobrowski, B. Marciniak1/, G.L Hug^ 11 Adam Mickiewicz University, Poznafi, Poland 21 University of Notre Dame, USA Carbonyl triplets can be potent oxidizing agents in duced in biological systems, by both enzymatic and biological materials. These triplets have been pro- non-enzymatic methods [1], Recently, the benzophe- 26 RADIATION CHEMISTRY AND PHYSICS none molecule has been proposed as a photoprobe in The radical cations identified were intermolecularly proteins and other macromolecules [2]. In an attempt (S.'.S)+-bonded cations, intramolecularly to characterize how these mechanisms arise in biolo (S.\N)+-bonded cations, these were observed in gical materials, we have studied the simpler systems of Met-Met, Met-Gly and Met-Gly-Gly, and an intra sulphur-containing carboxylic acids [3] and amino molecularly (S/.S)+-bonded radical cation, this adds [4,5] and methionine-containing dipeptides and tripeptides [6]. The aim of the present study is to extend quali tative and quantitative studies of the 4-carboxy- benzophenone (CB) sensitized photooxidation to other methionine-containing peptides [7J and to unravel a decay pattern of the (S.'.Ny species X_X X x which was a complex function of the pH [8]. The methionine-containing peptides were Met-Gly, • • a # • x pH 9.62 Gly-Met, Met-Met, Met-Gly-Gly, Gly-Met-Gly, and O pH 10.06 ; Gly-Gly-Met. * pH 10.58 The rate constants for quenching of the CB triplet by six methionine-containing peptides were A pH 11.1 determined to be in the range (1.8-2.9) x 109 M'V1. Time resolved transient spectra accompanying the Time (ps) 0.070 Fig.2. Comparison of the decays of (S. \N)+ at various pH's. Each point of time, at each pH, involved a separate spectral resolution. Each time/pH point required a series of kinetic traces, each trace at different wavelength. Concentrations 0.060 were all normalized to the initial concentrations at each pH.
0.040 was observed in experiments with Met-Met. Fig.l shows a spectral resolution of the transient absorp 0.030 - tion taken at 160 ns after the flash of an aqueous solution of 2 mM CB and 0.4 mM L-Met-L-Met at pH 5.9. The quantum yields of the transients and their kinetics of formation and decay were mea sured by flash photolysis and the quantum yields of CO2 formation were determined by steady state photolysis. The decay of the radical cations with an intra molecular sulphur-nitrogen bond in Met-Gly was multiexponential and the decay varied with pH. As Fig. 1. Spectral resolution of the transient spectrum taken 160 ns the example in Fig.2 shows, when the solutions after the end of 337 nm flash. Aqueous solution of 2 mM CB and 0.4 mM L-Met-L-Met at pH 5.9. were basic, the decay of the (S.-.N)+ radicals was not, in general, single exponential. Each of the quenching events were assigned to triplet states of (S.'.N)+ decays in Fig.2 can be well fit to separate CB, ketyl radicals of CB, radical anions of CB and two-exponential functions. From Fig.2 it can be radical cations that were derived from the peptides. seen that the initial decays of (S.'.N)+ appear to 4-CB flash photolysis rr rr ZS NH zS+' NHa
k,IOH-] S--NH, ^S'.NHg OH rr HO- s nh 2 'OH pulse ratSdyste Scheme 1. RADIATION CHEMISTRY AND PHYSICS 27 get faster as pH of the solutions increases. This is Using the rate constant kg already determined at reflected in the rate constants of the fast compo- pH 6.7 for the decay of (S.'.N)+ in the absence of OH" and from the plot presented in Fig.3, the rate constants ki and k% can be calculated. To determine whether the hydroxy sulphuranyl radical, >S -OH, is the SNOH species in Scheme 1, complementary pulse radiolysis experiments were performed at pH 9.6. In these experiments, the appropriate hydroxy sulphuranyl radicals were ge nerated and their transformation into (S.'.N)+ radical cations was monitored (Fig.4a-c). By re solving the transient spectra for a sequence of time windows, it was possible to separate the concen ^fastO18-1 ) = 1-3 + 6000 [OH~] tration profile of the (S.'.N)+ radical cation from that of the hydroxy sulphuranyl radical (>S"-OH). The concentration profile of the >S -OH has been simulated quantitatively as the superposition of a [OH-] x 103 (M) pseudo-first-order build-up (k = 7.0 x 107 s"1) and a first order decay (kj = 4.7 x 107 s"1) whereas the Fig.3. Linear least-squares fit of the fast rate constants of concentration profile of the (S.' .N)"1" radical cation followed a first order build-up (kb = 4.8 x 107 s'1) nent of the two-exponential decays. A plausible (Fig.4d). Since the values of k
time delay = 20 ns • Data » (S.-N)+ - 2.0 ° >SOH
time delay = 100 ns
.9.0 Wi.nAn
15 0.6 -
-3 0.2
j i 11 11 300 350 400 450 500 50 Wavelength (nm) Time (ns) Fig.4. Resolution of the spectral components in the transient absorption spectra obtained in the pulse radiolysis of NzO-saturated aqueous solution of Met-Gly (10 mM) at pH = 9.6 taken (a) 20 ns, (b) 35 ns, and (c) 100 ns after electron pulse, (d) growth and decay of >S' -OH intermediate and growth of (S. ‘ .N)+ intermediate obtained by the resolution of the spectral components in the transient absorption spectra taken at various time delays. the decrease in pH is the existence of an equi verse rate constant kg (Scheme 1) is one order of librium. The equilibrium is hypothesized to exist magnitude lower (k% = 1.3 x 106 s '). between (S.".N)+ and some unspecified interme diate (symbolized by SNOH) formed by the reac References tion of (S.\N)+ and OH". The simplest such a me [1]. Cilento G.: In: Chemical and Biological Generation of Ex chanism is given in Scheme 1. The kinetic equations cited States. Eds. W. Adam, G. Cilento. Academic Press, for Scheme 1 were solved by routine methods. New York 1982, pp. 277-307. 28 RADIATION CHEMISTRY AND PHYSICS
[2] , Dorman G., Prestwich G.D.: Benzophenone photophores in [6] , Marciniak B., Hug G.L., Bobrowski K., Kozubek H.: Me biochemistry, Biochemistry, 22,5661 (1994). chanism of 4-carbaxybenzophenone-sensitized photooxida [3] . Marciniak B., Bobrowski K., Hug G.L., Rozwadowski J.: tion of methionine-containing dipeptides and tripeptides in Photoinduced electron transfer between sulfur-containing aqueous solution. J. Phys. Chem., 22,13560 (1995). carboxylic acids and the 4-carboxybenzophenone triplet state [7] . Hug G.L., Marciniak B , Bobrowski K : Sensitized photo-oxi in aqueous solution. J. Phys. Chem., 2S, 4854 (1994). dation of sulfur-containing amino acids and peptides in [4] . Bobrowski K., Marciniak B., Hug G.L.: 4-carboxybenzophe- aqueous solution. J. Photochem. Photobiol., 25,81 (1996). none-sensitized photooxidation of sulfur-containing amino [8] , Hug G.L., Marciniak B , Bobrowski K: Acid-base equilibria acids. Nanosecond laser flash photolysis and pulse radiolysis involved in secondary reactions following the 4-carboxy studies. J. Am. Chem. Soc., 114.10279 (1992). benzophenone sensitized photooxidation of methionylglycine [5] . Bobrowski K, Hug G.L., Marciniak B , Kozubek H.: 4-carbo- in aqueous solution. Spectral and time resolution of the xybenzophenone-sensitized photooxidation of sulfur-con decaying (S.'.N)"1" radical cation. J. Phys. Chem. 1QQ, 14919, taining amino acids in alkaline aqueous solutions. Secondary (1996). photoreactions kinetics. J. Phys. Chem., 28,537 (1994).
'L9702088 GENERATION OF SULFUR RADICALS IN ZEOLITES BY MEANS OF IONIZING RADIATION S. Kowalak !/, Z. Stuglik, M. Str64yk1/, A.B. Wi$ckowski2/ 11 Adam Mickiewicz University, PoznaA, Poland 21 Institute of Molecular Physics, Polish Academy of Sciences, PoznaA, Poland
Natural and synthetic ultramarine is an alumino It was reasonable to presume that thermal energy silicate of sodalite structure. Anion-radicals S3" en required for the generation of radicals, as a result of capsulated in the sodalite cavities are believed to S-S bond scission, can be substituted by other forms play a role of chromophores responsible for intense of energy, for instance by ionizing radiation. deep blue color. Zeolites A and X impregnated with sodium or The technology of ultramarine production has ammonium polysulfide have been exposed to 1.25 been commercially applied since more than 150 MeV gamma rays and/or 10 MeV electron beams. years. The cheap substrates (kaolin, elemental sulfur, Various dose rates (from 1.24 up to 106 Gy/s) and sodium carbonate) and simple calcination procedure various doses (from 5.5 up to 396 kGy) were ap made the product very common and inexpensive. plied. A serious drawback of this method is an air The changes in the sample color upon the radia pollution with sulfur oxides developing with waste tion were significantly less pronounced than in the gases upon calcination. The main reason of our study case of thermal treatment. The samples modified was to eliminate the pollution during the ultramarine with ammonium polysulfide remained colorless. The synthesis. sample impregnated with sodium polysulfide turned The sodalite units are the building block not only light green or turquoise after the irradiation. The of sodalite but also of most common synthetic ESR measurement indicated the presence of sulfur zeolites such as zeolites A, X, Y. We successfully radicals, but the recorded signals were mostly much applied the matrices of those zeolites for the incor different than those for S3" radicals. poration of sulfur radicals. As a result we obtained Although the results collected so far are inte blue products analogous to ultramarine. The most resting from the scientific point of view they show promising procedure comprised an introduction of that the high energy ionizing radiation is less effec sulfur radical precursors (mostly sodium polysul tive than the thermal treatment for the generation fides) followed by high temperature treatment. The of sulfur radical inside zeolites. latter brought about a generation of desired radi cals from the precursors. L9702089
ESR STUDY OF RADIATION INDUCED RADICALS IN POLYCRYSTALLINE METHIONINE AND ITS HOMOPEPTIDES G. Strzelczak-Burlinska, K. Bobrowski, D, Pogocki, J. Michalik
A detailed knowledge of reaction products and re peptide structure, i.e. the location of methionine action mechanisms in the radiolysis of amino acids residue with respect to the terminal functions and and peptides is of essential importance for the the nature of the neighbouring amino acid located understanding of radiation-induced damage in both at the N-terminus and the C-terminus of complex biological systems like proteins. In recent methionine. studies [1, 2] on solid polycrystalline methionine- In the present work [3] methionine (Met) and its containing peptides, it has been found that radical two homopeptides: methionyl-methionine (Met-Met) processes exhibit a pronounced dependence on the and methionyl-methionyl-methionine (Met-Met-Met) RADIATION CHEMISTRY AND PHYSICS 29
(Chart 1) were y-irradiated at 77 K and studied over rile 1 BIM273.1U) the temperature range 77-293 K using the electron spin resonance (ESR) technique. H3N-CH-COCf ch 2 ch 2 i
methionine CH3
II CH-C -NH-CH-COO' Ih2 YH2 ch 2 ch 2 4 4
ch 3 ch 3
L-methionyl -L-methionine
+ 0 0 H3N-CH—C—NH—CH-C-NH—CH-COO" ch 2 ch 2 CH; ch 2 ch 2 CH. 4 4 4' 1 ch 3 ch 3 CH;
L-meth iony l-L-meth ionyl-L-meth ion ine Chart 1. The H-abstraction radicals in the side chain of methionine residue (a-alkylthioalkyl radicals) were detected over the temperature range 180-273 K. Over the temperature range 250-273 K decarboxylation Fig.l.The multiline component of the ear spectrum of L-me- radicals were also detected. The multiline spectrum of thionyl-L-methionc following y-irradiation at 77 K and Met-Met irradiated at 77 K and recorded at 273 K is recorded at 273 K (top). A simulated spectrum of the same shown in Fig.l (top). This spectrum can be simulated shape consists of a quintet (middle) and a triplet (bottom). as a quintet with g = 2.003 and hyperfine splittings: Assignments and hyperfine splittings, see text. The contri bution of both signals to multiline spectrum (top) is 22% a(aH) = 16 G (a-proton) and a(/3H) = 27 G (two /8 for a quintet and 78% for a triplet. protons) (Fig.l, middle) and a triplet with g = 2.0046 and an = ~ 20 G (Fig.l, bottom). The contribution of as it was calculated using MOPAC 6.0 software a quintet to the multiline spectrum of Met-Met is package. On the other hand, the observed differ 22% while that of triplet is 78%. The quintet com ence in /3-proton splittings for the decarboxylation ponent can be attributed to the decarboxylation radi radicals derived from methionine and its homo cal (HzN-CH-CH2-CH2-CH3) and the triplet peptides seems to result from different /3-proton component to the a-(alkylthio)alkyl radical. Similar orientations due to conformational effects. The spectral features are observed in Met-Met-Met and differences could be justified since methionine and Met, however, hyperfine splittings for quintet com its peptides are characterized by various crystallo ponent were found lower than in Met-Met. For graphic structures (e.g. L-methionine crystallizes in example, for the decarboxylation radical derived from the monoclinic form while L-Met-L-Met in the Met-Met-Met - a(oH) = 16 G, and a(/3H) = 21 G, orthorhombic form. Such differences in crystallo whereas if derived from methionine - a(«H) = 13 G graphic structures affect the torsion angles of the and a(/3H) = 19.7 G, respectively. methionine side chains and consequently their con The difference in hyperfine splittings of the formation. ct-protons for the same decarboxylation radical, in Upon warming to 293 K the spectrum observed methionine and its homopeptides, can be explained consists mainly of a stable triplet with g = 2.003 by different spin densities at the a-carbon. The spin and with the respective hyperfine splittings for density at the a-carbon site is reduced significantly /8-protons an~ 14 G in Met and ~ 17.7 G in in methionine in comparison to its homopeptides Met-Met and Met-Met-Met. These stable triplet PL9702090 30 RADIATION CHEMISTRY AND PHYSICS spectra can be attributed to the H-abstraction radi References cals with the localized radical site at the a-carbon of [1] . Burlirtska G., Michalik J., Bobrowski K.: An electron spin the C-terminal methionine residue. Since the ratio resonance study of gamma-irradiated polyctystalline methio of /3-splittings (a^) in homopeptides and methio nine-containing peptides. Radial. Phys. Chem., i2,425 (1994). nine is equal to the ratio of the values of spin den [2] , Burlirtska G,. Wqsowicz T., Michalik J., Bobrowski K.: sities ipa) at the a-carbon, the differences observed Radiation induced radicals in solid peptides. Mol. Phys. Rep., 6 134 (1994). in /3-proton splittings can be rationalized exclusively [3] , Strzelczak-Burlitiska G., Bobrowski K., Pogocki D., Michalik on the basis of differences of spin densities at the J.: Esr study of radiation induced radicals in polyctystalline a-carbon in these radicals. methionine and its homopeptides. Nukleonika (1997), in print.
ENDOR OF HUMAN TOOTH ENAMEL HEATED AT 400°C J. Sadlo, F. Callens1/, J. Michalik, W. Stachowicz, P. Matthys1/, E Boesman 1/ v University of Gent, Belgium
Hydroxyapatite, Caio(P04)6(OH)2, forms a basic constituent of calcified tissues such as bone and dental enamel. Human tooth enamel contains a mineral phase representing about 94 to 98% of the total weight. The rest is accounted for by water and/or organic matter. The mineralization process of biological apatites is largely determined by the presence and location of carbonate ions in the crystalline lattice. After X- and y-ray irradiation of both synthetic and biological apatites, asymmetric EPR signals are detected in the region around g=2. These signals are composite, i.e. they consist of several paramagnetic species differing in location (hydroxyl (A-site), phosphate (B-site) or surface site location) and molecular structure (CO3, C03“, COf, O', O3). Up to now, these hydro xyapatites have been intensively investigated by Fig.l.Typical EPR spectra of: a - heated tooth enamel, b - syn several authors with electron paramagnetic re thetic apatite at 20 K, 100fiW. sonance (EPR) spectroscopy but only a limited number of electron nuclear double resonance After X-ray irradiation of the samples of (ENDOR) studies of hydroxyapatites have been previously heated tooth enamel and synthetic undertaken to determine the location on para apatite, a strong, complex EPR spectrum is magnetic centers in crystalline lattice. observed. Fig.l shows typical spectra recorded at The aim of this study was to determine the 20 K The signal with the largest g anisotropy is nature, location and environment of radicals in assigned to an O" radical (g% = 2.0697, g y = 2.0640, powdered tooth enamel dried at 400°C and gz = 2.001 for heated tooth enamel and g% = 2.068, compare the obtained results with those on gy = 2.0580 and g% = 2.001 for the synthetic synthetic apatites reported earlier [1]. In addition, apatite). The small shift of the g% and gy values and the nature of the interactions will be further the narrowing of line components testify that the substantiated by ENDOR induced EPR (EIEPR) nearest environment is changed. Because these spectroscopy and discussed. The mature human tooth enamel samples, obtain ed from wisdom teeth extracted from adult patients for prosthetic reasons, were cleaned with a water- cooled rotating small bristle and a non-abrasive polishing paste, powdered by hand grinding with an agate mortar and dried at 400°C until they reached constant weight. The synthetic apatite sample, used to compare with heated tooth enamel, is a carbo nated calcium apatite, synthesized by sintering of appropriate mixtures of reagent grade CaHPC>4, CaC03 and Na2CC>3 [2]. X-ray irradiation was carried out at room temperature with absorbed dose of approximately 13 kGy. EPR, ENDOR and EIEPR v [MHz] spectra were recorded using on X-band Broker Fig.2. ENDOR powder spectrum of heated tooth enamel at 20 K. ESP-300 spectrometer equipped with an Oxford The corresponding g value is denoted in the upper right ESR10 flow cryostat. comer. RADIATION CHEMISTRY AND PHYSICS 31 changes concern mainly the g% and g y components, lobe oriented parallel to the hexagonal c axis. The they are probably located close to the xy-plane of model is shown in Fig.3. the O' ion. The difference in the environment The nearest-neighbouring phosphorus nuclei are should be related probably to the presence or distant of 0.35 nm and situated in the xy-plane of absence of charged nuclei with zero nuclear spin, the O' ion. The next-nearest-neighbouring phos i.e. most probably Ca2+ at z = 0.00 or 0.50. phorus nuclei are situated in the mirror planes The ENDOR spectra were recorded for several above and below the O' radical position. They are magnetic field settings within the EPR envelope, at a distance of 0.5 nm and the angle between the c from g = gx to g = 2.00. A typical ENDOR spec axis (p z lobe) and the direction, connecting the trum of heated tooth enamel is shown in Fig.2. The unpaired electron and the phosphorus nuclei (%), ENDOR spectrum consists of four sets of peaks is 46°. The third doublet of 31P corresponds with a centered around the nuclear Zeeman frequencies of nucleus located at a distance larger than 0.6 nm. The nearest-neighbouring proton (interaction 1) belongs to the OH group located at the nearest occupied hydroxyl site and is pointing away from the O' radical. This proton is 0.48 nm distant from O z= the average position of the unpaired electron. On the other hand one of the nearest hydroxyl sites is vacant (see also [1]). The next-nearest-neighbour ing proton, perhaps weakly visible in the synthetic apatite samples, originates from the hydroxyl group of z = -3/4. This nucleus is pointing towards the O' radical and is at a distance of 0.57 nm. This proton is labelled 2 and indicated by an arrow in Fig.3. All four resonances, as present in the ENDOR spectrum of the heated enamel powder, were examined by the EIEPR method. The EIEPR spectra of 3‘P and *H show, that two radicals con tribute to the total ENDOR spectra: the O' ion radical and a radical, which has the following spin Hamiltonian parameters: g, = 2.003, gy =1.997 and gz = 2.002. A radical with these parameters is well known: it is obviously the CO2 radical. The latter radical probably causes mainly the large 1H and 31P O z=- matrix ENDOR lines. The EIEPR spectra of 19 F and 23Na show evidently, that only the COJ radical is responsible for ENDOR resonances. This could Fig.3. Model of O' ion in heated tooth enamel hydroxyapatite as mean that probably fluor and sodium are located at detected from the EPR and ENDOR results. The addi the surface of the crystallites. The reason for the tional proton interaction, in comparison with the synthetic preferential position of F and Na close to the apatite, is indicated by the arrow. surface is not quite clear but could be related to the ^Na, 31P, 19 F and 1H, respectively, in contradistin heating procedure. ction to the synthetic apatite, where the interaction References with 19 F is not visible. The 3 P and 1H lines exhibit spectral resolution (three doublets for 31P and two [1] , Moens P., Callens F., Van Doorslaer S., Matthys P.: Phys. for 1H) and these two resonances were analyzed Rev., B S3, 5190-5197 (1996). [2] , Sadto J., Callens F., Michalik J., Stachowicz W., Matthys P., using "orientation selection principle" [3,4], Boesman E.: Calcif. Tissue Int. (1996), sent for publication. In our opinion, the ENDOR results support the [3] , Rist G., Hyde J.: J. Chem. Phys., 52,4633-4643 (1970). model given by Moens et al. [1] wherein the O' [4] , Moens P.D.W., Callens FJ., Matthys P.F., Verbeeck R.M.H.: radical is located at an A site with the p z orbital J. Chem. Soc. Faraday Trans., 90(8) . 2653-2662 (1994).
DAMAGE BUILDUP AND AMORPHIZATION IN ION - IMPLANTED GaAst.xPx S. Warchot, J. Krynickl, H. Rzewuski, R. Groetzschel 1^ 1/1FZR Forschungszentrum Rossendorf, Dresden, Germany PL970209
Ion implantation technique is widely used for doping may consist of various defect configurations, which and modifying semiconductor materials, providing for high ion doses create a heavily damaged or fully important means of fabrication of a variety of devices amorphous layer at the surface of a crystal. for micro- and optoelectronic applications. Various models have been used to explain the Depending on implantation conditions (ion mass, nature of heavily damaged crystals and to propose dose, dose rate, temperature) the damage produced the processes leading to amorphization. 32 RADIATION CHEMISTRY AND PHYSICS Two presently accepted phenomenological mo (Eg = 1.4-2.2 eV depending on relative composi dels describe the ciystalline-to-amorphous transi tion - x), being a promising ternary compound for tion [1, 2] for III-V compounds as: a homogeneous electronic and optonic devices (FET, HEMT, HBT, or CED model (the crystal becomes unstable at LED, solar cells, heterojunction lasers). some critical defect concentration taking place at In this paper we present results on the damage Critical Energy Density deposited into the sample) formation and amorphization of GaAsvxPx im or heterogeneous or Overlap Model (overlapping planted with As+ and P+ ions under various experi of the discrete amorphous zones directly created in mental conditions. the ion cascade). The CDD and CED for amorphization have Attempts to determine the crystal damage dose been evaluated providing the data for establishing (CDD) of implanted ions and the critical energy the sensitivity of those compounds for damage and density (CED) necessary for amorphous transition amorphous transition. have usually been made. RBS-c spectroscopy of 1.7 MeV He"1" ions was used Annealing properties and the crystal quality of the to measure the residual, postimplantation damage. implanted layer depend veiy strongly on the kind and Monocrystalline GaAsi-xPx epilayers 0.5 fim concentration of post-implantation defects [3], thick, grown by liquid phase epitaxy on <100> It was shown by J.S. Williams and M W. Austin GaAs (Te) substrate were used. The samples having [4] that under appropriate implantation conditions x = 0.15, 0.39 and 0.65 content of P have been it is possible to regrowth amorphous layer of GaAs investigated. For comparison, binary samples GaAs in a single-stage epitaxial process at temperatures and GaP were also measured. as low as 370-420 K (compared to oven annealing Table 1. Implantation conditions for GaAsj.x Px layers (x = 0, above 900 K [5]). 0.15,0.39,0.65,1.0). On the other hand, the defect structures in a Ions P + As+ heavily damaged layer can evolve upon annealing Temperature [K] 120 300 120 300 into a more extended dislocation network, which Ion energy [keV) 100 150 usually lowers dopant activation. In such cases 2 3 1 1 there is a need to avoid implantation conditions 4 6 2 1.5 favouring the amorphization. Ion dose [10^ cm'^J 9 3.5 2 From this point of view the knowledge of what 9 solid state properties dominate the amorphization 12 12 5 2.5 processes and the subsequent recrystallization 3.5 under given experimental conditions are of consi 5 derable interest. The implantation conditions are presented in
2000 Table 1. By way of example, random and aligned ' a»6x 10Dcnr2 1750 RBS spectra of GaAso.6iPo.39 implanted with As "v'a 1500 b - 9 x 1013 an-2 and P ions were given in Figs. 1 and 2. Similar 1250 *%y., 0-12x1013 cm*2 3 fL00 S 750 .y,: d - random
BOO 0.76 260 0 | 0.60 400 450 500 550 600 650 700 750 800
Channel number J 0-25
Fig.l. RBS spectra for GaAso.6lPO.39 implanted with As ions of 0.00 150 keV and for various fluences at 300 K. Depth [A]
Damage formation and amorphization processes Fig.3. Damage depth distribution for 2 x 10^ cm'^ 150 keV As in binary III-V compounds and some of ternary ion implantation of GaAsi-X^X at 300 K. ones (e.g. AlGaAs) have been studied extensively. However, only few papers have been devoted spectra were measured for other experimental to GaAsi-xPx [6 , 7], a wide gap semiconductor conditions shown in Table 1. They were used to
I
Channel number Depth (A) Fig.2. RBS spectra for GaAso.6lPO.39 implanted with P ions of Fig. 4. Damage depth distribution for 9 x 10^ cm"^, 100 keV P 100 keV and for various fluences at 300 K. ion implantation of GaA$i-XPX at 300 K. RADIATION CHEMISTRY AND PHYSICS 33
Table 2. Critical damage dose (CDD) and Critical Energy Density (CED) for GaAsi-xPX implanted with As and P ions. CDD [x 1013 cm"2] CED [x 1020 keV cm"3] As -150 keV P -100 keV As -150 keV P 100 keV 120 K 300 K 120 K 300 K 120 K 300 K 120 K 300 K GaAs 3.2 8 10.7 36 1.5 3.75 4.5 15.2 GaAso.85PO.15 2.4 3.5 10.7 26.7 1.1 1.6 4.4 10.9 GaAso.6lPO.39 2.5 3.5 9 12.4 1.05 1.47 3.4 4.7 GaAso.35P0.65 3.0 3.5 6.2 9 1.12 1.3 2.0 3.0 GaP 4.2 8 7.6 10.5 1.28 2.4 2.1 2.9 calculate the depth damage distributions (damage P - implantation, 100 keV, 300 K) for both low and profile) using a known formula [8] and a computer high temperature of implantation. program TRIM‘95 (Figs. 3 and 4). The CED results for binary samples GaAs and As can be seen from these spectra, the highest GaP are higher for GaAs and lower for Gap, with amorphization level, i.e. the highest sensitivity to accordance with the paper by Jones and Santana [9].
A-As, 150 koV, 120K A. As. ISO i»v, not B-As.lMkeV.300K B-Ai.HOSeV.30eK C-r.lO0faV, 120K C-r.lOOkeV.UOK D-r.100keV.300K D-r.1001sV.300K •2 20
O.BO
Fig.5. Critical damage dose and critical energy density for amorphization as a function of sample composition x after As and P ion implantation at 120 and 300 K. the damage, occurs for ternary samples implanted Further works on the model describing the crys- with As ("heavy ion") and for a binary GaP sample talline-to-amorphous transition for As and P ion implanted with P ("light ion"). implantation in the investigated ternary compounds Table 2 presents the CDD and CED values for GaAsvxPx will be carried on. GaAsvxPx for P and As ion implantation at 120 and 300 K. References The CDD is an extrapolated value of ion dose for [1] , Chadderton L., Eisen F.H.: Proc. 1st Int. Conf. on Ion 95% of the total amorphization measured at Rp . Implantation. Gordon and Breach, New York 1971, p. 445. The CED represents the energy deposited in a [2] , Gibbons J.F.: Proc. IEEE, 56,295 (1968). crystal to create full amorphization of a layer, calcu [3] , Wendler E., Muller P., Bachmann T., Wesh W.: Nucl. Instr. lated with the use of computer program TRIM‘95. Meth. Phys. Res. B, 80/81,711 (1993). These data vs. the compound composition x are [4] , Williams J.S., Austin M.W.: Nucl. Instr. Meth., 168, 307 presented in Fig.5. (1980). As could be expected from the previous results [5] . Grimaldi M.G., Paine B.M., Maenpaa M., Nicolet M.A., Sadana D.K.: Appl. Phys. Lett., 39, (1), 70 (1981). [8], a considerable nonlinearity of amorphization [6] , Mooney P.M.: Appl. Phys. Rev., J. Appl. Phys., 67, R1 (1990). degree vs. x occurred for both CDD and CED [7] , Krynicki J., Warchot S., Rzewuski H., Groetzschel R.: Acta values. Phys. Pol., A87, 249 (1995). Ternary compounds appeared more sensitive to [8] , Chu W.K., Mayer J.W., Nicolet M.A.: Backscattering amorphization with respect to the P content. Spectroscopy. Academic Press, New York 1978. The minimum of damage level occurs for a [9] . Jones K.S., Santana C.J.: J. Mater. Ri definite composition x (with the exception of CED, PL9702092 DOSIMETRIC RESPONSE OF MICROCRYSTALLINE L-cr-ALANINE AND STANDARD BONE POWDER TO HIGH-LET RADIATIONS Z. Stuglik, J. Sadlo Stable EPR-signals induced in bone and other nuclear contaminated areas [2]. In such kind non materials have been successfully used for nuclear -controlled conditions the doses accumulated by accidents retrospective dosimetry [1] and for the human beings arise from various kind of low- and estimation of doses accumulated by inhabitants of high-LET radiations. Thus, the accuracy of dost- 34 RADIATION CHEMISTRY AND PHYSICS metry depends on the accuracy of data about sen taken into account in dose reconstruction when sitivity of dosimetric materials to various kind of both the external and internal sources are taken ionizing radiations. Up to now only very few such into account (the internal sources of irradiation are data are available. mainly the bone seeking a-emitters). Our experiments on dosimetric response of In opposite to the situation for bone powder, the L-a-alanine and standard bovine bone powder to shape of EPR signal generated in L-a-alanine high-LET ionizing radiations have been done in depends on LET. The characteristic quintet, well co-operation with the Joint Institute for Nuclear known from gamma radiolysis, changes apparently Research, Dubna, Russia. Microcrystalline L-a-ala- on its borders [3]. The changes were observed even nine and a standard bovine bone powder were for very low total fluences, when each latent track irradiated with intermediate energy ion beams from had to be treated as a separate entity and it was a 4-metre U-400 cyclotron (Flerov Laboratory of concluded that they are connected with tracks Nuclear Reactions) and analyzed on an ESP-300 phenomena. Bruker spectrometer (INCT). Hie samples were Thus, the shape of EPR spectrum in alanine irradiated in the air, at ambient conditions and allows us to distinguish between the low and without any binders and additives. The bone high-LET radiations used for irradiation process. powder was not deproteinized. The main experi G-value of paramagnetic centers calculated from ments were done using 3.4 MeV/amu Co-59 ions linear part of the dose-effect curve was found to be (LET on the surface of alanine sample -5500 1.1 ±0.3 giving the relative effectiveness (in com eV/nm). Some other ions (C-12, Mg-24, Ca-40 and parison to gamma irradiated samples) 0.28. It is Fe-56) were also used. much higher than that for the bone powder. It was stated that the shape of the stable Alanine and bone powder can be used as EPR-signal generated by the heavy ions in the bone dosimetric materials for the total fluences < 1010 powder was identical as known for gamma irradiat ions/cm 2. For the fluences higher than 1E+11 ed samples. Additionally, the signal was very stable ions/cm 2 (mean dose about 600 kGy) the G-value of in a long period of time (16-350 days after irradi paramagnetic centers decreased in both materials to ation). Both these factors are very positive from the about half of the initial value and the saturation of dosimetric point of view. dose-response curves appeared. For low fluences (up to -3E+10 ions/cm 2) the concentration of paramagnetic centers increased References linearly and G-value of paramagnetic centers was [1] . Ikeya M.: In: New Application of Electron Spin Resonance. found to be 0.0080 ±002. The last figure gives the Dating, Dosimetry and Microscopy. World Scientific, Singa relative effectiveness in comparison to gamma radi pore 1993. ation of 0.1. [2] . Romanyukha AA el a!.: Appl. Radiat. Isot., 4$, 1195-1199 The low effectiveness of the EPR signal in the (1994). bone irradiated with high-LET radiation should be [3] . Stuglik Z., Sadto J.: Appl. Radiat. Isot., 42,1219-1222 (1996).
DOSIMETRIC PROPERTIES OF CDP-F2 FOILS L9702093 Z. Stuglik, T. Bryl-Sandelewskfl
In our Institute MeV electron accelerators are the the polymeric matrix is a real dosimetric material. main sources of ionizing radiation for technological Non-irradiated foils are yellow and non-transparent to purposes, so we are particulary interested in dosi the wavelengths shorter than 470 nm. The irradiated metric techniques suitable to these accelerators. foils measured against the unirradiated ones, show an Rather low ranges of MeV electrons cause that the absorption band at 512 nm. Optical density measured foil dosimeters are more convenient for such purposes at this wavelength is recommended by the producer for than any kind of massive dosimeters (calorimeters, dose determination. liquid dosimeters, glasses). Thin (um) dosimetric foils The main dosimetric experiments were done in allow to measure the dose distribution on the surface the High Dose Reference Laboratory, Risd Na of irradiated objects and also inside them. tional Laboratory, Denmark. The foils were placed There are rather few commercially attainable foil inside polystyrene calorimeter dummies and ir dosimeters recommended to electron radiations. radiated with 10 MeV electrons to doses from 10 up They are rather expensive and (which is normal) to 60 kGy. The linear response was observed in all each of them has some specific limitations. Because that region but the line not fit to zero. It shows that of such a situation further work on foil-dosimeters the radiolysis mechanisms at low doses is different are necessary. from that at the higher ones, probably because of Recently we investigated dosimetric properties the oxygen incorporated in the polymer matrix. of CDP-F2 foils produced in the Organic Inter The response of the CDP-F2 foils to gamma mediates and Dyes Institute, Moscow, Russia. radiation in the region 0-16 kGy was linear (line fit The CDP-F2 foils can be included to the group of to zero) but with a litle higher slope than for elec radiochromic dosimeters. The dye incorporated into tron radiation. RADIATION CHEMISTRY AND PHYSICS 35 The repeatability of dose determination was UV. This is a highly advantageous toward the wide ±9% (2a) before and ±5% (2a) after the cor used FWT radiochromic dosimeters. rection for foil thickness. The latter result is very The fading just after irradiation was low. good for this kind of dosimeters. The influence of time and storage conditions The non-irradiated foils are practically non-sen have also been investigated. sitive to the sun light and only slightly sensitive to PL9702094
THE FORMATION OF dCMP RADICALS FOLLOWING RADIOLYSIS, THE EFFECT OF CYSTEAMINE G. Przybytnlak, J. Huttermann1^ H. Ambroi, B. Weiland1/ 11 Universitat des Saarlandes, Germany
EPR spectroscopy was used to investigate the frozen aqueous solutions and their formation is influence of cysteamine on free radical formation in diminished in the BeF2 glasses at 77 K. In addition, the DNA nucleotide dCMP induced by ionizing spectra of thiyl and perthiyl radicals could be irradiation in a low temperature aqueous environ detected. After removal of the pattern of the thiyl ment. Both frozen aqueous solutions (both H2O radical in the frozen H2O solution, the spectrum of and D2O) and BeF2 glasses (H2O and D2O) were the one-electron reduced cytosine species can be applied. In the absence of cysteamine, the spectra isolated as a triplet with a total spread of about 2.6 obtained at 77 K are a superposition of signals of mT. Cysteamine has a little influence on the secon OH (or OD) radicals, of one-electron reduced dary reactions. A reaction with the (protonated)
dCMP + RSH in D^O thiyl radical in D O 77 K
160 K diff: 8 - 0.55 E
220 K perthiyl radical
Fig.l. cytosine base radicals and of radicals containing an "anions" in the frozen aqueous solutions is suggest unpaired electron at the Cl’ site of the deoxyri- ed by their early decay in the presence of thiol. In bosephosphate. Whereas the formation of the latter the Bep2 glasses, both Cl’ species and thiyl radicals is completed at 77 K in the frozen aqueous are increased in concentration from reactions with solutions, its yield grows between 77 and 140 K in the decaying 'OH radicals upon annealing. the Bep2 glasses. In both cases the final concentra In Fig.1 it has been depicted the X-band EPR tion of the sugar radical comes to about 20 to 25% spectra of 0.5 M 2’-deoxycytidine 5’-monophos- of all radicals of the nucleotide. In the presence of phate (dCMP) in the presence of 0.5 cysteamine cysteamine, no sugar radicals at all are found in the (RSH) in D2O, X-irradiated and measured at 77 K 36 RADIATION CHEMISTRY AND PHYSICS
(spectrum A). Spectra B and C were taken after in the absence of cysteamine at 160 K. It includes a annealing to the temperatures indicated. Spectrum further pattern (spectrum E), which can be isolated D represents the spectrum of the "OD radical in by subtraction of spectrum C from D. It is assigned the neat D%0 matrix at 77 K. Spectrum E shows the to the Cl’ radical at the deoxyribose. thiyl pattern from 0.5 M cysteamine in D2O after The influence of cysteamine on radical formation annealing to 160 K. By subtraction of the thiyl in frozen aqueous solutions containing dCMP mainly
dCMP + RSH in H O
dCMP in H O
thiyl radical in H,
diff: D - 0.82 C
tilff: A-0.66 B
5 mT
Fig-2.
radical from spectrum B, the doublet assigned to involves suppression of the Cl’ radicals at 77 K. In the anion is obtained (spectrum F). After annealing addition, a reaction with the protonated cytosine of dCMP and RSH to 230 K, the perthiyl radical base "anions" is likely to occur at elevated tempera (spectrum G) becomes observable at high power tures. In the BeF2 glass, there is an influence at 77 K (15 mW). Spectrum H is obtained at 180 K from expressed in diminishing the initial Cl’ radical con signal of 0.5 M dCMP in D2O after subtraction of tribution which is, however, smaller than the respec the doublet from the anion and the quartet from tive population in frozen solutions. Upon annealing, the CP radical to give a triplet assigned to undeter both cysteamine and dCMP compete for the decaying mined yet transient. " OH radical fraction with about the same efficiency. In Fig.2 there are X-band EPR spectra of 0.5 M There is no reaction between cysteamine and the 2’-deoxycytidine 5’-monophosphate (dCMP) in the base "anions", probably due to the dispersed distribu presence of 0.5 M cysteamine in H2O, X-irradiated tion of molecules in the glass. and measured at 77 K after annealing to 160 K The presence of cysteamine has allowed one, for (spectrum A). Spectrum B is from 0.5 M cysteamine the first time, to present the pattern of the dCMP in H2O after annealing to 160 K giving the thiyl base "anion" as a triplet similar in shape and coupl radical. Subtraction of spectrum B from A gives the ing to the triplets found in LiCl glasses. This find pattern of C, which is assigned to the one electron ing may contribute to the discussion of alkali metal reduced cytosine base, protonated at the amino coordination at the base as a requirement for triplet group. Spectrum D represents 0.5 M dCMP in H2O formation.
UV-Vis ABSORPTION SPECTRUM OF THE RADICAL ANION DERIVED FROM a-ALANINE BY DEAMINATION
PL9702095 Z.P. Zagdrski, G.K. Przybytniak Crystalline a-alanine (CH3CHNH3+COO ), either single ionization spurs. The remaining 20% of alanine d-, 1-, or dl-, undergoes ionization mainly (ca. 80%) in are subject of multi-ionization spurs in which only RADIATION CHEMISTRY AND PHYSICS 37
debris of molecules are formed (CO2 and other small slight elastomeric properties, it is possible to orient molecules not determined yet). They do not show crystals partially by streching the film. EPR or optical (UV and Vis) spectra and are not Irradiated films containing alanine crystals show needed to be taken into account in the investigation well developed spectra of the radical anion of one-ionization phenomena. The single ionized (CH3C HCOO-) formed by the deamination of alanine molecule undergoes deamination, as that the parent molecule of alanine. The light used as an reaction is energetically the most likely one. The analyzing tool in our spectrophotometer is unpola remaining radical anion CH3CHCOO- has been rized and therefore no dependence of the spectro- recognized early as a stable species at room tempera photometric response could have been expected, ture, permitting easy measurement of its EPR-res- when changing the angular position of the film. ponse [1]. Powder EPR spectra have been proposed Indeed, different orientation of microcrystals also early for dosimetric purposes, due to almost against the beam of analyzing light yielded the spec linear response of the dose from y, or electron beam tra of the height at the maximum and of the half radiation [2], However, alanine crystals embedded in width in the limits of ±1%, i.e. the limits of thin films, which are indispensable in electron beam confidence of the method. processing, are always oriented in a less or more The spectrum obtained by DRS (description of degree, which complicates the dosimetric application the method from the point of view of application to [3]. radiation chemistry see [7]) is recorded in the Slightly yellowish colour of irradiated alanines has coordinates of Kubelka-Munk function vs. wave been noticed early too and there was one only effort length. The theory of diffuse reflection spectro noted of the successful record of the absorption scopy dates back almost to the first quarter of the spectrum of the same radical [4]. Unfortunately, the XX century. Kubelka and Munk [8] (cf later authors of that paper did not try to measure the comments in [9] and [10]) have developed theo spectroscopic characteristics of the absorption, es retical treatment of the phenomenon, leading to pecially the molar extinction coefficient. There was equations connecting the new approach with not sufficient knowledge about the concentration of traditional equations of extinction, known as the the radicals in the crystal and its radiation chemistry. Lambert-Beer law. The Kubelka-Munk function We have measured the absorption spectra of the anion-radical in powdered 1-alanine crystals, em on bedded in a polyethylene matrix, by the diffuse reflected light spectrophotometry (DRS for short) [5]. Absorption spectra of the CH3CHCOO- radical, measured on a Perkin-Elmer Lambda 9 spectrophotometer with Integrating Sphere, were excellent and satisfying the dosimetric purposes, but the Kubelka-Munk equation, which describes the absorption, does not allow to determine the molar 240 270 300 330 360 390 420 450 4S0 510 540 580 extinction coefficient of absorbed species. Therefore the question of optical properties of the radical, well known from the EPR research, remained open until Fig. Absorption spectra of irradiated single crystal of I-alanine ir radiated with increasing dose of gamma radiation. Spectro the present investigation. photometer Unicam SP 1800. EPR spectra of the discussed radical anion depend on the orientation of crystals in the cavity of does not allow to determine the molar exctinction the spectrometer. Signals from the single crystal of coefficient, e, of the absorbing species because of irradiated 1-alanine, oriented in different crystallo the unknown value of S which describes the scatter graphic directions in the cavity are presented in our ing coefficient of a semitransparent matrix. There paper [6] together with the EPR spectrum of the fore preparation of single crystals of 1-alanine of random mixture of small crystal of irradiated 1-ala optical quality was needed. Single crystals have nine powder, as in dosimetric application. Partly been prepared of the size exceeding the beam of oriented crystals in the sample give mixed signals of analytical light of the conventional spectrophoto no use in dosimetry, as shown in our paper [3]. meter. The crystal was fixed in a suprasil cell and There has been no reason to assume that spectro- provided with black frames, so that the neat alanine photometric measurements will be sensitive to the was functioning as the spectrophotometric cell. The orientation of the radical anion in the sample. fixed position of the crystal allowed to irradiate it The commercial 1-a-alanine (Sigma) has been with increasing doses of y radiation. The suprasil used in the powder form to prepare disoriented cell played a function of the medium securing the arrays of crystals for averaged EPR spectrum ex electron equilibrium during irradiation, besides periments as well as for diffuse reflection spectro- keeping crystals in a fixed, optically reproducible photometric measurements of optical properties of position. Fig. shows spectra of the radical with the radical anion derived from alanine by deami increasing doses of radiation. Spectra are measured nation. The powdered alanine crystals may be against the air, because it was impossible to find investigated by the DRS method in cells or after two identical crystals as concerns the thickness. The embedding in a polymer film. If the latter has even difficulty of the resulting one-beam measurement 38 RADIATION CHEMISTRY AND PHYSICS has been overcome by using two doses of applied connected with an uncertainty of ±15%, both the radiation subsequently, thus compensating the un coefficients may be considered to be identical and avoidable dissipation of light inside the crystal. so are both the radical anions prepared in different Increased dose of radiation produces only the ad ways. The lifetimes of both modes of occurrence of ditional portion of the radical, but does not change the CH3CHCOO- radical anion differ by ca. 12 the extend of light dissipation. Debris of alanine orders of magnitude, but this does not put into formed in multi-ionization spurs do not influence question the identity of the discussed radical anion. the transparency of the crystal, because the crystal The difference in the lifetime is due to the role of line lattice has enormous capacity to incorporate the matrix: the "pulse radiolysis generated" radical the small molecules of the destruction products. anion is in the liquid, and the "radiation induced" Knowledge of the thickness of crystals, the absorb one sits firmly in the crystal lattice of the alanine. ed dose of radiation and the radiation yield of the Radiation generation of the radical in glassy, deep radical, allowed to calculate the e = 1100 M"1 cm"1 at frozen ice (not tried yet, but theoretically possible) A max = 350 nm. This band of absorption may be would most probably yield a much longer lived radi identified as the ji-tc* transition. Taking into cal than in the liquid aqueous solution at room account all the uncertainties involved, the precision temperature. The similarity of optical properties of of the measurement is estimated as not better than the same radical anion, but produced in different ±15%. The spectrum shows also a shoulder starting ways, indicates the absence of hydration pheno at 270 nm towards deep UV (probably by a—a*). The mena of the radical in water. The radical seems to same spectrum with a maximum and the shoulder be as naked in solution, as it is in the solid matrix. exhibited not only single crystals, but a randomized array of the polycrystalline material measured by References DRS. As expected, the spectrum and the oscillator [1] , McConnell H.M., Heller C., Cole T., Fessenden R.W.: J. strength is not influenced by the orientation of the Am. Chem. Soc., 82,766 (1960). sample in the analytical beam of light, because the [2] , Hansen K.W., Olsen KJ-, Wille M.: Radial. Prot. Dosim., 19,43 (1987). analytical light in applied spectrophotometers is not [3] , Przybytniak G., Zagdrski Z.P.: J. Radioanal. Nucl. Chem., polarized. Therefore the spectrophotometric method Letters, 212,373 (1996). for the determination of concentration of the radical [4] . Shields W.W., Marsh W., Hamrick P J.: J. Chem. Phys., 52, anion is preferred in thin layer dosimetry for electron 6437 (1970). beam applications. [5] , Zagdrski Z.P., Rafalski A: J. Radioanal. Nucl. Chem., It is interesting that the same radical anion, Articles, 196,97 (1995). created in a completely different way has been [6] , Zagdrski Z.P., Przybytniak G.: Nukleonika (1997), in print. observed before by the pulse radiolysis method in [7] , Zagdrski Z.P.: Nuclear Instruments and Methods B (1997), in print. aqueous solutions [11]. The abstraction of Cl from [8] . Kubelka P., Munk F.: Z. Tech. Phys., 12,593 (1931). the a chloropropionic anion, or of a hydrogen atom [9] . Kortum G.: Reflexionsspektroskopie. Springer, Berlin 1966. on the a carbon of the propionate anion, leads to [10] . Perkampus H.-H.: UV-VIS Spectroscopy and its applica the same characteristic absorption spectrum. What tions. (English translation). Springer, Berlin 1992. more, the molar extinction coefficient is similar [11] . Neta P., Simic M., Hayon E.: J. Phys. Chem., 73, 4206 (e = 950). As the pulse radiolysis experiment is also (1969).
EXAFS STUDY OF SILVER CLUSTERS IN ZEOLITE L9702096 H. Grigoriew, J. Michalik
The EXAFS (Extended X-ray Absorption Fine function transferable to the real space using Structure) method refers to the oscillatory variation Fourier transform. of the X-ray absorption as a function of photon en During the synchrotron experiment in HASYLAB ergy beyond an absorption edge. The recent avail at DESY three different silver rho zeolite were mea ability of synchrotron radiation has resulted in the sured: establishment of EXAFS as a structural tool esp Sample I: Ag?Cs - rho/dehydr - zeolite containing 7 ecially valuable for structural analysis where conven Ag + per unit cell and dehydrated at 130°C. tional diffraction methods are not applicable. Sample II: Ago.sCs - rho/dehydr - zeolite contain Theory of EXAFS has been elaborated in the ing 1 Ag + per 2 unit cells and dehydrated at 130°C. 70-ties using a short-range single-electron single- Sample III: Ag?Cs - rho/hydr - zeolite containing 7 scattering model. The oscillation rises from the Ag + per unit cell. interaction between X-ray waves scattered forward For EXAFS experiment samples were quickly and back close to an absorbing atom and brings transferred from sealed quartz tubings to containers information about its neighbouring atoms, their with mylar windows which were placed in a liquid kinds and distances. After synchrotron measure nitrogen chamber. As a standard sample a silver foil ments of absorption rate, as a function of energy, has been used [1]. To evaluate measured data, the we can convert the energy in wavevector to obtain a program EXAFS [2] was used. RADIATION CHEMISTRY AND PHYSICS 39 samples! Results of Fourier transform for all samples are shown in Fig. In the Fig., letters A, B and C refer to the positions of peaks, showed by vertical, broken lines. The positions are as follows: A - about 2 A, B - 2.4 A and C - 2.9 A Structural informations concerning the investi gated samples are the following: Sample I: The first peak (B) refers to Ag-O normal distance, and the second (C) to Ag-Ag distance in metallic structure. The peaks are narrow indicating well-defined distances. The coordination number of C can be estimated of about 4, by comparison with the C-peak for referring sample. The coordination number indicates that the nuclearity of a cluster is higher than 100. This means that metallic clusters exist in the sample, which are too large to be placed in zeolite voids. Sample II: There are two peaks, which are broad, indicating a considerable dispersion in interatomic distances. The A peak referring to Ag-O, of not a typical distance, can be related to the location of Ag or Ag + in various exchangeable sites with different distances to the zeolite framework oxygen. The co ordination number, evaluated from C-peak is about 1, and therefore it can be generated from small several-atom clusters. Sample III: The Fourier transform curve is close to that obtained for sample II. It means that the hydration causes a decay of large, metallic-type clusters. The work has proved that EXAFS is a proper method for distinction between small atomic and larger metallic clusters in zeolite. References [1] . Frahm R.: HASYLAB Jahresbericht 1994, p. 999. [2] , Bonin D., Kaiser P., Desbares J.: EXAFS program. Paris Fig. 1988. RADIOCHEMISTRY
STABLE ISOTOPES
NUCLEAR ANALYTICAL METHODS
CHEMISTRY IN GENERAL
NEXT PAGE(S) left BLANK RADIOCHEMISTRY, STABLE ISOTOPES, PL9702097 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL SOLVENT EXTRACTION OF GROUP 4 AND 14 METAL CHELATE COMPLEXES. MODEL EXPERIMENTS FOR CHEMICAL STUDIES ON COORDINATION NUMBER OF ELEMENT 104 A. Bilewicz
To verify the idea that the coordination number (CN) of element 104 can be influenced by relati vistic effects [1], studies on the complexation of homologs of element 104 (Zr4+, Hf4+ , Ti4+) and of metal ions in Group 14 (Sn4+, Pb4+) by thenoyl- trifluoroacetone (TTA) and tropolone (T) were performed. The multidentate ligands have much to recommend them as a probe for possible formation of complexes with high CNs. Contrary to mono- dentate ligands, TTA forms extractable octaco- ordinate complexes not only with Zr4+ and Hf44" but also with Ti4+. Tropolone forms octacoordi- nate neutral complexes with cations of Group 4
Fig.2.Effect ofHCl concentration on extraction of Zr4"1", Hf4"1", Ti44", Sn4+ and Pb4+ by tropolone. Concentration of tro polone in benzene - 0.01 mol dm"3. The behaviour of 1044+ in extraction experi ments with TTA or T should answer the question: is 1044"1" different in respect to CN from its lighter congeners Zr4+ and Hf44", and behaves more like Ti4* and Group 14 metal elements? As noted pre viously [3], relativistic effect stabilizes Is orbitals and splits the 6d orbitals into two 6*3/2 orbitals and three strongly destabilized 6*5/2 orbitals. The des tabilization of the 6*5/2 orbitals causes the pro Fig.l.Effect of HC1 concentration on extraction of Zr4+, Hf44" motion energy involving Is,Ip and 6*5/2 orbitals to and Ti4+by TTA Concentration of TTA in hexadecane - be too high for d*sp* hybridization. It should be 0.1 mol dm"3. noted that eight coordination requires 6*5/2 or bitals. The proposed studies will help to explain (Zr4+, Hf4+ and Ti4+) and also Group 14 metal whether element 104 in coordination compounds is cations (Sn4+ and Pb4+). Since octacoordinate similar to zirconium and hafnium as expected from complexes of TTA and T with Ti4+, Sn4+ and Pb4+ the general trends in the Periodic Table, or rather are much weaker than the respective complexes of to titanium and the heavy members of Group 14 as Zr4+ and Hf4+, extraction of these complexes to suggested by the results of our previous experi organic phase needs higher concentration of unpro- ments. tonated ligands and requires higher values of pH. The observed differences between the stabilities of References octacoordinate complexes of Zr4+, Hf4+ and Ti4+, [1] . Bilewicz A, Siekierski S., Kacher C D., Gregorich K.E., Lee Sn4+ and Pb4+ are due to the fact that according to D M., Stayer NJ., Kadkhodayan B, Kreek S.A, Lane M R., data reported by Glebov [2], smaller differences are Sylwester E.R., Neu M.P., Mohar M.F., Hoffman D C.: found for m, np and (n-1 )d orbital energies in Zr Radiochim. Acta, 75,121 (1996). [2] . Glebov VA, Kasztura L., Nefedov V.S., Zhiukov B.L.: and Hf than for 4s, 4p and 3d orbital energies in Ti Radiochim. Acta, 46,117 (1989). and for ns, np and nd orbital energies in Group 14 [3] . Johnson, E., Fricke, B, Keller, O.L., Nestor C.W., Tucker elements (Sn, Pb). T.C: J. Phys. Chem., 22,8041 (1990).
FRACTIONATION OF EUROPIUM ISOTOPES IN THE EXTRACTION SYSTEMS: Eu (III), HDEHPZEn(III), H+(C1', NOf, So| “). LIGAND ISOTOPE EFFECT
W. Dembitiski, R. Fiedler1^ Z. Janlszewski 1/ International Atomic Energy Agency, Safeguards Analytical Laboratory, Seibersdorf, Austria
A study was performed to verify the occurrence of beside the electron isotope effect related to the ligand isotope effect in extraction systems related exchange reaction: [Eu(II)]aq « [Eu(III)]or g. The to the exchange reaction: [Eu(III)]aq «* [Eu(III)]0rg, latter was a subject of our previous study [1].
PL9702098 RADIOCHEMISTRY, STABLE ISOTOPES, 44 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL
To answer this question, we have studied the The data in Table 2 indicate that fractionation of fractionation of 153Eu and 1’1Eu isotope pair in the the 153-151Eu isotope pair (ligand effect) really oc liquid-liquid extraction system containing Eu(III) in curs in the studied extraction system, however its both organic and aqueous phases. Di(2-ethylhe- absolute value is diminutive. It follows from the xyl)phosphoric acid (HDEHP) diluted with heptane relation Q > 1 and e > 1 that the heavy isotope, was used as the organic phase and water acidified 153Eu , is preferentially fractionated to the organic with hydrochloric acid as the aqueous phase, and phase, whereas the light isotope 151Eu is fractio- Table 1. Separation experiments.
No. Acid Dorg/aq Va q [ml/min] Vorg/Vaq t [min] X16 [mg Eu/ml] X16/X0 1 HC1 1.35 1.2 0.92 780 0.08 0.008 2 HC1 1.5 1.05 1.00 750 0.04 0.004 3 HNO3 1.25 1.1 1.04 800 0.025 0.0025 4 HNO3 1.4 1.2 1.02 830 0.015 0.0015 5 H2SO4 1.4 1.1 1.05 720 0.05 0.005 6 H2SO4 1.5 1.2 0.95 750 0.04 0.004 Vaq - flow rate of the aqueous phase. Vorg - flow rate of the organic phase. nitric or sulfuric acids were taken to verify the in nated to the aqueous phase. Due to the experi fluence of various counter-ions on the effect. mental error we could not distinguish the influence The fractionations were performed in a counter of the kind of counter ion. current extractor of the mixer-settler type [2] ac The data from Table 2, were compared to those ob cording to the scheme: tained [1] for the same extraction system (HDEHP/HO) but with Eu(III) in the organic phase and Eu(II) in Extractor the aqueous phase: Q < 1, q = 0.9993, t = -0.0007. T: I ITT I'ITT Y,.HDEHP | 1*16 HDEHP From this comparison it follows that the direction Xo. H*A" ■ I I IUI1 LI, Xi„H*A- of the observed ligand isotope effect is opposite to the direction of electron isotope effect, however its
X • Ee(lll) cone. In the organic phase absolute value is about one order of magnitude V - Eu(Mf) cone. In the aqueous phase lower. A" - NO, .Cl SO.* This finding is to be discussed in terms of the The ratio Xj^/Xo < 0.02 was fixed by choosing a theory of quantum effects in the molecular vibra proper acid concentration in the aqueous phase and tion of isotope species [4] as well as in the light of the related value which also affected on the Eu(III) the recent [5] suggestion that the chemical isotope Table 2. Total separation factor Q and unit separation gain e.
Counter ion Rl6 Rsd [%] Q RSD [%] *(1/16) Rsd [%] Cl- 0.91603 0.0410 1.00116 0.07199 0.000073 62 NO3 0.91696 0.0616 1.00218 0.09244 0.000136 42 NOJ 0.91670 0.0204 1.00189 0.05133 0.000118 27 SOf 0.91634 0.0410 1.00150 0.07195 0.000094 48 R0 = 0.91497; Rsd [%] = 0.031. extraction coefficient D o/a - The latter is linked to shift is composed of mass shift and field shift as it the acid concentration by the equation: occurs in optical atomic spectra. log(D) = d ■ log(cfi) The work was supported by the Polish State where d is a constant wit value of -2.6+-3.0 [3]. Committee for Scientific Research under contract The system was set off for 800 min to attain the 3TO9AO5209. isotope equilibrium. At the end of the experiment, samples from the Xi$ and Xo streams were with References drawn for the determination of the 153/151eu iso [1] . Dembirtski W., Mioduski T.: J. Radioanal. Nucl. Chem, tope ratio (Ri6 and Rq ) by mass spectrometric Letters, 122 (2), 159-171 (1995). analysis. They were done with a Finnigan MAT 261 [2] . Dembirtski W., Goroncck K., Phuc N.: J. Radioanal. Nucl. mass spectrometer in the IAEA Safeguards Analy Chem, Articles, H2 (1), 169-176 (1991). tical Laboratory. [3] . Krejzler J., Siekierski S.: Separation of lanthanoids by liquid-liquid extraction in HNO3-HDEHP system. Report In Table 1 the conditions of the separation experi INCT-2108/V/C/A Institute of Nuclear Chemistry and Tech ments performed with various counter ions: Cl-, nology, Warszawa 1990. NOJ, SO|“ are shown. The values of the total sep [4] . Bigeleisen J., Mayer M.G.: J. Chem. Phys., 15,261 (1947). aration factor Q = Rie/Ro, the unit separation gain, [5] . Bigeleisen J.: J. Am. Chem. Soc., 118. 3776 (1996). e = (l/16)lnQ, and the related values of the relative standard deviation are presented in Table 2. RADIOCHEMISTRY, STABLE ISOTOPES, PL9702099 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 45 FRACTIONATION OF YTTERBIUM ISOTOPES IN Yb(III)-ACETATE/Yb-AMALGAM SYSTEM. EVEN-ODD EFFECT W. Dembiriski, M. Poniriski, R. Fiedler^ v International Atomic Energy Agency, Safeguards Analytical Laboratory, Seibersdorf, Austria
A phenomenon called "even-odd effect" or "even- and its concentration increased to 0.015 +0.025 M odd staggering of the isotopes" was first announced Yb(II). The concentration of Yb(II) was determined by Fuji et al. [1]. They found that in the red-ox ex by measuring the absorbancy at 260 nm and 351 nm change system of U(IV)-U(VI), the unit separation bands, the extinction coefficients being G260 = 850 factor for a 238/235 u isotope pair did not fit the and €351 = 500 [10]. The results however were not linear interpolation between 23®^234U and 238 /236u, very precise because of the high rate of Yb(II) de which means that the relation: ln(q) =Am/(mi -n^) cay, resulting from the very low values of the does not cover the experimental results and cannot standard red-ox potentials: E^t>(ni)/Yb(ii) = -1.205 be explained by Bigeleisen-Mayer theory [2] based V; E^b(nn/Yb = -2.267 V [11]. The first order rate on quantum effects in the molecular vibration of constant (k) of Yb(II) reoxidation in the solution isotopic compounds. Then Nishisawa et al. showed containing 0.1 M Yb(Ac)g and 0.5 M of free acetic the same difference in the behaviour of even and acid was found to be in order of 0.1 min'1, causing odd isotopes of Sr and Ba [3], Zn [4] and Mg [5] in analytical problems. the liquid-liquid extraction systems with dicyclo- The conditions of the experiment, offering about hexano- 18-crown-6 (DC18C6). The even-odd stag 40% Yb extraction to amalgam are shown in Fig.l. gering of Gd isotopes was also announced by After separation of the phases, ytterbium was Nomura et al. [6] in cation exchange displacement recovered and a pair of new stock solutions were chromatography with EDTA and malonic acid as eluents, however with a reservation that the mea surement errors were too large to conclude the Amalgam deviation from the theoretical relation of the mass dependence. Parallel unsuccessful attempts of find ing the even-odd effect in fractionation of Sr [7] and Ba [8] by the cation displacement chromatography 1.115 have been announced. For our studies we have chosen ytterbium for the reasons described earlier [9]. The separation was Aoelat sol. performed in an atmosphere of Ar, in a separation cell of 100 ml volume, containing at the beginning 50 ml of 0.1 M Yb(III) acetate stock solution and 260 g Hg, stirred by a magnetic bar. Ytterbium was extracted to mercury by a slow addition of 2.5 M sodium amalgam, at a constant rate, under the Amalgam mercury surface. pH was controlled and when it reached a proper value, it was stabilized by the addition of acetic acid. The deep yellow Yb(II) acetate appeared in the solution along with the first drops of Na-amalgam
6.5
— Acetate sol. rx 6
£ / 5.5 / * 47 mmol y MsAnln 5 sample number X / Fig.2. 171/176y% an(j 174/176yt, isotope ratio in acetate/amal gam system (5-stage separation). / x 45 HAc prepared for the next stage of separation pro cedure. To attain 5-stages separation a simple cas X cade procedure with two branches: solution (S) and 0 5 10 15 202530364045 time [mini amalgam (A) was applied. The "S” and "A" fractions from the last separa Fig. 1. Separation experiment: 37% Yb extracted to amalgam. tion stage were analyzed for 176/171 Yb and 176/3'4Yb RADIOCHEMISTRY, STABLE ISOTOPES, 46 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL isotope ratio (R), by means of a MAT 262 | | > | 176A71£ | (Finnigan MAT) mass spectrometer. The method It is interesting to note that in the uranium iso of total evaporation of the sample was applied, so tope exchange system the opposite relation has been under normal conditions there should be no mass observed [1, 13]: the even-odd isotope pair, fractionation effect [12]. The results of the analysis 238/235 u, was separated by the factor 1.16 more are shown in Fig.2. efficient than the even-even pairs 238/236 u and The following values of the unit separation 238/234u. factors q = (Ra /Rs)1/5 and the unit separation gain To explain this difference, the nuclear field shift per isotope mass difference, e=(l/Am)lnq, were cal related to the electron density, and the charge, size, culated: and shape of nucleus should be considered beside 176/171qA/5=0.99729; 176/171e=-0.00054 (RSD±6%) the classic mass factor. The work is in progress. 176/174qA/S=0.99863; 176/174e=-0.00069 (RSD±7%) The work is supported by the Polish State Com Separation factors q, in general corresponds to mittee for Scientific Research, Poland under con the isotope equilibrium of the three electron ex tract 3T09A05209. change reaction between Yb(IlI) acetate complexes and Yb in amalgam: References LYb(Ac)3+HYb(Hg) « HYb(Ac)3+LYb(Hg) [1] . Fuji Y., Nomura M., Okamoto M., Onitsuka H., Kawakami where: L, H - light and heavy isotope. F., Takeda K.: Z. Naturforsch., 44a, 395 (1989). Another equilibrium, like Yb(III) «* Yb(II) and [2] , Bigeleisen J., Mayer M.G.: J. Chem. Phys., 15,261 (1947). Yb(II) <* Yb, should also be taken into account be [3] , Nisbisawa K., Nakamura K., Yamamoto T., Masuda T.: cause of the formation of Yb(II) ions as the inter Solv. Extr. Ion. Exch., H, 389 (1993). [4] , Nishisawa K., Nakamura K., Yamamoto T., Masuda T.: mediate species. Solv. Extr. Ion. Exch., 12,1073 (1994). Relation q < 1 means that in the studied [5J. Nishisawa K., Nishida K., Miki T., Yamamoto T.: Sep. Set. exchange system the lighter isotopes are pre Tech., 21(5), 643-654 (1996). ferentially fractionated to the amalgam phase. The [6] , Nomura M., Fuji Y., Kawakami F., Okamoto M.: J. Nucl. difference between the value of 176^7le and 176/174e, Sci. Tech., 2Z (1), 42-49 (1992). which amounted to 0.00015, may be taken as [7] , Oi T., Hose M., Kakihana H.: Sep. Sci. Tech., 22(5), evidence for the occurrence of even-odd effect in 631-643(1992). ytterbium isotope fractionation. Thus itterbium [8J. Kondoh A, Oi T„ Hose M.: Sep. Sci. Tech., 21, (1), 39-48 (1996). became, the first recognized element from the [9], Dembiliski W.: INCT Annual Report 1995, p. 48-49. f-electron group, and the fifth element in general [10] . Faraggi M., Tendler Y.: J. Chem. Phys., 56, (7), 3287-3293 which does not follow the classic relation of mass (1972). dependence. [11] , Greenwood N.N., Eamshaw A: Chemistry of the Ele From the presented data it follows that the ments. Pergamon Press Ltd., 1984, p. 1430. separation of even-even itterbium isotope pair is by [12] . Fiedler R., Donoheu D., Grabmucller G., Kurosawa A: Ini the factor 1.27 more efficient than the separation of J. Mass Spectr. and Ion Processes, 122,207-205 (1994). even-odd pair, as it results from the relation: [13] . Bigeleisen 1: J. Am. Chem. Soc., US, 3676-3680 (1996).
SEPARATION OF PROTIUM/DEUTERIUM AND OXYGEN-16/OXYGEN-18 BY MEMBRANE DISTILLATION G. Zakrzewska-Trznadel, A.G. Chmielewski PL9702 00 An attempt to explain large isotope effects in li where pi and pc are water vapour pressures on tne quid/vapour permeation of water through a hydro- feed and permeate sides, respectively and C - mem phobic FI FE membrane was made in a previous brane mass transfer coefficient. work [1]. However the high 160/18 0 separation If the water molecules diffuse through a sta factor, very different from H/D factors, was difficult tionary film of air trapped inside the pores, the to explain on the basis of Bigeleisen analysis of molecular diffusion model can describe the pro condensed phase isotope effect only [2]. The study of cess: the transport mechanism through hydrophobic, ND = ^ifRT(Fi-P°)- porous membranes could throw some light on the matter. For this reason the equations commonly used If the air is removed from the pores, the con for mass transfer in membrane distillation were vective models can be applied. When the mean free tested, then the model for description of permeate path of water molecules is greater than the pore flow was proposed [3]. size of the membrane then the dominant flux Mass transfer in membrane distillation takes mechanism is Knudsen’s diffusion. If the membrane place via diffusion and/or convective transport. The pore size is greater than the mean free path of driving force for mass flux is the difference in water vapour molecule, in the absence of air the viscous vapour pressure described by the relationship: flux dominates and the Poiseuille flow model N * C(pi - p 0) describes the process: RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 47 ration factors in membrane process are higher than Nfc - 1064^ (pi - p0) equilibrium separation factors. The diffusion effect enlarges the total effect of the MD process. Np = 0.063 ^^(P? - Po) In the case of H2160/H218 0 enrichment separa tion factors for the Knudsen and molecular diffusion where N q , N%, Np - mass fluxes described by mole are higher than the separation factors for distillation. cular diffusion, Knudsen diffusion and Poiseuille This phenomenon can explain the relatively large flow. All models have some limitations and some separation factors for membrane distillation even as times a combination of two different models has to large as 6 times the ratio of the vapour pressure iso be used. tope effect «iv = ln(P°7P°) [1]. The diffusion effect According to the theory of isotope separation, decides about the summaiy effect of MD process: the separation factor in molecular diffusion for two «K > «D > omd >«lv- components of the mixture of molecular weights For both H2G/HDO and H2160/H218 0 enrich Mi and M0 may be ex pressed as: ments the total separation factor can be expressed «d =3/M2(Mi + M0 . as follows: VMi(M2 + Mo ) «MD = «K-'OM For Knudsen's diffusion the separation factor is where au includes all the effects combined with the expressed by the relationsh ip: water vapour transport through the porous mem «k =a /M2. brane. These effects can be described by the V mt relationships derived from diffusion or convective Using the above equations the separation factors transport models. of Knudsen and molecular diffusion for H20/HD0 and H2160/H218 0 systems were calculated. For References [1] , Chmielewski AG., ZakrzewskaTrznadel G.: Efekty izotopo- H20/HD0 enrichment the separation factors esti we wodoru i tlenu w procesie permeacji wody przez membra- mated for diffusion models are lower than separation ny polimerowe. Prace Wydzialu Iniynierii Chemicznej i Pro- factors for distillation and membrane distillation: cesowej Politechniki Warszawskiej, XXII. 1-2,23 (1995). «MD > «iv > «K >«D- [2] . Bigdeisen J.: Statistical medianics of isotope effects on ther modynamics properties of condensed systems. J. Chem. Phys., The vapour pressure isotope effect (VPIE) for 34,5,34(1961). H20/HD0 is large enough to explain the significant [3] , ZaktzewskaTrznadel G., Chmielewski AG., MiljeviC N.: Sep isotope effect of membrane distillation which can be aration of protium/deuterium and ox> —------regarded as a combination of two effects acting membrane distillation process. J. Membr synergetically: VPIE and diffusion effect. The sepa (1996). •L9702 01
PRECONCENTRATION OF RADIUM FROM SALINE COAL-MINE WATER ON SELECTIVE ION EXCHANGER - a-CRYSTALLINE MANGANIC ACID J. Narbutt, A. Bllewicz, B. BartoS, R. Postek Radium contamination of saline waters from coal components being (in g/1): Na+(8-40), Ca2+ and mines makes serious environmental problems in Mg 2+(0.5-3), K+ (below 0.5), CV (20-70), and the region of Upper Silesia (Poland) and also in SOl- (0.15-3). CMA was synthesized by precipita other countries [1]. Underground purification of tion from 1 M KMn04 and MnS04 solutions in 1 coal mine water, consisting of a conventional M H2S04 [4]. X-ray diffraction patterns of the barium-radium sulphate coprecipitation process, CMA samples show a good agreement with those has been successively tested in Silesian coal mines reported for other a-crystalline forms of manganese [2]. The use of this technology requires a simple dioxide. The ion exchanger was washed with aque analytical method for rapid determination of low ous CHgCOONa solution to remove an excess acid. radium concentrations in the waste water to control Distribution studies of Ra2+ on CMA were car the course of decontamination process [3]. This ried out with the use of gamma emitting radio- work consists in preconcentration of radium (prior tracers: non-isotopic 133Ba and isotopic 2 jRa. The its determination) from the waste water of high sali distribution coefficients (K
10000: can be determined within several minutes. A small column containing e g. 0.5 g CMA will be required and the water sample would pass the column in less than 30 min. However, this way requires additional chemical operations including radium elution from the column and its deposition in the form of a thin- layer sample, which is not only time consuming, but may be too complex to be carried out in any mine. The developed rapid analytical procedure for preconcentration of radium ions from coal mine water containing no barium (type B water) makes it possible to determine low concentrations of 226Ra, above 0.7 Bq/dm 3, in highly saline solutions. The proposed method is sufficiently fast and simple to Fig. Breakthrough of the CMA bed with l33Ba j„ coal mine meet the requirements to control the run of the water at the flow rate 6.2 m/h. Decontamination factor (DF) technological process of radium coprecipitation vs. effluent volume (BV units). with barium sulphate, where very high accuracy of BV (Fig.). This allows for a very effective precon analysis is not crucial [3], centration of radium which is adsorbed on CMA References even stronger than barium. [1] . Jaworowski Z.: Radium and the coal fuel cycle. In: The Elution of the adsorbed 133Ba from the CMA Environmental Behaviour of Radium. Technical Report bed with 8 M HNO3 takes place with a relatively Scries No. 310. IAEA, Vienna 1990, vol. 2, p. 97. small volume (less than 10 BV) of the acid. Elution [2] . Lebecka J., Chahipnik S., Lukasik B., Wysocka M.: Inter of radium is somewhat less effective. The recovery national Workshop Ecological Aspects of Underground of Ba2+ (Ra2+) in 8 M HNCH is about 95%. Mining of Usable Minerals Deposits, Szczyrk, Poland, 23-25 November 1993. Workshop Papers, Central Mining Institute, The detection limit of 22”Ra in the sample is Katowice 1993, p. 198. below 0.7 Bq/dm 3 [3]. The developed procedure al [3] , Lebecka J.: personal information, 1994. lows us to preconcentrate radium ions from at least [4] , Tsuji M., Abe M.: Sotv. Extr. Ion Exch., 2.253 (1984). 4000 bed volumes of coal mine water containing no [5] . Gmelins Handbuch der anorganische Chemie. 8 Aufl. barium. So high preconcentration factor makes it Mangan. Teil Cl. Verlag Chemie, 1973, pp. 171,183,320.
SYNTHESIS AND ION EXCHANGE PROPERTIES OF VARIOUS FORMS OF MANGANESE DIOXIDE FOR CATIONS OF I AND II GROUPS B. BartoS, A. Bilewicz, R. Delmas1^ C. Loos-Neskovi<5 1/ PL9702 02 Pierre Stle Laboratory, C.E.N Saclay, Gif-sur Yvette, France Hydrous manganese (IV) dioxides (MnO% aq.) are the different ways the octahedra share oxygens to known to possess interesting ion exchange pro form tunnels. In the hollandite family, double chain perties [1, 2] and have been shown to exhibit of edge-sharing octahedra extend in two directions unusual ion exchange selectivity. They may be and share corners to form tunnels with a pore divided into two groups: layered and tunnel struc opening of about 460 pm [3, 4], The tunnels are tures. The oxides with tunnel structures occur in large enough to incorporate water and labile nature and can be synthesized as well. The tunnel cations. Related MnOg minerals are cryptomelane structure are all based upon MnO& octahedra and with K+ as the tunnel cation, and hollandite with RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 49 Ba2+ as the tunnel cation. The presence of ions in ions are sorbed in partially or fully dehydrated the tunnels requires some of the manganese atoms form. Small cations like Na+ are strongly hydrated to be in the oxidation states lower than 4. The and require large energy to be dehydrated. K+ and negatively charged framework is organized around Rb+ shed their hydration shell more easily and thus the exchangeable cations which can be easily re enter the exchanger phase more effectively. The tj moved by acid. of Cs+ (169 pm) is too large as against the Recently, MnOz in the H+ form has been de dimensions of the tunnels, so that Cs+ cannot enter monstrated to show excellent ion-exchange selecti- the MnC>2 phase. vities towards cations with crystal ionic radii (r,) of The ion exchange efficiency of the sorbents 130-150 pm, e.g. K+, NH|, Rb+ and Ba2+ [5-7]. towards alkaline ions decreases in the order: We suggest that - after exchange of K+ ions - the MnG2(K) e Mn02(NH4)= cryptomelane MnO% exhibits a memory effect of the s MnQ2(Rb) > >MnQ2(Na) >MnQ2(Cs). cation size, which could explain its high selectivity The high ion exchange affinity for K+ and Rb+ towards K+ and other cations with similar ionic was exhibited only by samples precipitated in the radii. A similar effect has been observed in com- presence of cations with a similar ionic size (K+, plexation of metal cations by macrocycles obtained NHj" and Rb+). These sorbents seem to demon in template synthesis [8]. strate the memory size effects of the cations. On the The aim of this work was to study the ion ex other hand, the MnOz(Na) and Mn02(Cs) sorbents change properties of cryptomelane Mn02 synthe have different crystalline forms and exhibit much sized by using various permanganates i.e. NaMnO*, smaller affinity for the cations studied. NHaMnOj, RbMnC>4 and CsMn04. We expect that K2(Na) exhibits poor radius of Ra2+ (r; = 148 pm), the sorbents ob sorption properties. The selectivity for radium of tained with NH4MnC>4 and RbMnC>4 should exhibit MnOz obtained from RbMn04 was the highest high affinity for Ra2+. Radionuclides of 226>228 Ra leached by water from uranium ores cause import ant environmental pollution in many regions [9]. The MnC>2 samples obtained from various per manganates were tested for sorption of alkali and alkaline earth metal cations. The Ka values of alkali metal cations in 1 M HNO3 solution were plotted as a function of the ionic radius of the elements studied (Fig.l). In all cases, the maximum Ka can be found for r, values of approximately 140 pm, i.e. between those of K+ and Rb+. As mentioned by Tsuji and Abe [5], the high selectivity of the MnOz samples for cations with r, = 140 pm is related to
100000c. Fig.2. Kd values of alkaline earth metal cations as a function of their ionic radii in the systems: MnC<2(K), MnC>2(NH4) 100000, and Mn02(Na) -1 M HNO3 solution.
10000; among all the samples studied. This may be due to the fact that the ionic radius of Ra2+(148 pm) is close to that of Rb+ (152 pm). The observation may | 1000, have a practical significance for developing a new efficient procedure for preconcentration and deter mination of radium isotopes present in natural waters at very low levels. References [1] . Bigliocca C, Oirardi F., Pauly J., Sabbioni E., Meloni S., Provasoli A: Anal. Chem., 29,1634 (1967). Fig.l. Ka values of alkali metal cations as a function of their ionic [2] , Tsuji M., Abe M.: Radioisotopes, 23,210 (1984). radii in the systems: Mn02(K), MnC>2(NH4), Mn02(Rb), [3] , Bystrdm A,. Bystrdm M.: Acta Ciyst., 2,146 (1950); 4, 469 Mn02(Cs) and Mn02(Na) -1 M HNO3 solution. (1951). [4] , Yin Yuan-Gen, Xu Wen-Quing, DeGuzman R., Suib S.L., the steric effect of the ion exchanger whose ex O’Young CL: Inorg. Chem., 32,4384 (1994). change centres have a diameter of approximately [5] , Tsuji M., Abe M.: Bull. Chem. Soc. Jpn., 58,1109 (1985). 270 pm. Due to the rigid MnC>2 structure, the cat [6] , Tsuji M., Komameni S.: J. Mater. Res., g, 611 (1993). RADIOCHEMISTRY, STABLE ISOTOPES, 50 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL
[7] . Tsuji M., Komameni S., Abe M.: Solvent Extr. Ion Exch., 11, [9]. Jaworowski Z.: In: The Environmental Behaviour of Radium. 143 (1993). Techt iiiiiiiiiiii|i|i,ii||i I,...... vol. 2, p. 97. [8] . Dietrich B., Viout P., Lehn J-M.: Macrocyclic Chemistry. VCH Verlag, Weinheim 1993, pp.108-112. PL9702103
HYDRATION AND COVALENCE OF THE Ln2+ AND An2+ IONS vs. ALKALINE EARTH IONS AS REFLECTED IN SOLUBILITY AND COCRYSTALLIZATION OF THEIR SULFATES T. Mioduskl Solubilities of some divalent lanthanide and SrS04 and close to BaSO^, while the stability of the actinide sulfates [1] were evaluated and compared Eu(II) complexes with EDTA, DCTA and 2-pico- [2] with the solubilities of alkaline earth sulfates linic acid is close to that for the respective Ca com (Table). plexes. The stronger interactions in the octaaqua- Table. Solubility product constants of MSO4 at 298 K.
rM2+ AG^oin Ksp . AH^oin ±5 M CN=6 [(mol dm"3)2] -RTlnKsp [kJ mol" 1] [pm] [kJ mol'T Ca 100 7.10 10“5 23.7 Yb 102 7.29 10~8 40.7 Tm 103 5.23 10“8 41.0 Fm 108 2.60 10~8 43.3 Es 110 1.74 10“8 44.3
Am 115 6.47 Hr* 46.3 Eu 117 4.86 10-9 47.5 37 Sr 118 3.44 10-7 36.9 8 Sm 119 6.99 10“10 48.2
Nd 121 7.22 10"10 49.0 Ba 135 1.07 10~10 56.9 43 Ra 141 4.02 10“11 59.4
It has been concluded [2] that the shift of the ions(II) than in the nonaaquaions(II) elucidate as solubilities of LnSO^ and AnSC>4 towards the solu well, why, in oposition to Sr2+, the ions of Eu2+, bility of BaSC>4 is a consequence of the differences Yb2+ and Es2* form inner sphere complexes with in the aquo ion structure between [Ln(OH2)9 ]|;|", tetraphenylborate anions in aqueous-ethanolic [An(OH2)9 ]lq +, [Ba(OH2)9 ]£+ and [Ra(OH2)9 ]f+ solutions [4], The same reason makes it clear, why - vs. [Sr(OH2)g]lq and [Ca(OH2)g]£f. This differ contrary to the Lnfq and An2q species - Sr2q does ence in the primary hydration number throws light not form complexes with o-phenantroline and di- on the problem of a nomadic behavior of Eu(II) pirydyl [5]. which, depending on the system, migrates from The stoichiometries of the aquo ions in question Ca(II) to Ba(II) on plots of the Gibbs free energies are discussed [2] in terms of the empirical rules of of solution and complexation. The virtual absence 16- and 18-electrons. of the covalent shortening in the Eu2q aquo ion slightly enlarges the Eu2+ ion [3], and this makes References its primary hydration number higher by 1 than that [1] , Mikheev N.B., Kamenskaya AN., Kulyukhin S.A: Radio of the Sr+ ion. The increase in the coordination khimiya,30,213 (1988). number (CN) for the Eu2q species in respect to the [2] . Mioduski T.: Comm. Inorg. Chem., in press. Sriq species is supported by the solution enthalpy [3] . Mioduski T.: Comm. Inorg. Chem., 12,93 (1997). and entropy values of the respective sulfates. In [4] , Mikheev N.B., Kulyukhin S.A, Rumer I.A: Radiokhimiya, particular, the difference in the primary hydration 30,218(1988). explains why the solubility product of EUSO4 is [5] . Mikheev N.B., Kamenskaya AN.: Radiokhimiya, 3L 95 about two orders of magnitude lower than that of (1989); ibid., 2L 48 (1989). RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 51 LIQUID-LIQUID PARTITION AND HYDRATION OF STRAIGHT-CHAIN OXAALKANES E. Gniazdowska, J. Narbutt
Group-contribution models are widely used to range of 5-50°C (Fig.l), and standard thermody describe physicochemical properties of various orga namic functions of partition were determined using nic and metalo-organic compounds. However, simple the formula: AH°=-R[d/rzP/d(l/T)], AG°=-RT In?, additivity of group properties is not always preserved, and AS°=(AH°-AG°)/T. and the molecule structure must be taken into lOflP account. Particularly interesting are studies on the properties of amphiphilic solutes in aqueous solu tions, because of practical importance of these systems in various fields - from biochemistry to tech nology of separations processes, and the diversity of molecular interactions encountered. Aliphatic ethers which consist of chemically inert alkyl groups and weakly basic [1] oxygen atoms may be regarded as simplest amphiphilic molecules. They can also serve as models for more complex species, e.g. coordinatively saturated neutral metal chelates, hydration of which has been extensively studied in this Department [2]. However, scarce data exist in the literature on the thermodynamics of aqueous solutions of oxaalkanes systematically studied along homologous series. In the present work thermodynamic studies were carried out on water - heptane partition of aliphatic ethers with n-alkyl radicals, and dioxaalkanes - acetals and diethers. The solutes contained from 0.6 two to eight carbon atoms in the linear molecule. Assuming that the properties of heptane solutions of oxaalkanes do not significantly deviate from ideality [3], we could attribute the differences ob served in standard thermodynamic functions of partition mainly to the differences in hydration of the solutes in the aqueous phase. Two types of hydration of these molecules can be distingushed [4, 5]: 1) hydrogen bond formation between water molecules and the ethereal oxygen atoms, and 2) Fig.l.Temperature dependence of the partition constant of ali hydrophobic hydration, i.e. water structure promo phatic monoethers (the numbers denote the number of carbon atoms in each n-alkyl radical) in the water-heptane tion near to non polar hydrocarbon parts of the system. solute molecule, including formation of a cavity in the solvent able to receive the guest molecule. We have already reported [6] that for monoethers Therefore, we studied the effect of the number of AG° is a linear function of the carbon atoms number oxygen atoms in the solute molecule, and of the («) in the molecule, with the slope of -3.7 kJ mol" 1 number of carbon atoms (or methylene groups) in characteristic for the homologous series of various the aliphatic radicals. It has already been recogniz organic compounds, and that methyl alkyl ethers are ed [4,5) that thermodynamic functions of hydration somewhat more hydrophobic than their more sym of solutes containing two hydrophilic centres are metrical isomers (Flg.2). In this work we have shown not additive because the centres influence each that the enthalpies of partition substantially decrease other with respect to the interaction with the sol at the beginning of the series, i.e. from dimethyl- vent. For that reason we also studied the effect of through methyl-ethyl ether, and then (from n = 4) the distance between oxygen atoms in the dioxa- remain fairly constant (AH° — 10.2 ±0.5 kJ mol" 1), alkane molecules. therefore the differences in AG° are of entropic Liquid-liquid partition method was used to study nature (Fig.2). No systematic studies on partition or intermolecular interactions of oxaalkanes in solu solubility of ethers in water are known, but a tion. Partition constant (?) was the ratio of molar comparison with similar systems is possible, based on concentrations of a given oxaalkane in the organic aqueous solubility data for some homologous series and aqueous phase at equilibrium. The concentra of homomorphic species [7], Because the enthalpies tions were measured by GLC in heptane solutions of solution in water of homomorphic aliphatic and/or in the vapour phases. The temperature hydrocarbons are close to zero [8], the positive va dependence of P was studied in the temperature lues of AH° observed for monoethers reflect the RADIOCHEMISTRY, STABLE ISOTOPES, 52 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL X, kJ/mol interacting with water molecules. Longer -(CH2V spacers in diethers make this disturbance weaker but still significant. According to Cabani [4] this disturbance in dialkoxyethanes (n = 2) decreases X, kJ/mol
-10 ■ ■
ft Fig.2. The dependence of standard thermodynamic functions of par tition of monoethers in the water-heptane system at 25°C: X = AO° (squares), X «= AH° (triangles), and X = TAS° (circles); on the carton atoms number (n) in the molecule. The closed symbols denote the methyialkyl ethers and the open ones - more symmetrical isomers. n hydrogen bond breaking between water and ether Fig.3. The dependence of standard thermodynamic functions of molecules, which accompanies transfer of ethers partition (symbols the same as in Fig.2) of dimethoxy- (closed symbols) and diethoxyalkanes (open symbols) in from water to heptane. The constancy of the AH° the water-heptane system at 25°C on the number (ft) of values along the series (from n - 4) seems to indicate carton atoms separating oxygen atoms. that the expected effect of slight strenghtening the hydrogen bond with increasing aliphatic chain [1] is enthalpy of hydration by 9 ±1 kJ mol" 1 towards the rather small. Relatively high AH° and TAS° values value expected from the group-contribution model, for dimethyl ether may perhaps be interpreted in and this effect decreases with increasing n. That terms of formation of a quasi-clathrate structure in picture qualitatively corresponds with our AH° data the aqueous solution; with the small ether molecules for n < 4 (diethoxy-) and n <5 (dimethoxyalkanes). located in the cavities formed in the tetrahedral However, the great decrease of AH° and TAS° structure of liquid water, and interacting with water observed for the longest (n = 4-5) diethers studied without disordering its structure. The AH0 vs. n rela is rather unexpected and can hardly be explained at tionship is, however, different from those observed in present. the homologous series of other compounds e.g. In summary, our results confirm the view that in n-alkyl sulphoxides homomorphic with monoethers the group-contribution model one cannot neglect studied, where the enthalpy of solution in water (of the effect of the structure of amphiphilic molecules the opposite sign to AH°) decreases from the begin of oxaalkanes, particularly of the number of the ning of the series [9]. hydrophilic centres in the solute molecule and of As expected, a more complex picture is observed the distance between them. The systems studied for dioxaalkanes with oxygen atoms separated by n seem to be more complex than expected, and there CHz groups: acetals (n = 1) and diethers (n > 1). fore the theory based on only two types of inter Water-heptane partition was studied on dioxaal action of amphiphiles with water, i.e. hydrophobic kanes belonging to two homologous series: dime- and hydrophilic hydration, appear to be insufficient thoxy- and diethoxyalkanes. As can be seen in Fig.3, to explain the thermodynamic properties of their distinct maxima appear on the plots of AG° vs. n for aqueous solutions. Not only the mutual influence of n = 2, and the subsequent decrease of AG° is much at least two hydrophilic centres in the molecule on smaller than that observed for monoethers. their hydration, but probably also conformational The dln?/d(lfT) dependences are no more linear changes of the solute molecules in both aqueous as is the case of monoethers, and the enthalpies of and organic solution have to be taken into account partition significantly depend on temperature, when considering liquid-liquid partition equilibria moreover to a different extent for various species. of amphiphilic species. Sharp maxima are observed on the plots of AH° and TAS° (298.2 K) vs. n. corresponding ton = 2-3 References (diethoxy-) and n = 4 (dimethoxyalkanes) (Fig.3). [1] . Paterson W.G., Cameron DM.: Can. J. Chem., 41, 198 The maxima well correspond with minima on the (1963), and the references cited therein. enthalpy of aqueous solubility curves for n-aliphatic [2] , Narbutt J.: Hydratacja /9-diketonian6w metali i jej wplyw na alcohols, a,co-diols, etc. [9]. The differences be rtiwnowagi podziatowe w procesach ekstrakcji. Report INCT-2119/V. Institute of Nuclear Chemistry and Tech tween acetals and lighter diethers may be due to the nology, Warszawa 1991. fact that two oxygen atoms separated by only one [3] , Kehiaian H.V., Tine M R., Lepori L., Mateolii E., Marongiu CH2 group prevent each other from full-strength B.: Fluid Phase Equilibria, 46,131 (1989). RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 53
[4] .Cabani S., Gianni P.: J. Chem. Soc. Faraday I, 75, 1184 [7J. Yalkowsky S.H., Banetjee S.: Aqueous Solubility. Methods of (1979); Cabani S., Gianni P., Molica V., Lepori L: J. Sol. Estimation for Organic Compounds. Marcel Dekker, 1992. Chem., 10,563(1981). [8) . Nelson H.D., De Ligny CL.: Rec. Trav. Chim., 87, 623 [5] , Wolfenden R.: In: Topics in Molecular Interactions. Eds. W. J. (1968). Orville-Thomas, H. Ratajczak, CN.R. Rao. Elsevier, Amster [9) . Corkill J.M., Goodman J.F. Tate J.R.: Trans. Faraday Soc., dam 1985, p. 121. 65,1742(1969). [6] , Gniazdowska E., Narbutt J., Siekierski S.: INCT Annual Report 1994, p. 42.
BEHAVIOUR OF THE SYSTEM: ARSENIC-PALLADIUM-MAGNESIUM DURING ATOMIZATION IN GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROMETRY L. Pszonicki, J. Dudck An investigation of the system: arsenic-pallad the literature. In the hydrochloric solution, however, ium-magnesium was caused by the fact that pallad this effect occurs only when a large excess of mag ium or mixture of palladium and magnesium are nesium nitrate is used. Addition of magnesium suggested as versatile modifiers used in the graphite chloride is ineffective. This suggests that magnesium tube atomization processes [1, 2]. Both the modifiers can affect arsenic when a sufficiently large amount of are also recommended for the determination of nitrate ions is present in the solution, i.e. when a arsenic. However, the mechanism of their activity sufficiently large amount of magnesium is present in proposed in the literature is not always consistent the nitrate form. An identical effect of magnesium is with some observed phenomena. Some of these observed when only it (without palladium) is used as abnormalities were already explained in the inves modifier. It keeps arsenic stable not only during the tigation of lead-palladium system [3, 4], but the drying phase but also during the pyrolysis phase up preliminary experiments showed that for arsenic the to about 1000°G The mechanism of magnesium situation is more complex. Since arsenic and its activity may be explained in the following way: compound are easy volatile, the possibility of their magnesium nitrate reacts with arsenic already at the losses at any thermal process should be taken into end of drying phase and protects it against the account. Therefore, the right understanding of the reaction with chloride ions and against the losses. mechanism of processes occurring in the graphite During the pyrolysis phase the magnesium-arsenic tube during atomization is of great importance. compounds are gradually transformed in the mixed Our investigation shows that for the samples magnesium-arsenic oxides stable to the temperatures dissolved in pure nitric acid medium palladium of about 1000°C. protects arsenic by the formation of stable pallad On the basis of the presented investigations it ium-arsenic compounds, as it is described in the may be stated: literature. When the sample is solved in hydro 1. Palladium should not be used as modifier for chloric acid, palladium does not protect arsenic and the determination of arsenic by graphite furnace its total amount is lost in the form of chlorides or AAS, since in the case when some amount of oxychlorides already at the temperature of 120°C. hydrochloric acid is present in the sample solu In the mixed hydrochloric and nitric acids medium tion, it not only does not protect arsenic against these losses are diminished proportionally to the the losses but it also interferes itself in the growing concentration of nitric acid. It results from arsenic determination. the fact that in the presence of nitric acid part of 2. Magnesium nitrate is a very good modifier for the arsenic is kept in the form of arsenic acid and it arsenic determination in nitric acid solution and decomposes to an oxide which is stable up to the in the mixed nitric and hydrochloric acid solu temperature above 400°C. In this temperature non tion. volatile arsenic-palladium compounds are formed. 3. When the mixed magnesium-palladium modifier However, the significant losses of arsenic are ob is used, magnesium nitrate plays a basic role. served even in the presence of a large excess of Addition of palladium causes only a small exten nitric acid. This phenomenon is caused by another sion (about 100°C) of the temperature range of mechanism, the same as that described for lead [3]. arsenic stability during pyrolysis and delays the Part of the palladium, which is present in the sys appearance of the arsenic peak during the ato tem in a relatively large amount, forms with hydro mization of about 0.5 s. chloric acid palladium chloride that is stable up to 500°C. In this temperature, during the pyrolysis References phase, it decomposes evolving free chlorine atoms [1] . Welz B., Schlemmer G., Mukadavit J.R.: 3. Anal. At. Spectr., which are able to attack the arsenic-palladium com 2,93-97 (1988). pounds and form volatile arsenic chloride. [2] . Idem, ibid., 3,695-701 (1988). Application of the palladium-magnesium modifier [3] . Pszonicki L., Eased AM.: Chem. Anal., 38,759-770 (1993). in the mixed nitric and hydrochloric solution elimi [4] , Idem, ibid., 38,771-778 (1993). nates completely the losses of arsenic, as it is given in RADIOCHEMISTRY, STABLE ISOTOPES, 54 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL DETERMINATION AND SPECIATION OF MERCURY IN NATURAL WATERS J. Chwastowska, W. Skwara, E. Sterlinska, J. Dudek, L. Pszonicki
Mercury belongs to the poisonous elements and sorption was carried out using 5% thiourea solu their concentration in the contaminated environ tion in 0.05 M hydrochloric acid. Both the forms of ment should be kept under the permanent control. the preconcentrated mercury, inorganic and me The toxicity of mercury is strongly dependent on its thylmercury, were determined sequentially from the chemical form. Particularly dangerous are the same solution by cold vapour atomic absorption inorganic compounds of mercury(II) and its methyl spectrometry [2]. At first inorganic mercury was derivatives because of their neuro- and embryo- reduced to the metal form by tin(II) chloride, toxicity. removed from the solution as the vapours and de The trace analysis of mercury is a difficult task termined. Then the methylmercury was decom since its various forms are very volatile and show posed by the addition of cadmium chloride, reduced also a large ability to adsorption on the walls of to the metal by an excess of tin(II)chloride and laboratory vessels. The speciation of its individual determined as previously. chemical forms is particularly difficult because of On the basis of this investigation the following their great lability in the natural environment. optimum conditions for the separation of inorganic Some types of bacteria can cause the formation of mercury(II) and methylmercury from 1 litter water the mono and dimethyl compounds from inorganic sample were established: 0.2 g of the sorbent on a mercury and the organic compounds decompose column, 0 = 4 mm; pH of the water sample = 2; easy when affected by various factors. Moreover, flow rate 5-7 ml/min; desoption by 10 ml of 5% the determination is required of a very low thiourea solution in 0.05 M HC1. concentration, near to or below the detection limit The method was tested on the basis of synthetic of the commonly used analytical methods, since the water containing all the components of natural accepted limits for mercury content is low. The waters and known concentrations of inorganic mer- limit for the fresh water is lpg/1. Therefore mercury cury(II) and methylmercury equal to 0.050 fig/l is usually separated from the sample to be analysed, each. The determined values established on the preconcentrated and then determined as total or as basis of 8 determinations were: 0.050 pg/1 of in individual forms. organic mercury and 0.049 /zg/l of methylmercury. The aim of the presented work was to prepare a The relative standard deviations were 7.1 and 6.1%, method for the determination of inorganic mer- respectively. The limit of determination of the me cury(II) and methylmercury in natural waters. For a thod was established as 0.02 ^gA. preliminary separation and concentration of mer cury the new, recently introduced by our Labora References: tory chelating sorbent [1]: thionalide (2-mercap- [1] . Chwastowska J., Zmijewska W., Sterlirtska E.: Anal. Chim. to-N-2-naphtyl-acetamide) immobilized on the ac Acta, 226,265 (1993) rylic resin Bio-Beads SM-7 (TTB) was applied. De [2] . Mingawa K., Takizawi
PL9702104 PREPARATION OF GEL PRECURSORS FOR SYNTHESIS OF MERCURY - BASED SUPERCONDUCTING CUPRATES FROM ACIDIC ACETATE-AMMONIA SYSTEMS A. Deptuta, T. Olczak, W. Lada, A. Di Bartolomeo 1'' v C.R.E. Casaccia, ENEA, Rome, Italy
Recently mercury based cuprates were recognized as Sols were then gelled to a blue-violet monolithic very promising high temperature superconductors. body by evaporation at 60°C. It was observed that Sol-gel process elaborated in the INCT for BSCCO gels containing calcium exhibits a perfect homoge- type HTS. [1] was applied for the preparation of gels nity in contrast to the gel for the composition n=l, of mercury based materials for a potential synthesis where some crystalline inclusions were observed. of HgBa2Ca„-iCu n02n+2+<$ (n = 1,23) supercon Shards formed after further heating of this gels at ductors. Respective sols were prepared by the ad 60°C and grinding were submitted for thermal dition of aqueous ammonia (12 M) to acetate solu analysis (TG, DTA). The results show a fast tions of Hg%+ (0,5 M); Ba2+ (0,8 M); Ca2+ (1,4 M) complex decomposition (weight loss approximately and Cu2+ (0,3 M), sometimes with acetate acid 60%) in the range 200-500°C, accompanied by 3 excesses. It is worth underlining that experiments exothermic effects. The final weight losses during with the application of a new variant of the sol-gel further calcination in the 500-800°C are relatively process (CSGP) elaborated in the INCT [2,3] failed small (< 2%). Mercury contents in the starting gels because after the addition of ascorbic acid practically and products of their calcination in the ambient all the Hg 2+ was precipitated. atmosphere are shown in Table. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 55
Table. Mercury contents in starting gels and products of their calcination. Nominal starting Hg content in gels calcined at indicated temperatures Sample composition® 60°C; 24 h 200%; 0.5 h 500%; 0.5 h Hg-1 HgBa2CuG4+<$ 16.5% 0.32% < 0.01 ppm Hg-2 HgBa2CaCu206+<$ 13.0% 0.60% < 0.01 ppm Hg-3 HgBa2Ca2Cu30s +& 11.8% 0.18% < 0.01 ppm ® H%0 and Ac not indicated. From the presented data it can be noted that In conclusion it can be expected that Hg vacan- during drying at 200°C more than 96% of the mer- ties in the synthesized precursors may facilitate the
wz—; 6°"9. ' JLj u 200% 0 200% 200% 0 1
------500% 500% e 366% e a
6 |36 66 |6 [36 66\6 |36 66 2- Theta Hg-1 Hg-2 Hg-3
Hg oxide-o Ba: acetate- •; carbonate-0 Ca: acetate- A; carbonate-A Cu: acetate- x; oxide-1 Fig. XRD patterns (CuKg) of materials described in Table. cury is lost. After calcination for 0.5 h at 500°C the formation of superconductors in the reaction with mercury is practically completely removed. mercury vapors. XRD patterns of materials indicated in Table are shown in Fig. References As it follows from XRD data in the gel samples [1] . Deptula A., Lada W., Olczak T., Bartolomeo Di A.: Pre with higher Hg contents dried at 60°C (Hg-1 and paration of BSCCO Precursors by Water Extraction Variant Hg-2) mercury oxides are observed. In all samples of Sol-gel Process. In: Better Ceramics through Chemistry V. crystalline acetates of the remaining elements exist. Eds. M.J. Hampden-Smith, W.G. Klemperer, CJ. Blinker. At 200°C the composition of materials is essentially MRS Proceedings, Vol. 271,1992, p. 161. similar. After calcination at 500°C a mixture of Cu [2] , Deptula A, Lada W., Olczak T., Lanagan M.T., Dorris S.E., Goretta KC., Poeppel R.B.: Formation of Phase-Pure, Carbo oxides and carbonates of the remaining elements nate-Free, Superconducting Ceramics from Organic Pre exists. The presence of carbonates was also observed cursors. Polish Patent pending no. P. 300 557 (October 1993). in IR spectra. Weak bands with a frequency of [3] , Deptula A, Lada W., Olczak T.lINCT Annual Renort 1991 - 3400 cm'1 is indicating the presence of hydrogen p.73. iiiiiiiiiiiiiiiii iiiiiliill 111111111 III Hill 1111 llll bonded OH group. PL9702105
A STUDY ON SUITABILITY OF THE ION CHROMATOGRAPHY EQUIPMENT OF DIONEX 2000i/SP FOR THE DETERMINATION OF ALKALI METALS AND OTHER INORGANIC CATIONS IN AQUEOUS SOLUTIONS K. Kulisa, R. Dybczynski, H. Polkowska-Motrenko
Ion chromatography is a fast, sensitive and accurate lions on ppm (mg/1) and ppb (wg/1) level [1-3]. The method for simultaneous determination of many necessity of determination of trace quantities of ions ionic (anionic and cationic) species in aqueous solu- in the presence of macro-quantities of other ionic RADIOCHEMISTRY, STABLE ISOTOPES, 56 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL species occurs frequently in analytical practice. In equipped with the Ion Pac CS10 Analytical Column this case a column overloading may occur, resulting was used in this study. The analytical column was in detonation of analytical results. In the previous preceded by a guard column CG10. The column was paper, the effect of column overloading and its in filled with new type "agglomerated" ion exchange fluence on the quality of analytical results when de resins of low ion-exchange capacity and the structure termining simple anions was presented [4]. This work enabling high velocity of ion exchange reaction, so has been carried out to study this problem in the that the chromatograms of complicated ionic mix case of determination of alkali metals and alkaline tures could be obtained in relatively short time. The earth cations by ion chromatography. A commercial chromatograph was equipped with a cation micro ly available ion chromatograph Dionex 2000i/SP membrane suppressor CMMS-1 regenerated with COLUMN CS10 COLUMN C810 ELUANT 40 mM HCI/2 mM DAP HCI ELUANT 40 mM HCI/2 mM DAP HCI □ A O ♦ ♦ • O A O + ♦ • Lf Ns* NHj K* Mg 2* Ca2* Ll* Ns* NH% K* Mg 2* Cs2*
200 •
JGL. D -B- 100 200 300 400 600 100 200 300 400 600
Concentration of Mg a*, ppm Concentration ol Mg **,ppm
COLUMN CS10 COLUMN C810 ELUANT 40 raU HCV2 mM DAP HCI ELUANT 40 raM HCI/2 mM DAP HCI D A O ♦ ♦ • □ A O • LI* Ns* NH% K* Mg**Cs 2* U* Ns* NHj K* Mg2 * Ca2"
7000
■e—e—©■ 2000 "|
100 200 300 400 500 100 200 300 400 500 a* Concentration of Mg ,ppm Concentration of Mt^*,ppm Fig. Dependence of chromatographic peak parameters on macro-constituent ion concentration. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 57 solution of 100 mM TBAOH, a Dionex conductivity Table. Precision of chromatographic analysis of water sample. detector CDM-II and an UV/VIS variable wave Results of Relative Arithmetic Standard length Detector VDMII. The signals from the detec single standard Cation mean, x deviation, s determination, deviation, sr tors were processed using a computer program [mg/lj [mg/1] Dionex AI-450. A 40 mM HC1/2 mM DAP HC1 %i [mg/1] [%] solution was used as a mobile phase. 65.55 The chromatograms were obtained as a function 64.60 of a cation being a macro-constituent. 4 series of Na+ 64.57 64.57 0.99 1.53 64.58 solutions, each consisting of 6 cations (Li+, Na+, 63.56 NHj", K+, Mg 2+ and Ca2+), where five were of 11.99 fixed concentrations (trace level) and the concen 10.96 tration of the sixth one (Na+, NHj", Mg 2+ and K+ 10.98 11.04 0.47 4.25 Ca2+, respectively) was changeable in a rather 11.00 broad range, were studied. 10.28 Series 1 - Li+ - 5 mg/1, NHj" - 40 mg/1, K+ - 20 16.99 mg/1, Mg 2+ - 20 mg/1, Car2 -100 mg/1 and Na+ - chang 15.72 Mg 2+ 16.80 16.47 0.48 2.91 ing concentration 20,40,100,150,200,300,500 mg/1. 16.47 Series 2 - Li+ - 5 mg/1, Na+ - 20 mg/1, K+ - 20 mg/1, 16.39 Mg 2+ - 20 mg/1, Ca2 -100 mg/1 and NHj" - changing 91.52 concentration 40,100,150,200,300,500 mg/1. 90.36 Series 3 - Ii+ - 5 mg/1, Na+ - 20 mg/1, NHj" - 40 Ca2+ 90.13 90.37 0.73 0.8 mg/1, K+ - 20 mg/1, Ca2 -100 mg/1 and Mg 2+ - chang 90.45 ing concentration 20,40,100,150,200,300,500 mg/1. 89.39 Series 4 - Li+- 5 mg/1, Na+ - 20 mg/1, NHf - 40 When analyzing the real samples care must be mg/1, K+ - 20 mg/1, Mg 2+ - 20 mg/1 and Ca2+ chang taken not to exceed the limiting concentration values ing concentration 100,150,200,300,500 mg/1. of the most abundant constituent. It is one of the For each of the investigated cations the basic main conditions to obtain precise and accurate re characteristics of chromatographic process as: peak sults of analysis. Results of the analysis of natural area, retention time, column efficiency and peak water taken from a well of Belgradzka Street in War shape parameters (asymmetry) were calculated as a szawa is shown in Table. Four cations, namely Na+, function of macro-constituent concentration in the K+, Mg 2"1" and Ca2+ were determined. Relative analyzed solution. In Fig. the example of above func standard deviation did not exceed 4.5% for all tions is shown. It follows from obtained results that determined cations, so that the precision of the limiting values of concentration below which the analysis can be considered as being good. In all cases linearity of calibration curves and the stability of re the concentration of the determined cations were tention times for macro-constituent were maintained below the limiting concentrations earlier established, are: for Na+ - 6.52 meq/1 (150 mg/1), for NH| - 8.33 so dilution of samples was not necessary. meq/1 (150 mg/1), for Mg 2+ - 6.25 meq/1 (200 mg/1), Determinations of transition metals (Fe3+, Co 2+, except for Ca2 , for which one can observe only Cu2+, Ni2+, Zn2+) were carried out using Ion Pac slight lowering of retention time above the concen CSS analytical column and Post Column Ion Pac tration of 5.0 meq/1 (200 mg/1), while the calibration Membrane Reactor device. The metals were separat curve maintained its linearity in the whole range of ed as anionic complexes with the PDCA (2,6-pyri- concentration investigated. Contrary to anions [4], dinedicarboxylic acid) chelating agent added to the the influence of macro-constituent concentration on eluant. A 6 mM PDCA + 50 mM CH3COOH + 50 peak areas and retention times of trace ions was mM CHgCOONa solution was used as a mobile small or negligible in the case of cation exchange phase. The absorbance of complexes formed with the separations for all the macro-constituents in the post column PAR (4-(2-pyridylazo)resordnol) rea whole range of concentrations investigated. gent was measured using UV/VIS detector at 520 The shape of a peak has also an influence on nm. The precision of the method and conditions of precision and accuracy of the determination. As one the analytical procedure were established on the can see from Fig., the tailing factor and column effi basis of replicated measurements. Relative standard ciency depend on the concentration of macro-con deviation was found to be below 3%. stituent both for macro- and trace cations. Hie symmetry of the peaks is the best and column References efficiency is the highest when the concentration of [1] . Haddad P.R., Jackson P.E.: Ion Chromatography Principles macro-constituent is low and both decrease with and Applications. Elsevier, Amsterdam 1990, p. 776. increasing concentration. For all the investigated [2] .Zach K., Frei R.W.: Sample Handling and Detection in cations, except for the Mg 2"1", the decreasing of High-Performance Liquid Chromatography. Elsevier, Amster dam 1989, p. 394. column efficiency values is rather low above the [3] . Yost R.W., Ettre L.S., Conlon R.D.: Practical Liquid limits of concentration of the macro-constituents Chromatography. Perkin Elmer, Norwalk USA 1980, p. 255 mentioned previously. In the case of Mg 2+ the limit [4] .Kulisa K., Dybczyliski R., Polkowska-Motrenko H.: INCT is of ca. 1.56 meq/1 (50 mg/I), above which the Annual Report, 1995, p. 57. number of theoretical plates drastically decreased. P L97021 06 RADIOCHEMISTRY, STABLE ISOTOPES, 58 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL IINS SPECTROSCOPY OF AMINOACIDS. PART IV. SULFOGLYCINE A. Pawlukojd, J. Tomkinson 1/, S.F. Parker^ y Rutherford-Appleton Laboratory, Chilton, Great Britain IINS spectra of normal and deuterized samples of recorded at 10 K on a TFXA spectrometer placed at sulfoglycine (aminomethanesulfonic acid) have been the Spallation Source ISIS, Rutherford-Appleton Laboratory. In the crystalline state the title compound exists in the dipolar (zwitterion) form +H3NCH2COO~ and exhibits three N-H...O hydrogen bonds. Three intensity modes have been observed in the IINS spectra of valine [1], leucine [2] and isoleucine [3] which are associated with out-of-plane /(N-H...O) hydrogen bond vibrations in the energy range up to 600 cm'1. It is known, that the NHj" group exhibits triple degenerate torsional vibration. However, | i«o HI NH jCH jSO, when the hydrogens from the NHj" group become involved in hydrogen bonds to carboxylate oxygens, this degeneracy is lifted, resulting in three bands. The experimental spectra of normal and deute ,, NH,HD jSOj rized samples of the title acid are shown in Fig. Intense bands are observed in the energy range 200-400 cm1 due to out-of-plane y(N-H...O) hydro ND jCH jSO, gen bond vibrations and CHg vibrations. In the en . .-/-X ergy region 500-700 cm"1 a band connected with the deformations of the SO3 group could be identified.
NO,CD, 80, References tVvv'- [1]. Pawlukojd A, Bobrowicz L., Natkaniec I., Leciejewicz J.: __ , ...... Spectrochim, Acta, 51A, 303 (1995). 0 woo 2000 3000 4000 [2], Pawlukojd A, Leciejewicz J., Natkaniec I.: Spectrochim. Energy Transfer (cm •’) Acta, 52A, 29 (1996). Fig. IINS spectra of normal and deutrized sulfoglycine recorded [3]. Pawlukojd A, Bajdor K., Dobrowolski J.C., Leciejewicz J., at 10 K. Natkaniec I.: Spectrochim. Acta, 53A (1997).
IINS SPECTROSCOPY OF AMINOACIDS. Part V. L-SERINE A. Pawlukojd, S.F. Parker1/ 197021 07 y Rutherford-Appleton Laboratory, Chilton, Great Britain As a continuation of our studies on the dynamical and d4-deuterized samples of L-serine (2-hydroxy properties of aminoacids, the IINS spectra of normal aminoethane carboxylic acid) have been recorded at
L - serine
normal A wh/ i til; 1 deuterized f
0 100 200 IDO 400 S00 800 700 100 000 1000 1100 1200 1300 1400 1600 1600 Energy transfer (cm-’) Fig. IINS spectra of normal and da-euterized L-serine recorded at 10 K. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 59
10 K using a TFXA spectrometer at the Ruther tween the amino group nitrogens and the carboxy- ford-Appleton Laboratory. late oxygens belonging to the nearest serine mole The L-serine exists in the crystalline state as a di cule. The peak at 1226 cm"1 has been identified as polar ion (zwitterion) ^HgNCHCHzOHCOO " and being due to the vibrations of the y(O-H.O) hy exibits three N-H...O hydrogen bonds (2.840 A), [1]. drogen bond operating between the carboxylate The experimental spectra of normal and d^-deu- oxygens. terized L-serine in the energy range up to 1600 cm'1 are shown in Fig. The strong peaks at 440 and 475 References cm"1 observed on the scattering pattern of the deu- [1]. Kistenmachcr TJ., Rand G.A, Marsh R.E.: Acta Ciyst., B30, terized sample are associated with the vibrations of 2573 (1974). three out-of-plane y(N-H...O) hydrogen bonds be
CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLIC ACIDS. PART XV. THE CRYSTAL AND MOLECULAR STRUCTURES OF DIAQUABIS (3-AMIN0PYRAZINE-2-CARB0XYLAT0-N,0)MAGNESIUM(II) MONOHYDRATE AND 3-AMINOPYRAZINE-2-CARBOXYLIC ACID DIHYDRATE H. Ptasiewicz-Bqk, J. Leciejewicz The structures of all up to now investigated com A network of hydrogen bonds operates between the plexes of pyrazine-2-carboxylic acid with divalent monomers and solvatation water molecules. ions contain monomeric molecules in which the The crystals of apza are also monoclinic - space central ion is chelated by two N.O bonding moieties group P2i/c. The structure contains molecular of two acid molecules. The characteristic for each ion coordination around the central ion is com pleted by water molecules. On the other hand, the structures of divalent ion complexes with pyra- zine-2,3-dicarboxylic acid are polymeric. In some of them both N.O sites are used for bonding acting in the bridging manner. Therefore it seemed of interest to find out how the chelating activity of the second nitrogen will be affected when the nearest t it carboxylic group will be replaced by an aminogroup. The 3-aminopyrazine-2-carboxylic acid (apza) offers a possibility to perform such an experiment. Its complex with magnesium has been Fig 2. The alignment of apza molecules in the structure. Dashed therefore synthetized and single crystals grown. lines indicate hydrogen bonds. Since the structure of apza itself has remained until now unknown, it has been also determined. layers in which the molecules are held together by a system of hydrogen bonds indicated by dashed lines in Fig.2 which illustrates the molecular layout in the layer. The bond distances and angles within the individual molecules are in fair agreement with those found earlier in other carboxylic acids con taining the pyrazine rings. X-ray data collection was performed using a KUMA KM4 (Cu Kq radiation) four circle diffrac tometer at this Institute. Data processing and struc ture refinement was carried out using SHELXL93 programme package.
Fig.l.The molecule of [Mg(apza)2(H2Q)2] H2O. References [1] . Part IV. Alcock N.W., Errington W., Kemp T.J., Lecieje The crystals of magnesium complex with apza are wicz J.: 5-nitro-2-furancarboxylic acid. Acta Ciyst., C52,188 monoclinic - space group Cc. The structure contains (1996). monomeric molecules. Each Mg ion is coordinated by [2] . Part V. Paluchowska B., Maurin J.K., Leciejewicz J.: The two acid molecules via their N,0 bonding sites with role of C-H...0 bonds in stabilizing 3-furancarboxylic acid and its complexes with calcium and strontium. Acta Ciyst., mean Mg-O bond distance of 2.070(1) A and Mg-N C52,342(1996). bond of 2.255(1) A and two oxygen atoms of water [3j. Part VI. Paluchowska B., Maurin J.K., Leciejewicz J.: molecules - mean Mg-O bond of 2.040(1) A The Carboxylate and furan ring oxygen bonded to calcium in coordination is octahedral. Fig.l shows the molecule. polimeric calcium furcate. Acta Ciyst., C52, 347 (1996). RADIOCHEMISTRY, STABLE ISOTOPES, 60 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL
[4] , Part VII. Alcock N.W., Errington W., Kemp TJ., Lecieje- [8] , Part XI Ptasiewicz-Bqk H., Leciejewicz J.: Apyrazine-bridged wicz J.: Diaquadioxobis(pyridine-3-carboxylato)uranium(VI). chain structure of magnesium complex with pyrazine-23-di- Acta Cryst., C52,615 (1996). carboxylicacid. Polish J. Chem., 71,493 (1997). [5] , Part VIII. Alcock N.W., Kemp TJ., Roe S.R., Leciejewicz [9] , Part XII. Paluchowska B., Maurin J.K., Leciejewicz J.: Direct J.: The roles of N- and O-coordination in the crystal and and outer-sphere coordination of the magnesium ions in the molecular structures of uranyl complexes wth anthranilic crystal structures of complexes with 2-furancarboxylic add (I) and pyrazinic acids. Inorg. Chim. Acta, 248,241 (1996). and 3-furancarbaxyiic add (II). J. Chem. Cryst., 22,185 (1997). [6) . Part IX. Paluchowska B., Maurin J.K., Leciejewicz J.: Variable [10]. Part XIII. Paluchowska B., Maurin J.K., Leciejewicz J.: coordination of barium in its complexes: crystal structures of Dinuclear copper(II) complexes with 3-furancarboxylic add barium compounds with 2- and 3-furancarbatylic acids. Polish and 2-thiophen carboxylic acid. Journal of Coordination J. Chetn., 70,1402 (1996). Chemistry, in press. [7) . Part X. Paluchowska B., Maurin J.K., Leciejewicz J.: [12]. Part XIV. Ptasiewicz-Bqk H., Leciejewicz J.: The crystal Heteroring oxygen coordination to strontium in the crystal structures of strontium complexes with pyrazine-2-carboxy- structure of strontium 2-furancarboxylate. Acta Cryst., C53, lic and pyrazine-2,3-dicarboxylic adds. Journal of Coordina 297 (1997). tion Chemistry, in press.
CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLIC ACIDS. PART XVI. THE CRYSTAL AND MOLECULAR STRUCTURE OF CALCIUM AMINOPYRAZINATE J. Leciejewicz, H. Ptasiewicz-Bqk, B. Paluchowska^ 1Z Institute of Atomic Energy, Otwock-Swierk, Poland
In contrast to all up to now studied complexes of oxygen atoms are coordinated by the Ca atom: one divalent ions with pyrazinic acid and magnesium of them is situated above the plane at 2.357 A, the aminipyrazinate dihydrate which in crystals appear other one below the plane at 2.362 A. They belong as monomeric molecules, the structure of the title to the carboxylate groups located on the adjacent compound is polymeric. It is composed of chains planes and bridge them into molecular chains. This propagating in the b direction of a monoclinic unit is shown in Figs. 1 and 2. The chains are held together by a system of hydrogen bonds in which
Oil
Fig.l Packing diagram of the structure of calcium aminopyrazi- nate. Fig.2 A fragment of the structure illustrating the coordination cell (space group Cc). Each calcium atom is bonded around the calcium atom. to two aminopyrazinate molecules via their (N.O) bonding sites with typical Ca-N and Ca-O distances the coordinated to Ca water molecules play a signi of 2.590 and 2.385 A respectively (average values). ficant role. The four circle KUMA KM4 (CuK* A water molecule at a distance of 2.377 A is radiation) diffractometer at this Institute was used additionally bonded to the Ca atom. The above Ca, for data collection. Data processing and refinement two N and three O atoms make a plane with the was carried out with SHELXL93 program package. maximum out-of-plane shift of 0.54 A Two more RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 61 CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLIC ACIDS. PART XVII. THE CRYSTAL AND MOLECULAR STRUCTURES OF PYRAZINE-2,5-DICARBOXYLIC ACID DIHYDRATE AND ITS MAGNESIUM COMPOUND H. Ptasiewicz-Bqk, J. Leciejewicz
Polymeric structures with a variety of bonding Magnesium pyrazine-2,5-dicarboxylate hexahydrate schemes have been found in the complexes of pyra- is monoclinic, space group P2i/c Each magnesium zine-2,3-dicarboxylic acid with a number of divalent atom is sorrounded by six water molecules located at ions. In some of them both (N.O) bonding moieties the apieces of an almost regular octahedron with mean Mg-O bond distance of 2.060(1) A - a typical value. The 2,5-pzdc molecules are planar with inter atomic distances and bond angles characteristic for the pyrazine carboxylic adds. A network of hydrogen bonds links the Mg(H 20)6 with carboxylate oxygen ' Hl« atoms. Fig.1 shows a fragment of the molecular pattern of the title compound.
Fig.l.A fragment of the molecular pattern in the structure of [Mg(H 20)]6(2,5-pzdc). are involved in chelating the central ion, in other the second carboxylic group acting either as mono- Fig. 3. A fragment of a sheet composed of 2,5-pzdc and water molecules. dentate or bidentate is bonded to the metal ion leaving its nearest heteroring nitrogen inactive. In Pyrazine-2,5-dicarboxylic add dihydrate is triclinic, contrast to the 2,3-pzdc, the molecule of pyra- space group PI. The structure is composed of mole zine-2,5-dicarboxylic add (2,5-pzdc), exhibiting also cular sheets consisting from 2,5-pzdc and water mole two potential (N,0) sites, shows different mutual cules held by a system of hydrogen bonds. The alignment of the heteroring nitrogens and the interatomic distances and bond angles values are carboxylic groups. New bonding schemes may be close to those found in other pyrazine carboxylic
Fig.2.Thc packing of molecular sheets in the structure of (2,5-pzdc) 2H2G. expected in its complexes. As the first step in our acids. Fig.2 displays the packing of the sheets, while studies on the crystal chemistry of 2,5-pzdc com Fig.3 - the alignment of molecules in the sheet plexes with divalent metals the magnesium complex X-ray data collection was performed using a KUMA has been synthetized and its structure studied. Since KM4 (Cu Kq radiation) four circle diffractometer at the structure of the acid has not been until now this Institute. Data processing and refinement was reported its structure has been also determined. carried out using SHELXL93 program package. RADIOCHEMISTRY, STABLE ISOTOPES, 62 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS WITH HETEROCYCLIC CARBOXYLIC ACIDS. PART XVIII. THE CRYSTAL STRUCTURE OF DIAQUABIS(THIOPHENE-2-CARBOXYLATE)ZINC(II) B. Paluchowska 1^ J.K. Maurln1^ J. Leciejewicz 1Z Institute of Atomic Energy, Otwock-Swierk, Poland
Furan ring oxygen atom of furoic acid molecule has been found to act as a ligand to the metal ion in the structures of calcium (see Part VI), strontium (see Part X) and barium (see Part IX) furcates. Little is known whether the sulphur atom of the thiophene ring can play the same role in the structures of metal complexes with thiophene-2 carbolic acid. Following our study of copper thiophenate (see Part XIII) the structure of zinc thiophenate has been determined. The title compound crystallizes in the monoclinic system (space group C2) and con tains monomeric molecules linked by hydrogen bonds. The coordination around the zinc ion is tetrahedral: four oxygen atoms located at the apieces of a distorted tetrahedron are donated by two monodentate carboxylic groups of acid mole cules and two water molecules with the mean Zn-O Fig.A fragment of the structure of diaquabis(thiophen-2-car- distance equal to 1.994 A. Fig. illustrates the frag boxylate)zinc(II). Broken lines indicate the hydrogen bonds. ment of the structure. X-ray diffraction data have been collected using meter at this Institute. Data processing and refinement KUMA KM4 (CuKa radiation) four circle diflfracto- was done using SHELXL93 program package.
MAGNETIC ORDERING IN LANTHANIDE INTERMETALLIC PHASES J. Leciejewicz, A. Szytula1/ PL9702 08 1/1 Institute of Physics, Jagellonian University, Krakbw, Poland
Magnetic properties of lanthanide ternary com Neutron diffraction pattern of TbCuSn taken at pounds with 1:1:1 stoichiometry have been the 12.6 K shows additional, small in intensity magnetic subject of our studies using neutron diffraction and peaks indicating the setting up of an incommen magnetometric methods. surate sine-modulated order with the wave vector k = [0.446,0,0]. This structure remains stable up to Antiferromagnetic ordering schemes the Neel point at 15.3 K at which both magnetic in ternary RCuSn (R = Tb - Hr) compounds structures vanish. The same effect has been detected Neutron diffraction patterns of RCuSn (R = Tb - Er) in HoCuSn - an incommensurate sine modulated compounds recorded in the paramagnetic state confirm ordering starts to set up at 5.8 K. The new structure the hexagonal LiGaGe-type crystal structure (space is described by the wave vector k = [0.130,0.050, 0). group P63 me) with atoms located in the following sites: It vanishes jointly with the colinear structure at 7.1 K 2R in the 2(a) 0,0,1/2; 2Cu in the 2(b) 1/3,2/3, zj; 2Sn in - the Neel point of HoCuSn. 2(b) 1/3, 2/3, z% zi = 0.07 and z% = 0.48. Neutron Neutron diffraction pattern of ErCuSn recorded diffraction patterns recorded at 1.5 K for polycrystalline at 1.5 K displays a fairly large number of peaks which samples of TbCuSn, DyCuSn and HoCuSn contain were indexable as due to two coexisting magnetic strong diffraction peaks of magnetic origin indicating a phases: the first with a colinear antiferromagnetic colinear antiferromagnetic structure described by the structure described by the wave vector ki = [1/3,0,0] wave vector k = [1/2,0,0]. The directions of the magnetic and a moment of 7.46(11) /zg at 1.5 K parallel to the moments are as follows: TbCuSn - aligned along the c-axis; the second - a sine modulated characterized by a-axis: DyCuSn - making the angle of 44.6 deg with the the wave vector k2 = [0.3925, 0.0596, 0] with c-axis; HoCuSn - parallel to the oaxis. The determined moments aligned along the the c-axis. The former is magnetic moments at 1.5 K localized on the lanthanide stable from 1.5 to 4.7 K - the Neel point, the latter ions amount to: 734(77)/zb in TbCuSn; 5.12(11)/zg in from 1.5 to 3 K. Fig.l illustrates the temperature DyCuSn and 7.92(9) /zg in HoCuSn. All are smaller than variation of magnetic peak intensities characteristic the free ion values for the respective R+3 ions. for the observed magnetic structures. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 63 k = [ki, 0, 0] with ki equal to 0.3610(4), 0.3381(4) and 0.3582(4), respectively. The Neel points are: 11.5, 4.5 and 5.7 K in TbCuGe, DyCuGe and HoCuGe, respectively. The moments are parallel to the [010] axis in Tb and Dy compounds and parallel to the [001] axis in HoCuGe. ErCuGe - neutron diffraction pattern recorded at 1.8 K contains magnetic peaks which could be described by two wave vectors: ki = [1/3, 0, 0] and Fig.l. The magnetic structure of NdCuGe at 1.5 K. k% = [1/6, 0 0], After combining the above wave vectors two possible models of magnetic structure Large R-R distances, metallic character of can be produced depending on whether the phase electric resistivity and oscillatory character of some shift is assumed to be either 0 or tc[2. The phase of the observed magnetic structures suggest that the RKKY mechanism of exchange interactions, be sides the crystal electric field effect, plays a domin ant role in determining the magnetic properties of the RCuSn compounds. Magnetic structures of RCuGe (R = Pr, Nd, Tb, Dy, Ho, ErJ The members of the RCuGe family crystallize in two structure types: AIB2 (hexagonal, space group P6/mmm) R = Pr and Nd. LiGaGe (hexagonal, space group PGgmmc) R = Tb, Dy, Ho and Er. Magnetometric measurements have indicated that all title compounds are antiferromagnetic at low temperatures. Neutron diffraction data collect ed at 1.5 K using the E6 instrument at the BER II reactor in the Hahn-Meitner Institute in Berlin confirmed these results. PrCuGe - below the Neel point at 2.2 K it orders o in a sine modulated structure with a magnetic Fig.2. The alternative magnetic structures of ErCuGe below 3 K. moment of 1.45(9) Bohr magnetons forming an angle of 46(11) deg with the c-axis. shift cannot be determined uniquely in experiments NdCuGe - the magnetic order below the Neel carried out on polycrystalline samples. The alter point at 3.2 K is described by the wave vector native structures are schematically displayed in k = [0.50(1). 0, 0], The magnetic moment localized Fig.2. This structure transforms at 3 K into a co- on the Nd+3 ion is 1.24(5) Bohr magnetons at 1.6 linear antiferromagnetic one with the wave vector K. It is aligned along the a axis (Fig.l). [1/3,0, 0]. The Neel point is at 5 K. Fig.3 shows the
o TbCuGe a HoCuGe • ErCuGe * DyCuGe PrCuGe
Fig.3. Temperature variation of magnetic peak intensities characteristic for the magnetic structures observed in the title compounds. TbCuGe, DyCuGe and HoCuGe - all exhibit a temperature variation of magnetic peak intensities sine modulated magnetic ordering schemes stable characteristic for each magnetic structure, between 1.5 K and the respective Neel points. The Like in other lanthanide ternary germanides and structures are represented by the wave vector stannides the RKKY mechanism of magnetic interac- RADIOCHEMISTRY, STABLE ISOTOPES, 64 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL lions via conduction electrons seems to be responsi X-ray and neutron diffraction measurements ble for the stability of magnetic ordering schemes ob performed at the room temperature indicate that served in the title compounds. the title compounds retain the Caln% - type struc ture. Magnetic susceptibility vs. temperature plots Spin glass behaviour observed recorded at the temperatures above 4.2 K show in the RGa^Nioj (R = Gd,Tb,Dy,Ho,Er) maxima and the magnetization curves obtained at and RGai,5Cuo.5 fR = Gd,Tb) phases 4.2 K in the presence of external magnetic fields up Lanthanide digalides crystallize in the hexagonal to 120 kOe indicate that the saturation is not Calna-tyoe structure (space group Pfy/mmc) and dis reached even at this field strength. play a variety of helcoidal ordering schemes; in some Neutron diffraction data collected, using the E6 compounds magnetic phase transitions have been instrument at the BER II reactor in the Hahn-Meit- also observed. It has been reported that substituting ner Institute, show that the title compounds do not a part of galium atoms by transition metals like ni exhibit any trace of long range magnetic order at 1.5 ckel and copper does not lead to a change of the K. Broad maxima due to magnetic diffuse scattering structure type resulting in solid solutions RGa^xNi* are observed in the samples with the exception of or RGaz-xCux with Ga and Ni (or Cu) atoms ran ErNiojGai.v which seems to be paramagnetic at domly distributed in the 4(f) site. It seemed therefore 1.5 K. The heights of the maxima vary with tem to be of interest to investigate how the substitution perature: for example in TbNio.gGau the maxi will affect the magnetic properties of RGa2 com mum vanishes at about 40 K. Spin glass proper pounds. Consequently the samples of RGa^Nioj ties may be thus assumed to be the characteristic (R = Gd-Er) and RGa% ;Cuoj (R = Gd, Cu) were feature for these pseudoternary systems. synthetized and their magnetic properties studied.
PL9702109 X-RAY STUDY OF WATER INFLUENCE ON CELLULOSE MEMBRANE STRUCTURE H. Grigoriew, A.G. Chmielewski
The process of water permeation through a polymer In our X-ray experiments we measured the dry membrane is little known, in spite of its application membrane as a referring sample, two vapoured mem in technology. Recently, even the isotope effect of branes and two other ones digged in liquid, applying H/D and 1®0/160 in the permeation process was light and heavy water. During measurements the obtained e g. for the cellulose membranes Tomophan membranes were covered with a thin mylar foil to and Cuprophan [1,2]. avoid diminishing of water contents. Structural research of water permeation through membrane was carried out only in a static stage and Small-angle scattering (SAXS) was concerned mainly with the structure of water The total radiation intensity scattered in the during the water-membrane contact. small-angle region can be expressed by the equa It is assumed that on the polymer surface a tion: several-atom layer of water exists, whose properties I(K)=2/jR/Jll/J)t/JxQ (x) p(t)W(l)D(R)m2(R) vapor , rrTTTTl | M I I I I M I | 0.000 0.005 0.010 0.015 Fig.l. Small-angle scattering of cellulose membrane, a - dry, b - after acting D2O vapour, c - after acting HgO vapour, d - after acting D2O liquid, e - after acting H%0 liquid. For clarity, curves are displaced by a constant value. assumed. The obtained D(R) functions are shown in Fig.2a,b. The function D(R) represents the relative values of the number of particles. A slight I I I I I I 7-1 "I | I I I I I I I I I '| drop below zero on these curves, apart from the 15 main maximum, is characteristic for this method. 2 theta Fig.3. Diffraction of cellulose membrane, a - dry, b - after acting D2O vapour, c - after acting H2O vapour, d - after acting D2O liquid, e - after acting H2O liquid. Curves are dis placed and grouped. In the sequence: the dry (Fig.3a), vapoured (Fig.3b,c) and watered (Fig.3d,e) membranes, both the maxima are lower. Interatomic distances, calculated from the posi tions of the maxima, using the Bragg law are: 0.72 and 0.45 nm for the dry cellulose, and are unchanged for the other samples. Differencies between curves for the vapoured material by D2O and H2O (Fig,3b,c) are real. For the D2O vapoured sample both the peaks in Fig.3c are much smaller than those for H2O (Fig.3b). 1—r—r~r-]—r Proportion of the height of both peaks is about 1.65 for the dry and vapoured samples (Fig.3a.b,c) and about 1 for the watered ones (Fig.3d,e). R (nm) This proves our SAXS results, because the second Fig.2. D(R) - dimension distribution of water inclusions in cellu peak partly coincides with the main peak of the bulk lose, a - after acting D2O liquid, b - after acting H2O liquid. Curves are displaced. water diffraction. The maxima on each curve result from mutual The main maxima are observed from 3 to 12 nm with packing of the polymer chains with the repeated a peak at about 8 nm. The differencies between watered distance. samples (D2O and H2O) are not distinguished. On the other hand, diminution of both the maxi Results of the SAXS study show that watering of ma for the succeeding samples means, that the the samples caused a creation of nanometric pores volumes of the ordered structure become smaller in filled with water inside the cellulose membrane. the row: dry - vapoured - watered membranes. RADIOCHEMISTRY, STABLE ISOTOPES, 66 NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL Summary drogen bonds with the OH-groups in the cellu It is shown that water acts on cellulose in two lose structure. The samples weight increased by ways: about 20% within 1 hour. The vapour effects on - First, the contact liquid-cellulose effects on en decreasing of molecular chains order. The effect tering bulk water inside it and forming nanome is bigger for heavy water. tric pores filled with water. The effect occurs in Considering a possible mechanism of water per some seconds and causes the weight to increase meation through the cellulose membrane, both ways twice. No difference between the light and heavy of the water action on cellulose structure should be water was observed. The effect was detected by taken into account. the SAXS method and also proved by WAX References measurement. Simultaneously, the ordering of [1] . Chmielewski AG., Zakrzewska-Trznadel G.: J. Membr. Sci., the molecular chains decreased which is visible 55,257 (1991). on the WAX curves. [2] , Chmielewski AG., Dlutowski J., Zakrzewska-Trznadel G., - Second, the contact vapour - cellulose causes, as Miljevid N.R.: Nukleonika, 34,273 (1989). it is known, the penetration of single water mole [3] . Clatter OJ.: J. Appl. Ciyst., 10,415 (1977). cules inside the cellulose and the creation of hy RADIOBIOLOGY I NEXT PAOE(S) | left BLANK PL970211 0 RADIOBIOLOGY 69 OXIDATIVE BASE DAMAGE IN DNA FROM L5178Y SUBLINES M. Kruszewski, T. Zastawny1/, T. Wrohska, R. 01inski1/ w Medical Academy, Bydgoszcz, Poland It is commonly accepted that reactive oxygen FapyGua and a similar yield of 5-OHUra, species (ROS) generated by ionizing radiation or 5-OHMeUra, 5-OHCyt and 8-OHGua. The major H2O2 produce a variety of DNA lesions. The most base product was FapyGua in all cases but the ratio important DNA damage induced by ROS is oxi FapyGua/8-OHGua was much higher in LY-S cells. dative base damage [1, 2]. Some lesions of this type Abnormal yield of FapyGua found in this study in may lead to mutagenesis, carcinogenesis and repro LY-S cells suggests that the intracellular environ ductive cell death (for review see [3]). ment of this cell line promotes induction of The purpose of the present work was to cha FapyGua over 8-OHGua or adenine damage. Since racterize and quantify DNA oxidative base damage hydroxyl radical adducts of guanine exhibit "redox in two murine lymphoma L5178Y (LY) sublines ambivalence", the reduction or oxidation of C-2 and inversely cross-sensitive to ionizing radiation and C-4 resonance by intranuclear milieu may lead to hydrogen peroxide [4]. LY-R subline is 2 times different DNA products, FapyGua or 8-OH-Gua, more resistant to killing by ionizing radiation than respectively [7]. the other subline, LY-S [5], In contrast, LY-S cells Higher content of GSH (reduced glutathione) are 3.6 times and 11 times more resistant to hydro and of other monobromobimane reactive thiols has gen peroxide at 37 and 4°C, respectively [6], been found in LY-S cells than in LY-R [8]; this In this study the yields of 7 oxidized DNA bases observation supports the above-mentioned assump (Table) were quantified by gas chromatography/iso- tion. However, there is evidence that GSH is Table. Relative yields of oxidized product in H2O2 treated or gamma-irradiated LY cells. Difference in the yield of oxidized product Product LY-R LY-S Radiation H2O2 Radiation H2O2 vs. Ctrl vs. LY-S vs. Ctrl vs. LY-S vs.Ctrl vs. LY-R vs. Ctrl vs. LY-R 5-OHUra 3.4 0.9 11.1 2.7 2.4 1.1 2.6 0.4 5-OHMeUra 7.4 0.7 19.1 7.8 11.3 1.4 2.7 0.1 5-OHCyt 2.1 0.9 2.0 1.7 2.9 1.1 1.0 0.6 FapyAde 1.7 0.3 1.6 1.0 4.6 3.3 1.3 1.0 8-OHAde 22.5 0.4 71.9 28.7 17.7 2.5 0.8 0.0 FapyGua 8.8 0.0 39.2 0.3 8.6 50.0 2.2 3.3 8-OHGua 5.9 0.8 15.1 9.7 4.5 1.3 1.0 0.1 Sensitivity low high high low Bold face font indicates significant difference at p < 0.01, Student’s t test. tope dilution mass spectrometry with selected-ion excluded from the immediate vicinity of DNA in monitoring, in chromatin that was obtained from mammalian cells [9, 10]. The yields of damaged gamma irradiated or hydrogen peroxide treated LY DNA bases found in the course of this study in cells. In hydrogen peroxide treated (2 mM, 1 h, gamma irradiated or H2O2 treated L5178Y cells are 37°C) LY-R cells we found a marked increase in related to the cell sensitivity to the respective the yield of 5-OHUra, 5-OHMeUra, 8-OHAde, damaging agent. This observation may indicate a FapyGua and 8-OHGua, whereas in hydrogen per cause-effect relationship between DNA base oxide treated LY-S cells the yields of all products damage induction and cell sensitivity. Nevertheless, increased only slightly as compared to the control this is not the only cause for different sensitivities levels (Table). In gamma irradiated (400 Gy) cells of LY-R and LY-S cells to ionizing radiation and we found a marked increase in 5-OHUra, H2O2. Our preliminary results show that the dif 5-OHMeUra, 8-OHAde, FapyGua and 8-OHGua ferent levels of base oxidation is accompanied by in LY-R cells and 5-OHMeUra, 8-OHAde, different capabilities of LY-R and LY-S cells to FapyGua, 8-OHGua and FapyAde in LY-S cells. repair these lesions [unpublished data]. The yield of damaged bases in untreated (control) The authors are grateful to Dr. M. Dizdaroglu for cells was similar in both LY sublines, with the providing labelled internal standards used in this work. exception of 8-OHAde and FapyGua that were This work was supported by the Polish State Com found at a much higher level in LY-S cells. In mittee for Scientific Research - grant 4PO5A121.08 hydrogen peroxide treated cells we found more and statutory grant for the INCT. 5-OHUra, 5-OHMeUra, 5-OHCyt and 8-OHAde in LY-R cells than in LY-S cells, a similar yield of References FapyAde, and less FapyGua. On the contrary, in [1] , Teoule R- Int. J. Radial. Biol., 21, 573-589 (1987). gamma irradiated cells we found more damaged [2] . Von Sonntag C.: Basic Life Sci., 23. 87-317 and 317-321 bases in LY-S cells - FapyAde, 8-OHAde and (1991). 70. RADIOBIOLOGY [3] , Painter R.B.: In Radiation Biology in Cancer Research. [7] , Breen VJ., Murphy A.: Free Rad. Biol. Med., IS. Eds. R.E. Meyn, H R Withers. Raven Press, New York 1033-1077 (1995). 1980, pp. 59-68. [8] .Bou4yk E., Iwanetiko T., Jarocewicz N., Kruszewski M., [4] , Bou2yk E., Buraczewska I., Rosiek O., Sochanowicz B., Sochanowicz B., Szumiel I.: Free Rad. Biol. Med., in press. Szumicl I.: Radial. Environ. Biophys., 21105-116 (1991). [9] , Smoluk G D , Fahey R.C., Ward J.F.: Radial. Res., 114, [5] . Beer J.Z., Budzicka E., Niepokojczycka E., Rosiek O., 3-10 (1988). Szumiel I., Walicka M.: Cancer Res., 42,4736-4742 (1983). [10]. Zeng S., Newton G.L., Gonick G., Fahey R.C., Ward I F.: [6] . Kruszewski M., Green M.H.L, Lowe J., Szumiel I.: Mutat. Radial. Res., 114,11-27 (1988). Res., 222,233-241 (1994). EFFECT OF COPPER CHELATOR, NEOCUPREINE, ON L5178Y CELLS E. Bouzyk, T. Iwanetiko, M. Kruszewski Our earlier studies on the cellular response of Fig.l shows dose-survival curves for neocup- L5178Y (LY) sublines to X rays and hydrogen reine-treated LY sublines (1 h, 37°C). Both curves peroxide pointed to the importance of iron and are fairly close in the low dose range but survival copper ions [1]. LY-R cells, more sensitive to hy dramatically drops at higher concentrations of neo- drogen peroxide and more radioresistant than LY-S cupreine for LY-R cells. This is consistent with the cells, contain more iron and less copper in the previous finding that copper content is lower in the nuclei than the radiosensitive, oxidant resistant nuclei of LY-R than LY-S cells [2]. Accordingly, counterpart of the cellular model, LY-S. We hypo there is more DNA damage in LY-R than in LY-S thesized that these differences are related to the cells, as determined by the comet assay (Fig.2). The extent of hydroxy radical generation due to the Fenton reaction. The reaction would be site-speci fic, depending on the localization of the respective ions in the vicinity of the target, DNA Hence, it could be expected that copper chelation would alter e 40 LY-S, O' 0.010 0.100 1.000 10.000 100.000 10004)00 .£ 1.0E-3 NEO concentration, micromoles Fig.2. Mean tail moments of nucleoids obtained from neocup reine-treated LY cells. ■2 0.1 1.0 10.0 100.0 results support the assumption [2] of different role NEO concentrotion, micromoles of copper ions in the maintenance of chromatin Fig. 1. Dose survival curves for neocupreine treated LY cells (1 h, organization in LY-R and LY-S cells. 37°C). Survival determined by cloning. Standard error of the mean indicated by bars. References [1] . Kruszewski M., Green M., Lowe J., Szumiel I.: Mutat. Res., chromatin structure and that these alterations 226,155-163(1995). would be reflected in survival as well as in the [2] . Kruszewski M., Iwanetiko T., Szumiel I., Kapiszewska M., nucleoid images in the comet assay. Lange C.S.: Radial. Environ. Biophys., 34,113-119 (1995). IRON CHELATOR, DESFERAL, DIFFERENTIALLY AFFECTS NUCLEOID DNA IN TWO SUBLINES OF L5178Y MURINE LYMPHOMA E. Bouiyk, T. Iwanetiko, M. Kruszewski Our earlier studies on the cellular response of action would be site-specific, depending on the L5178Y (LY) sublines to X rays and hydrogen per localization of the respective ions in the vicinity of oxide pointed to the importance of iron and copper the target, DNA Hence, it could be expected that ions [1]. LY-R cells, more sensitive to hydrogen iron chelation would alter chromatin structure and peroxide and radioresistant than LY-S cells, contain that these alterations would be reflected in nucleoid more iron and less copper in the nuclei than the images in the comet assay. Different extent of iron radiosensitive, oxidant resistant counterpart of the chelation was obtained by treating LY cells with cellular model, LY-S. We hypothesized that these desferal, a specific chelator of iron ions [2]. differences are related to the extent of hydroxy radi Fig. shows a striking difference in the effect of cal generation due to the Fenton reaction. The re iron chelation on the mean tail moments at differ- RADIOBIOLOGY 71 values lower than those in the controls. DNA con tinuity was not affected, as could be judged from the unchanged micronuclei frequency in comparison to the control level (not shown). This speaks for con formational changes of chromatin in desferal-treat- ed cells and points to the role of iron ions in the maintenance of higher order DNA structures. Dif ferences found between LY-R and LY-S cells re flect the long postulated differences in chromatin organization between these LY sublines. Ctrl 0.01 0.1 1 10 SO SM The work was supported by the Polish State Com DFO concentration, micromoles mittee for Scientific Research - grant GP04A 06010. Fig. Varying mean tail moments in nucleoids from desferal-treat- ed LY-R and LY-S cells. References [1] . Kruszewski M., Iwanefiko T., Szumiel L, Kapiszewska M., ent concentrations of desferal. Actually, at higher Lange C.S.: Radial, Environ. Biophys., 34,113-119 (1995). chelator concentrations, there was a considerable [2] . Halliwell B., Gutteridge J.M.C.: Arch. Biochem. Biophys., condensation of chromatin, leading to tail moment 246,501-514(1986). DETERMINATION OF DNA DAMAGE REPAIR IN CAMPTOTHECIN - TREATED MURINE LYMPHOMA CELLS BY THREE METHODS I. Grqdzka, I. Szumiel Two L5178Y (LY) murine lymphoma cell sublines, display inverse cross-sensitivity to camptothecin LY-R, resistant, and LY-S, sensitive to X-radiation (CPT): LY-R cells are more susceptible to this spe- LY-R. o—o TIME AFTER CAMPTOTHECIN REMOVAL HOURS Fig. Time-course of DNA break repair after 1 h treatment with 2/ INDUCTION OF DNA-PROTEIN CROSS LINKS BY GAMMA RAYS IN CELLS OF THREE MURINE LYMPHOMAS PL97021 N. Jarocewicz, I. Szumiel DNA-protein cross-links (DPC) are reported to be their covalent nature. DPC formation in ionizing or DNA lesions induced by ionizing radiation, ultra ultraviolet irradiated cells is dose-dependent. In violet radiation and some alkylating agents in mam X-irradiated Chinese hamster fibroblasts the DNA malian cells in vivo and in culture. After ionizing regions that contain transcriptionally active se and ultraviolet radiation proteins become tightly quences form DPC more easily than the nonactive associated with DNA by linkages which are in- ones [1], DPC formation in gamma-irradiated mouse lym phoma L5178Y cells and two related mitomycin-sen E—50 • sitive lines, MCE50 and MCN151 (classified into two N—151 &—A complementation groups) [2] were measured by a nitrocellulose filter assay [3], The increase in DNA crosslinked to proteins was approximately linear with dose within the range 0-700 Gy in the three lines examined (Fig.), reaching 7-9 per cent DNA retained on the filter at a dose of 700 Gy. Examination of the DPC repair in these three cell lines may lead to a better understanding of the repair process of DPC in mammalian cells. DOSE OF GAMMA RAYS, Gy References Fig. Per cent of DNA radioactivity left on the filter, a measure of DPC, as related to radiation dose. Cells were gamma ir [1) . Chiu S.M., Friedman L.R., Sokany N.M., Xue L.Y., Oleinick radiated on ice and immediately processed for DPC determi N.L.: Radial. Res., 1QZ, 24-38 (1986). nation. [2) . Hama-Inaba H., Hieda-Shiomi N., Shiomi T., Sato K.: Mutal. Res., 1@& 405-416 (1983). sensitive to organic solvent extraction, high salt [3) . Chiu S.M., Sokany N.M., Friedman L.R., Oleinick N.L.: Int. concentration or alkaline conditions, indicating J. Radial. Biol., 4ft, 681-690 (1984). PL97021 2 RADIOBIOLOGY 73 LACK OF CORRELATION BETWEEN DNA REPAIR KINETICS, RESIDUAL DAMAGE AND MICRONUCLEI FREQUENCY IN RADIOADAPTED HUMAN LYMPHOCYTES M. Wojewddzka, M. Kruszewski, I. Szumiel We have previously reported [1] that the kinetics of antibody to antigen CD38, the ligation of which DNA repair after X-irradiation with 1.5 Gy in radio- initiates tyrosine kinase activity and inhibits the adapted human lymphocytes differed from that in the dual enzymatic activities of CD38: adenosine di- non-adapted ones: the repair measured by the comet phosphoribose cyclase and hydrolase; assay was significantly faster. However, when a larger TMB-8, antagonist of calcium; number of experiments was carried out with cells staurosporine, inhibitor of protein kinases. Table 1. Initial and residual DNA damage estimated by the comet assay in radioadapted lymphocytes. Tail moment Treatment Control ±SD Initial damage ±SD Residual damage ±SD 1.5 Gy 4.44 ±3.97* 28.32 ±10.77* 6.23 ±6.38 1 cGy + 1.5 Gy 6.68 ±5.15* 30.96 ±11.36* 7.28 ±6.91 1 cGy + 1.5 Gy 6.73 ±5.36 31.60 ±11.89* 7.22 ±5.81 CD38 +1 cGy + 1.5 Gy 6.26 ±4.15 35.31 ±10.41* 7.83 ±5.25 1 cGy + 1.5 Gy 6.63 ±4.10 36.63 ±10.44* 10.22 ±5.19 TMB-8 + 1 cGy + 1.5 Gy 6.66 ±3.76 29.21 ±13.30* 10.25 ±5.78 1 cGy + 1.5 Gy 6.63 ±4.10 36.63 ±10.44* 10.22 ±5.19 Staurosporine + 1 cGy + 1.5 Gy 6.49 ±4.46 27.74 ±10.29* 9.45 ±5.32 • Significant difference estimated pairwise by Student’s t test, p < 0.05; SD - standard deviation. from other blood donors, this difference was no A similar lack of correlation between the effect longer observed, in spite of a clear adaptive response, at the chromosomal (aberrations or micronuclei) Table 2. Parameters of DNA repair kinetics*. Treatment a ±SD* b ±SD c ±SD* Correlation coefficient 1.5 Gy 22.089 ±4.382 0.108 ±0.067 1.792 ±2.415 0.969 1 cGy + 1.5 Gy 23.674 ±4.448 0.182 ±0.112 0.606 ±1.765 0.978 1.5 Gy 24.380 ±6.080 0.212 ±0.156 0.490 ±0.450 0.967 CD38 + 1 cGy + 1.5 Gy 27.480 ±5.160 0.098 ±0.037 1.560 ±1.100 0.987 1 cGy + 1.5 Gy 26.144 ±5.248 0.239 ±0.136 3.585 ±1.092 0.979 TMB-8 + 1 cGy + 1.5 Gy 18.955 ±7.514 0.223 ±0.071 3.588 ±2.027 0.993 1 cGy + 1.5 Gy 26.144 ±5.248 0.239 ±0.136 3.585 ±1.092 0.979 Staurosporine + 1 cGy + 1.5 Gy 18.293 ±4.97 0.131 ±0.056 2.963 ±0.866 0.986 * The data were fitted to the equation usually used to describe the kinetics of DNA repair y=a • exp(-bt) +c; SD - standard deviation. as revealed by the micronucleus test. The results of and molecular (DNA repair) levels was reported by these experiments are summarized in two Tables, Wdjcik et al. [2], showing initial and residual damage (Table 1) and parameters of DNA repair kinetics (Table 2). As References shown in Tables, no adaptation effect was found also [lj. Wojewddzka M., Kruszewski M., Szumiel I., Wdjcik A., in other experimental groups, where the adapting Streffer C, Gasifiska A: Nukleonika, iQ, 115-124 (1995). treatment (irradiation with 1 cGy) was combined [2], Wdjcik A, Sauer K, Zolzer F., Br— ------with agents that disrupt the transduction of cellular Mutagenesis, 11, 291-297 (1996). signalling. These were: 'L97021 APPLICATION OF THE COMET ASSAY FOR DETECTION OF DNA DAMAGE IN LYMPHOCYTES OF WORKERS EXPOSED TO LOW DOSES OF IONIZING RADIATION M. Wojewddzka, T. Iwanefiko, M. Kruszewski Detection of DNA damage after chronic exposure sensitive and fast. The best biological dosimeter, so to low doses of ionizing radiation presents a practi- far, is based on the determination of chromosomal cal problem; a suitable technique should be both aberration frequency. This, however, is time-con- 74 RADIOBIOLOGY suming and tedious and not suitable for large scale into groups according to risk of exposure, smoking screening. A promising alternative is the comet habits and gender. We used non-parametric tests of assay (single cell gel electrophoresis) combined Mann-Whitney and Kolmogorov-Smimov for two with application of specific enzymes which reco different samples or Student’s test (with correction gnize damaged bases. for separate variance estimation) for comparison of Following the lysis and electrophoresis of an un mean tail moments in control and hazard group. damaged cell one obtains a round nuclear envelope We compared the mean tail moments without with fluorescent halo formed by undamaged DNA enzyme treatment, with endonuclease III and FPG Cells with damaged DNA give a "comet" consisting (formamidopyrimidine glycosylase) in the tested of a "head" (nuclear envelope) and a "tail" (DNA groups. attached to the nuclear matrix, but migrating in the There was a significant difference (by both above electric field). The length of the tail multiplied by mentioned non-parametric tests) between the con the fraction of DNA present in the tail (the so trol and hazard groups without enzyme treatment called tail moment) is a measure of DNA damage. but the level of the oxidative damage was the same Digestion with specific enzymes which recognize in both groups. Higher DNA damage was also damaged bases cause an increase in tail moment. found in men than in women. There was no relation We examined a group of people occupationally of DNA damage to age and smoking habits not exposed to low doses of ionizing radiation (al withstanding the enzyme treatment. Additionally, together 49 individuals). Age, smoking habits, use analysis of distributions of tail moment values of therapeutic drugs, work-related exposure to pointed to a considerable individual diversity even hazardous agents, previous exposures to diagnostic in the control group. Therefore, further investiga X-rays such as patient and nuclear medical exami tions are necessary to establish the suitability of the nation were registered. For each individual the comet assay as biological dosimetry method; the occupational radiation burden received over the results obtained so far warrant such investigations. Table. Values of the mean tail moments of all donors compared according to occupational risk, gender and smoking habits. Kolmogorov-Smimov Treatment Tested group U Mann-Whitney test t Student test test Risk of exposure Control group Hazard group No. of people 40 49 Buffer 26.4 ±17.3 57.3 ±39.8 p = 0.000 p < 0.001 Mean tail moment ENDO III 99 5 ±40.5 88.4 ±32.6 ns FPG 36.9 ±30.1 31.7 ±23.5 ns ns Sex Women Men No. of people 28 61 Buffer 29.9 ±28.4 49.7 ±36.4 p = 0.000 p < 0.001 Mean tail moment ENDO III 105.9 ±36.2 87.7 ±35.6 p = 0.042 ns FPG 19.9 ±15.4 40.4 ±28.3 p = 0.002 p < 0.001 Smoking habits Non smokers Smokers No. of people 53 36 Buffer 46.1 ±36.6 39.6 ±33.1 ns ns Mean tail moment ENDO III 89.7 ±36.8 98.9 ±36.2 ns ns FPG 34.7 ±27.5 32.9 ±25.8 ns ns past period of 5 years was adopted from the official The work was supported by the European personal records based on film dosimetry con Commission - grant CIPA CT94 0129. trolled every month. A matched group of controls was chosen among the administrative employees References (40 individuals). The mean age of the studied [1]. Green M.H.L., Lowe J.E., Harcourt S.A, Akinluyi P., Rowe population at the time of blood sampling was 50 T., Cole J., Anstey AV., Arlett C.V.; Mutat. Res., 222, years (range 24-69). The individuals were divided 137-144 (1992). LOVASTATIN TREATMENT DIFFERENTIALLY ALTERS ACTIVATION OF TRANSCRIPTION FACTOR, NF/cB AND SENSITIVITY TO HYDROGEN PEROXIDE B. Sochanowicz, I. Szumlel Recently, we undertook an attempt to characterize L5178Y [1, 2]. These sublines are inversely cross- cellular features that determine sensitivity to hydro- -sensitive to hydrogen peroxide and X-rays. We gen peroxide of two sublines of murine lymphoma found that the amount of initial DNA damage and RADIOBIOLOGY 75 iron content contribute to the difference in sen trations were less effective (Fig.l). On the contrary, sitivity. The role of the transcription factor NF k B, a sensitizing effect was found in LY-S cells. Addi induced by reactive oxygen species in intrinsic cellu tionally, a 24 h treatment with lovastatin markedly lar sensitivity to oxidants has yet not been establish increased the amount of NF/cB in the nuclear frac ed. A recent report [3] on the role of EJras onco tion of LY-R cells, as shown by Western blotting gene in resistance to oxidants indicated another (Fig.2), whereas in LY-S cells it was diminished. possible direction of exploration of the cellular defense system. Activity of the ras protein can be modulated by cell treatment with lovastatin, an LY-R LY-S inhibitor of the mevalonate pathway of cholesterol synthesis [4], The ras-encoded protein, p21, is func tional when membrane-associated; the association depends on post-translational modification, includ ing an isoprenylation step that is inhibited by lova statin. Therefore, we undertook investigation on lovastatin effect on hydrogen peroxide treated L5178Y cells. Cytotoxic and cytostatic effects of lovastatin treatment of LY sublines was estimated from the frequency of dead cells in the treated cell cultures and the relative cell numbers. These effects did not differ in LY-R and LY-S cells. Lovastatin (25 //g/ml, 24 h) pre-treatment considerably increased Fig.2. Western blot showing NFxB subunit p65 expression in lovastatin pre-treated (25/zg/ml, 24 h) LY cells (lanes 2,4); LY-R CD C - control (lanes 1,3). LY-S In lovastatin treated LY-R cells, we found a con sistently increased (by 25%) monobromobimane fluorescence, an indicator of glutathione concen tration, lower oxidative stress in membrane lipids (ca. 25%), as well as a considerable (56%) increase in dihydrofluorescein fluorescence, pointing to a higher endogenous production of reactive oxygen species. This observation indicates a profound effect of p21ras function on the cellular antioxidant 0.8 ■- defense system. The work was supported by the Polish State Com mittee for Scientific Research - grant 3T09A 032 09. References LOVASTATIN, /zg/ml [1] , Kruszewski M., Green M.H.L., Lowe J.E., Szumiel I.: Mutat. Fig.l.Relative cell numbers in LY cell cultures treated for 24 h Res., 3Q8, 233-241 (1994). with the indicated concentrations of lovastatin and - after [2] , Kruszewski M., Green M.H.L., Lowe J.E., Szumiel I.: Mutat. medium change - with 50/^M hydrogen peroxide. Res., 226,155-163 (1995). [3] . Miller AC., Samid D.: Int. J. Cancer, 6fi, 249-254 (1995). cell numbers in hydrogen peroxide treated LY-R [4] . Sebti S.M., Tkalcevic G.T., Jani J.P.: Cancer Comm., 2, cell cultures. Lower and higher lovastatin concen 141-147 (1991). PL9702114 INITIAL DNA DAMAGE AND LETHALITY IN BLEOMYCIN - TREATED L5178Y CELLS J. Zalm, I. Szumiel The murine L5178Y (LY) lymphoma sublines and generates apurinic/apyrimidinic (AP) sites [1], LY-R (radiation resistant) and LY-S (radiation Its DNA damaging activity is dependent on iron sensitive) differ in responses to various DNA da ions. maging factors, such as ionizing radiation, UV The response of both lines to various BLM doses radiation and hydrogen peroxide. For that reason (concentration indicated, 1 h treatment at 37°C) both cell sublines provide a convenient model for was investigated by cloning. The results are shown studying susceptibility to an important radiomi- in Fig.l. According to the obtained dose-survival metic drug, bleomycin (BLM). BLM treatment curves LY-S cells are more sensitive to killing by induces single and double strand breaks in DNA BLM than LY-R cells (Dio, i.e. BLM dose that 76 RADIOBIOLOGY could be discerned. The nonhomogeneous distri bution of DNA damage after BLM treatment was previously observed in other cell populations, e.g. in CHO cells [2, 3]. This is in contrast with the BLM concentration (um) Fig. 1. Dose-survival curves for asynchronously growing LY-R and LY-S cells treated with bleomycin for 1 h at 37°C and cloned in soft agar. Mean values ± standard deviation from 3-5 independent experiments are given. BLM concentration (um) reduces survival to 10%, is equal to 26 and 46, respectively). Fig.2. BLM-induced initial DNA damage in LY-R and LY-S cells measured by the comet assay (mean tail moment +stan- DNA damage due to BLM treatment was studied dard deviation for 300 comets). by the alkaline comet assay. Fig.2 shows tail mo ments in LY cells treated with increasing BLM DNA damage distribution in X-irradiated cell po doses. In spite of the difference in cellular sensiti pulations. These findings suggest the presence of vity and in the iron ion content in the nuclei of LY cell subpopulations with enhanced sensitivity to sublines the initial DNA damage did not signifi BLM. The cause of such enhanced susceptibility cantly differ between LY-R and LY-S cells. There remains unknown. Our data indicate that it is not fore, DNA damage processing and/or pathways connected with the intrinsic radiosensitivity or leading to cell death can be expected to be critical sensitivity to BLM. for the fate of BLM treated LY cells and, in consequence, for the differential lethal effect of the References drug. [1] . Vig B.K., Lewis R.: Mutat. Res., 55., 121-145 (1978). From damage distribution (not shown) it follow [2] .OstIing O., Johanson K.J.: Int. J. Radial. Biol., 52(5), ed that in both LY-R and LY-S cell populations 683-691 (1987). there was a considerable variation of DNA strand [3] . Affentranger M.I., Burkart W.: J. Histochem. Cytochem., breakage: a subpopulation of heavily damaged cells 13(2), 229-235 (1995). NUCLEAR TECHNOLOGIES AND METHODS NEXT PAGE(S) left BLANK PL9702115 NUCLEAR TECHNOLOGIES AND METHODS 79 PROCESS ENGINEERING CONCEPTUAL DESIGN OF THE DEMO-INDUSTRIAL INSTALLATION FOR ELECTRON-BEAM FLUE GAS TREATMENT A.G. Chmielewski, E. liter, B. Tyminski, Z Zimek Introduction The boilers burn pulverized bituminous coal The emission of environmental pollutants such as with the following characteristics: sulphur dioxide (SO2) and nitrogen oxides (NO,) caloric value - 22820 kJ/kg, into the atmosphere from heavy industrial activity, sulfur content - 0.72+0.8%, and in particular from fossil fuel burning, is a global ash content - 21.8%, concern. These pollutants are the main cause of add moisture content - 7.8%. rain, which harms forests, farmland and lakes. A The boilers are equipped with modern flue-gas number of countries around the world have already dedusting systems employing four-zone electrosta imposed emission limits to reduce air pollution. Also tic precipitators with a removal efficiency of 99.8% the "Agenda 21" adopted at the Rio Conference in of fly ash. A maximum volumetric flow of flue gases from one boiler is 270 000 Nm3/h. June 1992 for environmental conservation, is being followed by many countries and international orga The flue gases after treatment in the ESP nizations. Such policies have generated renewed contain: interest in finding viable and cost-effective solutions S02 1.1 g/Nm 3 (385 ppm) to SO2 and NOx pollution control. The stientific NOx 0.6 g/Nm 3 (425 ppm) finding and engineering developments of the past 20 02 7-8% vol. years in the field of electron-beam technology indi COz 8% vol. cate that one such needed solution is available as an CO 0% vol. alternative to conventional technologies. n 2 to balance The electron-beam (EB) flue gas cleaning pro Fly ash 0.08 g/Nm 3 cess was developed in Japan and later in the USA, Humidity 5% vol. Germany and Poland. The main technical advan The temperature ranges from 151 to 165°C. For tages of the process are: design purposes the temperature is 151°C. - simultaneous removal of SO2 and NOx, After a detailed analysis it was decided to design - high removal efficiencies for SO2 and NOx, and construct an electron-beam installation treat - production of a usable product (fertilizer), ing a maximum of 270 000 Nm3/h stream flow of - simple process design, flue gas. The EB POMORZANY flue gas treat - no waste water. ment installation has been designed for the station Several large pilot plants were built and operated rated output obtained after the retrofit in 1998. By during the eighties. These projects proved, that the some combustion control modifications, but not EB process was feasible and safe to operate. Ac low NO* burners which cannot be installed, there cording to several sources the process costs were will be a slight decrease in NO* concentration after estimated in the same range or even lower than the the upgrade. Also minor SO2 and NO* fluctuations present technology. will occur with changes in load factor. These have This technology, the electron-beam diy scrubbing been considered in the design. There may be other process, will be employed at the POMORZANY upgrades of the plant in the future, so it is our Electric Power Station in Poland for a simultaneous intent to design a versatile system which is good for removal of SO2 and NOx from flue gases emitted by today ’s local conditions, and be adaptable for future the Benson boilers. requirements. The boilers were manufactured by the Bab High concentration of NO, and relatively low cock-Wilcox Company at Oberhausen, Germany, in content of SO2 in flue gas emitted from the Benson 1959/60 and were reconstructed in 1979. Each boilers establish specific conditions for flue gas boiler has the 142.5 MWt power output. The boiler treatment required for normal operation. The para is connected to a turbine and also operates as a meters of EB process are chosen so as to guarantee steam and water heating system with power output an efficiency of removal of NO, up to 80% and a of 56 MWe and 50 MWt. After a planned recon removal of up to 70% of SO2 for this operation. struction of the turbines which is intended in 1998, During normal operation the electron-beam in the output will increase to 68 MWe and 100 MWt. duced reaction will take place in the process vessel The annual operating time is 6500 h/yeax of equi at a higher temperature (80°C) than that which valent to full-load operation. would be selected for the more typical high removal 80 PROCESS ENGINEERING case (90% SO2, 80% NOx ). For the seasonal opera the present "normal" and "seasonal" operating parame tion up to 80% removal of NOx and 90% reduction ters. The national law sets a "not higher than" emission of SO2 are expected. level, but local governments establish much lower This method will allow the plant to comply with limits. In the present case of EPS POMORZANY they the environmental standards in existance at the exceed the emission limit of NO* and the ambient limit present time for all modes of operation. of SO2 In the case of NO, the emission limit is 170 id f FLUB GAS HUWDlfiCATON r AMMONIA STORAGE" end DOSAGE VNTT Fig. Flow diagram of EB installation. According to the Polish Ministry of Environ g/GJ and their present levels are 373 g/GJ. In the case mental Protection regulation enacted on 12.02.1990 of SO2 they meet the emission levels, but exceed the existing plants such as the EPS POMORZANY allowed ambient concentrations for 24-hour periods. after the year 1997 will have a permissable emission They are permitted to exceed these figures by 2% per of SO2 of 870 g/GJ of the boiler heat input and NO* year. The present value is 2.6%. The use of this process of 170 g/GJ. with 70% removal will reduce this value to 1.39%. In our consideration of the design of the process, We have offered a conservative and flexible design several environmental factors had to be considered for for this process to allow for changes in the local Table 1. Technical parameters and composition of process streams at key points of the EB installation (normal operation). Stream no. 1 2 3 4 5 6 7 8 9 Reaction System gas Spray cooler Spray Compressed chamber Process outlet Steam NH3 By-product inlet outlet water air outlet n 2 80% vol. 75% vol. 75% vol. 75% vol. 02 7% vol. 6.6% vol. 6.6% vol. 6.6% vol. co2 8% vol. 7.4% vol. 7.4% vol. 7.4% vol. SO2 1.1 g/Nm3 1.03 g/Nm 3 0.31 g/Nm 3 0.31 g/Nm 3 NO% 0.6 g/Nm3 0.57 g/Nm 3 0.12 g/Nm 3 0.12 g/Nm 3 NH3 0 0 0.03 g/Nm 3 0.03 g/Nm 3 HzO 5% vol. 11% vol. 11% vol. ll%vol. 11.1 Vh 3800 Nm3/h 4.5 t/h 180 kg/h 695 kg/h (NH4)2S04 0 0 415 kg/h 0.012 g/Nm3 NH4NO3 0 0 262kg/h 0.007 g/Nm 3 Solid particles 0.08 g/Nm3 0.06 g/Nm 3 2.45 g/Nm 3 0.02 g/Nm 3 Flue gas 270000 284 000 284 000 284 000 Nm3/h Nm3/h Nm3/h Nm3/h NUCLEAR TECHNOLOGIES AND METHODS 61 regulations, perhaps lower national emission levels, efficiently remove fly ash, at a design temperature of and other factors which will enable the utility to meet 151°C. The gas, stream 1, then passes through an the future conditions with minimum changes to the evaporative spray cooler to achieve the desired pro process. cess temperature by adiabatic cooling and a water vapour content up to 11% volume by the addition of System arrangement steam. The system arrangement is shown in Fig,, the After this humidification step, the flue gas, stream main technical parameters and composition of pro 2, flows into the irradiation chamber to be installed in cess streams are shown in Table 1. the existing building which formerly housed multi-cyc- Table 2. Design basis for the EB installation at EPS Pomorzany. Normal operation Seasonal operation FLUE GAS COOLING SYSTEM Inlet gas temperature at spay cooler 151°C 151°C Outlet gas temperature from spay cooler 80°C 65°C Water flow rate to spay cooler 11.1 t/h 12.4 t/h Steam flow rate to spay cooler 4.5 t/h 2.2 t/h Mode of operation dry bottom dry bottom REAGENT HANDLING SYSTEM Ammonia storage 80 1 80 1 Injection mode gas phase gas phase Evaporation media hot water hot water Ammonia flow rate 180kg/h 200 kg/h SOz-NO, REMOVAL SYSTEM SO2 removal 70% 90% NO* removal 80% 80% EB power dose 12kGy 12kGy EB system: required EB power to process 1200 kW 1200 kW inlet gas temperature 80°C 65°C outlet gas temperature 90°C 75°C pressure drop in vessel 15 mm H2O 15 mm H2O BY-PRODUCT COLLECTION AND HANDLING SYSTEM ESP ESP Collector type 99.2% 98.6% Removal efficiency < 20 mg/Nm* < 40 mg/Nm^ Particulate concentration at outlet of ESP 695kg/h 815 kg/h By-product yield 18 days 15 days By-product storage truck truck Mode of transport The flue gas containing particulate, SO; and NO, lone dust collectors in two side by side compartments, enters the existing electrostatic precipitator (ESP) to A two-process-train design is used with each train Table 3. Investment cost. Ordinal Total cost Portion Specification of objects, work and expenditures number in thousand USD [%] 1 Accelerators 2500 12.6 2 Flue gas humidification tower 600 3.0 3 Reaction chambers - reaction units 700 3.5 4 Electrostatic precipitator 2110 10.6 5 Booster fan 190 0.9 6 By-product handling system 840 4.2 7 Ammonia storage and dosing unit 1330 6.7 8 Measuring, monitoring, and control system 1900 9.5 9 Refurbishment of accelerator building 1400 7.0 10 Radiation shield walls of accelerators and of reaction chambers 600 3.0 11 Ventilation system for accelerator building 200 1.0 12 Accelerator cooling system 150 0.7 13 Sygnalling system of accelerator operation 100 0.5 14 Lighting system of accelerators building 80 0.4 15 Electrical power supply 710 3.6 16 Flue gas ducts, complete with connections and support structures 1200 6.0 17 Process water pumping and heating system 110 0.5 18 Compressed air system 230 1.1 19 Documentation, supervision 1350 6.8 20 Training 200 1.0 21 Commissioning 200 1.0 22 General civil engineering contracting; supervision on site 1400 7.0 23 Total 18100 90.95 24 Reserve 1800 9.05 25 Total 19900 100.0 82 PROCESS ENGINEERING processing a maximum of 135 000 Nm3/h of flue gas. The treated flue gas, stream 4, will be mixed with This solution was selected because of the existing dedusted, untreated flue gas. The proportioning of building space limitation. these streams will be such as not to harm the Ai the inlet to the irradiation chamber the gase existing stack by acid attack. The required minimum ous ammonia reagent, stream 8, is added to the flue stack temperature is 110°C. There is no need to gas via nozzles mounted at the side of the duct. provide special anticorrosion protection of the In each irradiation chamber the flue gas is treated by stack. Table 2 shows the main design parameters of the beams of high energy electrons emitted by the two the EB POMORZANY installation. accelerator heads each of 300 kW power rating. After exiting the chamber, the gases, stream 3, go to the by Current cost analysis product collector which is a diy ESP of special design. Table 3 is the current cost analysis of the project The collected by-product, stream 9, is granulated based on purchased items, and estimated of work in and transported to plant storage for loading and progress. shipment to buyers. FILTRATION OF AEROSOLS FORMED IN EB FLUE GAS TREATMENT PROCESS A.G. Chmielewski, B. Tymiriski, G. Zakrzewska-Trznadel, O. Tokunaga x/ , S. Machi^ 1Z Japan Atomic Energy Research Institute, Takasaki, Japan 21 International Atomic Energy Agency, Vienna, Austria In electron-beam (EB) flue gas purification process, in a proper amount and a proper time in agriculture gaseous polutants like SO2 and NO* together with is a valuable fertilizer. If, however, sprayed with flue the added NH3 form solid aerosols. gas could be harmful to the environment. The aerosols formed in the process are in the form of submicron particles. The size distribution of par ticles after the process vessel is presented in Fig.l. In a pilot plant for EB flue gas treatment at the EPS KAWIjCZYN there are two filters: a bag filter and a wet gravel bed filter. The bag filter consists of 4 units. One of them is in the regeneration section and three - in the operation section. The effective filtration area is 450 m2 and the total area is - 600 m2. Efficiency of ia.4 T# » Z3 1.11 0.7 0M <0.46 dust removal in the bag filter is ca. 99,8% but there median diameter [um] are some problems with the removal of deposits from the surface of the bags which lead to increase ■ NO*- ■ 804 <2*> □ "H+* SB eolubl# total the pressure drop. Variation of drop pressure in the Fig. 1. Size distribution of the components of aerosol collected in bag filter for bags made from different kinds of felt flue gas after the reaction chamber. Initial SO2 concen are presented in Fig.2. From this drawings it follows tration - 250 ppmV, NO* - 220 ppmV, flow rate - 14 400 that the bags manufactured by Moratex EC-1 have Nm3/h, dose - 5.1 kGy, humidity - 7.74% vol., NH3 stoi the lowest values of Ap/V. chiometry - 0.9. Wet filtration was performed in the two layers of The aerosols are a mixture of ammonium sul granules with the thicknes 0,9 m and 1,8 m. Irradiat phate and ammonium nitrate. The by-product used ed gas with the sprayed solution flowed cocurrently ------to 3* ------3« Merelt* K*t —— ie Polluter • • }■ — * — *.3 b Minrifx EC-% ■ «• tb fenteu'OorrttK Mefote* 1C 320 360 eff. time [h] Fig.2. Pressure drop of gas flowing through the various filtration bags. NUCLEAR TECHNOLOGIES AND METHODS 83 down through the layers of granules. The salt observed, probably by the condensation of water aerosols dissolved in solution, but part of fly ash de vapours on the particles of salt. The results of ex posed in pores between the granules. After about periments are presented in Tables 1 and 2. fifty hours of operation the first layer, where the Table 2. Removal efficiency of dust, SO2 and NO* grain dia deposed almost all fly ash should be washed. In our meter of 4 to 8 mm (in %). experiments were tested granules of two sizes: of 2 Process Run Filter 1 Filter 2 Total to 4 mm and 4 to 8 mm. The efficiency of filtration vessel no. in both the layers was 70 to 90%. SO2 NO* Dust Dust SOz NO, Dust 802 NO* Tablet.Removal efficiency of dust, SO2 and NO* grain dia 1 84.6 51.2 42.6 51.2 98.6 52.6 72.0 98.6 52.6 meter of 2 to 4 mm. 2 70.3 50.2 39.5 54.4 96.2 51.7 72.4 96.2 51.7 Process 3 64.3 44.3 16.5 63.7 95.0 50.0 69.7 95.0 50.0 Run Filter 1 Filter 2 Total vessel no. 4 65.9 53.3 33.0 67.4 85.6 55.5 78.1 85.6 55.5 SO2 NO, Dust Dust SO2 NO* Dust SO2 NO, 5 61.1 44.6 - 83.1 48.4 - 83.1 48.4 1 68.8 71.9 48.0 - 80.6 9.9 - 94.0 74.7 6 65.3 74.5 33.0 78.1 96.7 77.4 85.3 96.7 77.4 2 66.1 51.4 54.2 82.8 44.0 - 94.2 72.8 7 61.1 72.7 27.0 76.8 93.6 74.6 83.1 93.6 74.6 3 57.9 47.7 46.6 - 85.0 30.7 - 93.7 63.8 8 71.1 74.6 - - 98.6 78.0 - 98.6 78.0 4 35.1 36.0 42.7 - 87.2 15.9 - 91.7 45.5 9 65.0 69.7 51.9 63.3 95.8 72.0 82.3 95.8 72.0 5 34.6 32.9 - - 96.7 20.1 - 91.3 46.4 10 76.3 69.4 35.5 69.1 97.5 71.8 80.1 97.5 71.8 6 17.9 6.16 75.9 - 87.4 5.92 - 89.7 11.7 11 62.2 70.9 - - 92.4 74.2 - 92.4 74.2 7 60.4 59.7 74.2 3.44 81.6 12.9 75.1 92.7 64.9 12 75.0 68.3 30.6 62.7 98.0 73.8 74.1 98.0 73.8 8 59.3 67.4 87.5 16.4 87.5 28.3 89.6 94.9 76.6 13 62.5 55.9 41.9 65.5 98.6 58.8 79.94 98.6 58.8 9 18.0 12.8 83.9 17.2 88.9 12.4 86.6 90.9 23.6 14 74.2 55.1 24.4 80.6 99.7 57.3 85.3 99.7 57.3 In the filter another process is occurring like The by-product collected in the bag filter was humidification of gas almost to the saturation and tested as a fertilizer in the Agricultural University causing the reduction of the gas temperature. A of Warsaw. Results of the cultivation of several significant reduction of SO2 content in the gas to kinds of plants with the use of these by-product and few ppm, was observed. In the second stage of commercial fertilizers applied in the same amounts filtration the formation of liquid aerosols was have shown that their properties are the same. RADIOTRACERS IN ROTARY KILNS INVESTIGATION J. Palige, A. Owczarczyk PL97021 6 Continuous rotating kilns are widly used in the time, thickness of rolling layer, particles segrega chemical and metallurgical industries. Short drums tion caused by nonuniform particle size, density and (L/D = 2+5) with end constrictions are used for shape and so on. material mixing and as a crystallizer, medium rotat Material transport in a rotary kiln is generally ing drums (L/D = 5+20) are used for material described by the residence time distribution (RTD) drying or cooling. Long kilns (L/D > 40) are used function that characterizes the variation of resi for high temperature calcination of granular solids. dence time, flow structure and gives possibility to The scheme of the continuous rotary kiln reactor predict the flow model. Using the radiotracer [1] is presented in Fig.l, where L - kiln length; method the material movement parameters in a d>, Fig.2. RDT function for experiment no. 5 (a = 2.6°, T = 850°C). In the industrial installation for sodium hydro carbonate crystallization the dependence of flow structure i.e. t and Pe as a function of the solid Fig.3. RDT function crystallizer. 1 - experimental curve, 2 - model mass flow rate was determined. As a radiotracer the neutron irradiated sodium carbonate particles were Parallely the data gives the possibility of check used (Na-24 radioisotope). ing some models and scheme proposed by Mu and A series of 6 experiments for two values of the Perlmutter [3] for granular materials movement in flow rate was carried out. In each experiment the rotary cylinders. change of activity vs. time in 9 points of the crys tallizer, located along its axis, were measured. References Representative output signal of the crystallizer is [1] .Kohav, Richardson J., Luss D.: AIChE Journal, 41, 11, presented in Fig.3. For each experiment the signals 2465-2475 (1995). were fitted with the model curve 2 for calculation of [2] . Levenspiei O., Smith W.K.: Chem. Eng. Sci., 6,227 (1957). t and Pe. [3] , Mu J., Parlmutter D.D.: AIChE Journal. 26.6 (1980). The data obtained in the laboratory and in dustrial investigations were used for the evaluation PL97021 7 TRACER INVESTIGATION OF THE SEDIMENT AND SEWAGE FLOW DYNAMICS THROUGH AERATION TANK A. Owczarczyk, J. Palige, M. Strzelecki, A G Chmielewski Among biological methods of sewage treatment 1. good mixing conditions in transverse and verti particularly wide application finds the activation cal directions; sludge method. It consists in the aeration of sewage 2. prevention of permanent settling of the sedi containing activated sludge suspension and then ment at the chamber bottom; separation of the sediment from the purified liquid. 3. minimization of dead volume in the chamber; A typical commercial scale plant consists of an 4. delivery of oxygen to each particle of the sedi aeration tank and a settler. ment. The local oxygen concentration should be The subject of the study was an aeration tank in the range 1-2 mg/1 [1-3] in each element of working in a biological sewage treatment plant of the chamber volume. Ptock Petrochemistry Ltd. Tracer investigations have been conducted, si The aeration chamber (Fig.l) has been equipped multaneously for both liquid and sediment phases. with 8 surface aerators. The main goal of the work The La-140 permanently sorbed on the sediment was the identification of flow dynamics of both the surface has been used as a tracer of activated sediment and sewage and to select on this basis sludge. Fluorescein was the tracer for the sewage. optimal working parameters for achieving the The RTD curves have been obtained for the diffe following: rent input sediment concentrations. Model identi- NUCLEAR TECHNOLOGIES AND METHODS 85 sewage Inlet L~ sediment Inlet aeration chamber regeneration chamber Fig.l. Scheme of aeration chamber. fication of the tank dynamics has led to the flow ment concentrations are shown in Figs. 2 and 3, pattern consisting of ideal mixers-in-series with dif respectively. ferent time constant and a very low contribution to The general conclusion is that the permanent the plug flow (about 5%). Also the bathymetry of control and regulation of the initial sediment sediment occupying the bottom of the chamber as well as the local oxygen concentration have been measured. Fig.3. Balimetric pattern of high (7.4 g/l) initial concentration of sediment. concentration is needed. The load of the sediment Fig.2. Balimetric pattern of low (4.0 g/l) initial concentration of sediment. in the chamber should be constant in time. The in put concentration of sediment should be kept in the It has been found that the local oxygen con range 4.0-5.0 g/l (the flow rate of sediment stream is centration in the sewage was in the range 2-8 mg/1, constant). The mixing conditions and capability of but in the layer of sediment, occupying the bottom, aerators for oxygen delivery is good enough but the it amounts to zero, so this leads to very unprofitable circulating loop of sediment should be equipped in digestion processes. The initial concentration of regulation systems allowing to avoid the actually sediment entering the aeration chamber plays a existing troubles with occupying and digestion of very important role for the bathymetry and ex- sediment. tention of the settling processes at the bottom and References dead volume. When the initial sediment concen tration exceeds the value 5.5 g/l the picture of bed [1] . Gartczarczyk J.: Oczyszczanie Sciekdw metodq osadu czynnego. Arkady, Warszawa 1969. occupying the sediment dramatically changes. [2] , Piotrowski J., Roman M.: Urzqdzenia do oczyszczania wody i The sediment "hills" are created in the area be Sciektiw. PWN, Warszawa 1974. tween the two successive aerators. The two bathy [3] . Cywifiski B. et al.: Oczyszczanie 6ciek6w. Arkady, Warszawa metric patterns for the low and high initial sedi 1983. PL9702 8 86 PROCESS ENGINEERING MEMBRANE DISTILLATION EMPLOYED FOR CONCENTRATION OF LIQUID RADIOACTIVE WASTE A.G. Chmielewski, M. Harasimowicz, G. Zakrzewska-Trznadel The possibility of liquid radioactive wastes treatment - high selectivity of the process, higher than for by membrane distillation (MD), non-isothermal pro conventional evaporators; cess employing hydrophobic polymer membrane, was - moderate operational conditions enable the ap tested. The process has been investigated for many plication of plastics for apparatus construction, years at this Institute as a method for separation of instead of stainless steel, therefore minimizing isotopes [1,2], capital costs and corrosion; Laboratory tests were performed with a setup - simple apparatus, without movable parts existing which consists of two systems: a warm feed and cold in film-layer evaporators; distillate cycles, which are arranged in the direct - elimination of fouling and scaling phenomena on contact membrane distillation configuration. The hydrophobic surface of the membrane; main part of the setup is a capillary module BFMF - possibility of running the process to high solute 06-30-33 (Euro-Sep, Polish-Scottish Ltd., Poland) concentration; permeation unit, effective area 0.3 m2. The module - small distance between evaporation and condensa is equipped with Accurel® polypropylene capillary tion surfaces makes the apparatus more compact; membranes, characterized by the following para - low energy consumption and low operating costs meters: for medium-capacity plants, the possibility of utili - length of capillaries - 200 mm, zation of cheap, low-energy sources, as waste heat - inside/outside diameter - 0.33/0.63 mm, from the cooling system of a nuclear reactor. - cut off - 0.6 fxm, As opposed to other membrane methods, the - porosity - 30%. membrane distillation allows for complete purifica The experiments were performed with simulated tion of radioactive wastes in one stage and does not and original radioactive waste samples of a specific need additional processes to insure sufficient purity of activity of 2-103 to 4.7-104 Bq/dm 3. Initial con water discharged to the environment. centration of the ballast salts was usually in the range 0.8 to 2.2 g/dm 3. The final concentration of References the salts after the experiment was about 20 g/dm 3. [1] . Chmielewski AG., Matuszak A, Zakrzewska-Trznadel G., As a distillate, pure water, without radionuclides, Van Hook W.A, Miljevid N.R.: Sep. Sci. Technol., 28, 1-3, was obtained [3]. 909 (1993). There are many advantages of membrane dis [2] . Chmielewski AG., Zakrzewska-Trznadel G., Miljevid N.R., tillation applied for radwastes treatment. They in Van Hook W.A: Sep. Sci. Techno!., 30,7-9,1653 (1995). clude: [3] . Chmielewski AG., Harasimowicz M., Zakrzewska-Trznadel - moderate process conditions: ambient pressure G.: Purification of Radioactive Wastes by Membrane Dis tillation. IX Symp. on Sep. Sci. and Technol. for Energy Ap and moderate temperatures, close to the ambient plications, Gatlinburg, USA 1995. Program and Abstracts, temperatures; pp. 50-51. METAL RECOVERY FROM DILUTE STREAMS M. Harasimowicz, J. Palige Main parameters of the membrane process applied membrane modules MPT-34 (Kiryat Weizmann) were for the purification of a galvanic rinse bath with a used; they can operate at pH = 0+14. At a 20-fold simultaneous metal recoveiy (Cr, Ni, Au) and a 20-time waste volume reduction on an 1-stage unit the 85+93% volume reduction of the wastes have been determined. removal of K+ and Na+ ions and more than 96% of the The permeate received from TR70-2514HR membrane other metal ions (Ca, Mg, As, Cu) has been reached. RO module has the purity grade compared to distilled The permeate can be directed to a communal waste water and can be used again for the preparation of collector or used again as the industrial water. electrolytic solutions or for rinse bath. On a 2-stage RO The process of electrolytic Zn2+ ion removal from unit with TR70-2514HR modules the metal recovery the bath used for zinc-plating has been investigated. 98-99% has been reached. This method has been The experiments were carried out on a fluidal elec- applied in two galvanic factories in Warszawa. trolyser CHEMELEC (BEWT Ltd.). During the 70 A method for the immediate membrane separation hr electrolysis the Zn concentration decreased by a (without pH correction) of add waste (pH = 0.5+1.0), factor of 15. Comparison of the electrolyser mention arise in a gas preparation process for H2SO4 ed above with other similar apparatus was made and a production, has been applied to the treatment of some technical project of a stream-electrolyser with better waste streams at the KGHM-Copper Mill "Legnica". working parameters (shorter electrolyse time) has As the separators, the chemical resistant Sel RO been prepared. NUCLEAR TECHNOLOGIES AND METHODS 87 APPLICATION OF PARTICLE TRACK MEMBRANES IN A DYNAMIC FILTRATION DEVICE W. Starosta, M. Buczkowski, S. Wronskl 1/, A. Adach^ 1/ Warsaw University of Technology, Poland Nowadays dynamic filtration systems are being of Chemical and Process Engineering. As filtration developed and applied in many fields mainly in solution, aqueous suspensions of yeast cells (with advanced biotechnology. In such systems one can cell size similar as bacteria cells) have been used use different types of filtration membranes [1,2]. giving compressible sediment. A general scheme of the dynamic filtration device is given in Fig.l. In this device PTMs with pore size in the range: 0.2-0.3 mm and porosity approx. 12% have been used. The membranes mentioned above were made of PETP film, 12 /zm in thickness, in two versions: non-lami- nated and laminaned with unwoven fabric. For comparison, tests nylon membranes (Ultipor-Pall) with nominal pore size 0.2 pm and porosity 70-80% have been taken. Measurements have been carried out at a rotating frequency of the cylinder: 800-2400 r.p.m., outer pressure: 0.2-1.2 bar and yeast concentration: 0.3-2%. Some results are shown in Fig.2. Conclusions Fig. LA general scheme of the dynamic filtration device: 1 - rotat ing cylinder with membrane, 2 - valve for retentate, 3 - con Laminated PTMs have a proper mechanical tainer with filtrated solution, 4 - peristaltic pump, 5 - valve for strength suitable to be used in rotating devices with permeate, 6 - manometer, 7 - motor, 8 - regulator of motor speed, 9 - measured volume. cylindrical filtration surface. Non-laminated PTMs are not mechanically strong enough to be used in The present authors have applied particle track such devices. membranes (PTMs) in a rotating cylindrical device. Efficiency of filtration for the dynamic device PTMs used in that device are advanced technology with PTM (surface of the membrane: approx. 200 Vtot «cw«nrMio>: 1 to k 0.7 to YuM o uwMMtoto : 3 * Speed et revolution: Speed ofenoMen: l300ff.*L ' " " . * w « 1 Z ! ? • 4 4 A A * A A A A A Fig.2. Efficiency of filtration vs. time of filtration: a - for different speeds of revolution of rotating cylinder, b - for different values of outer pressure. filtration membranes manufactured from thin poly cm2) in the case of yeast filtration, changes in the meric films by means of heavy ions beam from a range: 100-250 dcnr/h m2, which is economically cyclotrone. Such membranes are characterized by profitable. some unique parameters as precise size of cylindrical A general model of filtration mechanism has been micropores and flat membrane surface. PTMs used in found. Precise values of parameters and separation experiments have been manufactured in JINR (the efficiencies can be defined after a bigger number of Flerov Laboratory of Nuclear Reactions) at Dubna measurements. (Russia) [3,4]. The rotating device has been designed and mecha References: nically tested in the INCT. [1]. Holeschovsky U.B., Cooney Ch.L.: Quantitative Description Filtration experiments have been carried out at of Ultrafiltration in a Rotating Filtration Device. AIChE the Warsaw University of Technology, Department Journal, 32,8,1219-1226 (1991). PROCESS ENGINEERING [2] , Wroriski S, Rudniak L.: Wptyw napr^iert fcinajqcych na [4). Proc. of the 3rd Conference on Particle Track Membranes separacjq mikroorganizmdw w filtrach dynamicznych. Ini. and their Applications, Jachranka, Poland, 26-29 October Chem. Proc., 4 (1996), in print. 1993. Institute of Nuclear Chemistry and Technology, War [3] .Spohr R.: Ion tracks and microtechnology, principles and szawa 1995. application. Vieweg, Braunschweig 1990. NUCLEAR TECHNOLOGIES AND METHODS 89 PL9702 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS NEW APPARATUS FOR PREPARATION OF GASEOUS METHYL BROMIDE AND RECORDING LEAKS IN UNDERGROUND PIPELINES J. KraS, S. Myczkowski The apparatus for the preparation of methyl - reduce the total activity of methyl bromide ne bromide labelled with radioactive Br 82, as well as cessary for control of pipelines with diameters in the follow-up detectors (ABSR-1 and ABSR-3) the range 200-300 mm without reducing the sen routinely used in this Institute for leakproof control sitivity of the control, of underground pipelines must be continuously mo - enable leadless transmission of data from the de dernized in order to meet customer ’s needs. Such tector to an external computer. modernization has been carried out recently. In order to achieve the above mentioned objec The modernization of the methyl bromide gene tives a new detector DN1 and a new generator were rator was aimed at: designed. Their construction and field-testing will - reducing its total weight, be carried out in the last quarter of 1997. - making it possible to handle potassium bromide In 1996 we carried out leakproof control of a of an activity up to 60 GBq, pipeline (230 mm in diameter) along the route MoSci- - eliminating KW2MSP valves, ska-Emiljan6w as well as of 28 technological objects in - making it possible to assemble the generator on the petrochemical industry. Control of a pipeline on the a uniaxial car trailer. route MoSciska-Plock is being carried out In addition, The modernization of the follow-up detector has the experts of the Institute carried out leakproof been carried out in order to: control of a pipeline (16 inches in diameter), in Iran - increase the recording time up to 100 hours, using the apparatus supplied in this Institute to the - enable continuous record of the way passed by Nuclear Research Centre Teheran (NRCT), under an the detector in the pipeline, IAEA contract localizing three leaks. - making possible control of pipelines with diame The NRCT has obtained further orders for leak- ters up to 600 mm using a detector with a 3" x 3" proof control of underground pipelines from the scintillation crystal, Iran Petroleum Company. PL9702 20 INTENSE PLASMA PULSES; TWO MODES OF THE USE FOR SURFACE PROCESSING PURPOSES J. Piekoszewskl, J. Langner lz, L. WaliS, Z Werner^ 11 Soltan Institute for Nuclear Studies, Otwock-Swierk, Poland Pulsed ion and plasma beams under appropriate (DPE mode). In the present work we demonstrate, conditions can modify the surface properties of for the first time, a continuous transition from PID materials by melting their near-surface regions and to DPE mode. The process was conducted with: simultaneously doping it with the portions of nitrogen as the working gas, cooper as the electrode foreign atoms reaching in a single pulse doses as material, and stainless steel as the substrate. The large as 1017 atoms/cm 2. Such processes can be energy density of pulses amounts to about 6 J/cm2, accomplished using the Rod Plasma Injector (RPI) pulse duration is in the microsecond range. The type of generators [1], These devices can operate in samples were characterized by: weighing before and two modes. The plasma pulses are generated as a after processing to determine the total mass change result of a low-pressure, high-current plasma dis Amt (fig/cm2 pulse); energy dispersive X-ray fluore charge between two concentric, cylindrical sets of scence (EDXRF) on CuK^ line measurements to rod-type electrodes. The discharge is initiated by determine the copper contribution to mass change applying a high voltage after some delay time At Amcu (wg/cm 2 pulse); Auger Electron Spectro from the moment of injection of working gas into scopy (AES) to follow the mixing of the plasma and the interelectrode space. If At is sufficiently long, substrate elements. the plasma contains almost exclusively elements Fig. illustrates the comparison between the total from the gas (PID mode). For short At, the beam is mass change and copper mass contribution Amcu a mixture of elements of working gas and metallic in the samples processed with various delay time t electrodes chosen deliberately for a given purpose ranging from 160 fts up to 210 fis. The principal 90 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS u[mTTini|iiiiiiinymiijii|iiimni|i ly PID regime. This last fact makes it impossible to state unambiguously that in the x range where the loss of total mass is observed, there is a pure PID regime, in spite of the fact that the nitrogen dose is about 4 times as large as Cu dose for x = 210 /is. The PID regime manifests itself more clearly when the electrodes are made of more refractory material, like molybdenum. In the case of molybdenum after 5 pulses for x - 200 /is, the surface concentration of Mo is below the detection limit, i.e. below 1 x 1016, whereas the surface concentration of N amounts to 1.6 x 10l/ at.N/cm2. The facts pointed out in (i) and (ii) make it obvious that for delay times x 2: 180 /is ablation dominates over deposition. This means that an effective mixing between the substrate and coating constituents occurs, other ,elay time wise the plasma supplied Cu would be comple tely removed by ablation. This mixing effect is Fig. Total mass change and copper content of AISI321 stainless even more evident in our AES results. For short steel substrates irradiated with copper - nitrogen plasma delay time the AES spectrum reveals only the pulses, determined by weighing and EDXRA methods, res pectively, vs. the discharge delay time i. presence of Cu, N, C, and O lines. For longer delay times one observes a progressive growth of features which emerge from these data are the N line and a decrease of Cu lines. following: In conclusion: the most effective mass deposition (i) The largest total mass gain Amt is observed for occurs for short delay times, i.e. for metal-rich plas the shortest x i.e. for a definite DPE regime. ma pulses. The most effective mixing takes place for When t rises, the Amt decreases, changes the long delay times, i.e. for working-gas rich plasma sign at about r = 190 ps and with a further rise pulses. It is therefore possible to adjust the dis of r the mass loss increases, reaching the largest charge parameters in the same equipment to form value for the longest x, i.e. for 210 /is. first the well mixed intermediate layer, and then to (ii) For a short x (160-175 /is), the total mass continue the layer formation at the parameters changes equal to the amount of Cu deposited on favouring an effective coating. the surface. For further rise of x the values of Amt and Amcu diverge, Amcu being no negli References gible even for the longest r, i.e. for the nominal [1], Piekoszewski J. et al.: Nucl. Instr. Meth., B53,148 (1991). USE OF HIGH INTENSITY PULSED PLASMA BEAMS IN FORMATION CERAMIC/METAL JOINTS J. Piekoszewski, J. Langner lz, A. Krajewski2/, L. WaliS, W. Wtosinski 2'' 1/ Soffan Institute for Nuclear Studies, Otwock-Swierk, Poland PL9702 21 ^ Warsaw University of Technology, Poland The interest in using ceramics has increased in the as an intermediate layer between the surfaces to be past ten years in many structural applications. Due to joined. To form metallic coatings, high intensity plas specific desirable properties, ceramics are selected ma beams were used, as described in the preceding for various components of systems which largely are abstract of the "Annual Report"; see also ref. ibidi. made of metallic materials. The successful perform The plasma pulses of duration in the microsecond ance of such systems depends on the quality and range and of 6-7 J/cm2 energy densities used in our reliability of ceramic-to-metal joints. In a number of experiments rapidly heat the near surface layer of the studies brazing with an active filler metal was used to substrate to a high temperature (well in excess of the form joints with a high sheer strength. One of the melting point of even refractory metals) and simul difficulties in bonding ceramics to metal may arise as taneously deposit a metallic layer. It is expected that a result of the differences in their interatomic bond such conditions will produce a good adhesion at the ing and physical properties. The low surface tension metal-ceramic interface. In the course of the first of various ceramics makes it unlikely for many series of experiments it was believed that the metallic molten metals to satisfy the wetting conditions ne component of the plasma beam origins exclusively cessary for reaction to take place at the ceramic from the outer set of the rod-type electrodes in an interafce. The key concept of the present work was to IBIS facility. Therefore only these electrodes were alloy a metallic coating into ceramic surface to serve varied in the experiments, whereas the inner elec- NUCLEAR TECHNOLOGIES AND METHODS 91 trades made of molybdenum were fixed. The metals -ceramic joints were obtained using Cl cycle, selected for alloying were: Mo, Ni, Cu, Ti. The whereas all the structures processed according to working gas was N2 of technical purity. The delay C2 cycle - except for the Cu/graphite - have been time t was set on 170 fts to attain the metal-rich well joined. plasma regime (DPE). The substrates were platelets The EDXRF analysis revealed unexpectedly that of polycrystalline ceramics: AI2O3, SigN* SiC and all the metal coatings were contaminated by molyb graphite-35. Using a variable number of pulses (from denum originating from the inner set of electrodes. 5 to 40) the following structures were formed: Therefore, in subsequent series of experiments Ni/Mo/Al 203, Cu-Ti/Al203, Ni/Mo/SiC, Ni/Si^ conducted with the Cu/graphite structures, both the and Cu/graphite. outer and the inner electrodes were made of Cu Of over 40 structures prepared as outlined rods. The 99.996% pure (instead of technical above, several specimens were selected for brazing purity) N2 was used as a discharge gas. Also, the with 0.15-0.2 mm thick FeNL# foils under the load metallization process was modified by using a of 1.3 kPa. Two brazing thermal cycles with dif sequence of pulses at a different t, i.e. of a different ferent filler metals were adopted. In one cycle (Cl) metal-nitrogen ratio, as indicated in Table. The the sandwich of metallized ceramic plus FeNi# foil brazing process was performed according to C2 with the AgCu^ filler in between was heated in a procedure with two values of both Ty and ty, and vacuum furnace up to 500°C at a rate of 30°C/min, Ti-platelets as the base metal. The most important Table. Parameters of processing and tests of Ti/graphite joints. Pulsed plasma processing Brazing parameters Joint tests Number Number Cu density Joint formed Shear strength of sample Tb[°C) tW of pulses [/Kg/cnor] tb [min] yes/no [MPa] 200 10 990 l/II 800 10 no - 180 10 990 2/11 800 10 no - 160 60 990 3/11 850 5 no - 4/JI 850 5 yes 7 200 20 750 1/V 800 10 no - 180 10 750 2/V 800 10 no - 160 60 750 3/V 850 5 yes 29 4/V 850 5 yes 23 1A> 800 10 no - Non processed 2/0 800 10 no - 3/0 850 5 no - 4/0 850 5 no - kept at 500°C for 10 min, heated up to the brazing data concerning this part of experiments are sum temperature Ty = 850°C, kept at this temperature marized in Table. The real values of the shear for 20 min and then cooled down at a rate of strength of the joints are certainly larger than those 10°C/min before the furnace was switched off. The given in Table, because in all 3 cases a fracture other cycle (C2) was modified in respect to the Cl occurred in bulk of graphite and not in the joint. As one by using AgCu^Tigln; filler, adding an addi is obvious from these data, more detailed investiga tional constant-temperature step before reaching tions are necessary to clarify the dependence of the brazing temperature T& (750°C for 10 min), and quality of metal-ceramic joints on-mocessinff with shortening the brazing time tp to 5 min. No metal- pulses of plasma. L97021 22 THE PLASMA DISCHARGE DEVICE FOR MODIFICATION OF SURFACE PROPERTIES OF PARTICLE TRACK MEMBRANES W. Starosto, M. Buczkowski, D. Wawszczak, T. &6frowski Nowadays membrane processes play a very important neutral particles in various excited states and also to role in advanced technologies for research and intense plasma ultraviolet radiation. Depending on industry. For many applications it is necessery to the conditions of plasma discharge and gas mixture change surface properties of filtration membranes. used for plasma creation it is possible: Plasma discharge processes provide a unique and - to "etch" the surface; powerful! technique for alternating the surface - to form individual reactive groups on the surface: chemistry of polymers without changing their bulk carboxylic (-COOH) - negatively charged, amine properties. The reason for this is that under dis (-NH3) - positvely charged, hydroxyl (-OH) and charge conditions the polymer surface is subjected to other charge neutral functionalities; intense fluxes of energetic and reactive charged and - to deposit a "polymer-like" coating. 92 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS From the application point of view plasma dis PET after tretament in the RF discharge [4]. charge techniques are of great value as they give Corona air discharge and oxygen and ammonia RF possibilities of: discharge were carried out for different polymers - attachment of different biomolecules to modified used for manufacturing of PTM for investigations surfaces having chemical groups specific for these of their influence on cell adhesion [5]. In order to biomolecules, investigate the possibilty of improving the perfor - improvement of adhesion strength in the case of mances of our PTM we have carried out some mea coating and fabrication of composites by creating surements on the membranes made of PET. more attachment points on the surface for bond The plasma discharge treatment has been per ing, formed on a device installed in the Centre for - changing of wettability of surfaces (hydrophobic Molecular and Macromolecular Studies of the or hydrophilic properties could be obtained). Polish Academy of Sciences in L6dl Samples of All this can be achieved in one step process, PTM with the following value of pore size have eliminating the necessity of complex wet chemical been taken: 0.16, 1.4, 2.1 ftm. After plasma dis manufacturing processes. Some biomedical applica charge a decrease of angle of wettability (about tion are reviewed in [1,2]. 38%) was observed. At the same time such para Recently the plasma treatment was applied to meters as mean pore size and permeability increas particle track membranes (PTM), high precision ed respectively about 10% and 20-57% depending 1 on primary pore size. Rather encouraging results of preliminary in vestigations stimulated us to build our own device for plasma discharge treatment of PTM. A general scheme of this device is shown in Fig. The device consists of a plasma chamber mounted on a Vacuum Pumping Stand SP-800P, equipped with rotary and diffusion pumps. A high frequency generator 1.25 Mhz, 2 kW was adopted as power source. At present investigations of main parameters of plasma generated in our device are in progress. Acknowledgement The authors are very grealful to Assoc. Prof. J. Tyczkowski from the Centre for Molecular and Macromolecular Studies in L6d2 for carrying out plasma treatment of PTM samples. References [1] , Yasuda H., Gazicki M.: Biomedical Applications of Plasma Polymerization and Plasma Treatment of Polymer Surfaces. Biomaterials, 3,68 (1982). [2] . Hoffman AS.: Biomediai Applications of Discharge Pro cesses. Journal of Applied Polymer Science: Applied Polymer Symposium, 42,251 (1988). Fig. A section of the device for plasma treatment of PTM. 1 - va cuum chamber, 2 - strip of the membrane, 3 - electrodes, 4 - gas [3] , Vilensky AI., Berzkin V.V., Mchedlischviii B.V.: Kolloidnyj inlet, 5 - output to HF generator, 6 - output to vacuum pumps. Zhumal, 53,117(1991). [4] , Dmitriev S.N., Kravets L.I., Sleptsov V.V.: Modification of filters obtained by irradiation of thin polymer foils Track Membranes Structure by Gas Discharge Etching with heavy ions in a cyclotrone and subsequent method. JINR Report E18-96-292, 1996. [5] . Dewez J.L, Doren A, Schneider Y.J., Legras R., Rouxhet chemical etching of latent track created during P.G.: Surface Study of New Microporous Polymeric Mem irradiation. The etching of pores was observed in branes Used as a Substratum for Animal Cell Culture. glow discharge [3], changing of pores shape and Interfaces in New Materials, 84-5 some improvent of permeability of PTM made of Illllllllllll lUllll 111 [111 PL9702123 PREPARATION OF HIGH PURITY BORON ON A LARGE LABORATORY SCALE A. Nowicki A method was developed for the preparation, on a An apparatus, with induction heating, used in laboratory scale, of high purity boron (> 5N) to be this method has been designed and constructed in used as a dope for silicon used in the manufacturing the Department of Nuclear Methods of Material of integrated circuits [1]. Engineering of this Institute. NUCLEAR TECHNOLOGIES AND METHODS 93 In 1996 the Institute supplied the SILICON The course of the processes of the preparation of COMPANY Ltd. with 450 g of boron (of a value individual boron batches was in agreement with exceeding 31,000 US$). The boron has been pre adopted assumptions. In particular a very high effi pared using the above mentioned apparatus. The ciency (3 g of boron per 1 hour) was achieved. The course of the process was similar to that described technology developed at the INCT makes it possi in [1] and [2], Taking into account the scale of the ble to manufacture up to 1000 g of boron per year. process an imported BBra preparation (manufac tured by Aldrich, USA) of a purity > 99.9% [3] was References used as raw material. The purity of the obtained [1] , Nowicki A: INCT Annual Report, 1993, p. 66. crystalline boron was examined with the aid of [2] .Nowicki A, Szczepankiewicz C, Olza J.: Internal Report reactor neutron activation analysis. The concentra INCT No. 51/1/92. tions of impurities found were negligible. [3] , Aldrich Technical Reference No. 20,220-7. The achieved purity meets the requirements of the semiconductor industry. ORGANIC FIBRES IMPREGNATED WITH POLYMERIC COMPLEXES OF AMINOTRIAZOLE WITH METALS AS NEW FILTERS AND SORBENTS A. Lukasiewicz, L WaliS It has been found earlier [1] that polymeric com a 0.1% aqueous solution of the CuAXp complex plexes of aminotriazole with metals of a general and heated. The cotton wool and the cotton fabric formula (M - transition metal Cu2+, Ni2+, bound the complex in an amount corresponding to Co 2+, Ag + or two different metals, A - acetate anion, 50 //moles of copper per 1 g of the fibre. The res X - 3-amino- 1,2,4-triazole, (p) - polycondensed com pective value for polypropylene fibre was 20 plex with formaldehyde) are effectively bound by pmoles. Acid dyes with the SOaNa groups were mineral carriers containing anionic centres on their used as model acid compounds. Basic dyes, so surface. called cationic dyes (not containing the free amine Binding the complexes, denoted below as MAXp, groups), as well as dyes with free amine groups proceeds very effectively at elevated temperatures as were used as basic compounds. The dyeing was a result of coagulation of the polymeric complex on carried out at room temperature. The binding of the surface of the carrier (s). It has been found that the dye was evaluated on the basis of the leaching the surface materials s-MAXp effectively bind ni with water or (for acid dyes) with an NaaSO* trogen oxides from the air [2], as well as various solution. The SO$- anion displaces the anions that anionic compounds from aqueous solutions [3]. The are less strongly bound with the MAXp. The results materials s-MAXp can be used for preparation of are presented in Tables 1 and 2. Table 1. Affinity of add dyes (anionic) to f-CuAXp materials. Binding stability No. Name Structure (SOgNa groups) f-cel-CuAXo fpp-CuAXo 1 Acid Red 88 1 + + + + 2 Acid Red 97 2 + + + + 3 Acid Red 27 3 + +- 4 Acid Orange 8 1 + + 5 Acid Orange 63 2 + + + + 6 Eriochrome Black T 1 + 4- ++ 7 Acid Black 24 2 + + - + + the dye non-leachable with water or 1 % sodium sulphate solution. +- dye non-leachable with water but leachabie with sodium sulphate solution. + - weekly coloured fibre, the dye completely leachabie with sodium sulphate solution. filters and sorbents. Fabrics made of organic fibres of The fibres f cel-CuAXp and f pp-CuAX p have a suitable properties can be of interest as filtration similar affinity for acid and basic dyes. This indi materials. It has been found that cellulose fibres (f cates that the dyes are bound by the CuAXp com cel) and polypropylene fibres (f pp) can be impreg plex on the fibre suface and not by the fibre itself. nated with MAXp complexes at elevated tempera The f pp fibres exhibit no affinity for the dyes in tures, which leads to new materials f-MAXp . aqueous solutions. The affinity of f-MAX materials has been exa The affinity of anionic dyes to f-CuAXp depends mined (as potential filters and sorbents) for model on their structure. The number of SO^Na groups in acid and basic compounds in aqueous solutions. the molecule affects the affinity only to a limited The copper complex CuAXp was used for impreg extent. Cationic dyes without free amine groups nating the fibres. Cellulose fibre (cotton wool, have no affinity to f-CuAXp. The highest affinity is cotton fabric) or polypropylene fibre was placed in shown by dyes containing the NHg group. 94 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS Table 2. Affinity of basic dyes for f-CuAXp materials. Binding stability No. Name Structure (free amine groups) f-cel-CuAXp fpp-CuAXp 8 Basic Red 22 no - - 9 Basic Blue 3 no - 10 Basic Blue 9 tertiary + +- 11 Basic Green 1 tertiary + + + + 12 Basic Brown 4 NHz + + + + 13 Mordant Brown 4 NH2 + + + + - no stable colour of the fibre. +- weakly coloured. + weak non-leachable colour. + + intense, non-leachable colour. The affinity of dyes with a tertiary amine group of acidic and basic character. The f-MAXp fibres depends on the structure of the dye (no. 10 and 11, and fabrics can be utilized as filters and sorbents of Table 2). new type. The affinity of add dyes to CuAXp is connected with the displacement of the acetate anions (A) by the SO3 References anions, while that of basic dyes with the formation of a [lj. Lukasiewicz A, Walii L., Michalik J., Sadto J.: Mater. Lett., common metal complex with a ligand X 29 (1996)149. The new materials f-MAXp have been descibed [2] . P. 229505. in [4], [3] , Lukasiewicz A, Michalik J., Sadto J., Wqsowicz T., WaliS L.: New surface layers materials from polymetallic aminotriazole complexes on various supports. Report INCT-1/94. Institute Conclusions of Nuclear Chemistry and Technology, Warszawa 1994. Cellulose and polypropylene fibres impregnated [4] , Lukasiewicz A, WaliS L.: Materials Letters, in press. with MAXp show different affinity for compounds PREPARATION OF CALCIUM PHOSPHATE SPHERICAL POWDERS AND COATINGS BY COMPLEX SOL-GEL PROCESS (CSGP) A. Deptula, W. Lada, T. Olczak, R.Z. LeGeros 1/, J.P. LeGeros 1/ 1Z New York University, USA Recently, calcium phosphates have attracted much 1.67M C* (AC); in acidic aqueous solution attention as coatings on metal implants [1], Actually (I.46M)----- > in all the known methods pure caltium phosphates 0.87 M of Bcsorb'.c arid (ASC) in the CSGP variant —— > irregularly shaped powders, mainly HA, are used as starting materials. The plasma spray technique is actually the only one extensively used in the implant Ultrasonic mixing, industry. It is well known that spherical powders are 2 min very attractive for this application. viscous sol, (71=5-10 First in 1991 some of the present authors from cP,pH«4) the INCT [2, 3] reported the preparation of spheri <— (eventually) NH Calcination temperature [°C] XRD structure* Sample Ca/P Process parameters Washing solvent /3 TCP/HA weight symbol molar ratio time - 48 h time -1 h ratio after 48 h 1 AC fresh EH, 200 ml of starting sol * * acetone 200 900 1.52 DCPD 68/32 (SS) (easy process) 1.63 2 AC EH after gelation of sample 1 AC acetone 60 900 1.50 DCPD 59/41 200 ml ofSS (easy process) 1.52 3 ASC EH after gelation of sample 2 AC acetone 90 900 1.54 DCPD 40/60 200 ml ofSS (easy process) 1.52 4 ASC EH after gelation of sample 3 ASC petroleum benzin 60 900 1.53 DCPD 27/73 200 ml ofSS (difficult process) 1.61 5 ASC-(A) EH after gelation of sample 4 ASC acetone 60 900 1.35 DCPD 39/61 200 ml ofSS (easy process) 1.59 5 ASC-(E) Note. Sample 5 ASC was divided petroleum benzin 60 900 1.50 DCPD 38/62 for washing (difficult process) 1.51 * - the TCP/HA ratios established using X-ray diffraction analyses. ** - feeding rate 30 ml of SS/h. Detailed preparation conditions of spherical small exotherms, with maxima at about 350°C, powders are shown in Table. without distinct weight drop, can be due to the It has been found that the final composition of formation of crystalline phases. The last very sharp the synthesized powders is a mixture of (i TCP and superimposed exothermics, at about 450 and 490°C, HA instead of pure HA. It was observed that the accompanied by a very drastic weight loss (approxi HA content was definitely higher (60-75%) for mately 20%) can be attributed to the combustion of samples prepared from ascorbate gels than from residual carbon and phase transformation. those without this additive (30-40%). This indicates Thermal decomposition of ASC gels is more that ascorbic acid promoted the formation of complex. In the discussed region several broad homogeneous gels. superimposed exotherms (with onset points about 330, 380 and 450°C), accompanied by continuous mass losses, were observed. The total mass loss for ASC gel ASC gels above about 500°C was 10% higher than for AC gels because of higher organics content. Above that temperature, till about 800°C, for AC gels and 780°C for ASC the weight of the sample was stable. At these temperatures small drops in Fig.3. Photographs of HA coatings obtained from ASC gels on Ti. IOC 300 500 700 900 temperature, °C the TGA, very distinct for ASC samples, accom panied by endothermic effects, indicate the carbo Fig.2. Thermal analysis of calcium phoshate AC and ASC gels. nate decomposition and formation of final crystal line compounds. The differences between thermal The results of thermal analysis of AC and ASC characteristics of AC and ASC gels appear to be gels, dried at 60°C, are shown in Fig.2. For both connected with the extent to which they are 96 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS Fig.4. Electron Probe Analysis and XRD patterns of HA (x) coatings on Ag (o) substrate. amorphous. This is presumably a reason of easier Photographs of the coatings are shown in Fig.3. formation of HA phases in ASC gels. Their XRD and Electron Probe Analysis (Fig.4) is For film coating formation the dipping machine indicative of pure HA phase of coating. described in [5] was used. Silver and titanium plates were used as substrates. The substrates were im References mersed in a sol and withdrawn at a speed of about 5 [l].LeGeros R.Z., LeGeros IP , Daculsi G., Kijkowska R.: In: cm/s. Since preliminary experiments indicated that Encyclopedic Handbook of BiomateriaU and Bioengineering. acetate (AC) sols did not wet the substrate surface a Part A. Materials. Vol. 2.1995, p. 1429. modification of the process was necessary. The [2j. Deptula A, Lada W., Olczak T., BoreDo A, Alvani G, Bartolo meo Di A: Preparation of Spherical Powders of Hydroxyapatite modification consists in introducing the strong by Sol-gel Process. J. Non-Cryst. Solids, 147&148. 537 (1992). complexing agent - acsorbic acid (ASC) - to the sol. [3] , Deptula A, Olczak T., Lada W., Alvani G, Lorenzini L., The formation of high amorphous gels with a Bartolomeo Di A: Preparation of Calcium Phosphates strong net bond is presumably the reason, why only Powders by Water Extraction Variant of Sol-gel Process. In: the ascorbate sols perfectly wet the support and Hy- droxyapatite and Related Materials. Boca Raton CRC Press, USA 1994,263 p. form coatings on metallic surface. [4] . Deptula A, Majani C.: Sol-gel Processes and theirs Applica The substrates covered by gel film were then tions. ENEA Report No. /TIB/86/25. Roma 1986. subjected to thermal treatment for 1 h at 900°C. [5] , Lada W., Deptula A, Olczak T., Torbicz W., Pijanowska D, Coatings, thickness of several tens pm, are very ad Bartolomeo Di A: Preparation of Thin SnO% Layers by Inor herent and mechanically resistant. Theirs thickness ganic Sol-gel Process. J. Sol-Gel Sci. Technol., 2,551 (1994). can be increased by increasing the number of im mersions of the substrate in the sols. PL97021 24 DETERMINATION OF TRACE ELEMENTS IN LEAD WHITE FROM LANCKORONA PAINTING COLLECTION BY INSTRUMENTAL NEUTRON ACTIVATION ANALYSIS E. Paficzyk, P. Rudniewski17, L. WaliS 17 Academy of Fine Arts in Warsaw, Poland INTRODUCTION of the 17th and 18th centuries and belonging to the Warsaw Castle collection. The determination of trace elements in lead The determination of trace elements was carried white has been commissioned to this Institute by out using instrumental neutron activation analysis the Academy of Fine Arts in Warsaw. (INAA). This method enables fast, nondestructive This work was aimed at providing documentation determination of several tens of elements that form of a part of the Lanckorona Collection as well as at gamma-ray emitters in nuclear reactions with ther developing a model method for complex examination mal neutrons. The major advantage of INAA is its of objects of ancient easel painting. Such a method ability to determine a great number of elements would make a basis for proper conservation of art with extremely high sensitivity. Of primary import objects as well as for research in the field of art ance is the fact that the principal components of history, conducted in accordance with assumptions of the analysed matrix-lead white are insensitive to the method for "novel expertness". reactions with thermal neutrons. The object of the present study was a set of 19 Their sampling and preparation of the samples were paintings originating from Dutch and Polish Schools carried out at the Academy of Fine Arts in Warsaw. NUCLEAR TECHNOLOGIES AND METHODS 97 DETERMINATION The standards of Zn (1 mg), Sn (10 mg), Fe (10 mg) OF TRACE ELEMENTS CONCENTRATIONS and Ni (1 mg) were wrapped in an aluminium foil. IN THE SAMPLES EXAMINED The samples are described in detail in Table 1. The analysis of the samples was carried out by Irradiation and activity measurement INAA using standards of the elements to be deter The samples were irradiated in the MARIA re mined which significantly extended the time of actor at Swierk at a neutron flux of 8 x 1013 n/cm2s analysis. Application of the previously developed for 24 h and cooled for 8 h. single comparator method was not possible because After irradiation the ampoules were washed with of the shut down of the EWA nuclear reactor (pre 1:1 HC1 solution, followed by alcohol, in order to viously used for irradiation) and unstable irradia remove surface contamination. The standards were tion conditions in the new MARIA reactor. washed out of the ampoules or, in the case of Sc and Au, dissolved together with the aluminium foil using Preparation of samples and standards for irradiation appropriate solvents. Aliquots of the obtained The samples were weighed, sealed in quartz solutions (0.01-0.1 ml) were transferred onto glass ampoules and packed together with standards of measuring plates and evaporated to dryness. The the elements to be determined (Na, K, Sc, Cr, Mn, activity of the samples and standards was measured Fe, Co, Zn, Ga, Br, Mo, Ag, Cd, Sn, Sb, Cs, Ba, La, using an HP germanium detector of an active volume Ce, Eu, Yb, Tb, Hf, Ta, W, Ir, Au, Hg, Th and of 80 cm3 and a resolution of 1.95 keV for the energy 238 U). Each package contained 5 samples and 40 1333 keV (Co 60), coupled to an S100 analyser standards. In addition, each package contained (CANBERRA) controlled by an IBM/PS computer. standards of Sc and Au as neutron flux monitors. Analysis of complex gamma ray spectra was carried Most standards were prepared by evaporating small out using a micro-SAMPO program. volumes (0.01-0.1 ml) of standard solutions to dry The obtained lower limits of determination of ness in quartz ampoules which were then sealed. some elements in white lead are presented in Table 1. Characteristics of the examined objects. Sample Catalogue Sampling point Author of picture Name of picture no. no. of lead white [cm] i Ph. Wouwermans (-1650) Man with a grey horse, oak board; 26 dog 35.9x31.9 cm x-21.8; y-4.6 2 unknown Portrait of Jan Kazimierz (octahedral) jewel of the lead gear, (impast)x-30.7; y-50.3 3 D. Teniers Jr. Vodka vendor, oak board; 25.7 x 19.6 cm 24 collar x-12;y-19.0 4 D. Teniers Jr. Couple of vodka vendors, oak board; 23 bottle 25 x 19 cm x-2.1; y-19.5 5 A van Ostade Fireman, oak board; 19.8 x 16.9 cm 16 shirt x-8.6; y-5.1 6 Corneille de Lyon Antoine de Bourbon, the King of Navarra, 3 ruff walnut board; 16.4 x 13.7 cm x-8.6; y-9.5 7 Comellis Decker Landscape with a mill, canvas; 5 water dropping onto the wheel 100.5 x 89.3 cm x-17.0; y-37.5 8 Polish painter (18th century) Adam Tarlo (?), canvas; 61.5 x 75 cm 33 collar x-22.2; y-40.7 9 Jdzef Grassi (?) Prince Jtizef Poniatowski, canvas; 8 epoulette 85.5 x 69.5 cm x-33.5; y-43.0 10 Jean Marc Nattier (krqg) Adam Tarlo (?), canvas; 79.6 x 65.1 cm 13 breast pin x-33.5; y-43.0 11 according to Rembrandt Expiating St. Peter, canvas; 50.7 x 64.3 cm keys x-35.4; y-8.9 12 Jan Frans Soolmaher Italian landscape, canvas; 60.7 x 79.2 cm 22 goats rump x-47.9; y-7.2 13 Frederik de Mucheron Woodland scenery, canvas; 79,4 x 67.2 cm 12 donkey x-9.2; y-6.7 14 Frederik de Mucheron Woodland scenery, canvas 12 donkey ’s head x-5.2; y-5.7 15 Etienne de la Hyre (1626) Art study of Royal Prince Wladystaw x-7.0; y-25.0 Zygmunt Waza 16 Portrait of Zygmunt August (octahedral) impast on the armour x-6.3; y-16.8 17 PP. Rubens workshop after 1620 The battle of Amazons 18 x-19.6; y-48.3 18 Rembrandt (1641) Portrait of a young woman, poplar board; 18 impast on the edge 105.5 x 76.3 cm x-74.5; y-98.0 19 Rembrandt (1641) Scientist at the desk, polar board; 19 pages of the book (impast) 105.7 x 76.4 cm x-23.2; y-17.1 98 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS Table 2. Elemental concentration for lead white [ppm]. 1 2 3 4 5 6 7 8 9 10 Na 110 57 217 293 82.8 182 81 234 301 131 K 229 90.7 419 652 137 276 142 304 756 167 Sc 0.014 0.0083 0.038 0.045 0.013 0.026 0.012 0.036 0.026 0.016 Cr 14.9 6.43 28.3 45.4 11.4 26.8 11 13.1 11.4 4.76 Mn 15.3 33.7 57.6 64.7 36.3 41.9 12 16.7 76.3 15.7 Fe 207 90.8 347 543 139 353 125 360 311 146 Co 0.33 0.3 0.74 0.68 0.2 0.43 0.44 0.72 0.4 0.19 Ni 212 30.3 95 87.5 15.3 4.53 3.9 18.5 - 20.8 Cu 0.56 16.2 225 53.6 70.5 20.1 190 91.8 23.3 25.3 Zn 0.27 0.49 4.43 2.04 0.85 0.95 0.75 2.33 3.13 1.3 Ga 2.31 0.13 80.6 3.03 - 5.15 4.88 9.53 2 2.89 Gc 9.07 1.66 - 29.4 7.63 - 4.78 37.9 14.2 8.16 As 0.7 0.37 0.93 1.38 0.32 1.02 0.67 22.6 21.1 1.3 Sc 0.17 - - 2.33 0.091 0.026 0.02 0.021 0.014 0.017 Br 70.3 39.2 90.7 134 5.03 101 47.5 69.4 120 63.4 Rb 0.49 0.57 0.42 0.86 1.04 0.2 1.28 2.26 0.75 Sr 28.4 13.5 43.1 55 15.5 40.2 14.2 56.1 51.6 20.2 Zr 84 3.03 26 15.5 9.05 12.5 12 29 26.3 7.86 Mo 1.58 0.58 0.34 3.13 0.53 1.01 0.91 1.19 1.43 1.2 Ru 793 490 1170 1480 365 1600 725 906 1640 604 Ag 1.18 0.13 0.16 0.36 0.11 0.25 0.2 0.21 0.17 0.14 Cd 1.95 - 0.59 0.18 0.98 - 7.95 1.38 - 6.98 Sn 17.3 13.5 3.7 43.3 7.85 31.4 13.8 162 2.61 20.4 Sb 0.8 0.38 1.19 1.92 0.46 1.11 1.16 1.37 1.1 0.86 Tc 10.5 0.63 20.8 7.93 1.32 8.7 11.4 9.06 1.57 3.82 Cs 0.68 0.37 1.19 1.8 0.35 0.85 0.52 0.15 0.16 0.066 Ba 1.59 0.68 8.13 3.13 0.74 4.14 3.88 2.78 15.3 7.78 La 0.16 0.14 0.42 0.63 0.13 0.41 0.37 0.45 0.4 0.38 Ce 1.15 0.86 1.85 3.35 0.77 1.77 0.94 0.85 1.94 0.56 Pr 0.22 - 0.98 1.66 0.29 - 0.53 0.72 - 1.5 Nd 1.84 0.63 - 1.78 0.4 1.83 0.62 0.37 0.6 Sm 0.025 0.027 0.081 0.13 0.022 0.06 0.03 0.11 0.038 0.048 Eu 3.9 0.025 0.12 0.38 0.064 0.032 0.015 0.022 0.071 0.011 Tb 1.13 0.038 0.094 0.058 0.079 0.16 0.018 0.092 0.043 0.063 Dy 4.2 - - - - 36.9 1.9 16.4 4.24 5.88 Ho - 0.81 - 0.5 1.91 1.22 - - - - Er - - - - - 0.027 1.71 - - 0.22 Yb 1.03 0.042 0.15 0.28 0.063 0.23 0.034 0.16 0.062 0.015 Lu 0.026 0.0006 0.14 0.027 0.0044 0.11 0.043 0.041 0.056 0.0086 Hf 0.0095 0.0051 0.017 0.057 0.0072 0.021 0.016 0.025 0.02 0.012 Ta 233 0.029 0.021 - 0.049 0.092 0.066 0.024 0.022 0.023 W 4.2 4.08 17.3 9.25 1.04 3 2.93 13.7 1.95 4 Ir 0.0002 0.0023 0.0016 0.0009 0.0005 0.0017 0.0001 0.0022 0.0002 0.0002 Au 0.0085 0.0027 0.0038 0.023 0.004 0.0054 0.0025 0.013 0.0062 0.0025 Hg 490 65.2 257 15.3 1.37 36 355 19.7 5.8 13 Th 0.13 0.079 0.233 0.56 0.16 0.26 0.1 0.095 0.098 0.042 235u 0.87 0.044 0.228 1.08 - 0.17 0.11 0.23 0.3 0.3 Tables 2 and 3. They were determined according to lifted and determined in the samples examined. The Currie’s method. Thirty three elements were iden- preliminary results (results of a single run) are NUCLEAR TECHNOLOGIES AND METHODS 99 Table 3. Elemental concentration for lead white [ppm]. 11 12 13 14 15 16 17 18 19 Na 59.5 263 204 236 378 440 232 364 478 K 70.4 343 661 228 329 344 225 355 420 Sc 0.04 0.027 0.024 0.019 0.031 0.037 0.026 0.043 0.037 Cr 2.97 12.9 10.9 8 14.2 16.6 6.5 11.3 16.5 Mn 25.2 31.4 22.3 4.6 62.8 239 36.3 27.3 67.8 Fe 123 400 383 491 785 812 510 686 1150 Co 0.25 0.5 2.93 0.58 0.82 1 0.55 1.26 1.25 Ni 3.7 46.5 - - - 20 - - - Cu 31.9 141 114 17.1 23.4 52.2 6 25.3 24.9 Zn 0.76 1.91 2.16 0.42 1 1.18 0.57 1.38 1.91 Ga 9.61 4.94 - 20.5 24.9 17.2 3.82 - 20.5 Ge 3.9 110 11.2 41 23.2 9.1 8.4 31.3 16.9 As 6.06 33 32.7 20.1 31 47.3 23.1 42 42.2 Se 0.026 0.039 0.15 0.21 0.082 0.11 0.2 0.31 Br 22.1 180 102 49.1 84.6 107 34.8 93.3 128 Rb 0.34 1.68 1.29 2.35 3.45 4.44 2.26 2.63 3.65 Sr 13.9 58.2 40.5 15.8 24.3 33.9 1.48 33.8 33.3 Zr 6.78 17 20.6 6.53 27.7 44.2 - 21.9 18 Mo 0.44 1.7 1.23 0.92 1.8 3.98 2.34 2.2 2.64 Ag 0.18 0.21 0.15 0.23 0.21 0.32 0.17 0.45 0.4 Cd 0.46 0.8 1.09 2.93 2.33 4.76 0.15 - 9.21 Sn 8.19 - 27.8 15.5 45.1 29.7 0.73 51.3 - Sb 0.65 1.41 1.22 1.75 2.77 3.04 1.57 5.88 2.63 Te 0.87 4.61 3.92 12.1 6.85 2.13 - 15.5 - Cs 0.063 0.2 0.19 0.19 0.28 0.37 0.21 0.35 0.33 Ba 0.92 5.8 5.51 1.26 3.28 18.8 1.59 18.6 16.3 La 0.17 0.39 0.68 0.87 1.05 1.36 1.07 0.52 0.41 Ce 0.36 1.55 1.17 3.1 6.02 14 7.85 6.16 7.55 Pr - - - 1.54 - - - 2.39 1.49 Nd 0.96 0.32 0.62 - 0.83 2.09 3.45 - - Sm 0.021 0.059 0.049 0.032 0.031 0.078 0.048 0.1 0.066 Eu 0.0063 0.015 0.0091 0.013 0.023 0.039 0.022 0.027 0.026 Tb 0.061 0.049 0.036 0.025 0.037 0.053 0.016 0.17 0.18 Dy 3.16 20.1 12.6 18.7 42.4 4.3 32.6 33.3 36.3 Ho 0.44 1.23 - - - 2.86 2.05 4.6 0.12 Er 0.47 - - 2.55 - - - - - Yb 0.023 0.14 0.2 - 0.3 0.045 0.036 0.039 0.33 Lu 0.0029 0.054 0.14 - 0.0044 0.012 0.026 0.47 0.0061 Hf 0.013 0.013 0.01 - 0.15 0.16 0.067 0.088 0.071 Ta - 0.093 0.021 - 0.041 0.024 0.033 0.2 - W 1 8 6.22 11.1 20.2 10.7 6.4 7.06 15.1 Ir 0.00028 0.0011 0.0016 0.0014 0.0016 0.00092 0.00068 0.0012 0.0016 Au 0.071 0.047 0.056 0.0049 0.01 0.0065 0.0042 0.014 0.016 Hg 146 38.3 156 20.8 48.2 328 147 494 37 Th 0.037 0.18 0.071 0.11 0.33 0.29 0.087 0.22 0.29 z»u - 2.61 0.14 2.5 - 2.65 2.39 1.72 3.97 given in Tables 2 and 3. Altogether 8 determina- will be subjected to multivariate statistical analy- tions were carried out for each sample. The results sis. PL9702125 100 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS APPLICATION OF X-RAY FLUORESCENCE ANALYSIS FOR EXAMINATION OF THE AUTHENTICITY OF THAI CERAMICS A. Kalicld, E. Panczyk, L, WaliS Introduction II. The latter exhibit random correlation of the X-ray fluorescence analysis is a nondestructive, concentrations of those elements. For white-blue multielement method applicable in situ. The method porcelain from the period of Cing dynasty and the can be advantageously used for the determination of Republic the values of the concentration ratio of the elemental composition of art objects. manganese to cobalt range from 0.2-0.4 while for In the case of ceramic objects the examination is contemporary forgeries the ratio of Mn/Co is about concerned either with surface analysis, aimed at 0.07. It should be noted that the above conclusions identifying pigments in glaze, or determination of have been drawn for collections composed of trace elements as geochemical indicators of the 30-150 pieces of various objects. In such cases origin of the examined object. numerical statistical programs are used for treat About 20 elements can be determined in ment of results. Such a method was used by Yap [9] ceramics [1,2]. in his work concerning a part of the Chinese Museums often face the problem of the authenti porcelain (blue-white and white) collection origi city of porcelain. Traditional methods of identifica nating from a well documented marine discovery of tion of art objects do not permit univocal dating. 1750 called the Nanking Cargo. The concentrations Additional difficulties are due to the fact that in the of 9 elements (Fe, Cu, Zn, As, Pb, Sr, Y, Zr, Nb) world market there appear a vast number of forgeries were determined. Their correlations in terms of manufactured at the turn of the 19th and 20th cluster areas well characterize the origin of the centuries which ideally imitate the shape, ornamenta objects which was confirmed by comparing the tion and colouring of ceramic objects of the period of obtained results with data obtained for objects from Ming and Cing dynasties, and Thai ceramics. other periods and contemporary objects. The first works on the determination of the chemi Experimental cal composition of materials employed in the manufac turing of art objects of that type using physico-chemical This Institute collaborates with the Museum of methods were carried out in 1924 [3]. Asia and the Pacific on the identification of Thai X-ray fluorescence analysis was used to deter ceramics objects. Preliminary measurements were mine the age of white-blue porcelain on the basis of carried out on two ceramic containers, shaped like a the concentration ratio of manganese to cobalt [4], flattened ball and resembling in style Sawankhalok Many works were carried out at Singapore [4], The ceramics (Fig.1). X-ray spectra excited by means of age of porcelain was also detemined on the basis of Cd-109 and Pu-238 sources were measured using a the concentration ratios of: potassium to iron [5], Si(Li) detector. Seventeen elements were identified zinc to rubidium [6], zinc to arsenic [7] and zircon by measuring unglazed (foot) and glazed surfaces ium to niobium [8]. (inner surface of the container and inner surface of It has been found that porcelain of the Ming the cover), each part of the container being treated period from Cing-techen has low zinc and arsenic as a separate object (no certainity that the objects contents, while similar objects from the same make a set) (object number 1,2,3,4,5,6). Fig.l. Bowls from Thaic ceramic. geographical region of the period after the World On the basis of the obtained spectra the intensity War II exhibit significantly higher arsenic concen ratios of the lines K/Fe, Ti/Fe, Nb/Zr and Zn/Rb tration. Different relationships were established by (Fig.2) were plotted for the Thai ceramics and examining the correlation of the intensities of Nb% Chinese) 16th-17th century stoneware (bowl) and Zn% lines of objects dating from the Cing (object 7, 8) in order to illustrate the differences in period and replicas fabricated after the World War the elemental composition of the examined objects. NUCLEAR TECHNOLOGIES AND METHODS 101 Ratio of Zn to Rb Ratio of K to Fa 100 10 1 0,1 ♦ ♦ ♦ ♦ 0,01 Ratio of Nb to Zr Ratio of Tl to Fa 0.1 ♦ ♦ ♦ 0,08 ♦ ♦ 0,06 ♦ 0,04 0,02 ♦ ♦ 0 - 0 2 4 6 8 Fig.2. Ratio of the intensities Zn/Rb, K/Fe, Ti/Fe, Nb/Zr of Thai and Chinese ceramics. A high concentration of zinc was found in the [2] , Kierzek J., Matozewska-Budko B.: Badanie ceramiki chi A foot of one of the Thai comtainers which may sug skiej melody rentgenowskiej analizy fluorescencyjnej. INCT gest that it is a contemporary filling. Internal Report no. 16,1995. [3] , Neuburger A.: Echt Oder Falschung. Leipzig 1924. The examination of further objects of Thai cera [4] . Yap C.T.P., Tang S.M.: X-ray fluorescence analysis modem mics is in progress. and recent Chinese porcelains. Archaeometry, 26 (1984). Microsamples were taken from all the objects [5] . Yap C.T.: X-ray fluorescence studies on low-Z elements of examined in order to determine the concentration of strait Chinese porcelains using Fe-55 and Cd-109 annular elements by instrumental neutron activation analysis. source. X-Ray Spectrometry, 16 (1987). Correlation between results obtained with the aid [6] . Yap C.T., Tang S.M.: ZnK»/RbK.. ratio of Ch’ing Republic and modem Chinese porcelains. X-Ray Spectrometry, 14 of both methods (i.e. X-ray fluorescence and instru (1985). mental neutron activation analysis) will enable more [7] . Yap C.T.: X-ray fluorescence determination of trace element precise characterization of the collection. concentrations of zinc and arsenic and their relation to cera mic attribution. X-Ray Spectrometry, 16 (1987). References [8] . Yap C.T.: EDXRF analysis of straits Chinese porcelains for [1]. Paflczyk E., Lig$za M., Kierzek J., WaliS L.: Zastosowanie zirconium and nobium using a Cd-109. Appl. Spectrosc., 40 instrumentalnej analizy aktywacyjnej oraz rentgenowskiej (1986). analizy fluorescencyjnej w badaniu dziet sztoki. "Technika ra- [9] , Yap C.T.: Studies of the Nanking Cargo with principal diacyjna i izotopowa w konserwacji zabytkdw", L6di, Poland, component analysis of trace elements. Appl. Spectrosc., 45, 23-24 kwietnia 1996. Materialy z konferencji, pp. 52-67. 584-587 (1991). STUDIES OF MILLINGABILITY OF COAL COMBUSTED IN HEAT POWER STATIONS P.J. Bukowski Decreasing of exploitation life of milling facilities, this reason, examinations were carried out on 50 working in energetic boiler-rooms, occurs mainly due samples of coal supplied to the Heat Power Station to erosive over-consuming by milled coal. Substantial SIEKIERKI from seven different mines. Characteris erosive defects of working surfaces of mills are caused tics of these sorts of coal differed mainly in ash content. by big and hard particles existing in mineral ballast A comparative method was used for milling which concentrates in mills and formes an abrasive qualities of particular sorts of coal, consisting of an mass for milling surfaces. Increasing number of major attempt to milling in steady conditions (preselec repairs in the year have a significant effect on increase tion stage of a study), the sieve analysis, and macro of unit cost of heat and electric energy production. scopic studies of mineral ballast obtained after The aim of these studies was to determine sorts of decarburization of that sample fraction which did coal having the most erosive properties for working not undergo breaking up during milling. Removing surfaces of mills installed in a heat power stations. For of coal from the particle surface was carried out 102 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS of hard elements (H.E.) in particular sorts of coal (Table, Fig.), were determined. Table. Ranges and average contents of hard elements (H E.) in coal in particular mines. Symbol Arav. rs ys av. yio ylO av. of a mine [%] [g/kg] [g/kg] [g/kg] [g/kg] 1 16.27 0.05-1.84 0.71 0.072-1.10 0.30 2 19.30 0.10-0.96 0.51 0.30-0.38 0.20 3 26.25 1.51-4.88 2.19 0.64-3.15 1.05 4 23.66 0.26-6.19 2.32 0.17-3.51 1.24 5 18.58 0.60-3.20 1.45 0.30-2.30 0.86 6 20.39 0.33-1.85 0.79 0.11-0.96 0.24 7 18.78 0.68-1.27 0.90 0.15-0.48 0.33 y5 - weight fraction of hard elements in coal mineral ballast, Average esh contain [%] diameter of 5 mm < T < 10 mm. Fig. Hard elements (H E.) contents as a function of ash average yiQ - weight fraction of hard elements of diameter > 10 mm in contents in coal. coal mineral ballast. y5 av. - average weight fraction of hard elements (diameter 5 mm using isothermic gasification in the temperature < T < 10 mm) in coal mineral ballast. range 280-550°C. ylO av. - average weight fraction of hard elements of diameter > The method of selection of mineral ballast ele 10 mm in coal mineral ballast. ments, based on surface tint, size, and mechanic and Results of the studies show that among the magnetic properties of particles, was elaborated. examined sorts of coal the best milling qualities The amounts of mineral ballast and concentration have mines described by symbols 1,2,6 and 7. TOTAL-REFLECTION X-RAY FLUORESCENCE ANALYSIS FOR EFFECTIVENESS OF MICROFILTRATION MEASUREMENTS M. Buczkowski, J. Kierzek, D. Wawszczak, U, Waldschlftger 1/ PL9702126 v Institut fUr Umwelttechnologien GmbH, Berlin, Germany Studies were undertaken in order to establish the tability limits about 1 ppb for most elements of the usability of total-reflection X-ray fluorescence analy Periodic Table [1,2]. sis (TXRF) to determine the filtration , effectiveness Environmental samples consisting of 3 kinds of for track membranes. The TXRF method has detec water, 3 samples of drinking water, and 3 samples of Table. Concentration of different elements in 5 samples before and after filtration. ♦ • • • • Sample -* lc lc 2c 2c 8c 8c 9c 9c 12 12 Element R.F.I. Cone, mg/1 i S 0.015 103.264 98.779 229.753 247.506 9.808 11.515 15.760 20.100 Cl 0.025 1.316 0.715 116.501 115.538 0.415 0.422 0.346 0.000 1138.272 1594.579 K 0.043 26.169 24.413 21.120 18.830 2.146 2.690 18.468 15.423 84.995 75.742 Ca 0.102 85.248 81.984 253.003 272.031 16.387 16.722 9.914 10.864 26.851 25.329 Ti 0.152 V 0.151 0.062 0.044 Cr 0.242 Mn 0.272 0.118 0.134 0.165 0.117 0.199 0.163 Fe 0.332 2.903 0.509 4.012 0.207 1.851 0.190 2.100 0.074 2.586 0.890 Ni 0.525 0.068 0.035 0.026 0.062 0.041 Cu 0.616 0.019 0.025 0.019 0.020 0.035 0.023 Zn 0.709 0.350 0.288 0.133 0.119 0.688 0.451 2.339 1.488 0.092 0.586 Br 1.762 0.139 0.106 0.218 0.191 0.024 0.025 0.036 0.030 0.208 0.145 Sr 1.646 1.119 1.088 0.816 0.845 0.049 0.049 0.114 0.106 Rb 1.975 0.022 0.018 Y 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 Pb 0.770 0.021 0.014 0.013 0.012 0.027 0.010 Ba 0.088 0.043 0.147 0.098 • results of measurements after filtration, lc, 2c - samples of drinking water. 8c, 9c - environmental samples of water from snow. 12 - a biomedical sample of physiological multielectrolytic solution. R.F.I. - relative fluorescence intensity. NUCLEAR TECHNOLOGIES AND METHODS 103 physiological solutions applied in medicine, were such a case, it is possible to determine the filtration prepared. Standard samples (without filtration) and effectiveness in dependence on micropores diameter. samples obtained after filtration through syringe Recapitulating, one can state that the total-reflec filters (among others, disposable syringe filters tion X-ray fluorescence analysis can be useful for the mass-produced in Poland on the licence contract determination of effectiveness of small volume filtra between "Q3" firm, this Institute and the Warsaw tion systems. University of Technology), were used [3]. Filters Work enabling the determination of mechanism containing track membranes of various pore size (0.1, and effectiveness of microfiltration for different track 0.2, 0.45, 1.3 jum) were applied. In the obtained membranes is forecasted. samples of the filtrate, the following elements S, Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Br, Sr, Rb, Pb were References determined. As an inner standard, Y was taken. [1] , Proc. of the 3rd Conference on Particle Track Membranes Measurements were carried out using the TXRF and their Applications. Jachranka, Poland, 26-29 October apparatus named PICOTAX, which was elaborated 1993. Eds. W. Starosta, M. Buczkowski. Institute of Nuclear and set working in Institut fiir Umwelttechnologien Chemistry and Technology, Warszawa 1995. (IUT) in Berlin (Table). [2] , Prange A., Schwenke H.: Trace element analysis using total- The gathered results allow to state that in the reflection X-ray fluorescence spectrometry. Adv. in X-Ray Analysis, 35,899-923 (1992). filtration process the track membranes whose diame [3] . Kielkiewicz J,, Buczkowski M., Starosta W., Olczyk P., Z6ho- ter belongs to the 0.1-1.3 fim range do not eliminate wski T., Meinhardt E., Frydrych H., Fiderkiewicz A: Sposdb substances being in the state of solutions. Elements wytwarzania nasadek filtracyjnych oraz nasadka filtracyjna. able to form conglomerates, for example Fe or Mn, Patent Application P. 302 895. are held on the filtration membranes surface and, in 104 RADIATION TECHNOLOGIES 'L9702 27 RADIATION TECHNOLOGIES RADIATION STERILIZATION OF MEDICAL DEVICES I. Katuska, Z. Stuglik Sterilization is defined as validated process used to - short exposure times with minimal oxygen gene render a product free from viable microorganisms rated degradation of irradiated materials; and is described by an exponential function. There - focused electron beams with controlled penetra fore, the presence of microorganisms on the indivi tion gives a high beam power utilization efficiency; dual item can be expressed in terms of probability. - small treatment zones with few packages in a While the probability may be reduced to a very low beam room which allows for quick changes for number, it can never be reduced to zero. The proba different products; bility can be expressed as a sterility assurance level - easy change of accelerator parameters allowing (SAL), it means the probability of a viable micro to accommodate different process requirements organism being present on the product unit after for various products. sterilization [1]. Additionally: There are several chemical and physical methods - process validation need not be repeated after of sterilization. In the case of radiation sterilization, routine maintenance of the equipment; inactivation of microorganisms occurs either through - accelerator can be shut off when not needed, to direct ionization of a vital cellular molecule (DNA, reduce operating costs and simplify maintenance; key enzyme, etc.) or indirectly through the reaction - after shut off there is no radiation emission so of the free radicals produced in the cellular fluid. accelerators are perceived to be less dangerous For radiation sterilization one applies ionizing than radioactive sources [2], radiation from: There are two international standards corcerning - radioactive isotopes (gamma rays from Co-60 or radiation sterilization, ISO 11137 and EN 552, rarely, from Cs-137); where one can find a typical validation programme - accelerators of particles (high-energy electrons). for radiation sterilization process. The choice of radiation source for a particular ISO 11137 contains the main section where step application depends on such requirements as pro by step is descibed the sterilization process valida duct configuration, minimum dose, max./min. dose tion and also three infoimative annexes are includ ratio, economical factors, etc. ed: The Institute (INCT) has been promoted radiation - device and material qualification (Annex A), sterilization with high-energy electrons for over 20 - dose-setting methods of radiation sterilization years. Two accelerators have been used for this pur (Annex B), pose: the LAE 13/9 and ELEKTRONIKA10/10. The - dosimetry and equipment control (Annex C). LAE 13/9 is the first accelerator installed in the INCT and is used also for other tasks like polymer crosslink References ing or pulse radiolysis. The ELEKTRONIKA 10/10 is located at the Pilot Plant for Radiation Sterilization [1] . Standard ANSI/AAMI/ISO 11137-1994. [2] .Cleland M.R., O’Neill M.T., Thompson C.C.: Sterilization and is used only for radiation sterilization. with Accelerated Electrons. InL Sterilization Technology. The main advantages of electron beam steriliza Eds. R.F. Morrissey, G.B. Philli] tion are: New York 1993, pp. 219-253. PL9702128 GERMINATION TEST APPLIED TO IRRADIATED GRAIN AND CORN K. Malec-Czechowska, A M. Dancewicz, Z Szot Irradiation of grain destroys moulds and insects cation whether a given food has been irradiated or prolonging effectively storage time, even for years, not become urgently needed. Few methods have without worsening the quality of cereals or com. been developed and even applied in practice, but Although the FAO/IAEA/WHO committee of ex others are still investigated [2]. In our quest for perts already in 1980 concluded that irradiation of such methods we have started to check the germi food commodities with doses up to 10 kGy does not nation of irradiated grains. Germination was found pose toxicological hazard or other nutritional prob to be diminished after irradiation of wheat with lems [1], there are countries where irradiation of doses over 3 kGy, while the growth of shoots and food is not permitted. Hence, methods for identifi roots was inhibited at lower doses (0.33-0.5 kGy) NUCLEAR TECHNOLOGIES AND METHODS 105 [3], Thus, the germination test and measurement of DUET variety. All these varieties were of Polish the elongation of shoots and roots can be a method origin from 1996 crops and were obtained from a of choise for checking, whether grain was irradiated. local Station distributing sowing grains. The results reported here confirm, in general, that Irradiation was carried out using a cobalt gamma radiation inhibits the growth of shoots and roots of source (ISSLEDOVATIEL) with a dose rate of the studied grain and corn when the dose delivered 4.92 kGy/h. The doses applied on a time basis were was higher than 300 Cry. 100,300,500,800,1000,1500, and 2000 Gy. The following cereals were used in this study: Few days after irradiation all seeds, unirradiated winter rye, WARKO variety, winter wheat, ROMA also, were checked for their germination power variety, winter barley, SIGRA variety and corn, using the standardized method of placing seeds CORN " DUET " CORN "DUET" to-r 80 70 80 50 t 40 t u u 30 20 10 0 1 CO XX) 500 800 1000 1500 2000 DOSE, Oy eo 50 I* l ” 10 0 RYE "WARKO* 143 ■ 0 100 300 500 800 1000 1500 2000 D0SE,9y Fig. The effect of gamma irradiation on the growth of com, tye and wheat grains incubated 7 days at 22°C. The mean±SD of shoots and roots length is given. 106 RADIATION TECHNOLOGIES onto a wet filter paper in a covered flat box con of roots growth was observed already after irradia taining 50 ml of water, and keeping it at 25 ±1°C. tion of grains with 100 Gy. A significant inhibition The germinated seeds were counted after 3,5 and 7 of roots growth was caused by irradiation doses of days and the per cent of germinated seeds was 300 Gy and higher. The growth of shoots was not calculated. retarded in seeds irradiated with the 100 Gy dose Table. Per cent of germinated grains in dependence on irradiation dose and incubation time at 25°C. Dose [Gy] No. Grains Incubation days 0 100 300 500 800 1000 1500 2000 Per cent of germinated grains 3 99 98 99 98 97 95 96 96 1 Com DUET 5 99 98 99 99 98 95 96 96 7 99 98 99 99 98 95 96 96 3 95 86 91 84 87 92 88 88 2 Winter iyeWARKO 5 95 86 91 84 89 92 88 92 7 95 86 91 84 89 92 88 92 3 97 96 97 94 92 94 89 95 3 Winter wheat ROMA 5 97 96 97 94 92 94 92 95 7 97 96 97 94 92 94 92 95 3 92 91 94 90 90 90 95 97 4 Winter barley SIGRA 5 92 93 95 92 98 96 96 97 7 92 93 95 92 98 96 96 97 To measure the length of shoots and roots, 25 with the exception of rye. Irradiation with doses of seeds were placed on a wet A4 sheet of filter paper 300 to 2000 Gy effectively inhibited the growth of along its longer side. Then, the seeds were covered shoots in all the grains investigated. Similar effects with a 2 cm wide strip of wet filter paper and the were observed after 5 days of incubation while, at 3 whole sheet was rolled up and placed in a beaker day difference between the control and the irra containing small volume of water. In one beaker 7 diated seeds was less pronounced. The results ob rolls were placed with irradiated seeds and one with tained lead to the conclusion that the germination unirradiated ones. The beakers were covered with test cannot reveal whether grain has been irradiated plastic caps to prevent evaporation of water. All the with doses up to 2 kGy. On the other hand checking samples were incubated at 22 ±1°C. Measurements the growth of shoots and roots 5 to 7 days after sow were made after 3,5 and 7 days of incubation. ing might prove to be a good method for identifica The mean values and their standard deviations tion of grain irradiated with such doses. Because of were used for constructing graphs indicating dose some differences in response of various grains to dependence on the growth of shoots and roots. the doses applied, further study with a larger The germination power of irradiated seeds used collection of grain varieties seems to be advisable. in this study is illustrated by figures in Table, where The work reported here was sponsored by the per cent of seeds germinating after 3, 5 and 7 days Polish State Scientific Research Committee - grant of incubation at 25°C is listed. Almost all the seeds, no. 5 PG6G 00109. irrespectively of the irradiation dose applied (up to 2000 Gy) germinated already after the third day of References incubation. Zhu et al. [3] have reported that inhibi tion of wheat germination began at 3300 Gy and [1] . Wholesomeness of irradiated food. WHO Techn. Rep. Ser. was completely sloped at 10 kGy. No. 659. Geneva 1981. [2] . Stevenson M.H.: Detection methods for irradiated food. In: Dose dependence of the length of shoots and Schreiber G.A, Helle N., Bogl K.W.: New Developments in roots of seeds grown for 7 days at 22°C is presented Food, Feed and Waste Irradiation. Soz. Ep. Hefte, 16 (1993). in the form of graphs in Fig. Similar graphs were [3] . Zhu S., Kume T., Ishigaki J.: Radial. Phvs. Chem.. 42. constructed using the data obtained for seeds in cubated 3 and 5 days (not shown here). Retardation PL9702129 SPATIAL DOSE DISTRIBUTION IN REACTION VESSEL MEASUREMENTS USING PVC AND CTA FILMS P. Panta, S. Butka, W. Ghiszewski Polymer film dosimeters (PVC and CTA foils) for KAWE Table 1 Energy of electrons 500 to 700 keV Instability of electron energy 5% Average electron beam current (max.) 100 mA Instability of electron beam current 5% Average electron beam power (max.) 50 kW Homogeneity of linear density of scanned beam measured at the distance of 50 mm 10% from output Fig.2. Positioning of the metal frame during dose distribution Outup window dimensions 75 x 1500 mm measurements inside the process vessel. Thickness of window titanium foil 50 pm (it is controlled by a computer program elaborated Maximum electron beam scanning angle 30° in the Institute of Nuclear Physics at Novosibirsk). 1.5 nrVh Cooling water flow rate Radiation induced absorbance of PVC and CTA 200nrVh Cooling air flow rate stripes was spectrophotometrically sampled accord After critical selection of published dosimetric ing to Tanaka [4] and Bulhak [5] with the step of 3 methods only two polymer systems i.e. PVC and CTA cm along each stripe. At the lowest energy (i.e. 500 Table 2. Polymer foil CTA (41 PVC (51 Composition (Ci2Hi608)n cellulose triacetate 85%, triphenyl phosphate (CzHgClJn polyvinyl chloride 98% about 15% Manufacturer FUJI., Ltd. Kunstoffwerke Staufen Thickness 0.125 mm (±5%) 0.26 mm Width of tape 8 mm 8mm Specific weight 1.32 g/cm 3 1.4 g/cm 3 Electron density 3.18 x 10^3 e/g 3.15 x 1023 e/g Effective atomic number Z 6.7 11.37 Effective Z/A* 0.526 0.5 Mass stopping power: 1 MeV 1.75-1.8 MeVcmz/g 1.64 MeVcmz/g Linearity range 10-200 kGy 5-50 kGy Wavelength of measurements 279.9 nm 394 nm Precision of measurements 8-10% 6-10% foils were chiefly used for spatial dose distribution keV) the reading level from the seventh film stripe measurements (Table 2). of the matrix the closest to the bottom was undis- Spatial dose distribution inside the process vessel was measured by both PVC and CTA film dosimeter tapes cut in the form of long stripes of about 115 cm. The dosimetric film stripes were placed in a especial ly designed square frame (shortly speaking "holder") of external dimensions approximately 113 x 113 cm in seven levels of 20 cm step (Fig.l). Fig.l.Schematic presentation of the metal frame for stretching PVC and TCA dosimetric stripes inside the process vessel. Fig.3. Radial dose distribution for 500 keV electrons. The total EB charge transferred to the system is 500 mAs. The For radial dose distribution measurement the average EB current is 1 mA Dose is expressed in kGy. frame positioning was perpendicular to the geome trical axis of the process vessel. Longitudinal dose tinguishable from the unirradiated film absorbance. distribution determination needed consecutive shift Obtained measurement results are presented in ing of the frame along the main geometrical axis of Figs. 3 and 4. the process vessel with a step of 35 cm. Only four steps were enough for measurement inside the Conclusion spatial dose distribution zone (contour). The frame Results of spatial distribution measurements of construction secure to avoid the mutual self-screen the electron dose from the ELV-3A accelerators ing of the dosimetric film stripes (Fig.2). mounted on the process vessel at electron energies The measurements were performed at 500, 600 of 0.5, 0.6 and 0.7 MeV are presented as isodose and 700 keV of electron energy and 1 mA EB curves. Electron beams of both ELV-3A accelera current to keep the 500 mAs integral value constant tors do not interfere with each other because their 108 RADIATION TECHNOLOGIES References /// / / [1] . Panta P., Bulka S., Gtuszewski W.: Dose distribution mea surements in reaction vessel of pilot plant at EPS "Kawq- czyn". Raporty IChTJ. Seria A nr 1/97, in print. [2] . Chmielewski A.G., IUer E., Romanowski M.: Pilot Plant for Electron Beam $02 and NO* Removal from Combustion Flue Gases. Report INCT-2125/VI. Institute of Nuclear Chemistiy and Technology. Warszawa 1991. [3] , Chmielewski AG., Zimek Z, Panta P.P., Drabik W.: The Double Window for EB Injection into the Flue Gas Process Vessel. Radial. Phys. Chem., 45(6), 1029-1033 (1995). Fig.4. Axial dose distribution for 700 keV electrons (500 mA-s, 1 [4] , Tanaka R., Yotsumoto K., Misuhaski K., Tamura N.: JAERI mA, kGy). memo 6948,1977. [5] , Buthak Z.: An application foil dosimetry for the linac mutual distance along the geometric axis of the pro "LAE-13/9" commercial irrac cess vessel is about 2 m. INR, Warszawa 1976. PL9702 30 INVESTIGATIONS OF STRUCTURAL CHANGES IN HEAVY IOin IRRADIATED POLYESTER FILMS K. ClcSla, E. Ferain!/, K. Grzebieniak2^ R. Legras 1/, H. Frydrych 1Z Unit6 des Hauls Polymeres, UniversitS Catholique de Louvain, Belgium 21 Institute of the Chemical Fibers, L6dt, Poland Physico-chemical changes occurring in polymer films (PBTP) and biodegradable copolimers of PETP with under the influence of heavy ion irradiation were lactic add (PETP-LA) were selected. studied. This work is connected with the search for Granules with four compositions of PETP-LA new materials for heavy ion detectors and particle (containing 14.1-34.3 wt. % of LA) were prepared in track membranes (PTM). The knowledge about the the Institute of Chemical Fibers in L6d2. The device processes occurring during irradiation and identifica used for making the films was constructed in the tion of the resulting products is essential for the selec Department of Structural Research, the INCT, and tion of the etching conditions and production of PTM. thin polymer films (23-30 fiva) were prepared by Our previous studies [1-3] were concerned with chemical precipitation from chloroform solution. A physico-chemical transformations taking place under series of PBTP films (70-80 fim thick) were prepared the influence of heavy ions irradiation on poly(ethyl- by hot pressing of commercial granules (products of enetherephthalate) (PETP), a very common ma terial used to make PTM. Now, studies have been started on the influence of heavy ion irradiation on physico-chemical properties of films prepared from other polyesters. The poly(butylenetherephthalate) 69.0 - M.o- 220.8=1 84.0 - 59.0- 81.0 - Temperature (=C) Fig.2. Tg transformation and effects of structural relaxation in the amorphous state recorded during the second heatig to 200°C of unirradiated and irradiated (Ar ions, 5.5 MeV/u, 10*1 ions/cm^) PETP-LA films with LA content equal to 47.0 - 14.1%. 250.0 Jelchem, Poland, and of G.E.), applying different Fig. 1. Melting endothermal effects observed during second heat heating and cooling conditions. The samples of ing of a selected PBT film, uniiradiated and irradiated with PETP-LA films were irradiated in UCL with Ar ions Pb ions (5.5 MeV/u, fluence 10*® ions/cm^). (5.5 MeV/u) with a fluence of 10n ions/cm 2. The NUCLEAR TECHNOLOGIES AND METHODS 109 PBTP films were irradiated in GSI, Darmstadt, with in the processes, like Tg transformation, structural Pb ions (11.4 MeV/u) applying fluences of 109 and relaxation in the amorphous phase, melting behav 1010 ions/cm 2. iour and exothermal processes taking place during The WAXS results show the presence of a large heating of the reference and the irradiated films. but different amount of amorphous phase in all the PETP-LA films and the differences in the crystal References linity of the PBTP films. These differences were confirmed by infrared spectroscopy (FTIR) results. [1J. CieSla K, Trautmann Ch., Vansant E.F.: Physico-chemical changes occurring in heavy ions irradiated thin polymer foils Raw and irradiated films were examined applying by differential scanning calorimetry. Proceedings of the 3rd differential scanning calorimetry (DSC) and FTIR International Conference on Particle Track Membranes and (transmission and reflection patterns). The results their Applications, Jachranka, Poland, 26-29 October 1993. Institute of Nuclear Chemistry and Technology, Warszawa show that structural transformations occur in the 1994, pp. 31-34. amorphous and crystalline phases of the polymers [2] . CieSla K., Trautmann Ch., Vansant E.F.: Nukleonika, 4Q, 3, and the new chemical products in the PBTP films 141-152(1995). were formed after heavy ion irradiation. In particular, [3] . CieSla K., Starosta W.: Nucl. Instr. and Me" the DSC results made possible to observe differences m 115-119(1995). L9702 POSSIBILITIES OF INSTRUMENTAL NAA APPLICATION FOR MULTIELEMENT LARGE-SCALE ANALYSIS OF MATERIALS IMPORTANT FOR ECOLOGY AND GEOLOGY M. Wasek, Z. Szopa, R. Dybczynski Neutron activation analysis (NAA) [1] and its radio ammounted to 8000 and 12000 counts/s, respectively. chemical version (RCNAA) [2, 3] as well as the The ways of correction of these types of errors in case instrumental one (INAA) [3,4] have been widely ap of a need of measurements for which the total plied in science and technology. In the recent years, it counting rates exceed the above limits have been plays a significant role in trace/ultratrace analysis and proposed as well. as a control method for other analytical methods and The other group of errors establish those ob techniques [2, 5]. This is mainly due to the very good served at the stage of gamma-ray spectra analysis detectability (low detection limits) for the majority of itself, performed with the aid of the commercial elements, its ability for multielement analysis, the software TUKAN. The reliability of two different commonly used purely instrumental version and ways of the analytical signal processing has been generally its good precision and accuracy i.e. its high estimated taking into account and comparing the reliability. Furthermore, due to the common use of results of quantitative analyses of samples contain high-resolution gamma-ray and/or X-ray spectrome ing filters with the air-born pollutants and the ters together with the appropriate software and the samples of tobacco leaves. A malfunctional perfor general ability of INAA to automatization - which mance of automatic peak searching procedure has enables large-scale routine analyses - this method has been found. The errors, measured in the means of become more attractive among the other, non-ex- relative standard deviation, reach 50% for some pensive and fast methods for chemical analysis [2,6], analytical signals. For routine analyses, the method The purpose of the present work was the ability where one selects the region of a peak, has been recognition of the application of multielement INAA recommended because the results obtained with the for large-scale analyses of samples of ecological use of this method were not biased. Furthermore, and/or geological origin with a special attention be the latter method fulfils criteria of both the preci ing paid to the analysis reliability [4,6, 7]. A general sion and accuracy at given concentration levels. An scheme of INAA used in this work as well as the alternative approach for automatic spectra pro present state of equipment and software, serving for cessing on large-scale routine analyses [6] is the use processing and interpretation of gamma-ray spectra, of the package SAWAP. When compared with the has been presented. Subsequent stages of multiele commercial software it has got numerous various ment analysis were described, especially those, where options and features [9] and together with the potential systematic and random errors that might accompanying procedures it serves for "off-line ” reflect the analysis reliability could be expected [7]. spectra analyses. It could be used at the stages of The first group of errors are those arriving due to both the qualitative as well as quantitative analyses. the frequency overload of the spectrometric lines [8]. For a selected group of problems, concerning the As a result of appropriate experiments, the limits analysis of overlapping peaks, the use of a procedure of the total counting rates (i.e. the counting rates in called the DUBLET has been proposed [10,11]. the whole spectrum) have been determined for two The last group of errors investigated in the present types of measurement. One type of measurements work were the errors arriving at the stage of irradia has been performed with the aid of life-time mea tion of large packages of samples in a nuclear reac suring option, the other ones - using the pulser tech tor. These errors have come from the gradient/micro nique. The obtained limits of total counting rates gradient of neutron flux that could be observed along 110 RADIATION TECHNOLOGIES the irradiated package. The magnitude of this error [4] , Non-destructive Activation Analysis. Ed. S. Amiel. Elsevier, type has been estimated as being of the order of 30%. New York 1981. Correction of the final results, taking into account [5] , Reeves R.D., Brooks R.R.: Trace Element Analysis of Geological Materials. Wiley-Interscience Publication, New the above phenomenon, has been proposed. York-Chichester-Brisbane-Toronto 1978. Conclusions concerning the possibilities of large- [6] .Szopa Z., Dybczyliski R., Kulisa K, Sterliliski S.: Chem. scale, routine INAA analyses performed in the Anal. 39,497 (1994). Laboratory of Radiometric Methods have been [7] , Sterliliski S., Dybczyliski R, Szopa Z, Kulisa K., Kaczo- reached. The present state of equipment as well as rowski J.: Chem. Anal., 32,551 (1987). the existing software therein have been taken into [8] , Wasek M.: Ph D. Thesis. 1991. account and discussed. Some needs for the future [9] . Szopa Z., Staszelis J., Plejewska M.: INR-1945/V1I1/E/B. progress, concerning the equipment and develop Warszawa 1982. ment of the software serving for multielement [10] . Sterliliski S., Wasek M.: Melody analizy pikdw natozonych w routine analyses have been pointed. analitycznej spektrometrii promieniowania gamma. Cz. 1. We lyfikacja prostych metod analizy. INCT-2077/VIII/C/B. Insti References tute of Nuclear Qiemistry and Technology, Warszawa 1989. [11] . Sterliliski S., Wasek M.: Melody analizy pikdw natozonych w [1] . De Soete D., Gijbels R., Hoste J.: Neutron Activation Analysis. analitycznej spektrometrii promieniowania gamma. Cz. 2. WUley-Intersdence, London-New York-Sydney-Toronto 1972. Nowa meloda analizy dubletdw. INCT-2078/V1I1/C/B. Insti [2] . Dybczyliski R : Chem. Anal., 30,749 (1985). tute of Nuclear Chemistry and Technology, Warszawa 1989. [3] , Hoste J., Op de Beeck J., Gijbels R., Adams F., Van den Winkel P., De Soete D.: Instrumental and Radiochemical Activation Analysis. Butterworths, London 1971. NUCLEAR TECHNOLOGIES AND METHODS 111 PL97021 32 NUCLEONIC CONTROL SYSTEMS RADON MEASUREMENTS IN AIR B. Machaj Activities concerning measurements of radon as An air pump and an air filter that are incor well as radon daughters concentration in the air porated in the outfit of the measuring stand permit were continued in two directions: to remove radon daughters from the air fed to - Construction of a laboratory stand for ex radon concentration gauges under investigations. perimental measurements of radon and radon To investigate the variation of the activity of radon daughters concentration. daughters deposited on the air filter, a computer - Development of computer programs for simula controlled programmable pulse counter was de tion of radon and radon daughters monitors in veloped and was incorporated into the outfit of the the air. measuring stand. Computer program of the counter permits for basic statistic processing of the Laboratory stand obtained results. The latter are also stored on the The main component of a laboratory stand for computer disk in ASCII format for further pro measurement of radon and radon daughters cessing or making diagrams of the count rates concentration in the air is a radon chamber. A (activity Po-218+Po-214) against the elapsed time. Ra-226 radiation source in the form of liquid An additional air pump allows for flushing the solution, contained in an open aluminum container measuring chamber with fresh (ambient) air. is placed in a 5 1 chamber. The Ra-226 source of activity 170.31 kBq, after liquid solution being Simulation of radon decay products monitors evaporated, is deposited in the form of a thin Employing known relations describing decay crystalline layer at the bottom of the container. series of three radionuclides A -» B -* C [1,2]: Efficiency of the Ra-226 source, as radon generator, A = Aoe" AAt (1) defined as the ratio of the number of radon to the number of Ra-226 disintegrations is 18.4% at B = B0e-AB‘ + Ao (e~* At - e~*B») (2) radiation equilibrium state, producing radon con centration of 6.25 Bq/cm 3 inside the chamber of the C = Coe- ;ct + Bq (e~ABt _ e-'ici) + Ra-226 source. The efficiency was measured with calibrated Lucas cells. To produce variable radon + Ao(h Ae-AAt + hge^Bt + hcC-lct) (3) concentration a known gas volume of highly con where: centrated radon from the Ra-226 source chamber is injected to the 0.8 m3 radon measuring chamber , Aa Ag Aa Ag A Ac - Aa Ag - A a’ b Aa - Ag Ac - Ag ’ where investigated instruments for radon and radon k _ _ Aa Ag decay products are placed. Known volumes of gas bc-%A^%cZF^3? samples from the Ra-226 source chamber to a measuring chamber are withdrawn by means of a Ao, Bg, Cg - number of atoms of nuclide A, B, C at medical syringe. The needle of the syringe is intro time t = 0; duced into the chambers through rubber mem A = 0.693/Ti# - decay constant of the nuclide; branes at the input of air valves, ensuring thus the T1/2 - half period of the nuclide, tightness of the chambers during sampling. A typi and relation to their activities: A@= Aa A, Ba=AgB, cal sample of 100 cm3 taken from a 5 1 volume of Ca=AcC, a computer program was developed for the Ra-226 source chamber contains 612.7 Bq of the computation of activity of Po-218, Pb-214 and radon activity (dilution of radon to 5100 cm3). The Bi-214 (Po-214) deposited on an air filter against sample introduced to the radon measuring chamber elapsed time. Deposition of radon daughters on the produces a radon radioactivity of 766 Bq/m 3. The air filter is simulated in the following manner [3-7]. ambient pressure, temperature and relative humi The number of radioactive decay products collected dity are controlled inside the measuring chamber. A on the filter within 1/10 min is introduced as Ay, B0 grab sample of radon decay products concentra and Q> in equations (1-3) and their activity is com tion gauge with a 10 L air sample forced to flow puted every 1/10 s against time of such single por through the investigated gauge air filter in the tion of activity. To simulate the activity deposited measuring chamber, causes a decrease of the radon on the air filter within sampling time T an appro daughters concentration by 10/800 = 1.3% which is priate number of such portions are summed. For reasonably low figure for such a kind of investi example to simulate a 5 min sampling time 50 such gations. spectra are summed (Fig.). The program allows for 112 NUCLEONIC CONTROL SYSTEMS RADON DECAY PRODUCTS that set limits to the sensitivity of the gauge. The Po-218:Pb-214fli-214 « 200:100:50 daAnin two interval method exhibit lower statistic errors but introduces errors from the deficiency of the me Legend thod. Its advantage is the shortest measuring cycle. A - Po-218 The one count method can be used for the determi B- Pb-214 nation of alpha energy only and exhibits the lowest C- BL214 (Po-214) statistic error, but the measuring time is long. Table. Measuring errors of simulated methods. Type of Method AA [%] AB [%] AC [%] AEp [%] error Three method < 0.1 < 0.1 <0.1 <0.1 count 30 statistic 17.0 24.6 39.9 9.4 1x = 1/10 min min 36.5 Fig. Distribution of the activity of the decay products deposited on Two count method 24.4 49.3 18.3 the air filter. The activity of the decay products deposited on 15 min statistic 22.1 7.3 21.9 7.3 the filter within 1 min is: Po-218:Pb-241:Bi-214 * 200:100:50 One count method - - - 11.2-14.2 dis/min. Sampling time T - 5 min. 40-60 min statistic - - - 2.3-34 the simulation of activity for different degrees of The measured statistic errors of alpha energy of radiation equilibrium of the decay products, as well two gauges employing the two count method, as the activity of the decay products registered at during International Intercomparison organized in the selected time intervals with a selected detection 1994 by the International Protection Agency (EPA) efficiency of the deposited activity, allowing thus and the International Atomic Energy Agency simulation of grab sample gauges. Alpha energies (IAEA) in Las Vegas [14] were 10.0% and 11.6% of the decay products are also computed. Results of relative at 0.069 .. 0.089 WL concentration (in the measurements are stored on the computer disk radon chamber), whereas the simulated error for for further processing or drawing diagrams. such a gauge is 11.7% at 0.08 WL. This result quite Employing the above program, three types of well agrees with the measurements. grab sample gauges operating on the principle of References registration of alpha radiation of Po-218 + Po-214 at different time intervals of the deposited alpha [1] . Evans R.D.: The atomic nucleus. McGraw-Hill Company, 1970,972 p. activity were simulated. They included: a gauge re [2] , Nazarotf W.W., Nero A.V.: Radon and its decay products gistering alpha particles activity at one time interval in indoor air. John Willey & Sons, New York 1988. within 21 .. 60 min [8], at two time intervals 7 .. 9 [3] . Machaj B.: Obliczanie koncentracji radonu i jego produktdw min and 13 .. 15 min inclusive [9-11], and at three rozpadu w funkcji czasu. Program komputerowy. Raporty time intervals 1 .. 10 min, 11 .. 20 min and 21 .. 30 IChTJ. Seria B nr 6/96. Institute of Nuclear Chemistry and min inclusive [12, 13] from the start of deposition Technology, Warszawa 1996. [4] , Machaj B.: Symulacje koncentracji produktriw rozpadu of the decay products on the air filter. The Rn-222 osadzanych na filtrze. Opis programu komputero- simulation was carried out for 5 min deposition wego radonl.pas. Raporty IChTJ. Seria B nr 7/96. Institute time, deposition and counting efficiency rj = 0.3, of Nuclear Chemistry and Technology, Warszawa 1996. and wide variation of radiation equilibrium degree [5] . Machaj B, Bartak J.: Some radiometric instruments for ranging from Po-218:Pb-214:Bi-214 = 200:200:200 environmental protection. Third International Symposium and Exhibition on Environmental Contamination in Central dis/min/L to 200:0:0 dis/min/L and the air flow and Eastern Europe, Warszawa, Poland, 10-13 September through the air filter 1 L/min. Simulated count 1996. Abstract no. 390, p. 153. numbers were processed according to the formulas [6] . Machaj B., Bartak J.: A microprocessor instrument of radon appropriate to the gauges. Relative errors resulting daughters in mines. International Conference on Technolo from the deficiency of the methods and statistic gically Enhanced Natural Radiation Caused by Nonuran ium Mining, Szczyrk, Poland, 16-19 October 1996. Central error resulting from counting statistics are given in Mining Institute, Proceedings, pp. 131-139. Table. Po-218, Pb-214, Bi-214 (Po-214) and alpha [7] , Machaj B., Bartak J.: Grab sample measurement of radon energy of decay products are denoted in Table as decay products in air. International Conference on Radio A, B, C and Ep, respectively. The errors of de isotope and Radiation Application in Industry and Environ ficiency of the method are the result of variation of ment - RRAI96, Berlin, Germany, 20-23 October 1996. Abstracts, p. 88. degree of radiation equilibrium between the radon [8] . Domatiski T., ChruScielewski W.: Med. Pr., XXVII. 29 (1976). daughters that are measured. Statistic error in [9] , Markov K.P, Ryabov N.V, Stas K.N.: Atomnaja Energia, 12, Table was computed for the degree of radiation 315 (1962). equilibrium described by the concentrations [10] . Gierdalski J., Bartak J., Urbartski P.: Nukleonika, 28, 4, 37 Po-218:Pb-214:Bi-214 = 200:100:50 dis/min depo (1993). sited on the air filter. Counting statistics of the [11] , IAEA Safety Series No. 95. IAEA Vienna 1989. registered pulses was computed from the relation: [12] . Machaj B.: Wstqpna ocena blqddw miemika koncentracji s(n) = VJn where n is the number of counts and produktdw rozpadu radonu w powietrzu. Raporty IChTJ. Seria B nr 8/96. Institute of Nuclear Chemistry and Tech J = 2.05 is the coefficient varying from 1.2.. 2.9. nology, Warszawa 1996. As expected, it can be seen from Table, that the [13] . Thomas J.W.: Health Phys., 23,783 (1972). method error is eliminated in the three count in [14] . Braganza E.B., Bud GJ.: US Office of Radiation and In terval gauge, but quite a large statistic errors exist door Air. Las Vegas 1994. Private communication. 19702133 NUCLEAR TECHNOLOGIES AND METHODS 113 APPLICATION OF ANN FOR CALIBRATION OF SOME RADIOMETRIC GAUGES E. Kowalska, P. Urbafiski Network 1. 28 spectra measured for the entire calibration set (original spectra); Since the middle of the last decade an increasing 2. 28 spectra as in case 1, but in the channels 34-90 drive towards application of the artificial neural instead of count rates their reciprocal values network (ANN) is observed. One of the field where were encountered; ANN offer a powerful set of tools for solving 3. 21 spectra from set 1; problems is non-linear mapping [1], or multivariate 4. 21 spectra from set 2. calibration of sophisticated measuring system [2-6]. The seven spectra were used for testing pre In our work we try to use ANN for calibration of diction ability of the calibration models with the some nucleonic gauges applying a low dispersive training data from set 3 and 4. Testing results of the XRF method. The "feed forward" network (Fig.) ANN calibration model are compared with the Par consisting of two layers: the first (hidden) with a tial Least Squares (PLS) regression model [8, 9]. Results are presented in Tables 1 and 2. Prediction Table l.Root mean square errors of estimation (RMSEE) and prediction (RMSEPr) obtained using ANN method. No. RMSEE [%] RMSEPr [%] 1 original spectra n=28 1.2 2 corrected spectra n=28 1.2 3 original n=21 1.6 1.25 spectra nl=7 4 corrected n«=21 1.0 0.84 spectra nl=7 ability of the PLS model was validated using cross- validation technique [9,10]. Comparing the achieved Fig. Diagram of the network. values of RMSEPr for ANN model with RMSECv for the PLS model it is seen that in both the cases variable number of neurons 1 and non-linear, tan- better results are obtained for the corrected spectra. sigmoid, transfer function f, and the second with The ANN calibration model seems to have slightly one neuron and linear transfer function F was used. Table 2. Root mean square errors of estimation (RMSEE) and The calibration model computed by the network crosvalidation (RMSECv) obtained using PLS method. can be expressed as: Number of No. RMSEE [%] RMSECv [%] ]£w2lfi (l)wUPl + bi) +Bzj. components A = F 1 original a=l 4.48 4.55 spectra n=28 a=2 1.99 2.09 where: pj - vector of inputs data; wy, w2i, bi, B2 - pa a=3 1.64 1.89 a=4 0.89 1.7 rameters to be estimated. Number of ANN inputs j is a=5 0.57 1.78 chosen individually for a given problem and equals to 2 corrected a=l 6.00 6.16 the number of channels in the spectrum. The input spectra n=28 a=2 1.31 1.49 data (in considered case a set of n spectra) were a=3 1.11 1.29 normalized so that all the presented to the network a=4 0.97 1.10 values were within 0-1 range. The backpropagation is a=5 0.54 1.16 used as a learning rule, so the values of weights w and better prediction ability than that computed using biases b are computed under the constraint to reach the PLS regression. It can be noted that the increas the predetermined value of either the sum of squared ing number of the PLS components above 4 does not differences between the reference and computed cause diminishing of the RMSECv value. values of the calibration set or the number of training epochs. Two parameters are used for validation of Measurement of thickness and composition the model, root mean square error of crossvalidation o/Sn-Pb layers and root mean square error of prediction. Determination of thickness and composition of thin Sn-Pb layers by the low resolution XRF me Determination of ash content in coal thod is rather difficult since a strong overlapping Intensity of X-rays of Pu~238 source back- of the peaks in the measured spectra is observed. scattered from a powdered sample of the black coal The problem can be solved using multivariate cali depends on its ash content [7], Calibration set of 28 bration technique, particularly the PLS regression coal samples of ash content ranging from 2 to 30% [11, 12]. It was expected, that better prediction was obtained from one of the Polish coal mines. ability of the calibration model can be achieved The four data sets were collected from measure using the ANN technique. A set of 24 reference ments of those samples and were used for training samples of Sn-Pb coating thickness ranging from 2 of the network: to 9.5 fim and the Sn content in the layer within 114 NUCLEONIC CONTROL SYSTEMS 60-81% was used for calibration and prediction case becomes much faster. It seems that better re testing. The X-ray spectra from 16 samples were sults of the coating thickness measurement obtain used as the training set and 8 for testing prediction ed for the ANN calibration model can be explained ability of the computed models. The network was by the fact, that relationship between the intensity learnt successively for each of the parameters of the registered radiation and the coating thickness (thickness and Sn content). Number of neurons in is strongly non-linear. It can be expected, that the the hidden layer varied from 1 to 4. The network ANN calibration model computed for the tansig- was learnt in two ways: moid transfer function should exhibit better pre 1 - preset values of weights and tresholds of the diction ability than the linear PLS model. One can neurons in the hidden layer were random numbers observe also that the number of neurons (SI) in the ranging from -1 to +1. first layer of the ANN corresponds to the number 2 - the weights of the hidden layer neurons were of the components in the PLS model. For SI = 4 chosen as the loadings computed by the PLS some overfiting can be seen, and the same effect regression for the same set of the calibration samp can be noticed for the number of PLS components les. higher than 4. Prediction abilities of both the ANN and PLS models are computed and results are presented in Conclusions Tables 3 and 4. The models were tested using the Presented results show that the linear calibration set of 8 prediction samples but for the PLS model models for the considered radiometric methods Table 3. Root mean square errors of prediction for different developed, using ANN and PLS regression, exhibit number of neurons in the first layer. a similiar performance. However, in the case of Training Determined non-linear models lower values of root mean Sl = l SI =2 SI =3 Sl=4 ANN with parameter square error of prediction were achieved using the Thickness 0.41 0.31 0.33 ANN technique. Slightly better results were ob random 0.35 [um] 0.45 0.27 0.27 1 weights and tained when the PLS loadings were included as biases Tin content 3.14 2.28 1.81 3.26 weights in the first layer of the ANN. Generally, [% Sn] 2.06 obtained results confirmed feasibility of the ANN weights of Thickness 0.25 0.27 as the method for developing multivariate calibra the first layer l«m] 2 0.28 0.28 tion models of the radiometric instruments, es as loadings Tin content 1.20 1.1 from PLS pecially in the case of non-linear relationship be [% Sn] 1.27 0.82 tween the measured quantity and the intensities of additionally the crossvalidation technique was also registered radiation. applied. It is seen that in the case of the coating References thickness measurement the RMSEPr value is consi derably lower for the ANN model than for the PLS [1] , Bishop C.: Rev. Sci.Instrum., 65,6,1803 (1994). [2] . Bos M., Weber H.: Anal. Chim. Acta, 247,97 (1991). Table 4. Root mean square errors of estimation!, crossvalidation and prediction for PLS regression. [3] . Bos A, Bos M., Van der Linden W.: ibid, 222,289 (1993). [4J. Bro R.: J. Chemometrics, 2,423 (1995). Determined Errors a=l a=2 a=3 a=4 a=5 [5] , Gemperline P, Long J., Gregoriu V.: Anal. Chem., 62, 2313 parameter (1991). RMSEE [pm] 0.625 0.417 0.210 0.100 0.05 [6] . Naes T., Kval K., Isaksson T., Miller C.: J. of Near Infrared Thickness RMSECv [pm] 0.605 0.457 0.362 0.409 0.41 Spec.,LI (1995). RMSEPr [pm] 0.646 0.520 0.350 0.395 0.41 [7] . Kowalska E., Urbafiski P.: Nukleonika, 22, 3,77 (1992). , E.: 70 RMSEE [%] 8.82 2.05 1.20 0.720 0.426 [8] Urbafiski P., Kowalska X-ray Spectrometry, 24, (1995). Tin content RMSECv [%] 8.29 2.40 2.42 2.59 2.63 [9] , Martens H , Naes T.: Multivariate Calibration. Willey & RMSEPr [%] 5.20 1.31 0.83 0.90 1.10 Sons, Chichester 1991. [10] Seculic S., Seasholtz M., Wang Z., Kowalski B., Lee S., Holt but for the Sn content determination the ANN 6.: Anal. Chem., 65, 835 A (1993). model gives generally worse results. However, when [11] . Urbafiski P.: Appl. Radial. Isot., 41,6,659 (1994). the PLS loadings are used as the weights of the [12] . Urbafiski P., Kowalska E., Antoniak W.: Nukleonika, 40, 1, neurons in the hidden layer the RMSEPr for Sn 61 (1995). content improves and the learning process in this PL9702134 DOSE READER B. Machaj, J. Strzalkowski, K, Smolko 1/ v Medical Apparatus and Electronics EMCO, Warszawa, Poland Functional diagram of a dosimetric foil dose reader, covering the range from UV up to IR light illustrating its principle of operation, is shown in wavelength. Selection of light wavelength range is Fig.l. The dose reader is composed of a two beam done by switching on a deuterium lamp for the UV spectrophotometer employing two light sources range or a halogen lamp for the VIS and IR range. NUCLEAR TECHNOLOGIES AND METHODS 115 The requested wavelength is selected by varying the play of the obtained results is done by a personal position (angle) of a monochromator in respect to computer. The personal computer controls also the incident light beam by means of a micrometer measuring cycles, and switches on/off the foil move screw. The light beam from the halogen or deuter- ment drive. i DL HL •X MS O^'—|fD^" NR CHV l8 U , L2 "01 V Dii* 1 DF 01 mMWvring 3C1 ?d-EH_ PC Fig.l. Functional diagram of computer controlled dose reader: HL - halogen lamp; DL - deuterium lamp; MS - mirror light switch; CH - light chopper; M - monochromator; MR - mirror reflector; LS - light splitter; LI, L2 - focusing lenses; DF - measuring diaphragm; Dl, D2 - photodiode; Al, A2 - pulse amplifier; GC1, GC2 - gain control circuit; A/Cl, A/C2 - analog to digit converter; MP - microprocessor system; RS - serial port; PC - personal computer; IF - computer interface; F - dosimetric foil; FD - foil drive. ium lamp is chopped 100 times a second, which Light intensity reaching light detector is given by facilitates amplification of the measured head the relation: signals. The monochromatic light beam is splitted J = J0e"kd (1) into two beams, one of them is directed to the mea where: suring channel the other to the reference channel. J0 - light intensity without dosimetric foil, Often only one light beam is employed in this type k - attenuation coefficient, of gauges [1], but a two beam solution enables com d - optical density. pensation of instabilities of the gauge, especially Absorbance of the foil is defined as (Fig.2): the instabilities of light sources. The light beam in Ax = = -log^ (2) the measuring channel after collimation passes through a diaphragm with an aperture of 5 x 1 mm and through the investigated dosimetric foil. where: Attenuation (absorbance) of the light beam by the S, = Jx - Jd - measuring signal; foil is a measure of radiation dose accumulated by S0 = Jo - Jd - maximum amplitude of measuring the foil. After passing the foil, the intensity of light signal. is detected by a photodiode, amplified and convert The ratio of the maximum amplitude of the ed into a digital signal that is primarily processed by measuring signal S0 to the maximum amplitude of a microprocessor system. Final processing and dis- the reference signal Sr is kr = So/Sr , thus Sc = krSr. Introducing this new value for SQ to eq. (2) one gets: measuring channel Sx (3) Ax — -log Srkr Processing signals according to eq. (3) allows for compensation of the variation of light source J = Jo cxp(-kd) instability. This requires only that during the calibration procedure the value of kr coefficient is measured and kept in the memory. The relation between the absorbance of the dosimetric foil and the radiation dose absorbed is described by the relation [2]: dx optical density Dx = kd(Ax - Ao) (4) where: Dx - absorbed radiation dose, Fig.2. Illustration of absorbance of the dosimetric foil. Jo - light kd - proportionality coefficient, intensity reaching photodiode when there is no foil in the measuring chamber, Jd - dark current (no light), J% - light Ax - absorbance of irradiated foil, intensity when foil present in the measuring chamber. Ao - absorbance of unirradiated foil. 116 NUCLEONIC CONTROL SYSTEMS Measured results, 1000 measuring points of the foil including description of the foil, are presented in the form of diagram (Fig.3) or in the form of a table and stored on a computer disk. Hardcopy of measuring results can be made if needed. A standard length foil up to 100 cm or up to 500 cm can be measured. A step motor driven foil ensures good indication of foil length. Variable foil drive speed ensures speed from 0.6 up to 5 cm/s. The dose reader was developed in the frame of contract no. 1280/C.T10-8/95 between the Institute of Nuclear Chemistry and Technology and the Polish State Committee for Scientific Research which provided financial support for the project. References [1]. Tanaka R, Sunaga H., Agematsu T.. Methods for measure ment dose and beam profiles of processing electron accelera Fig.3. Illustration of performance of dose reader. Dose showed in tors. International Symposium on High Dosimetry, Vienna, the diagram was computed according to eq. (4): D% ■= Austria, 8-12 October 1984. IAEA-SM-272/18. ly(Ax - Aq ), where kd = 100, Ao = 0. The diagram shows [2]. ASTM Subcommittee. Stand thus total absorbance of dosimetric foil. The absorbance acetate dosimetry system. 1 scale is 100 times smaller than the dose scale. Dosimetry for Radiation Pro< PL97021 35 NANOSECOND GENERATOR FOR THREE ELECTRODE ELECTRON GUN Z. D£wigalski, Z. Zimek The electron accelerator LAE 10 was designed to The principal circuit diagram of a 4 kV/10 ns deliver nanosecond pulses suitable for pulse radiolysis generator is presented in Fig.l. A transistor switch HTS 80-12-UF [4] was used. It can be triggered by a relatively slow pulse with an amplitude of 2-10 V. The switch is energised during approximately 10 ns. The typical pulses provided by the generator can be seen in Fig.2. The rise time t„ measured at the output of the generator depends on the total load capacitance Cq (Cq = load capacitance Cq + coaxial cable capaci tance Qc + montage capacitance Cm). In the case of Ro = Zf = Rs = 50fi and Co < 38 pF, the rise time Fig. 1. The principal circuit diagram of the 4 kV/10 ns generator. will be tn < 3 ns. It is well known that the shape of the pulse experiments [1, 2], To achieve this, a coaxial three depends on the relation between the coaxial cable electrode gun was built which is capable to form short parameters and the resistance R$ and Ro. Some pulses of electrons [3], A high voltage modulator (80 distortion of the pulse shape is caused by a stray kV, 100-200 ns) and a nanosecond generator (4 kV, inductance of the circuit which can be seen in Fig.2. Fig.2. Typical pulses provided by generator. 10 ns) should be applied to provide pulses necessary It is quite difficult to avoid the inductance Lp re for electron gun operation. The appropriate rise and lated to the connections between the circuit com fall time should be not higher than 3 ns. Good quality ponents. When the current rise is high (di/dt < 50 R and C components must be used as well. A/ns) a 10 mm long wire (corresponding to Lp = 10 PL97021 36 NUCLEAR TECHNOLOGIES AND METHODS 117 ns) may introduce a distortion signal with an ampli [2]. DZwigalski Z., Zimek Z.: Elektronika, 6,19-21 (1994). tude of several hundred volts. [3J. Diwigalski Z., Roman K.: Wyrzutnia elektronowa liniowego akceleratora elektrontiw LAE 10. 6th Corf. ELTE‘97, Kiyni- References ca, Poland, 6-9 May 1997, in press. [1], Zimek Z.: Radial. Phys. Chem., 3& 2,81-83 (1990). [4], Fast high voltage transistor switches. BEHLKE Catalogue. 80 kV/100 ns ELECTRON GUN MODULATOR OF LAE 10 ACCELERATOR Z. Diwigalski, Z. Zimek An acceleration process requires certain initial switch. It is triggered by an HTS 31 transistor unit parameters of electron beam at the input of the which can deliver strong pulses without any pulse acceleration section of a LAE 10 accelerator [1, 2]. transformer. This unit is energised during 100 ns omr + iiw HTS Si Tin Fig.l . 80 kV/100 ns electron gun modulator circuit. The electrons should have a velocity of v = 0,5c which is sufficient to charge the Ci capacitor. The which corresponds to an electron energy of 80 kV. stable trigger pulses with an amplitude of 800 V were This can be obtained by using the voltage pulses obtained owing to the diode forming circuit. Such a between the anode and cathode with an amplitude configuration may accept a relatively high supply of 80 kV to operate the electron gun. voltage fluctuation (±15%) without any significant A pulse modulator was designed and built to pro change of the trigger amplitude. vide the pulses with the 80 kV amplitude and a pulse duration of 100 ns. The main high voltage circuit was based on a thyratrone (Fig.l). The TGI1000/25 cera mic thyratrone was applied as powerful and fast Fig.3. Trigger and the output pulses. The shape of the high voltage pulse at the mo dulator output is shown in Fig.2. The delay between Fig.2. The shape of the high voltage pulse on the modulator the trigger and the output pulses is approximately output (time marker intervals = 250 ns). 700 ns (Fig.3). The trigger pulse has a very low 118 NUCLEONIC CONTROL SYSTEMS jitter, less than 100 ps. It allows to obtain a precise References synchronisation between the high voltage and the [i].ZimekZ.-. Radial. Phys.chem., 26,2,81-83(1990). nanosecond pulses which are used to operate the [2].D2wigaiskiz.,ZimekZ.:Eiektronika,6, 19-21 (1994). electron gun. THE INCT PUBLICATIONS IN 1996 119 THE INCT PUBLICATIONS IN 1996 1. Alcock N.W., Errington W., Kemp TJ., Leciejewicz J. Diaquadioxobis(pyridine-3-carboxylato) uranium(VI). Acta Crystallographica, C52,615-617 (1996). 2. Alcock N.W., Errington W., Kemp T.J., Leciejewicz J. 5-nitro-2-furancarboxylic acid. Acta Crystallographica, C52,188-189 (1996). 3. Alcock N.W., Kemp T.J., Roe S.M., Leciejewicz J. The roles of N- and O-coordination in the crystal and molecular structures of uranyl complexes with anthranilic and pyrazinic acids. Inorganica Chimica Acta, 248,241-246 (1996). 4. Ambroi H.B., Komacka E., Przybytniak G.K., Wrotiska T. Radiation-induced damage to DNA, transition metal ion effects. 14th International Conference on Radical Ions. Book of Abstracts. Uppsala, Sweden, 1-5.07.1996, p. 1. 5. Ardisson G, BartoS B,, Bilewicz A., Delmas R., Hussonnois M., Neskovid C. A chemical separation scheme of ^Na the decay product of the cluster radioactivity of 232Th. 4th International Conference on Nuclear and Radiochemistry. Extended Abstracts. Volume I. StMalc, France, 8-13.09.1996, pp. A-P6. 6. Baran S., Leciejewicz J., Stiisser N., Szytula A., Zygmunt A., Ivanov V. Magnetic properties of PrPdSb and NdPdSb compounds. Journal of Physics: Condensed Matter, 8,8397-8405 (1996). 7. Baran S., Szytula A., Leciejewicz J,, Stiisser N., Zygmunt A., Tomkowicz Z., Guillot M. Magnetic structures of RCuGe (R=Pr, Nd, Tb, Dy, Ho and Er) compounds from neutron diffraction and magnetic measurements. Journal of Alloys and Compounds, 243,112-119 (1996). 8. Bazela W., Zygmunt A., Szytula A., Ressouche E., Leciejewicz J., Sikora W. Magnetic properties of CeRhGe and NdRhGe compounds. Journal of Alloys and Compounds, 243,106-111 (1996). 9. Bilewicz A., Bazarraghaagiin A., Narbutt J. Selectivity of ion exchange on crystalline antimonic acid. Radiotracer study on heavy metals in hydrochloric acid and ammonia solutions. Journal of Analytical Chemistry, 51,12,1175-1178 (1996). 10. Bilewicz A., Siekierski S., Kacher C D., Gregoricb K.E., Lee D M., Stoyer N.J., Kadkhodayan B., Kreek S A., Lane M R., Sylwester E.R., Neu M.P., Mohar M.F., Hoffman D C. Chemical studies of rutherfordium (element 104): Part I. Thin film ferrocyanide surfaces for the study of the hydrolysis of rutherfordium. Radiochimica Acta, 75,121-126 (1996). 11. Bilewicz A., Siekierski S., Kacher C D., Hoffman D C. The studies on hydrolysis of element 104. 4th International Conference on Nuclear and Radiochemistry. Extended Abstracts. Volume I. StMalo, France, 8-13.09.19%, pp. A-P4. 12. Bobrowski K. Fragmentacja peptydbw zawierajqcych motioning indukowanq rodnikami OH" (OH radical-induced fragmentation of methionine-containing peptides). Sympozjum Chemii i Techniki Radiacyjnej. Streszczenia. Karpacz, Poland, 17-21.09.19%, p. C-3. 120 THE INCT PUBLICATIONS IN 1996 13. Bobrowski K, Indukowane radiacyjnie procesy utleniania peptyddw zawierajqcych grupq tioeterowq (Radiation-induced oxidation processes of thioether group-containing peptides). Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inzynierdw i Technik6w Przemyslu Chemicznego. Streszczenia. Poznali, Poland, 23-26.09.1996, pp. S2, Cl. 14. Bobrowski K., Holcman J., Poznanski J., Wierzchowski K.L. Long range electron transfer (LRET) accompanying Trp -* TyrO intramolecular radical transformation in hen egg-white lysozyme (HEWL). Abstracts of the Workshop on "Genes and their Products in Basic Research and Biotechnology". Book of Abstracts. Warszawa, Poland, 28-30.11,1996, p. L14. 15. Bobrowski K., Schttneich C. Decarboxylation mechanism of the n-terminal glutamyl moiety in y-glutamic acid and methionine containing peptides. Radiation Physics and Chemistry, 47,3,507-510 (1996). 16. Bojarski J., Strzelczak-Burlinska G., Zimek Z. Radiation effects in polyolefine blends treated by electron beam. International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.1996, p. 38. 17. BorkowskiM. Przygotowanie wskainikowego roztworu 237NpO^ (Preparation of 237NpO^ labelling solution). Materialy XI Sympozjum Fizykochemicznych Metod Rozdzielania Mieszanin. Ars Separatoria. Minikowo, Poland, 17-20.06.1996, p. 66. 18. Borkowski M., Lis S., Choppin G.R. Badanie kompleksowania jondw UO^+ i NpOj z wybranymi ligandami organicznymi w roztworach o wysokiej sile jonowej (Study of complexation of UOl+ and NpOj" with some organic ligands in high ionic strenght solutions). Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inzynierdw i Technikdw Przemyslu Chemicznego. Streszczenia. Poznali, Poland, 23-26.09.1996, pp. S4, E4. 19. Borkowski M., Lis S., Choppin G.R. Complexation study of NpOj and UO2 ions with several organic ligands in aqueous solutions of high ionic strength. Radiochimica Acta, 74,117-121 (19%). 20. Buczkowski M., Starosta W., Fiderkiewicz A., Zdltowski T. Trekowe membrany filtracyjne oraz ich zastosowania (Particle track membranes and their application). Postspy Techniki Jqdrowej, 39,1,24-30 (19%). 21. Campanella L., Pyrzyfiska K., Trojanowicz M. Chemical speciation by flow-injection analysis. A review. Talanta, 43,825-838 (1996). 22.. Chmielewski A.G. Design parameters of electron beam flue gas purification plant and economic-technical benefits of the process. National Environmental Technology Seminar "Electron Beam Technology for Purification of Flue Gases". Proceedings. Kuala Lumpur, Malaysia, 21.05.19%, 17 p. 23. Chmielewski A.G. Economics and feasibility. Regional Training Course on Electron Beam Technology for Purification of Flue Gases. Book of Abstracts. Takasaki, Japan, 5-9.02.19%, pp. 55-56. 24. Chmielewski A.G, Electron beam flue gas treatment. International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.19%, p. 18. THE INCT PUBLICATIONS IN 1996 121 I 25. Chmielewski A.G. V The insight of electron beam process: Sophisticated technology made possible. National Environmental Technology Seminar "Electron Beam Technology for Purification of Hue Gases". Proceedings. Kuala Lumpur, Malaysia, 21.05.1996,11 p. 26. Chmielewski A.G. Nowa technology oczyszczania spalin z elektrowni (New technology of gases purification from electron power station). WiadomoSci z Japonii, 27,4,6 (1996). 27. Chmielewski A.G. Techniczno-ekonomiczne aspekty technologii wykorzystujqcej wiqzkq elektrondw w procesie jedno- czesnego usuwania SO2 i NO* (Technical-economic aspects of technology using electron beam in simultaneous process of removal SO2 and NOx). I Forum Iniynierii Ekologicznej "Technika i Technology w Ochronie Srodowiska. Referaty. Lublin-Nalqczdw, Poland, 14-16.10.1996, pp. 207-210. 28. Chmielewski A.G. Technological development of electron beam flue gas treatment based on physics and chemistry of the process. National Environmental Technology Seminar "Electron Beam Technology for Purification of Hue Gases". Proceedings. Kuala Lumpur, Malaysia, 21.05.1996,5 p. 29. Chmielewski A.G., Dobrowolski A., Kruszewski M., Zakrzewska-Trznadel G., Wasiak R. Badanie wzrostu biomasy na granulowanym w^glu aktywnym w procesie oczyszczania wody (Study on biomass growth on granulated activated carbon in water purification process). VI Ogdlnokrajowa Konferencja Naukowa "Postspy InZynierii Bioreaktorowej". Proceedings. L6dz, Poland, 24-26.09.1996,4 p. 30. Chmielewski A.G., Harasimowicz M., Zakrzewska-Trznadel G. Application of membrane processes in purification of radioactive wastes. In: Towards Hybrid Membrane and Biotechnology Solutions for Polish Environmental Problems. Wroclaw 1996, pp. 227-233. 31. Chmielewski A.G., Harasimowicz M., Zakrzewska-Trznadel G. Low-temperature evaporation employed for radioactive wastes concentration. 4th International Conference on Nuclear and Radiochemistiy. Extended Abstracts. Volume II. StMalo, France, 8-13.09.1996, pp. G-P23. 32. Chmielewski A.G., Harasimowicz M., Zakrzewska-Trznadel G Membrane permeation employed for radioactive wastes treatment. The 5th World Congress of Chemical Engineering. Proceedings. San Diego, California, 14-18.07.1996, pp. 831-836. 33. Chmielewski A.G., Harasimowicz M., Zakrzewska-Trznadel G. Membrane technology applied for low-level radioactive waste cleaning. Proceedings of the 1996 International Congress on Membranes and Membrane Processes. Yokohama, Japan, 18-23.08.1996, pp. 914-915. 34. Chmielewski A.G., Harasimowicz M., Zakrzewska-Trznadel G., Palige J. Membrane processes for liquid radioactive waste treatment. Third International Symposium and Exhibition on Environmental Contamination in Central and Eastern Europe. Symposium Program. Book of Abstracts. Warszawa, Poland, 10-13.09.1996, p. 152. (35./ Chmielewski A.G., liter E. - V Outline of basic engineering for electron beam flue gas treatment plant. Regional Training Course on Electron Beam Technology for Purification of Hue Gases. Proceedings. Takasaki, Japan, 5-9.02.1996, pp. 49-54. 36. Chmielewski A.G., filer E., Tyminskl B., Dobrowolski A., Zimek Z., Lick! J. Fizyko-chemiczne podstawy technologii jednoczesnego usuwania SO2 i NO* z gaz6w spalinowych przy wykorzystaniu wiqzki elektrondw. (Physico-chemical basis of electron beam technology for simultaneous removal of SO2 and NOx from flue gases). 122 THE INCT PUBLICATIONS IN 1996 IV Ogdlnopolskie Sympozjum "Ochrona Powietrza w PrzemySle". Materiafy Sympozjum. L6dt, Poland, 27-29.05.1996, pp. 309-317. 37. Chmielewski A.G., Iller E., Tymihski B., Zlmek Z., Lickl J. Industrial implementation of electron beam flue gas treatment process. Third International Symposium and Exhibition on Environmental Contamination in Central and Eastern Europe. Symposium Program. Book of Abstracts. Warszawa, Poland, 10-13.09.1996, p. 152. 38. ) Chmielewski A.G., Lickl J., Tymihski B., Iller E., Zimek Z - v' Optimization of process parameters for efficient removal of SOz and NOx. Electron Beam Hue Gas Treatment - Research Cooperation Among JAERI, IAEA and INCT. Proceedings. Warszawa, Poland, 28-30.10.1996, pp. 24-42. 39. Chmielewski A G., Licki J., Tymihski B., Iller E., Zimek Z Zintegrowany system do jednoczesnego usuwania wielu zanieczyszczeft z gazdw spalinowych (Integrated system for simultaneous multi pollutants removal from combustion flue gases). Mi^dzynarodowa Konferencja Naukowa Teoria i Praktyka Ochrony Powietrza". Program i Streszczenia. Zabrze-Ustroli, Poland, 11-13.06.1996, p. 75. 40. Chmielewski A.G., Palige J. Nowy typ wysokoefektywnego osadnika-uSredniacza Sciekdw (New type high-effective equilizer-settle tank for waste waters). I Forum InZynierii Ekologicznej "Technika i Technologia w Ochronie Srodowiska. Referaty. Lublin-Nalqcz6w, Poland, 14-16.10.1996, pp. 325-328. 41. Chmielewski A.G., Palige J., Owczarczyk A. Radiotracer investigations of industrial waste water clarifiers. International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.1996, p. 66. 42. Chmielewski A.G., Tymihski B., Hulewicz Z Z , Zakrzewska-Trznadel G., Licki J. Separation of fine aerosols from irradiated flue gas in wet granular bed filter. International Symposium on Filtration and Separation of Fine Dust. Proceedings. Vienna, Austria, 24-26.04.1996, pp. 30-41. 43. Chmielewski A.G., Tymihski B., Iller E., Zakrzewska-Trznadel G., Licki J. Filtracja aerozoli powstajqcych przy radiacyjnym usuwaniu SO2 i NOx z gazdw spalinowych (Aerosol filtration in electron beam process for simultaneous removal of SO2 and NOx from flue gases). IV Ogdlnopolskie Sympozjum "Ochrona Powietrza w PrzemySle". Materiaty Sympozjum. L6di, Poland, 27-29.05.1996, pp. 125-140. 44. Chmielewski A.G., Tymihski B., Zakrzewska-Trznadel G., Tokunaga O. Separation of aerosols from irradiated flue gas in bag filter. International Symposium on Filtration and Separation of Fine Dust. Proceedings. Vienna, Austria, 24-26.04.1996, pp. 140-151. 45. Chmielewski A.G., Tymihski B., Zakrzewska-Trznadel G., Tokunaga O., Sato S. Collection of by-products by bag filter. Electron Beam Hue Gas Treatment - Research Cooperation Among JAERI, IAEA and INCT. Proceedings. Warszawa, Poland, 28-30.10.1996, pp. 43-54. 46. Chmielewski A.G., Zimek Z Zastosowanie technology radiacyjnych w ochronie Srodowiska (Application of radiation technologies in environmental protection). Sostojanie, Problemy i Ochrana Okruzajuszczej Sredy Baltijskogo Georegiona Belarus!. Novye podchody, metody i technology. Vypusk I. Brest 1996, pp. 69-73. 47. Chmielewski A.G., Zimek Z , Iller E., Tymihski B., Dobrowolski A., Licki J. Reaktor do radiacyjnej obrdbki gazdw spalinowych (The reaction vessel for electron beam treatment of flue gases). Sympozjum Chemii i Techniki Radiacyjnej. Streszczenia. Karpacz, Poland, 17-21.09.1996, p. C-5. THE INCT PUBLICATIONS IN 1996 123 ' 48. Chmielewski A.G., Zimek Z., Panta P., Bulka S., Tokunaga O., Namba H. The dose distribution in the reactor of the Kawqczyn pilot plant. Electron Beam Hue Gas Treatment - Research Cooperation Among JAERI, IAEA and INCT, Proceedings. Warszawa, Poland, 28-30.10.1996, pp. 74-85. 49. Chwastowska J., Sterlinska E., Zmijewska W., Dudek J. Application of a chelating resin loaded with thionalide to speciation analysis of As(III,V) in natural waters. Chemia Analityczna, 41,45-53 (1996). 50. Danko B., Dybczynski R. Determination of uranium by radiochemical NAA and its significance for accurate determination of molybdenum in biological materials. 4th International Conference on Nuclear and Radiochemistry. Extended Abstracts. Volume I. StMalo, France, 8-13.09.1996, pp. B-P8. 51. DembitiskiW. Stan i perspektywy zaopatrzenia energetyki jqdrowej w paliwo (Present state and trends in supplying the nuclear energy with fuel). Postspy Techniki Jqdrowej, 39,1,43-48 (1996). 52. Deptula A., Lada W,, Olczak T. Preparation of titanium hexacyanoferrate microspheres (diameter < 70 fim) by water extraction variant of sol-gel process and its application to sorption of I37Cs from nuclear reactor cooling water. Material Research Society Symposium. Proceedings. Vol. 412,653-658 (1996). 53. Deptula A., Chmielewski A.G., Lada W., Olczak T., Wlosinski W.K. Fabrication of solid and hollow spherical particles of ceramics and metals by water extraction variant of sol-gel process. Cost estimation. Die 5th World Congress of Chemical Engineering. Proceedings. Volume V. San Diego, California, 14-18.07.1996, pp. 939-944. 54. Deptula A., Lada W., Olczak T., LeGeros R.Z., LeGeros J.P. Preparation of calcium phosphate coatings by complex sol-gel process (CSGP). Bioceramics, 9,313-316 (1996). 55. Deptula A., Olczak T., Lada W., Goretta K.C., Bartolomeo Di A., Brignocchi A. Thermal conversion of gels to YBazCusOx, BizSrzCaCuzOx and (Bi, P^zSrzCazCusQ* and their decarbonization by low-temperature treatment with nitric acid. Journal of Material Research, 11,1,1-4 (1996). 56. Dldyk A.Yu., Gulbekian G.G., Wronski W. Comparison of radiation effects on the operation of MOS devices under various types of nuclear radiation. Nuclear Instruments and Methods in Physics Research B, 111, 84-86 (1996). 57. Dybczynski R. Materialy odniesienia i ich rola w zapewnieniu jakoSei w nieorganicznej analizie Sladowej (Reference materials and their role in quality assurance in inorganic trace analysis). In: Problemy Jakodci Analizy Sladowej w Badaniach Srodowiska Przyrodniczego. Partstwowa Inspekqa Ochrony Srodowiska, Warszawa 1996, pp. 39-76. 58. Dybczytiski R. Metody vysokotocnogo opredelenija sledovych koncentracii nekotorych vaznych ill toksicnych elementov v biologiceskich materialach s ispol ’zovaniem nejtronno-aktivacionnogo analiza i kolo- nocnoj chromatografii. Zumal Analiticeskoj Chimii, 51,12,1328-1336 (1996). 59. DybczyrtsldR. The significance of reference materials and "very accurate" or "definitive" methods for quality assurance in inorganic trace analysis. Proceedings of the International Symposium "Development in Chemical Analysis of Environmental Samples at the Edge of the 21st Century". Warszawa, Poland, 21-22.11.1996, pp. 1-8. 124 THE 1NCT PUBLICATIONS IN 1996 60. DybczynskiR. The significance of very accurate methods by RNAA for QA and certification of candidate reference materials. International Symposium on Harmonization of Health Related Environmental Measurements Using Nuclear Isotopic Techniques. Extended Synopsis. Hyderabad, India, 4-7.11.1996, pp. 23-24. 61. DybczyAskl R. Very accurate methods by radiochemical NAA and their significance for the certification of the candidate reference materials. 4th International Conference on Nuclear and Radiochemistry. Extended Abstracts. Volume I. StMalo, France, 8-13.09.1996, pp. B-P10. 62. Dybczyfiski R. Very accurate methods for the determination of some essential or toxic trace elements in biological materials by neutron activation analysis and column chromatography. Journal of Analytical Chemistry, 51,12,1206-1213 (1996). 63. DybczyAski R., Polkowska-Motrenko H., Samczyriski Z , Szopa Z., Kulisa K., Wasek M. Certification of a new biological reference material - Virginia Tobacco Leaves (CTA-VTL-2) and homogeneity study by NAA on this and other candidate reference materials. Report of the 2nd Research Co-ordination Meeting on Reference Materials for Microanalytical Nuclear Techniques. Mexico City, Mexico, 30.05.-5.06.1996, pp. 118-132. 64. Genuario R.D., Confuorto N., Chmielewski A.G., Paur H. Acid rain and dust emissions from the Estonian power plants: Technical solutions. Third International Symposium and Exhibition on Environmental Contamination in Central and Eastern Europe. Symposium Program. Book of Abstracts. Warszawa, Poland, 10-13.09.1996, p. 180. 65. Grqdzka I., Iwanenko T., Kruszewski M., Szumiel I., Kapiszewska M., Lange C.S., Afanasjev G. Modulation of the effect of camptothecin in X-irradiated L5178Y-R and L5178Y-S cells by benza- mide. Radiation Environmental Biophysics, 35,185-191 (1996). 66. Grqdzka I., Szumiel I. Discrepancy between the initial DNA damage and cell survival after camptothecin treatment in two murine lymphoma L5178Y sublines. Cell Biochemistry and Function, 14,163-171 (1996). 67. Grqdzka I,, Szumiel I., Iwanenko T., Skierski J.S. DNA repair, G2 arrest and cell death after murine lymphoma L5178Y treatment with camptothecin. 6th Conference on Cell Biology. Book of Abstracts. Lublin, Poland, 12-14.09.1996, p. 58. 68. Grodkowski J., Neta P., Abdallah Y., Hambright P. Reduction and alkylation of rhodium porphyrins in alcohol solutions. Radiation chemical and photo chemical studies. Journal of Physical Chemistry, 100,7066-7071 (1996). 69. Guldi D M., Field J., Grodkowski J., Neta P., Vogel E. One-electron oxidation of metalloporphycenes as studied by radiolytic methods. Journal of Physical Chemistry, 100,32,13609-13614 (1996). 70. Hug G.L., Marclniak B., Bobrowski K. Acid-base equilibria involved in secondary reactions following the 4-carboxybenzophenone sensitized photooxidation of methionyl-glycine in aqueous solution. Spectral and time resolution of the decaying (S.".N)+ radical cation. Journal of Physical Chemistry, 100,36,14914-14921 (1996). 71. Hug G.L., Marclniak B., Bobrowski K. Acid-base equilibria involved in secondary reactions following the 4-carboxybenzophenone sensitized photooxidation of methionyl-glycine in aqueous solution. Spectral and time resolution of the decaying (S.'.N)+ radical cation. Proceedings of the Twentieth Doe Solar Photochemistry Research Conference. French Lick Indiana, USA, 8-12.06.1996, p. 119. THE INCT PUBLICATIONS IN 1996 125 72. Hug G.L., Marciniak B., Bobrowski K, Acid-base equilibria involved in secondary reactions following the 4-carboxybenzophenone sensitized photooxidation of methionyl-glycine in aqueous solution. Spectral and time resolution of the decaying (S.'.N)+ radical cation. XVIth IUPAC Symposium on Photochemistiy. Book of Abstracts. Helsinki, Finland, 21-26.07.1996, p. 276. 73. Hug G.L., Marciniak B., Bobrowski K. Sensitized photo-oxidation of sulphur-containing amino acids and peptides in aqueous solution. Journal of Photochemistry and Photobiology A, 95,81-88 (1996). 74. Iller E,, Owczarczyk A., Palige J., Chmielewski A.G. Radiotracer experiment at irradiation gas flow system. International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.1996, p. 75. 75. Ivanov V., Kolenda M., Leciejewicz J., Sttisser N., Szytula A. Antiferromagnetic ordering in PrCuzSiz, PrCuzGez and TbCuzSiz- Journal of Alloys and Compounds, 234, L4-L6 (1996). 76. Jankowska T. Profesor Doktor Slawomir Siekierski - 2yde i dzialalnoSd w siedemdziesiqtq rocznicq urodzin (Professor Slawomir Siekierski - life and activities on the 70-ieth Birthday Anniversary). Postqpy Techniki Jqdrowej, 39,4,2-4 (1996). 77. Jaworska A,, Sochanowicz B. Bcl-2/Bax ratio and radiation sensitivity of two L5178Y cell lines cross-sensitive to ionizing radiation and H2O2. 27th Annual Congress of European Society for Radiation Biology. Book of Abstracts. Montpellier, France, 1-4.09.1996, p. 64 78. Kacher C D., Gregorich K.E., Lee D M., Watanabe Y., Kadkhodayan B., Wlerczinski B-, Lane M R., Sylwester E.R., Keeney DA., Hendricks M., Hoffman D C., Bilewicz A. Chemical studies of rutherfordium (element 104): Part III. Solvent extraction into triisooctylamine from HF solutions. Radiochimica Acta, 75,135-139 (1996). 79. Kacher C D., Gregorich K.E., Lee D M., Watanabe Y., Kadkhodayan B., Wlerczinski B., Lane M R., Sylwester E.R., Keeney DA., Hendricks M., Stoyer N.J., Yang J., Hsu M., Hoffman D C., Bilewicz A. Chemical studies of rutherfordium (element 104): Part II. Solvent extraction into tributylphosphate from HBr solutions. Radiochimica Acta, 75,127-133 (1996). 80. Kaiuska I., Mirkowski K. Radiation degradation of polypropylene. Proceedings of the 11th Bratislava IUPAC/FECS International Conference on Polymers "Thermal and Photo-Induced Oxidation of Polymers and its Inhibition in the Upcoming 21th Century". Stara LeSna, Slovak Republic, 24-28.06.1996, p. 84. 81. Kierzek J., Matoiewska-Budko B. Determination of ash in coal based on natural gamma ray activity and X-ray backscattering methods. Nukleonika, 41,1,89-96 (1996). 82. Kierzek J., Starosta W., Matoiewska-Budko B., Bukowski P. Determination of ecological properties of coal by nuclear analytical methods. International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.1996, p. 37. 83. Kierzek J., Starosta W., Matoiewska-Budko B., Bukowski P. Investigation of ecological properties of Polish coals by nuclear analytical methods. Third International Symposium and Exhibition on Environmental Contamination in Central and Eastern Europe. Symposium Program. Book of Abstracts. Warszawa, Poland, 10-13.09.1996, p. 153. 126 THE INCT PUBLICATIONS IN 1996 84. Kleczkowska H.E., Althaus F.R. Biochemical changes associated with the adaptive response of human keratinocytes to N-methyl-N‘-ni- tro-N-nitrosoguanidine. Mutation Research, 368,121-131 (1996). 85. Kleczkowska H E., Althaus F.R. Response of human keratinocytes to extremely low concentrations of N-methyl-N‘-nitro-N-nitrosogua- nidine. Mutation Research, 367,151-159 (1996). 86. Kleczkowska H E., Althaus F.R. The role of poly(ADP-ribosyl)ation in the adaptive response. Mutation Research, 358,215-221 (1996). 87. Kleczkowska H E., Szumiel I., Althaus F.R. Low dose ionizing radiation effect on poly(ADP-ribose) binding proteins. 27th Annual Congress of European Society for Radiation Biology. Book of Abstracts. Montpellier, France, 1-4.09.1996, p. 121. 88. Kolenda M., Leciejewicz J., Szytula A., Stiisser N., Tomkowicz Z. Magnetic transition in TbMnzSia. Journal of Alloys and Compounds, 241, L1-L3 (19%). 89. Kostrzewa E., Owczarczyk B. Wybrane zagadnienia dotyczqce przypraw ziolowych stosowanych w przemySle spoiywczym (Selected problems concerning herbal spices used in food industry). Seminarium z cyklu "Zwiqzki Nauki z Praktykq" "Stan Aktualny i Perspektywy Rozwoju Wybranych Dziedzin Przetw6rstwa ZywnoSci". Polagra ’%. Tom 3. "Ziola i przyprawy zidowe". Poznaft, Poland, 19-24.09.1996, pp. 47-77. 90. Kowalak S., Stuglik Z, Strdiyk M., Wi^ckowskl A.B. Wytwarzanie rodnikdw siarkowych w zeolitach za pomocq promieniowania jonizujqcego (Generation of sulphur radicals in zeolites by means of ionizing radiation). Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia In2ynier6w i Technikdw Przemyslu Chemicznego. Streszczenia. Poznati, Poland, 23-26.09.19%, pp. S18, E24. 91. Kowalska E., Urbanski P. Feasibility study of artificial neural network as a calibration method of nucleonic gauges. International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.19%, p. 56. 92. KraS J., Dziewonski Z , Kalicki A., Kielak W., Myczkowskl S., WallS L New detectors for leak-proof control and localization of leakages. International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.1996, p. 70. 1 93.\,Kulczycka E., Kisielinski M., Moroz Z., Sowinski M., Wojtkowska J., Chmlelewskl A.G., Hashlmoto S. 'Experimental studies of the prototype internal beam monitor in Kawgczyn power station installation. Electron Beam Flue Gas Treatment - Research Cooperation Among JAERI, IAEA and INCT. Proceedings. Warszawa, Poland, 28-30.10.19%, pp. 86-92. 94. Leciejewicz J., Stiisser N., Kolenda M., Szytula A., Zygmunt A. Magnetic ordering in HoCoSi and TbCoGe. Journal of Alloys and Compounds, 240,164-169 (19%). 95. Licki J., Chmielewski A.G., Iller E. System for measurement of gas composition at the outlet of desulphurisation and denitrification installation. Mi^dzynarodowa Konferencja Naukowa "Teoria i Praktyka Ochrony Powietrza. Program i Streszczenia. Zabrze-Ustroft, Poland, 11-13.06.19%, p. 76. 96. Licki J., Chmielewski A.G., Iller E., Tokunaga O., Hashlmoto S., Sato S. Development of e-beam process monitoring system. THE INCT PUBLICATIONS IN 1996 127 Electron Beam Flue Gas Treatment - Research Cooperation among JAERI, IAEA and INCT. Proceedings. Warszawa, Poland, 28-30.10.1996, pp. 55-65. 97. Ltcki J., Lysiak W., ,Radzlo B., Chmielewski A.G., filer E., Zakrzewska-Trznadel G. Manualne i instrumentalne metody analizy skladu spalin na wylocie z elektrowni w^glowej (Manual and instrumental methods of analysis of flue gases composition at the outlet of EPS). Materiafy Seminarium "Czujniki w Ochronie Srodowiska*. Referaty. Gdalisk, Poland, 27.05.1996, pp. 31-38. 98. Lis S., Borkowski M., Choppln G.R. Wyznaczanie st$2enia jondw wodorowych w roztworach elektrolitdw (NaCl i NaCIO#) o wysokiej sile jonowej (Determination of H+ concentration in the electrolyte solutions (NaCl and NaCKXt) at high ionic strenght). Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia InZynierdw i Technikdw Przemyslu Chemicznego. Streszczenia. Poznart, Poland, 23-26.09.1996, pp. S4, E3. 99. Lukasiewicz A., WaliS L., Michalik J., Sadlo J. New surface layer materials from polymerized complexes of aminotriazole with transition metals. Materials Letters, 29,149-153 (1996). 100. Mach%| B., Bartak J. Grab sample measurement of radon decay products in air. International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.1996, p. 88. 101. Machaj B., Bartak J. A microprocessor instrument of radon daughters in mines. International Conference on Technologically Enhanced Natural Radiation Caused by Non-Uranium Mining. Proceedings. Szczyrk, Poland, 16-19.10.1996, pp. 131-139 102. Machaj B., Bartak J. Some radiometric instruments for environmental protection. Third International Symposium and Exhibition on Environmental Contamination in Central and Eastern Europe. Symposium Program. Book of Abstracts. Warszawa, Poland, 10-13.09.1996, p. 153. 103. Majdan M., Fuks L., Majdan I. Review of the lanthanide extraction chemistry. Mineralia Slovaca, 28,412-420 (1996). 104.. Malec-Czechowska K., Dancewicz A.M., Szot Z s~ Application of thermoluminescence analysis for detection of irradiated foodstuffs. Nukleonika, 41,3,67-76 (1996). 105. Michalik J. Silver atoms and clusters in molecular sieves and clays. Applied Magnetic Resonance, 10,507-537 (1996). 106. Michalik J., Sadlo J. Radiation induced silver agglomeration in zeolite rho. Trombay Symposium on Radiation and Photochemistry. Proceedings. Trombay, India, 8-12.01.1996, pp. 398-400. 107. Michalik J., Sadlo J., Jong-Sung Yu., Kevan L. Tetrameric silver clusters in rho zeolite stable above room temperature - ESR studies. Colloids and Surfaces, 115,239-247 (1996). 108. Michalik J., Sadlo J., Kevan L., Jong-Sung Yu. Radiation-induced silver agglomeration in zeolite rho. 11th International Zeolite Conference. Book of Abstracts. Seoul, Korea, 12-17.08.1996, p. RP139. 109. Michalik J., Sadlo J., Reverse E.J., Pol van der A. EPR and ESEEM studies on silver hydroxymethyl radicals in molecular sieves. 14th International Conference on Radical Ions. Book of Abstracts. Uppsala, Sweden, 1-5.07.1996, p. 1. 128 THE INCT PUBLICATIONS IN 1996 110. Michalik J., Wqsowicz T., Jong-Sung Yu., Kevan L. Stabilne aglomeraty Agl + w napromienionych zeolitach rho (Stabile silver dusters in irradiated rho zeolite). Sympozjum Chemii i Techniki Radiacyjnej. Streszczenia. Karpacz, Poland, 17-21.09.1996, p. C-16. 111. Michalik J., Wqsowicz T., Jong-Sung Yu, Kevan L. Tetrameric silver clusters in zeolite rho. 2nd International Conference of the Polish EPR Association "Electron Paramagnetic Resonance of Radicals and Metal Complexes". Book of Abstracts. Warszawa, Poland, 9-13.09.1996, p. 43. 112. Michalik J., Wqsowicz T., Sadto J., Reverse E.J., Kevan L. Pulsed EPR for studying silver clusters. Radiation Physics and Chemistry, 47,1,75-81 (1996). 113. Michalik J., Yamada H., Brown D.R., Kevan L. Small silver clusters in smectite clay interlayers. Journal of Physical Chemistry, 100,10,4213-4218 (1996). 114. Migdat W., Malec-Czechowska K., Owczarczyk B. Study on application of e/X conversion for radiation processing. Nukleonika, 41,3,57-66 (1996). 115. MioduskiT. Krdtka historia WszechSwiata - esej Swiatopoglqdowy (A brief history of the Universe). Postspy Techniki Jqdrowej, 39,4,37-45 (1996). 116. MioduskiT. R6znice we wlaSciwoSciach chemicznych jzotopdw na przykladzie 238 U i 235U (Differences in chemical behaviour of isotopes as exemplified by 238 U and ^U). WiadomoSci Chemiczne, 50,9-10,701-719 (1996). 117. Moore P., Josceanu A M., Jackson M L., Priimov G., Narbutt J., Rawle S.C., Sheldon P., Smith S.M., Turonek M.L., Wild K. pH and metal ion sensors based on azamacrocycles and azacrown ethers with N-pendent[Ru(BIPY)3]2+ groups. 6th European Conference on ElectroAnalysis. Durham, England, 25-29.03.1996, p. 1. 118. Narbutt J., Bilewicz A. Distribution of Zn2+, Cd2+ and Hg 2+ in-simulated environmental systems. Crystalline antimonic acid as a selevtive adsorbent of Cd2+and Hg 2+ from mineral acids. Co-ordination Meeting of the Co-ordinated Research Programme on Nuclear Techniques for the Evaluation of Healing Pathways of Pollutant Damage in the Environment, Urbino, Italy, 15-19.04.1996, 14 p, 119. Narbutt J., Bilewicz A., BartoS B. Ion-size selectivity of some inorganic ion exchangers and separations of radionuclides. Proceedings of the Sixth Conference on Nuclear Sciences and Applications. Volume I. Cairo, Egypt, 15-20.03.1996, pp. 107-118. 120. Narbutt J., Bilewicz A., BartoS B. Ion-size selectivity of some inorganic ion exchangers and separations of radionuclides. Sixth Conference of Nuclear Sciences and Applications (An International Event). Book of Abstracts. Cairo, Egypt, 15-20.03.1996, p. 49. 121. Narbutt J., Bilewicz A., BartoS B. SelektywnoSd jonowymienna krystalicznych form kwasu antymonowego(V) i manganowego(IV) wzglqdem kationdw o okreSlonych promieniach (Ion-size selectivity of crystalline antimonic(V) and manganic(IV) acids as ion exchangers). Materialy XI Sympozjum Fizykochemicznych Metod Rozdzielania Mieszanin. Ars Separatoria. Minikowo, Poland, 17-20.06.1996, pp. 32-37. 122. Narbutt J., Bilewicz A., BartoS B., Postek R. Analytical extraction and preconcentration of radium and barium from coal mine water by crystalline manganic acid. THE INCT PUBLICATIONS IN 1996 129 In: Decontamination of Aqueous Waste Streams. Final Report Appendix E AEA Technology, Harwell 1996, pp. 1-21. 123. Narbutt J., Bilewicz A., BartoS B., Postek R. Preconcentration of radium from saline coal-mine water on selectivite ion exchanger-a-crystalline manganic acid. 4th International Conference on Nuclear and Radiochemistty. Extended Abstracts. Volume II. StMalo, France, 8-13.09.1996, pp. E-P57. 124. Narbutt J., Fuks L. Outer-sphere hydration - a factor differentiating tetrakis(acetylacetonato)actinides(IV) in liquid-liquid partition systems. 4th International Conference on Nuclear and Radiochemistry. Extended Abstracts. Volume I. StMalo, France, 8-13.09.1996, pp. C-P17. 125. Narbutt J., Taleb H., BartoS B. Radiocaesium removal from synthetic steam-generator cleaning solutions. Proceedings of the Sixth Conference on Nuclear Sciences and Applications. Volume I. Cairo, Egypt, 15-20.03.1996, pp. 131-138. 126. Narbutt J., Taleb H., BartoS B. Radiocaesium removal from synthetic steam-generator cleaning solutions. Sixth Conference of Nuclear Sciences and Applications (An International Event). Book of Abstracts. Cairo, Egypt, 15-20.03.1996, pp. 3-4. 127. Neta P., Grodkowski J., Ross A.B. Rate constants for reactions of aliphatic carbon-centered radicals in aqueous solution. Journal of Physical Chemistiy Reference Data, 25,3,709-1051 (1996). 128. Novak C.F., Borkowskl M., Choppin G.R. Thermodynamic modeling of neptunium(V)-acetate complexation in concentrated NaCl media. Radiochimica Acta, 74,111-116 (1996). 129. Ostrowski K., Dziedzic-Gociawska A., Michalik J., Stachowicz W. Centres paramagnetiques induits par les radiations dans l’os et d’autres tissus mineralisds. Journal de Chimie Physique et de Physico Chimie Biologique, 93,174-181 (1996). 130. OwczarczykA. Localization and quantitative estimation of leakages in big water reservoires and dams. Acta Geologica Hungarica, 39,143-145 (1996). 131. Owczarczyk A., Pruszak Z., Szpllowskl S., Wierzchnicki R. Measurement of bedload and pollutant transport parameters in sea coastal zone by the use of radiotracer method. 12th International Congress of Chemical and Process Engineering. Summaries. Volume 1. Praha, Czech Republic, 25-30.08.1996, p. 131. 132. OwczarczykA.,Wierzchnicki R. Bed-load movement processes in marine near-shore zone. International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.1996, p. 95. 133. OwczarczykA.,Wierzchnicki R. Concept and verification of radiotracer method for quantitative estimation of leakages in dams and big water reservoires. 12th International Congress of Chemical and Process Engineering. Summaries. Volume 1. Praha, Czech Republic, 25-30.08.1996, p. 142. 134. OwczarczykA.,Wierzchnicki R., Strzeleckl M. Investigation of effluent dispersion in the Vistula river. Third International Symposium and Exhibition on Environmental Contamination in Central and Eastern Europe. Symposium Program. Book of Abstracts. Warszawa, Poland, 10-13.09.1996, p. 152. 130 THE INCT PUBLICATIONS IN 1996 135. Palucbowska B., Maurin J.K., Leciejewicz J. Carboxylate and furan-ring oxygen bonded to calcium in polymeric calcium furcate. Acta Crystallographica, C52,347-351 (1996). 136. Palucbowska B., Maurin J.K., Leciejewicz J. The role of C-H...O bonds in stabilizing 3-furancarboxylic acid and its complexes with calcium and strontium. Acta Crystallographica, C52,342-347 (1996). 137. Palucbowska B., Maurin J.K., Leciejewicz J. Variable coordination of barium and its complexes: Crystal structures of barium compounds with 2- and 3-furancarboxylic acids. Polish Journal of Chemistry, 70,1402-1410 (1996). 138. Panta P., Redko W.M. Ceramiczny element grzejny jako detektor dawki promieniowania w liniowym akceleratorze (Ceramic heat element as a dose detector in a linear accelerator). Szklo i Ceramika, 47,18 (1996). 139. Panta Zimek Z., Gluszewskl W., Kowalewski R., Wojtytiska E. Dozymetria wiqzki szybkich elektrondw akceleratorowych w badaniach wpiywu promieniowania jonizujqcego na wlaSciwoSci samoprzylepnych klejdw akrylowych (Electron beam dosimetry usage in the investigation of ionizing radiation effects on the properties of self-adhesive acrylic glues). Sympozjum Chemii i Techniki Radiacyjnej. Streszczenia. Karpacz, Poland, 17-21.09.1996, p. C-17. 140. Paficzyk E., Chmielewskl K., WaliS L., Kalicki A. Identification of the XV-th century panel paintings of the Silesian school by means of INAA International Conference on Radiosiotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.1996, p. 22. 141. Panczyk E., Ligfza M., Kierzek J., WaliS L. Zastosowanie instrumentalnej analizy aktywacyjnej oraz rentgenowskiej analizy fluorescencyjnej w badaniu dziel sztuki (Application of INAA to identification of the Malopolska school panel paintings). Postspy Techniki Jqdrowej, 39,4,15-21 (1996). 142. Pawlukoid A., Leciejewicz J. Spektroskopia neutronowa aminokwasdw alifatycznych (Neutron spectroscopy of aliphatic amino adds). Postspy Techniki Jqdrowej, 39,1,31-33 (1996). 143. Pawlukojc A., Leciejewicz J., Natkaniec I. The HNS spectroscopy of amino acids: 1-leucine. Spectrochimica Acta Part A, 52,29-32 (1996). 144. Pawtowski K., Kostrzewski R., Chmielewskl A.G., Iller E. Demonstracyjna przemystowa instalaqa jednoczesnego usuwania SOz i NOx z gazdw odlotowych przy uiydu wiqzki elektrondw w Elektrowni Pomorzany (Demonstrative industrial installation of simultaneous SO2 and NOx removal from flue gases using electron beams in Power Station Pomorzany). Konferencja Regionalna "Inwestycje w Ochronie Srodowiska w Regionie Szczecihskim - Historia i Perspektywy". Pogorzelica, Poland, 17-18.10.1996, pp. 91-105. 145. Piekoszewski J., WaliS L, Langner J., Werner Z., Biatoskdski J., Nowkki L., Kopcewkz M, Grablas A Alloying of austenitic stainless steel with nitrogen using high-intensity pulsed beams of nitrogen plasma. Nuclear Instruments and Methods in Physics Research B, 114,263-268 (1996). 146. Pogocki D., Bobrowski K. The fragmentation of a-aminoalkyl radicals derived from sulphur containing amino adds. VII International Symposium on Organic Free Radicals. Book of Abstracts. Bardolino, Italy, 16-21.06.1996, p. 135. 147. Pogocki D., Bobrowski K. Mechanizm utleniania aminokwasdw zawierajqcych grupq tioeterowq generowanymi radiacyjnie rod- nikami hydroksylowymi. Procesy fragmentacji (Oxidation mechamism of thioether group-containing amino acids by radiation generated hydroxyl radicals. Fragmentation processes). THE INCT PUBLICATIONS IN 1996 131 Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia In2ynier6w i Techniktiw Przemyshi Chemicznego. Streszczenia. Poznari, Poland, 23-26.09.1996, pp. S2, C3. 148. Pogocki D., Bobrowski K. Mechanizm utleniania S-alkilowych pochodnych cysteiny generowanymi radiacyjnie rodnikami hydro- ksylowymi. Fragmentacja rodnikdw a-aminoalkilowych (Oxidation mechamism of s-alkylcysteine derivatives by radiation generated hydroxyl radicals. Fragmentation of alpha-(amino)alkylradicals). Sympozjum Chemii i Techniki Radiacyjnej. Streszczenia. Karpacz, Poland, 17-21.09.1996, pp. C-19. 149. Pol van der A., Mlchalik J., Reverse E., Boer de E. Identification of a silver hydroxymethyl radical in Ag-NaA zeolite using electron spin echo envelope modulation spectroscopy. Journal of Physical Chemistry, 100,9,3728-3731 (1996). 150. Poikowska-Motrenko H., Dybczytiski R., Danko B., Becker DA. Bardzo dokiadna metoda jednoczesnego oznaczania Co i Ni w materiaiach biologicznych za pomocq neutronowej analizy aktywacyjnej (Very accurate method for simultaneous determination of Co and Ni in biological materials by neutron activation analysis). Materialy V Poznariskiego Konwersatorium Analitycznego "Nowoczesne Melody Przygotowania i Oznaczania Sladowych IloSci Pierwiastkdw". Poznari, Poland, 25-26.04.1996, pp. 13. 151. Poikowska-Motrenko H., Dybczyriski R,, Danko B., Becker DA. Very accurate, simultaneous determination of trace amounts of Co and Ni in biological materials by radiochemical neutron activation analysis. Journal of Radioanalytical and Nuclear Chemistry, Articles, 207,2,401-412 (1996). 152. Poikowska-Motrenko H., Dybczynski R., Danko B., Becker DA. Very accurate, simultaneous determination of trace amounts of Co and Ni in biological materials by radiochemical neutron activation analysis. International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.1996, p. 34. 153. Przybytniak G., Htlttermann J., Ambroz H,, Welland B. Cysteamine as radical scavenger in frozen aqueous matrices containing dCMP and TMP. 2nd International Conference of the Polish EPR Association "Electron Paramagnetic Resonance of Radicals and Metal Complexes*. Book of Abstracts. Warszawa, Poland, 9-13.09.1996, p. 91. 154. Przybytniak G., Zagdrski Z.P. Orientation of crystals in alanine dosimeter assessed by DRS, as seen in EPR spectra evaluation. Journal of Radioanalytical and Nuclear Chemistry, Letters, 212,5,373-382 (1996). 155. PszonickiL. Rola metod ekstrapolacji przy interpretacji sygnatow analitycznych (Significance of extrapolation methods for the evaluation of analytical signals). In: Problemy JakoSci Analizy Sladowej w Badaniach Srodowiska Przyrodniczego. Paris twowa Inspekq'a Ochrony Srodowiska, Warszawa 1996, pp. 77-108. 156. RafalskiA. Spektrofotometria DRS w badaniach radiolizy polimerdw o malej przejrzystoSci (Diffuse reflectance spectrophotometry in polymers of low transparency radiolysis study). Sympozjum Chemii i Techniki Radiacyjnej. Streszczenia. Karpacz, Poland, 17-21.09.1996, p. C-20. 157. Sadto J., Cullens F., Matthys P., Mlchalik J., Stachowicz W., Boesman E. ENDOR of human tooth enamel heated at 400°C. 2nd International Conference of the Polish EPR Association "Electron Paramagnetic Resonance of Radicals and Metal Complexes". Book of Abstracts. Warszawa, Poland, 9-13.09.1996, p. 95. 158. Sadto J., Mlchalik J., Pol van der A., Reverse E. Badania rodnikdw hydroksymetylosrebrowych w sitach molekularnych metodami EPR i ESEEM (EPR and ESEEM studies on organosilver radicals in molecular sieves). Sympozjum Chemii i Techniki Radiacyjnej. Streszczenia. Karpacz, Poland, 17-21.09.1996, p. P-8. 132 THE INCT PUBLICATIONS IN 1996 159. Sadto J., Michalik J., Reijerse E.J., Pol van der A. EPR and ESEEM studies on organosilver radicals in molecular sieves. VII International Symposium on Organic Free Radicab. Book of Abstracts. Bardolino, Italy, 16-21.06.1996, p. 141. 160. Salnikov L.I., Nichipor H., Radjuk E., Chmielewski A.G., Zimek Z SOz, NOx and H2S oxidation by simultaneous application of electron beam and electric field in human air. 11th International Conference on High Power Particle Beams "Beams’96". Proceedings. Volume I. Prague, Czech Republic, 10-14.06.1996, pp. 824-827. 161. Samczynski Z , Dybczyriski R. Ion exchange behaviour of cadmium on amphoteric ion exchange resin retardion 11A8 and its application for the determination of cadmium in biological materials by neutron activation analysis. Chemia Analityczna, 41,873-890 (1996). 162. Samczyftski Z., Dybczyfiski R. Wymiana jonowa pierwiastkdw na jonicie amfoterycznym Retardion 11A8 i jej zastosowanie do selektywnego wydzielania kadmu i jego dokladnego oznaczania za pomocq NAA (Ion exchange behaviour of elements on amphoteric ion exchange resin retardion 11A8 and its application for the selective separation of cadmium and its accurate determination by neutron activation analysis). Materiafy V Poznaftskiego Konwersatorium Analitycznego "Nowoczesne Melody Przygotowania Prdbek i Oznaczania Sladowych DoSci Pierwiastkdw". PoznaA, Poland, 25-26.04.1996, p. 16. 163. Skwara W., Pszonickl L. Zachowanie sis selenu w obecnoSci jondw chlorkowych podczas atomizacji w kuwecie grafitowej (Behaviour of selenium in the presence of chloride ions during atomization in graphite furnace atomic absorption spectrometry). Materiafy V Poznaliskiego Konwersatorium Analitycznego "Nowoczesne Melody Przygotowania Prdbek i Oznaczania Sladowych IloSci Pierwiastkdw". PoznaA, Poland, 25-26.04.1996, p. 22. 164. Sochanowicz B., Szumlel I. Arachidonic acid metabolism in murine lymphoma cell sublines differing in radiation sensitivity. Prostaglandins, Leukotrienes and Essential Fatty Acids, 55,4,241-247 (1996). 165. )sowifiski M., Kowalski M., Iller E., Kupczak R., Lickl J., Hashlmoto S., Tokunaga O. J Data acquisition and control system. Electron Beam Flue Gas Treatment - Research Cooperation Among JAERI, IAEA and INCT. Proceedings. Warszawa, Poland, 28-30.10.1996, pp. 103-109. 166. Stachowicz W., Strzelczak-BurlMska G., Michalik J. EPR detection of irradiated mushrooms and condiments. 2nd International Conference of the Polish EPR Association "Electron Paramagnetic Resonance of Radicals and Metal Complexes". Book of Abstracts. Warszawa, Poland, 9-13.09.1996, p. 97. 167. - Stachowicz W., Strzelczak-Burlinska G., Michalik J., Dziedzic-Goclawska A., Ostrowski K. - EPR spectroscopy for the detection of foods treated with ionizing radiation. In: Detection Methods for Irradiated Foods. Current Status. Ed. C.H. McMurray. The Royal Society of Chemistry, Cambridge 1996, pp. 23-32. 168. Staron K., Kowalska-Loth B., Nleznatiski K., Szumlel I, Phosphorylation of topoisomerase I in L5178Y-S cells is associated with poly(ADP ribose) metabolism. Carcinogenesis, 17,3,383-387 (1996). 169. Staron K., Kowalska-Loth B., Szumlel I. Lowered phosphorylation of topoisomerase I is a direct reason for reduced sensitivity of L5178Y-S cells to camptothecin. The Camptothecin. From Discovery to the Patient. New York, USA, 7-10.02.1996, pp. 321-323. 170. StarostaW. Determination of iron containing minerals in coal by MOssbauer spectroscopy. International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.1996, p. 25. THE INCT PUBLICATIONS IN 1996 133 171. Staszewski P., Lipkowskl J., Udachln K., Narbutt J. On supramolecular architecture of water molecules form in hydrophobic hydrates. 5th International Summer School on Supramolecular Chemistry. Program and Abstracts. Ustroti, Poland, 16-26.06.1996, p. P-67. 172. Strzelczak-Burlitiska G., Bobrowskl K., Holcman J. Reakcje elektronu uwodnionego z oligopeptydami (Reactions of the hydrated electron with oligopeptides). Sympozjum Chemii i Techniki Radiacyjnej. Streszczenia. Karpacz, Poland, 17-21.09.1996, p. P-9. 173. Strzelczak-Burlinska G., Bobrowskl K., Holcman J. Reakcje elektronu z peptydami metioninowymi (Reactions of electron with methionine-containing peptides). Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Iniynierdw i Technikdw Przemyslu Chemicznego. Streszczenia. Poznati, Poland, 23-26.C8.1996, pp. S2, F19. 174. Strzelczak-Burlldska G., Bobrowskl K., Michalik J. ESR study of solid peptides. Second International Conference on Electron Paramagnetic Resonance of Radicals and Metal Complexes. Notebook. Annex. Warszawa, Poland, 9-13.09.1996, p. 1. Zl75?Strzelczak-BurMska G., Bojarski J., Michalik J, ^ Studies on irradiated polypropylene, its copolymers and blends-1. ESR studies. Radiation Physics and Chemistry, 47,3,449-451 (1996). 176. Stugiik Z. ESR/alanine dosimetry. International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.1996, p. 86. 177. Stugiik Z. Ion beam dosimetry. International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.1996, p. 87. 178. Stugiik Z., Sadto J. ESR analysis of microcrystaline L-a-alanine and standard bone powder irradiated with Co-59 ion beam. International Conference of the Polish EPR Association "Electron Paramagnetic Resonance of Radicals and Metal Complexes". Book of Abstracts. Warszawa, Poland, 9-13.09.1996, p. 98. 179. Szopa Z., Dybczynski R. AQCS - A PC program for evaluation of intercomparison results as applied to certification of some Polish CRMs. Proceedings of the Central European Conference on Reference Materials. Liptovsky Jan, Slovakia, 30.09.-4.10.1996, pp. 72-75. 180. Szopa Z., Jaszczuk J., Dybczynski R. A new multifunctional PC program for evaluation of interlaboratory comparison results. Nukleonika, 41,4,117-128 (1996). 181. Szumiell. Regulacja cyklu komdrkowego w napromienionej komdrce zwierz^cej (Cell cycle regulation in the irradiated animal cell). Postspy Biologii Komdrki, 23,1,49-61 (1996). 182. Szytuia A.,Penc B., Kolenda M., Leciejewicz J,, Sttisser N., Zygmunt A. Antiferromagnetic ordering in RPtSn (R = Dy, Ho, Er) compounds. Journal of Magnetism and Magnetic Materials, 153,273-278 (1996). 183. Urbanski P., Kowalska E. Application of the biased regression methods in the calibration of nucleonic gauges. International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.1996, p. 57. 134 THE INCT PUBLICATIONS IN 1996 184. Urbanski Kowalska E., Antoniak W. A simple XRF instrument for rapid analysis and thickness measurement of Sn-Pb layers deposited on the printed boards. International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.1996, p. 55. 185. Urbanski T.S., Fomari P., Abbruzzese C. The extraction of cerium(III) and lanthanum(III) from chloride solutions with LIX 54. Hydrometallurgy, 40,169-179 (1996). f 186. Villanueva L., Ahumada L., Chmielewski A.G., Zimek Z., Bulka S., Licki J. X. ^Possible use of electron beam treatment for removal of SO2 in off-gases from copper smelters. Preliminary tests results. In: Clean Technology for the Mining Industry. Concepcion-Chile University of Concepcion, 1996, pp. 165-174. 187. WaliS L., Rowinska L., Nowicki A Evaluation of the effectiveness of metal purification under slugs using radioactive tracers. International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.1996, p. 71. 188. Wasek M., Kulisa K., Dybczytiski R, A method of the determination of lanthanides in environmental and geological materials by neutron activation analysis after ion exchange preconcentration. Chemia Analityczna, 41,647-660 (19%). 189. Wierzchnicki R., Owczarczyk A. Radiotracer application for bedload movement study in rivers and nearshore marine zone. Acta Geologica Hungarica, 39,208-211 (19%). 190. WiSniowski P. Uczestnictwo sqsiadujqcych grup funkcyjnych w procesach rodnikowych w wybranych organicznych tioeterach (Neighbouring groups participation in radical processes in thioethers). Zjazd Naukowy Polskiego Towarzystwa Qiemicznego i Stowarzyszenia Irtiynierdw i Technikdw Przemystu Chemkznego. Streszczenia. Poznali, Poland, 23-26.09.1996, pp. S2, F22. 191. WiSniowski P., Bobrowski K. Wplyw sqsiadujqcych grup funkcyjnych na przebieg utleniania wybranych organicznych tioeterdw. Stabilizacja utlenionego centrum siarkowego (Influence of functional groups on the oxidation of selected thioethers. Stabilization of the oxidized sulphur center). Sympozjum Chemii i Techniki Radiacyjnej. Streszczenia. Karpacz, Poland, 17-21.09.19%, p. P-11. 192. Wojewddzka M., Kruszewskl M., Szumiel I. Anti-CD38 prevents the development of the adaptive response induced by X-rays in human lymphocytes. Mutagenesis, 11,6,593-5% (19%). 193. Wojewddzka M., Szumiel I. DNA repair in adapted human lymphocytes. 27th Annual Congress of European Society for Radiation Biology. Book of Abstracts. Montpellier, France, 1-4.09.19%, p. 117. ^ 194. jWojtkowska J., Moroz Z, Chmielewski A.G. x Calculations of the spatial dose distribution during irradiation of a gas sample by low-energy electron beam. Electron Beam Flue Gas Treatment - Research Cooperation among JAERI, IAEA and INCT. Proceedings. Warszawa, Poland, 28-30.10.19%, pp. 93-102. 195. Wdjcik A., Streffer C. Analysis of the relationship between radiosensitivity and cell age in proliferating mouse spleen lymphocytes. Radiation Research, 146,577-581 (19%). 1%. Zag6rskiZ.P. Aspekty militarne, spoleczne i polityczne sprawy czarnobylskiej (Military, sociological and political aspects of the Chernobyl accident). THE 1NCT PUBLICATIONS IN 1996 135 XVI Szkoia Jesienna Czamobyl -10 lat pd£niej. Skutki zdrowotne, skatenie Srodowiska i zywnoici. Materiafy konferencyjne. Zakopane, Poland, 14-18.10.1996, pp. 241-249. 197. Zagdrski Z.P. Diffuse reflectance spectrophotometry (DRS) in investigations on radiation chemistry of polymers. 2nd International Symposium on Ionizing Radiation and Polymers. Book of Abstracts. Guadeloupe, Guadeloupe, 3-8.11.1996, p. 008. 198. Zagdrski Z.P. Emission spectra and decay kinetics of pulse irradiated polycrystalline tryptophans. Radiation Physics and Chemistry, 47,3,385-388 (1996). 199. Zagdrski Z.P. Fotochemia, chemia radiacyjna, sonochemia - elementy wspdlne ale i rdinice (Photochemistry, radiation chemistry and sonochemistry: common aspects but also differences), Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Iniynierdw i Technikdw Przemyslu Chemicznego. Streszczenia. Poznali, Poland, 23-26.09.1996, pp. S2, Kl. 200. Zagdrski Z.P. Konsekwencje gniazd wielojonizacyjnych w radiolizie ciala stalego (Consequences of multi-ionization spurs in solid state radiolysis). Sympozjum Chemii i Techniki Radiacyjnej. Streszczenia. Karpacz, Poland, 17-21.09.1996, p. C-28. 201. Zagdrski Z.P. Prdba analizy przyczyn przeklamali dziennikarskich w sprawie czarnobylskiej (An attempt to analyse media-misinformations concerning the Chernobyl accident). Sympozjum Naukowe Czarnobyl 1986-1996. Referaty. Kutno, Poland, 25.05.1996, pp. 89-103. 202. Zagdrski Z.P., Przybytniak G.K. Optical properties of the anion radical derived from a-alanine by deamination. 2nd International Conference of the Polish EPR Association "Electron Paramagnetic Resonance of Radicals and Metal Complexes". Book of Abstracts. Warszawa, Poland, 9-13.09.1996, p. 106 203. Zagdrski Z.P., Rafalski A. Diffuse reflectance spectrophotometry in polypropylene radiolysis study. Radiation Physics and Chemistry, 48,5,595-600 (1996). 204. Zakrzewska-Trznadel G., Chmielewski A.G., Miljevid N.R. Separation of protium/deuterium and oxygen-16/oxygen-18 by membrane distillation. Journal of Membrane Science, 113,337-342 (1996). 205. Zhitariuk N.I., Fiderkiewicz A., Buczkowski M., Kovalev G.N., Orelovich O.L., Zdttowski T. Tensile properties of electron irradiated track membranes. European Polymer Journal, 32,3,391-395 (1996). 206. ZimekZ. Profesor Doktor Zbigniew Pawel Zagdrski - iycie i dzialalnoSd w siedemdziesiqtq rocznicq urodzin (Professor Zbigniew Pawel Zagdrski - life and activities on the 70-ieth Birthday Anniversary). Postspy Techniki Jqdrowej, 39,4,5-7 (1996). 207. ZimekZ. Radiation sterilization facilities of INCT. International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.1996, p. 51. \ 208.' Zimek Z , Bulka S., Hashimoto S. Electron beam scanning and centering automatic control system. Electron Beam Flue Gas Treatment - Research Cooperation among JAERI, IAEA and INCT. Proceedings. Warszawa, Poland, 28-30.10.1996, pp. 66-73. 209. Zimek Z., Krejzler R., Wofnlak A. Radiation processing of heat shrinkable tubes and tapes. 136 THE 1NCT PUBLICATIONS IN 1996 International Conference on Radioisotope and Radiation Application in Industry and Environment. Book of Abstracts. Berlin, Germany, 20-23.10.1996, p. 39. 210. Zimek Z., Panta P., Gluszewski W., Kowalewski R., Wojtynska E. Zastosowanie akceleratorowej wiqzki elektrondw w badaniach wptywu promieniowania jonizujqcego na wlaSciwoSci samoprzylepnych Mejdw akrylowych (Electron beam application in the investigations of ionizing radiation effects on the properties of self-adhesive acrylic glues). Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Iniynierdw i Technikdw Przemyslu Qiemicznego. Streszczenia. Poznafi, Poland, 23-26.09.1996, pp. S14, D43. 211. Zygmunt A., Szytula A., Kolenda M. Tomkowicz Z., StUsser N., Leclejewicz J. Magnetic properties of RAgGa (R = Tb, Dy, Ho) compounds. Journal of Magnetism and Magnetic Materials, 161,127-132 (1996). SUPPLEMENT LIST OF THE INCT PUBLICATIONS IN 1995 212. Chudziak A., Bryl-Sandelewska T., Trojanowicz M. Zastosowanie HPLC z odwrdconymi fazami do monitorowania radiolitycznego rozkladu chlorofenoli (Application of reversed-phase HPLC in monitoring of radiolytic decomposition of chlorophenols). Materialy V Polskiej Konferencji Chemii Analitycznej "Analityka w Shtfbie Czlowieka i Srodowiska". Streszczenia. Gdafisk, Poland, 3-8.09.1995, p. 522. 213. Grodkowski J., Neta P., Hambright P. Radiolytic reduction of rhodium porphyrins. Chain reaction in alkaline 2-propanol. Journal of Physical Chemistry, 95,16,6019-6023 (1995). 214. Palige J., Chmielewski A.G. Some aspects of the destructive impact of fossil fuel combustion and mining on the environment. Proceedings of an International Symposium on "Electricity, Health and the Environment: Comparative Assessment in Support of Decision Making". Vienna, Austria, 16-19.10.1995, pp. 810-817. 215. Stuglik Z. Performance of the radiation facility at JINR U-400 cyclotron as checked through fricke dosimeter measurements. JINR Dubna 1995, Scientific Report 1993-1994, p. 309. 216. Stuglik Z. Some technical problems of A > 50 heavy ion radiation experiments. JINR Dubna 1995, Scientific Report 1993-1994, p. 72. 217. Stuglik Z , Mlchalik J., Stachowicz W., Ostrowski K., Zvara I., Dziedzic-Gociawska A. EPR spectroscopy investigation of bone powder bombarded by y-rays and high-let radiations (a-particles, I2C and ^Mg ions). JINR Dubna 1995, Scientific Report 1993-1994, p. 308. 218. Stuglik Z , Sadto J. Latent tracks generated in a-L-alanine and bovine bone powder by 59 Co ion beams as investigated by EPR-method. JINR Dubna 1995, Scientific Report 1993-1994, p. 307. THE INCT REPORTS IN 1996 137 THE INCT REPORTS IN 1996 1. Annual Report 1995. IChTJ, Warszawa 1996,156 p. 2. Dybczyliski R., Polkowska-Motrenko H., Samczytiski Z., Szopa Z. Preparation and certification of the Polish reference material ORIENTAL TOBACCO LEAVES (CTA-OTL-1) for inorganic trace analysis. IChTJ, Warszawa 1996. Raporty IChTJ. Seria A nr 1/96,60 p. 3. Kruszewski M., Wojewddzka M., Iwaneflko T. Test kometkowy. 1. Teoria i praktyka (Comet assay. 1. Theory and practice). IChTJ, Warszawa 1996. Raporty IChTJ. Seria B nr 1/96,18 p. 4. Kruszewski M. Test kometkowy. 2. Analiza statystyczna wynikdw (Comet assay. 2. Statistical analysis of results). IChTJ, Warszawa 1996. Raporty IChTJ. Seria B nr 2/96,18 p. 5. Wojewddzka M. Indukcja odpowiedzi adaptacyjnej i naprawa w napromienionych ludzkich limfocytach kiwi obwodowej (Induction of the adaptive response and DNA repair in irradiated human peripheral blood lymphocytes). IChTJ, Warszawa 1996. Raporty IChTJ. Seria B nr 3/96,14 p. 6. Dybczyliski R., Samczytlski Z. Devising of the method for the determination of small and very small amounts of cadmium in biological materials by radiochemical version of neutron activation analysis. IChTJ, Warszawa 1996. Raporty IChTJ. Seria B nr 4/96,16 p. 7. Kulisa K., Dybczyliski R., Polkowska-Motrenko H. Badanie zjawiska przeladowania kolumny i jego wplywu na jakoSd wynikdw analitycznych w procesie oznaczania aniondw za pomocq chromatografii jondw (A study on the effect of column overloading and its influence on the quality of analytical results when determining simple anions by ion chromatography). IChTJ, Warszawa 1996. Raporty IChTJ. Seria B nr 5/96,18 p. 8. Machaj B. Obliczanie koncentracji radonu i jego produktdw rozpadu w funkcji czasu. Program komputerowy (Computations of concentration of radon and its decay products against time. Computer program). IChTJ, Warszawa 1996. Raporty IChTJ. Seria B nr 6/96,16 p. 9. Machaj B. Symulacja koncentracji produktdw rozpadu Rn-222 osadzanych na filtrze. Opis programu kompute- rowego radonl.pas (Simulation of Rn-222 decay products concentration deposited on a filter. Descri ption of radonl.pas computer program). IChTJ, Warszawa 1996. Raporty IChTJ. Seria B nr 7/96,12 p. 10. Machaj B. Wstqpna ocena blqdbw miernika koncentracji produktdw rozpadu radonu w powietrzu (Preliminary assessment of errors of radon daughters concentration in air). IChTJ, Warszawa 1996. Raporty IChTJ. Seria B nr 8/96,20 p. 11. Katuska I., Stuglik Z. Radiacyjna steiylizacja sprzqtu medycznego (Radiation sterilization of medical devices). IChTJ, Warszawa 1996. Raporty IChTJ. Seria B nr 9/96,18 p. 138 THE INCT REPORTS IN 1996 12. Urbaliski P. Aproksymacja za pomocq wielomianowych regresyjnych funkcji sklejanych (Function approximation with polynominal regression splines). IChTJ, Warszawa 1996. Raporty IChTJ. Seria B nr 10/96,12 p. 13. Urbaliski P. Programy wyznaczania wielowymiarowych liniowych i nieliniowych model! PLS i PCR w j$zyku MATLAB (Programs for computation PCR and PLS multivariate calibration models using MATLAB package). IChTJ, Warszawa 1996. Raporty IChTJ. Seria B nr 11/96,26 p. 14. Antoniak W., Urbaliski P. Wygladzanie widm promieniowania X metodami regresyjnych funkcji sklejanych i szybkiej transformaty Fouriera (Smoothing X-ray spectra with regression splines and fast Fourier transform). IChTJ, Warszawa 1996. Raporty IChTJ. Seria B nr 12/96,22 p. 15. Kowalska E., Urbaliski P. Badanie mozliwoSci wykorzystania sztucznych sieci neuronowych do wzorcowania przyrzqddw radio- izotopowych (Study of application of artificial neutral network for calibration of nucleonic gauges). IChTJ, Warszawa 1996. Raporty IChTJ. Seria B nr 13/96,16 p. 16. Chwastowska J., Zmijewska W., Sterlifiska E. Badanie wlasnoSci analitycznych sorbentdw chelatujqcych otrzymanych w wyniku osadzania czynnikdw chelatujqcych na stafym podtoZu. Otrzymywanie sorbentu z pyrolidynoditiokarbaminianem amonu i jego zastosowanie do analizy specjacji chromu w wodach naturalnych (Examination of analytical properties of chelating sorbents obtained by deposition of chelating agents on solid supports. Preparation of a sorbent with ammonium pyrollidinodithiocarbamate and its application to spedation analysis of chromium in natural waters). IChTJ, Warszawa 1996. Raporty IChTJ. Seria B nr 14/96,18 p. 17. Migdal W., Owczarczyk H.B. Zbadanie moZliwoSci wykorzystania wiqzki elektrondw w procesie wyjalawiania wybranych fitotera- peutykdw (Microbiological decontamination of some medical herbs by irradiation). IChTJ, Warszawa 1996. Raporty IChTJ. Seria B nr 15/96,22 p. 18. Iwanetiko T., Kruszewski M., Szumiel I., Kapiszewska M., Afanasjev G. Camptothedn effect on nucleoid DNA in X-irradiated and benzamide-treated L5178Y-R and L5178Y-S cells. IChTJ, Warszawa 1996. Raporty IChTJ. Seria B nr 16/96,12 p. 19. ^lonkonen V.A, Chmielewski AG. Electron beam flue gas treatment process. Review. IChTJ, Warszawa 1996. Raporty IChTJ. Seria B nr 17/96,26 p. 20. Migdal W., Owczarczyk H.B., Malec-Czechowska K Badanie wplywu promieniowania jonizujqcego na stopieti czystoSd mikrobiologicznej i wartoSd uZytko- wq wybranych surowcdw oraz wyrobdw kosmetycznych nowej generacji (Investigation of the effect of ionizing radiation on the level of microbiological contamination and usefulness of selected raw materials and cosmetics of new generation). IChTJ, Warszawa 1997. Raporty IChTJ. Seria B nr 18/96,16 p. (in print). NUKLEONIKA 139 NUKLEONIKA THE INTERNATIONAL JOURNAL OF NUCLEAR RESEARCH EDITORIAL BOARD Prof. Andrzej G. Chmielewski, Ph.D., D.Sc. (Editor-in-Chief); Krzysztof Andrze- jewski, Ph.D. (physical sciences); Prof. Bohdan Dziunikowski, Ph D., D.Sc. (technical physics, nuclear physics); Stanislaw Latek, Ph.D. (reactor physics and engineering), Assoc.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, cell radiobiology), Assoc.Prof. Piotr Urbafiski, Ph.D., D.Sc. (measuring instruments, nucleonic control systems) ADVISORY BOARD Prof. Gregory R. Choppin (USA), Dr William C. Cramp (Great Britain), Prof. Andrei Gagarinsky (Russia), Prof. Alexander Van Hook (USA), Prof. Zbigniew Jaworowski (Norway), Prof. Larry Kevan (USA), Prof. Evgeni A. Krasavin (JINR-Dubna), 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. 1/96 1. Kordyasz A.J., Wojtasiewicz A, Nosatewska-Ortowska E, Szarnecki J. Measurement of fission fragments from ^Cf with silicon AE-E telescope 2. Hussein M.O. Nuclear spallation reaction - an intensive source of neutrons 3. Pihowicz W., Kruk K. Method of complex optimization of containments of stationary NPP with PWR reactors 4. Fidziukiewicz I., Kulikowska T. Application of the WIMSD-5A code to reactors with tubular fuel 5. Kowalska M. I. Oncological transformation induced in mouse C3H10T1/2 cells by single doses of 250 kVp X-rays 6. Ignatowicz S. Combined use of gamma irradiation and the bioinsecticide DIPEL 2X, in controlling larvae of the Indian meal moth, Plodia interpunctella (Hiibner) (Lepidoptera; Phycitidae) 7. Ignatowicz S., Wrdblicka-Sysiak M. Reproductive performance of the bulb mite, Rhizoglyphus echinopus IF. et R./, after treatment with low doses of gamma radiation 8. Kierzek J., Matozewska-Budko B. Determination of ash coal based on natural gamma ray activity and X-ray backscattering methods 9. In memory of Professor Jan Andrzej Czubek (1935-1995) 10. In memory of Professor Kazimierz Kurpisz (1947-1995) 140 NUKLEONIKA CONTENTS OF No. 2/96 1. Zychor I. Computer simulation of beam formation in therapeutic accelerators 2. Wysocka A Physical aspects of stereotactic radiosurgery with application of the linear accelerator ARC method 3. Bigolas J., Kuliftski S., Pachan M. Design of the new Polish linear medical electron accelerator (15+18) MeV Limex 15A 4. Cebulska-Wasilewska A, Niediwiedi W., Nowak D., Pawliliski R. Hydrogen peroxide and radiation induced DNA damage investigated by the "comet assay" 5. Antoniuk M., Kulakowski K. Relaxation time of genetic systems 6. Cebulska-Wasilewska A, Wierzewska A, Kasper E., Krzykwa B. Adaptive response after combined treatment of human lymphocytes with deltamethrin and radiation 7. Bielaftski W., Konturek S.J., Dobrzaftska M.J., Plonka M., Sito E., Stachura J., Hoffman S.R., Mar shall B.J. Validation of low activity 14C-urea breath test in diagnosis of Helicobacter pylori in humans 8. Lorkiewicz J., Olszewski J., Plawski E., Sura J., Wojtkowska J. The C-30 compact isochronous cyclotron at 6wierk as a potential source for production of short life-time isotopes 9. Kalmykov L, Gur E. Results of study of Sr-90 and Cs-137 content in organism and effective doses of internal and external irradiation of Ukrainian population residing in different regions 10. Milano F. Mailed Fricke dosimetry of radiotherapy electron and photon beams 11. Niewiadomski T., Bilski P., Budzanowski M., Olko P., Ryba E., Waligdrski M. Progress in thermoluminescent dosimetry for radiation protection and medicine at the Institute of Nuclear Physics, Krakdw 12. Gudowska I., Brahme A Neutron radiation from high-energy X-ray medical accelerators 13. Golnik N., Zielczyliski M. The concept of RIQ and its adaptation to recent recommendations of ICRP for external neutron fields 14. Zielczyftski M., Golnik N., Shvidkij S. V. Recombination chamber and a measuring system with sensitivity sufficient for in-flight and low-level dosimetry 15. Prokert K., Mann G. Photon dose measurements in the environment with LiF: Mg, Cu, P-dosimeters - advantages and prob lems 16. Budzanowski M., Bilski P., Olko P., Delgado A, Saez-Vergara J.C., Waligdrski M.P.R. Shot-term measurements of natural radiation using high-sensitive TL detectors CONTENTS OF No. 3/96 1. Baran A, Lojewski Z. Systematics of a half-lives of heaviest nuclei 2. Wlodek D., Olive P.L. Chromatin structure influence on DNA damage measurements by four assays: pulsed- and cons tant-field gel electrophoresis, DNA precipitation and non-dentaurating filter elution 3. Kowalska M. II. Oncological transformation induced in mouse C3H10T1/2 cells by tritiated water NUKLEONIKA 141 4. Kowalska M. III. Relative biological effectiveness of tritiated water for induction of oncological transformation in mouse C3H10T1/2 cells 5. Migdal W., Malec-Czechowska K, Owczarczyk B. Study on application of e/X conversion for radiation processing 6. Malec-Czechowska K, Dancewicz AM., Szot Z. Application of thermoluminescence analysis for detection of irradiated foodstuffs 7. Bednarek B., JeleA K, Kowalski T.Z., Ostrowski K.W., Rulikowska-Zarqbska E., Sikora T., Nocufi J., Lorek A Application of proportional counters in Polish industry, medicine and agriculture CONTENTS OF No. 4/96 1. B6t5k E., Kapusta M., Rurarz E., Tys J. Calculated cross sections for 123I formation in photon-, proton- and hellium-ion induced reactions on highly enriched 124Xe targets 2. Kordyasz A, Nossarzewska-Orlowska E., Sarnecki J. Large area silicon epitaxial detectors with build in field 3. Aziz M. The effect of temperature and pressure on the coagulation and deposition of aerosols 4. Kulikowska T., Fidziukiewicz I. Criticality calculation for a spent fuel storage of the MARIA reactor 5. Navratil J.D., Stewart AE. Waste treatment using molten salt oxidation 6. Merciano Larosa M.E., Martins de Albuquerque A, Nakahira S., de Castro Rubi Poli D. River water quality studies by using radioactive tracers. A practical case 7. Ignatowicz S. Identification of irradiated insects: alterations in total proteins of irradiated adults of the confused flour beetle, Tribdium confusum Du Val. (Coleoptera: Tenebrionidae) 8. Ignatowicz S., Kamkowski W. Development of the stem nematode, Ditylenchus dipsaci (Kahn) Filipjev, and the potato tuber nema tode, D. destructor Thorne, after gamma irradiation 9. Przylibski T., Zebrowski A Origin of radon in medicinal waters of Swieradtiw Zdrdj 10. Szopa Z, Jaszczuk J., Dybczyliski R. A new multifunctional PC program for evaluation of interlaboratory comparison results Information and subscription INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY NUKLEONIKA Dorodna 16,03-195 Warszawa, Poland phone: (+48-22) 11-06-56 or 11-30-21 int. 14-91; tlx 813027; fax: (+48-22) 11-15-32; e-mail: [email protected] 142 THE INCT PATENTS AND PATENT APPLICATIONS IN 1996 THE INCT PATENTS AND PATENT APPLICATIONS IN 1996 PATENTS 1. Method for obtaining of new materials of metal oxide structure. A Lukasiewicz, L. WaliS, Z. Bazaniak, I. Woiniak Polish Patent 169166 2. Method for obtaining of a new composite based on polypropylene. Z. Zimek, Z. Bulhak, J. Bojarski, K. Mirkowski, W. Stachowicz Polish Patent 169177 3. Method for removal of acid gaseous impurities like SO2 and NO* from industrial flue gases. AG. Chmielewski, Z. Zimek, J. Licki, B. Tymiliski, E. Iller Polish Patent 169749 4. An absorbent for removal of impurities, especially nitrogen oxides, from the air. A Lukasiewicz, L. WaliS, J. Michalik Polish Patent 170570 5. Method for obtaining surface materials from polymerized complexes of 3-amino-l, 2,4-triazole with transition metals. A Lukasiewicz, L. WaliS, J. Michalik Polish Patent 170800 6. Method for obtaining a selective sorbent for ammonium ions. A Bilewicz, L. Fuks Polish Patent 170876 PATENT APPLICATIONS 1. Method for obtaining layers of calcium phosphate, especially of hydroxyapatite. A Deptula, W. Lada, R.Z. LeGeros, T. Olczak, J.P. LeGeros P. 314453 2. Method for removal of sulphur dioxide from gases and for production of sulphuric acid, and a device for application of this method. AG. Chmielewski, T.S. Urbaliski, B. Tymihski, E. Diet, A Krytowicz, C. Wawrzak, Z Ratajewicz, J. Usidus P. 314766 CONFERENCES ORGANIZED BY THE INCT IN 1996 143 CONFERENCES ORGANIZED BY THE INCT IN 1996 1. 2nd INTERNATIONAL CONFERENCE OF THE POLISH EPR ASSOCIATION "ELECTRON PARAMAGNETIC RESONANCE OF RADICALS AND METAL COMPLEXES", 9-13 SEPTEMBER 1996, WARSZAWA, POLAND Lectures • Radicals in DNA as seen by ESR spectroscopy M.C.R. Symons (DeMontfort University, Leicester, Great Britain) • Electron and hole transfer within DNA and its hydration layer M.D. Sevilla, D. Becker, Y. Razskazovskii (Oakland University, Rochester, USA) • Models for photosynthetic reaction center: steady state and time resolved EPR spectroscopy H. Kurreck, G. Eiger, M. Fuhs, A. Wiehe, J. von Geisdorff, P. Tian (Freie Universitat, Berlin, Germany) • Free radical formation in red blood cell components upon paraquat treatment K. Gwofdzitiski (University of L6d2, Poland) • Very high field EPR of multispin metal complexes with semiquinone ligands Ya.S. Lebedev (Institute of Chemical Physics, Russian Academy of Science, Moscow, Russia) • ESR and cyclic voltammetry studies of the cations and anions of a-aminoanthraquinones obtained by electrochemical oxidation/reduction J.A Pedersen (Aarhus University, Denmark), V. Vatanen (University of JyvSskyla, Finland) • Electron spin relaxation and dynamics of radicals in inclusion compounds M. Brustolon (Universita di Padova, Italy) • Transient free radicals and spin polarization K A McLauchlan (Oxford University, Great Britain) • Motional spin relaxation in photoexcited triplet states D. Harryvan, E. van Faassen (Utrecht University, the Netherlands) • ESR of organic radical ions: a personal account F. Gerson (Universitat Basel, Switzerland) • EPR spectroscopy and electron distribution AG. Davies (University College, London, Great Britain) • Electron spin resonance imaging (ESRI) of transport processes in polymeric systems J. Pilar, Z. Gao, K. Malka, K. Kruczala, S. Schlick (University of Detroit, USA) • Electronic structure of charge carriers in polysilane quantum wire J. Kumagai, H. Yoshida, T. Ichikawa (Hokkaido University, Sapporo, Japan) • Pulsed EPR studies of transition metal ions in microporous materials L. Kevan (University of Houston, USA) • A systematic analysis of ID and 2D 14N-ESEEM spectra; application to a nitrogen coordinated oxo-vana- dium complex E. J. Reijerse (University of Nijmegen, the Netherlands), AM. Tyryshkin (Institute of Chemical Kinetics and Combustion, Novosibirsk, Russia), S. A Dikanov (Pacific Northwest National Laboratory, Richland, USA) • CW and pulse EPR study of paramagnetic complexes on the catalytical surfaces R. I. Samoilova (Institute of Chemical Kinetics and Combustion, Novosibirsk, Russia), S.A Dikanov (Pacific Northwest National Laboratory, Richland, USA), AV. Fionov (Moscow State University, Russia), AM. Tyryshkin (Institute of Chemical Kinetics and Combustion, Novosibirsk, Russia), E.V. Lunina (Moscow State University, Russia), M.K. Bowman (Pacific Northwest National Laboratory, Richland, USA) • 2D FT-EPR exchange spectroscopy of organic radicals in solution S. Kababya, D. Goldfarb (Weizmann Institute of Science, Rehovot, Israel) 144 CONFERENCES ORGANIZED BY THE INCT IN 1996 • Study of photoreduction of quinones by Fourier transform EPR D. Beckert (Max Planck Society, Leipzig, Germany) • EPR studies of the role of copper in bio-organic free radical reactions B.C. Gilbert (University of York, Great Britain) • Free radical reaction patterns in condensed media A Ptonka (Technical University of L6dt, Poland) • Kinetics of electron self-exchange reactions measured by EPR-spectroscopy and the application of Marcus theory G. Grampp (Technical University of Graz, Austria) • Muon spectroscopy of organic radicals in biology, catalysis and materials research ChJ. Rhodes (Liverpool John Moore ’s University, Great Britain) • EPR monitoring of plant degradation, humification and coalification A Jezierski (University of Wroclaw, Poland) • Phosphavinyls and other phosphorus containing radicals A Alberti (Istituto del Compost! del Carbonio contenenti Eteroatomi e loro Applicazioni, Consiglio Nazionale delle Ricerche, Bologna, Italy) • Comparative EPR and ENDOR results on carbonate derived radicals in different host materials F. Callens (University of Ghent, Belgium) • Water complexed Mn2+ as a probe in the ESR study of silica glasses obtained by the sol-gel process N. Abidi, B. Deroide, J.-V. Zanchetta (University de Montpellier II, France) • Tetrameric silver clusters in zeolite RHO J. Michalik, T. Wqsowicz (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), Jong-Sung Yu (Han Nam University, Taejon, Korea), L. Kevan (University of Houston, USA) • Cu2+0' hole pairs and O spin bags in Laz-xMxCuCU oxide mixtures C. Oliva, L. Forni (Centro per lo Studio sulle Relazioni tra Struttura e Reacttivita, Consiglio Nazionale delle Ricerche, Milano, Italy; Universita di Milano, Italy), A.V. Vishniakov (D.I. Mendeleev University of Chemical Technology of Russia, Moscow, Russia) • Degradation of paper and characterization of white marbles: examples of ESR applications in the field of cultural heritage D. Attanasio (Istituto Chmica dei Material!, Consiglio Nazionale delle Ricerche, Roma, Italy) • Current state of EPR dose reconstruction with teeth A. A Romanyukha (Institute of Metal Physics, Russian Academy of Sciences, Russia), A Wieser GSF-Forschungszentrum ftir Umwelt und Gesundheit, Institut ftir Strahlenschutz, Neuherberg, Germany), S. Kozheurov , M. Degteva (Urals Research Center for Radiation Medicine, Russia) • EPR of graphite and fullerene J. Stankowski, J. Martinek, W. Kempifiski, L. Piekara-Sady (Institute of Molecular Physics, Polish Academy of Sciences, PoznaA, Poland) • EPR and ENDOR analysis by simulation in disordered and single crystal matrices: influence of strong NQI and microwave power A Lund, R. Erickson, O. Eid (LinkOping University, Sweden) • Analysis of electron spin echo decay and electron spin echo envelope modulation of Cu(II) and Mn(II) in DzO/perfluoropolyether ammonium carboxylate systems S. Ristori, M. Romanelli (Universita Degli Studi di Firenze, Italy), V. Kurshev, L. Kevan (University of Houston, USA) • Emerging techniques to study compartmentalized liquids using EPR B. L. Bales (California State University at Northridge, USA) • ESR investigation of y-irradiated hyperquenched glassy water J. Bednarek, A Ptonka (Technical University of L6di, Poland), E. Mayer, A Hallbrucker (Innsbruck University, Austria), M.C.R. Symons (DeMontford University, Leicester, Great Britain) • EPR study of metallocene-substituted a-nitronyl nitroxide radicals J. Vidal-Gancedo, O. Jurgens, J. Veciana (Institute de Ciencia de Materials de Barcelona, Spain), K Wurst, C. Sporer, K Worm, P. Jaitner (Innsbruck University, Austria) • In situ UV-VIS ESR spectroelectrochemistry A Petr, L. Dunsch, A Neudeck (Institut ftir FestkOperforschung, Dresden, Germany) CONFERENCES ORGANIZED BY THE INCT IN 1996 145 Posters • ESR characterization of catalytically active V centres supported on titania-, zirconia-, and alumina-pillared montmorillonite clays K. Bahranowski (Academy of Mining and Metallurgy, Krakdw, Poland), M. Labanowska (Jagiellonian University, Krakdw, Poland), E.M. Serwicka (Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Krakdw, Poland) • ESR study of some solvent effects on Cu(II)-oxazepam complexes L. David, V. Chris, O. Cozar, E. Forisz, C. Criftiun (University of Cluj-Napoca, Romania) • ENDOR and pulsed ESR study of glycine radicals M Brostolon, AL. Maniero (Universita di Padova, Italy), V. Chris, O. Cozar (University of Cluj-Napoca, Romania) • General conclusions on EPR and ENDOR studies of homogeneous and heterogeneous diatomic chalcogen defects in alkali halides S. van Doorslaer (Laboratorium fiir Physikalische Chemie EidgenOssische Technische Hochschule, Zurich, Switzerland), F. Callens, F. Maes, E. Dobbeleir (University of Ghent, Belgium) • SPIN dosimetry in catalytic research K. Dyrek, E. Bidzifiska, A Made), A Rokosz (Jagiellonian University, Krakfiw, Poland) • EPR studies of synthetic pheo- and mixed type-melanins A DzierZ$ga-L$cznar, B. Pilawa, K. Trzepietowska-Stspiefi, T. Wilczok (Silesian Medical Academy, Sosnowiec, Poland) • EPR of high-spin octaethylporphynatoiron (III) alkoxy complexes K. Dzililiski, T. Szymafiska (Czestochowa Technical University, Poland), N.V. Ivashin, AM. Shulga (Institute of Molecular and Atomic Physics, Byelorussian Academy of Sciences, Milisk, Byelorus), H. Drulis (Institute of Low Temperature and Structural Researches, Polish Academy of Sciences, Wroclaw, Poland) • Effect of EPR spectra resolution degree on accuracy of hyperfine structure parameters determined for isotope substituted Zn-chlorin radicals K. Dzililiski, T. Szymafiska (Czestochowa Technical University, Poland), R. Krzyminiewski (Adam Mickiewicz University in Poznafi, Poland), G.N. Sinyakov, AM. Shulga (Institute of Molecular and Atomic Physics, Byelorussian Academy of Sciences, Mifisk, Byelorus) • Electron spin echo spectroscopy of the glycine radical in diglycine nitrate single crystal M. Gramza, J. Goslar, W. Hilczer, S.K. Hoffmann (Institute of Molecular Physics, Polish Academy of Sciences, Poznafi, Poland) • ESR studies of Cu(II) and VO(IV) ions in organically modified and doped oxide gels B. Grobelna, A Jankowska-Frydel, K. Kledzik, AM. Kkmkowski, T. Widernik (University of Gdafisk, Poland) • ESR spectroscopic investigation of an electron transfer from hydrogen to platinum A Gutsze (Medical Academy in Bydgoszcz, Poland), U. Roland (University Leipzig, Germany), H.G. Karge (Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin, Germany) • Electron spin echo measurements of the free radical spin relaxation in Li(NzH5)SG4 W. Hilczer, P. Morawski, S.K. Hoffmann (Institute of Molecular Physics, Polish Academy of Sciences, Poznafi, Poland) • EPR of Mn2+ in low temperature phase of KzZnCU R. Hrabaftski (Czestochowa Technical University, Poland), A Kassiba (University du Maine, France) • Double-stacked dielectric ring resonator for EPR measurements of biological samples M. Jaworski, A Sienkiewicz (Institute of Physics, Polish Academy of Sciences, Warszawa, Poland), Ch.P. Scholes (State University of New York at Albany, USA) • Paramagnetic resonance and magnetism of binuclear copper(II) complexes with octadentate ligand N, N’,N”,N’”-tetrakis(2-pyridyImethyl)-l,4,8,ll-tetraazacyclotetradecane(tpmc) J. Jezierska (University of Wroclaw, Poland), V.K. Voronkova (Zavoisky Physical-Technical Institute, Kazan, Russian Federation), G. Vuikovid (University of Beograd, Yugoslavia), J. Mrozifiski (University of Wroclaw, Poland), Yu.V. Yablokov (Zavoisky Physical-Tedmical Institute, Kazan, Russian Federation) • The effect of near infrared radiation on the erythrocyte membrane H. Czyzewska, M. Komorowska (Technical University of Wroclaw, Poland) 146 CONFERENCES ORGANIZED BY THE INCT IN 1996 • Radicals as probes of phase transitions in EPR investigation of pyridinium tetrafluoroborate single crystals R. Krzyminiewski, R.M. Kowalczyk, A Bielewicz-Mordalska (Adam Mickiewicz University, Poznati, Poland) • Influence of pressure and temperature on b% spin-hamiltonian parameter for Gd3+ ion in CszNaLaCle single crystal M. Krupski, P. Morawski (Institute of Molecular Physics, Polish Academy of Sciences, Poznati, Poland), AE. Usachev (Zavoisky Physical-Technical Institute, Kazan, Russian Federation) • Potential dependence of a number of the paramagnetic centers in the electronically conducting polymer matrix A Kudelski, J. Bukowska, K. Jackowska (University of Warsaw, Poland) • EPR of divalent manganese in non-Kramers ’ hosts J. Lech, A. Slqzak (Czestochowa Technical University, Poland) • Metalloporphyrin (Cd, Hg) radicals H. Manikowski, M. Loiytiski, E. Kubaszewski (Poznati Technical University, Poland) • A PC-controlled kinetic ESR-experiment with 10 ps time resolution R. Martschke, T. Zytowski, H. Fischer (University Zurich, Switzerland) • Phase transitions in doped systems L.E. Misiak (Marie Curie-Sklodowska University, Lublin, Poland) • EPR study of Gd3+ in Lao.9Ndo.1F3 single crystal M L. Paradowski, L.E. Misiak (Marie Curie-Sklodowska University, Lublin, Poland) • EPR study of copper (II) dipyridine halogenide single crystals F. Nseir, M. Januszczyk, R. Krzyminiewski, J. Pietrzak (Adam Mickiewicz University, Poznati, Poland) • Effects of ultrasound irradiation on the properties of biological homogenates C. Oliva, R. Morelli (Centro per lo Studio sulle Relazioni tra Struttura e Reacttivita, Consiglio Nazio- nale delle Ricerche, Milano, Italy; Universita di Milano, Italy), E. Monti (Istituto di Farmacologia, Universita di Milano, Italy) • A combined EPR and quantum chemical approach to the structure of surface F^" (H) centers on MgO M. C. Paganini (Universita di Torino, Italy), D. Murphy (University of Wales, Cardiff, Great Britain), E. Giamello (Universita di Torino, Italy), AM. Ferrari, G. Pacchioni (Universita di Milano, Italy) • ESR study and MM+ calculus of some asymmetric-triasines copper(II) complexes having high anti viral activity C.G. Palivan, H.M.N. Palivan (University of Bucharest, Romania), B.A Goodman (Scottish Crop Research Institute, Dundee, Great Britain) • EPR study of configuration of divalent copper ion W.E. Panek, J. Pietrzak (Adam Mickiewicz University, Poznati, Poland) • Reactions of substituted boryl radicals with nitroalkanes. An EPR study M. Lucarini, L. Valgimigli, G.F. Pedulli (Universita di Bologna, Italy) • EPR characteristics of metal ions-fungal melanin complexes B. Pilawa, L. BulaS, M. Latocha, E. Buszman, T. Wilczok (Silesian Medical Academy, Sosnowiec, Poland) • The effect of chloroquine on free radical properties of metal ions-dopa-melanin complexes B. Pilawa, K. Wielgosz, M. Latocha, E. Buszman, T. Wilczok (Silesian Medical Academy, Sosnowiec, Poland) • • Multicomponent structure of the EPR spectra of bituminous coal modified in potassium-liquid ammonia system B. Pilawa (Silesian Medical Academy, Sosnowiec, Poland), AB, Wiqckowski (Pedagogical University, Zielona G6ra, Poland), M. Koztowski, H. Wachowska (Adam Mickiewicz University, Poznati, Poland) • EPR studies of thermal decomposition of coal samples B. Pilawa (Silesian Medical Academy, Sosnowiec, Poland), AB. Wiqckowski (Pedagogical University, Zielona G6ra, Poland), M. Lewandowski (Institute of Coal Chemistry, Polish Academy of Sciences, Krakdw, Poland) CONFERENCES ORGANIZED BY THE INCT IN 1996 147 • Cysteamine as radical scavenger in frozen aqueous matrices containing dCMP and IMP G. Przybytniak (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), J. Htittermann (Universitat des Saarlandes, Germany), H. Ambroi (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), B. Weiland (Universitat des Saarlandes, Germany) • Tetragonal site of transition metal ions in chrysocolla R.V.S.S.N. Ravikumar, B.J. Reddy, Y.P. Reddy (Sri Venkateswara University, Tirupati, India) • EPR and optical absorption spectral investigations on Cr-tremolite AV. Chandrasekhar, R.V.S.S.N. Ravikumar, Y.P. Reddy, B.J. Reddy (Sri Venkateswara University, Tirupati, India), P S. Rao (Pondicherry University, India) e Time-resolved ESR-spectroscopy of transient radicals generated by laser flash photolysis K. Dietliker, D.G. Leppard (Ciba-Geigy Ltd., Marly, Switzerland), A Liegard, M. Kunz, G Rist (Ciba-Geigy Ltd., Basle, Switzerland), P. Rzadek (Ciba-Geigy Ltd., Basle, Switzerland; University of Basle, Switzerland), J. Wirz (University of Basle, Switzerland) • ENDOR of human tooth enamel heated at 400°C J. Sadto (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), F. Callens, P. Matthys (University of Ghent, Belgium), J. Michalik, W. Stachowicz (Institute of Nuclear Chemistry and Technology, Warszawa, Poland), E. Boesman (University of Ghent, Belgium) • EPR investigation of the activation of NzO on Mo/SiOz catalysts Z. Sojka (Jagiellonian University, KrakAw, Poland), M. Che (Laboratoire de RAactivitA de Surface, University Pierre et Marie Curie, France) • EPR detection of irradiated mushrooms and condiments W. Stachowicz, G. BurliAska, J. Michalik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • ESR analysis of microcrystalline L-a-alanine and standard bone powder irradiated with Co-59 ion beam Z. Stuglik, J. Sadto (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Kinetic behaviour of photoproduced radical-cations in anionic micelles E. Szajdzinska-Pietek, A Pfonka (Technical University of LAdf, Poland) • EPR as a tool for studying slags and slag-like systems A Slqzak, J. Lech (Czqstochowa Technical University, Poland) • Stabilization of polymer radicals in aqueous solution by electrostatic repulsive forces P. UlaAski, J.M. Rosiak (Technical University of L6dt, Poland) • Numerical methods in resonance line shape analysis AB. Wiqckowski (Pedagogical University, Zielona G6ra, Poland; Institute of Moleculat Physics, Polish Academy of Sciences, PoznaA, Poland) • Electron paramagnetic resonance studies of proteins in ozone treated erythrocyte membranes A WrAbel (Technical University of Wroclaw, Poland), A Jezierski (University of Wroclaw, Poland), J. Gomutidewicz (Technical University of Wroclaw, Poland) • ESR study on molecular dynamics of NOz adsorbed on cation-exchanged mordenites H. Yahiro, M. Nagata, M. Shiotani (Hiroshima University, Japan), M. Lindgren, A Lund (LinkOping University, Sweden) • Electron spin resonance and electron spin echo modulation spectroscopic analysis of cupric ion species in Cu(II)-exchanged K-offretite gallosilicate and Cu(II)-exchanged K-offretite aluminosilicate Jong-Sung Yu, Jang Wang Ryoo (Han Nam University, Taejon, Korea), L. Kevan (University of Houston, USA) • Optical properties of the anion radical derived from a-alanine by deamination Z.P. ZagArski, G.K. Przybytniak (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Antioxidative properties of flavonoids as studied by EPR A ZieliAska (University of Warsaw, Poland), I. Wawer (Medical Academy, Warszawa, Poland), Z. Kq- cki (University of Warsaw, Poland) • ESR study of solid peptides G. Strzelczak-BurliAska, K. Bobrowski, J. Michalik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) 148 CONFERENCES ORGANIZED BY THE 1NCT IN 1996 • An EPR study of radiation damage in a y-irradiated single crystals of selected corticosteroids A Szyczewski, J. Pietrzak (Adam Mickiewicz University, Poznaft, Poland), K. MObius (Free University of Berlin, Germany) • Radicals of melanin as a protector against environmental stress V.V. Teslenko (Institute of Surface Chemistry, National Academy of Ukraine, Kiev, Ukraine) • ENDOR induced by electric field (ELENDOR) V.V. Teslenko (Institute of Surface Chemistry, National Academy of Ukraine, Kiev, Ukraine) • Inhomogeneous line broadening effects in 1H hyscore spectra of betaine phosphite/phosphate single crystals A. Ptippl, R. BOttcher, G. VOlkel (Universitat Leipzig, Germany) e Radical formation in X-irradiated hippuric acid single crystals. ESR/ENDOR study N.A. Salih, A. Sanderud (University of Oslo, Norway), O. Bid, A Lund (University of Linkaping, Sweden), E. Sagstuen (University of Oslo, Norway) 2. THE 7th RESEARCH COORDINATION MEETING OF IAEA, JAERI AND INCT, 28-30 OCTOBER 1996, WARSZAWA, POLAND • Development of EB technology for cleaning flue gases in member states of the IAEA S. Machi (International Atomic Energy Agency, Vienna, Austria) • R&D of technologies relating to environmental conservation in JAERI I. Ishigaki (Japan Atomic Energy Research Institute, Takasaki, Japan) • Electron beam treatment of lignite - burning flue gas S. Hashimoto (Takasaki Radiation Chemistry Research Establishment, Japan Atomic Energy Research Institute, Takasaki, Japan) • Feasibility study of EB technology for flue gas cleaning based on achievements of pilot scale experi ments at Nagoya S. Hashimoto (Takasaki Radiation Chemistry Research Establishment, Japan Atomic Energy Research Institute, Takasaki, Japan) • Contribution of EB Pilot Plant experiences in development of EB technology A. G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Radiotracer experiments in EB installation (flow pattern) E. Iller (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Influence of gas flow patterns on NOx removal efficiency B. Tymifiski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • EB dosimetry in process vessel S. Butka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Measurement of NH3 slip and N2O concentration in flue gas after EB treatment J. Licki (Institute of Atomic Energy, Otwock-Swierk, Poland) • Environmental impact of EB Industrial Demo Plant E. Iller (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • High power electron accelerators Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Engineering characteristics of process units of EB Industrial Demo Installation B. Tymiliski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Radiation protection problems in design works of EB Industrial Demo Plant M. Romanowski (Study and Design Nuclear Technique Office PROATOM. Warszawa, Poland) • Up-date of measuring and control system M. Sowiftski (Sohan Institute for Nuclear Studies, Otwock-Swierk, Poland) CONFERENCES ORGANIZED BY THE INCT IN 19% 149 3. SYMPOSIUM IN HONOUR OF PROFESSOR ZBIGNIEW PAWEL ZAG6r SKI - 45-YEARS OF SCIENTIFIC RESEARCH "RADIATION CHEMISTRY AND TECH NOLOGY. HISTORY AND PERSPECTIVE", 3 DECEMBER 1996, WARSZAWA, POLAND • Characterization of scientific activity of prof. Z.P. Zagdrski (Charakterystyka dzialalnoSci naukowej prof, dra hab. Z.P.Zag6rskiego) Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Fashionable and unfashionable chemistry in twentieth century (Chemie modne i niemodne XX wieku) Z.P Zagdrski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland • Radiation chemistry in relation to biochemistry and photochemistry (Chemia radiacyjna a biochemia i fotochemia) K. Bobrowski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Contribution of radiation chemistry to the development of contemporary theories of reaction dynamics in condensed phases (Wklad chemii radiacyjnej w rozwdj wspdiczesnych teorii dynamiki reakcji w fazach skondensowanych) A Ptonka (Technical University of Ldd£, Poland) • Technological applications of electron beams. We and the world (Technologiczne zastosowania wiqzki elektrondw. My i Wat) AG. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • Charge transport in irradiated polymers (Transport ladunkdw w napromienianych polimerach) J. Kroh (Technical Univeristy ofLddZ, Poland) • Application of biomaterials (Zastosowania biomaterialdw) J.M. Rosiak (Technical University of tddf, Poland) • Freons (Freony) M. ForyS (Agricultural and Teachers University, Siedlce, Poland) • Microporous materials (Materialy mikroporowate) J. Michalik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) • NOa-radical (Rodnik NO3) J. Kaleciliski (W.Trzebiatowski Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Wroclaw, Poland) • Accelerators (Akceleratory) Z Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland) 150 PhD THESES PhD THESES Dariusz Pogocki, M.Sc. Badanic procesdw rodnikowych w aminokwasach 1 peptydach zawierajqcych grup$ tioeterowq indu- kowanych rodnikami wodorotlenkowymi (Investigation of radical processes induced by hydroxyl radical In amino acids and peptides containing thioether group) supervisor: Assoc. Prof. Krzysztof Bobrowski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology, 18.12.1996 DOCTOR OF CHEMISTRY DEGREE PROGRAMME The Institute of Nuclear Chemistry and Technology offers the four years Ph.D. degree programme to graduates of chemical, physical and biological departments of universities, engineers in chemical tech nology and material science and graduates of 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 and in material science. Besides of the employment for candidates accepted for the forementioned programme, the Institute offers an opportunity of application for supplemental doctorial scholarship. During the programme each participant participates in 45 h course of lectures of fundamental physical chemistry, 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 publica tion; • final examination and public defense of the dissertation theses. 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: 11-27-35), or from the Scientific Information Department of the Institute (phone: 11-25-78). RESEARCH PROJECTS AND CONTRACTS 151 RESEARCH PROJECTS AND CONTRACTS RESEARCH PROJECTS GRANTED BY THE POLISH STATE COMMITTEE FOR SCIENTIFIC RESEARCH IN 1996 AND IN PREVIOUS YEARS 1. Investigation of homogeneity of reference materials intended for microanalysis by means of neutron activation analysis method. supervisor: Prof. Rajmund Dybczyliski, PhD., D.Sc. 2. The computer spectra simulation in high resolution gamma-ray spectrometry as a tool enabling optimization of the costs, labour and time in instrumental neutron activation analysis. supervisor: Zygmunt Szopa, M.Sc. 3. Concentration of radioactive wastes using the membrane distillation (MD) process, supervisor: Prof. Andrzej G. Chmielewski, Ph D., D.Sc. 4. Application of the ultrafiitration (UF) and hyperfiltration (HF) to the concentration of liquid radio active wastes. supervisor: Prof. Andrzej G. Chmielewski, PhD., D.Sc. 5. Isotope effects of deuterium and oxygen-18 in the permeation process with phase transition, supervisor: Prof. Andrzej G. Chmielewski, Ph D., D.Sc. 6. Examination of activation of the nuclear transcription factor NF«B in two sublines of L5178Y ceils damaged with X-rays or hydrogen peroxide. supervisor: Prof. Irena Szumiel, Ph D., D.Sc. 7. Identification of irradiated food by use of single cell electrophoresis (comet assay), supervisor: Prof. Zbigniew Szot, PhD., D.Sc. 8. Investigations of new generation of particle track membranes and their applications, supervisor: Assoc-Prof. Tadeusz Zditowski, Ph.D., D.Sc. 9. The influence of the even-odd nucleus number and other factors on the isotope effect accompanying the extraction of the f-electron elements. supervisor: Wojciech Dembifiski, PhD. 10. High coordination number of metal ions in chelate complexes, supervisor: AssocProf. Jerzy Narbutt, Ph.D., D.Sc. 11. Investigations of radical processes induced by hydroxyl radicals in amino acids and peptides containing thioether group. supervisor: Assoc.Prof. Krzysztof Bobrowski, Ph.D., D.Sc. 12. EPR studies of radiation induced radical processes in polycrystalline amino acids and peptides containing sulfur. supervisor: AssocProf. Jacek Michalik, Ph.D., D.Sc. 13. Optical spectra of free radicals in polypropylene at room temperature, supervisor: Prof. Zbigniew P. Zagdrski, Ph.D., D.Sc. 14. The inelastic incoherent neutron scattering investigation of hydrogen bonds vibrations in aliphatic amino acids. supervisor: Prof. Janusz Leciejewicz, Ph.D., D.Sc. 15. Polymer materials with adhesive properties modified by fast electron beams, supervisor: Przemysiaw Panta, Ph.D. 16. Polypropylene composites with thermoplastic elastomers modified by radiation processing, supervisor: Assoc.Prof. Jacek Michalik, Ph.D., D.Sc. 17. 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. 152 RESEARCH PROJECTS AND CONTRACTS 18. Determination of a small and extremely small amounts of uranium in biological materials by radiochemical neutron activation analysis. supervisor: Prof. Rajmund Dybczyliski, PhD., D.Sc. 19. Research on the influence of "protective enzymes" on cell resistance of two L5178Y sublines to hydro gen peroxide. supervisor: E12bieta Bouiyk, Ph D. 20. Characteristics of action of camptothecin, inhibitor of topoisomerase I, in murine lymphoma cells L5178Y. supervisor: Prof. Irena Szumiel, Ph D., D.Sc. 21. Optimization of radiation removal process of SOz and NO* from flue gases containing high concentration of SOz (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 1996 1. Absorptiometer for analysis of dosimetric films. 8 8749 95 C/2294 2. Thermo-melt glue polymer composites with adhesive properties for heat-shrinkable products. 3T 09B 544 96 C/2871 3. Irradiation method for microbiological decontamination of herbal raw materials. 5 PG6G 004 96 C/2870 RESEARCH PROJECTS OF MARIA SKLODOWSKA-CURIE JOINT FUND II IN 1996 1. Reactivity of silver clusters in zeolites. PAA/NSF-92-91 principal investigator: AssocProf. Jacek Michalik, Ph D., D.Sc. 2. Accurate method for the determination of molybdenum, uranium traces in biological materials. PAA/NIST-93-154 principal investigator: Prof. Rajmund Dybczyliski, Ph D., D.Sc. IAEA RESEARCH CONTRACTS IN 1996 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 radionuc lides. POL/7216/RB principal investigator: Aleksander Bilewicz, Ph D. 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 Dybczyliski, Ph.D., D.Sc. 4. To provide a PC implementation of the agency ’s analytical quality control service (AQCS) inter comparison program. 7741/RB/TC principal investigator: Zygmunt Szopa, M.Sc. 5. 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 153 6. Thin layer alanine dosimeter with optical spectrophotometric evaluation. 8533/RB principal investigator: Prof. Zbigniew P. Zagdrski, Ph.D., D.Sc. IAEA TECHNICAL CONTRACTS IN 1996 1. Electron beam flue gas treatment POL/8/013 2. Industrial scale demonstration plant for electron beam purification of flue gases. POL/8/D14 3. Universal radioisotope relay. Continuous level gauge. Coating thickness gauge. Thickness gauge for glass sheets. Density gauge. IRA/8/012/133C 4. Development and construction of electronic unit for coal ash gauge with automatic gain control circuit, scintillation probe with Nal Scintillator 2x2", In industrial housing incl.: electronics for gauge, soft ware. IRA8/D12/190C EUROPEAN COMMISSION RESEARCH PROJECTS IN 1996 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: Martin Kruszewski, Ph.D. 2. Decontamination of aqueous waste streams. CIPA-CT93-0224 supervisor: AssocProf. Jerzy Narbutt, PhD., D.Sc. 3. Examination of homological recombination in mammalian cell mutants defective in DNA double strand break repair. ERB CIPD CT-930417 supervisor: Prof. Irena Szumiel, Ph.D., D.Sc. 4. Establishment of an Eastern European Network of Laboratories for Identification of Irradiated Foodstuffs. a) ERB CIPA CT 940134-2 supervisor: Watiaw Stachowicz, Ph.D. b) ERB CIPA CT 940134-3 supervisor: Wojtiech Migdal, PhD. OTHER FOREIGN CONTRACTS IN 1996 1. Preparation of cathodic materials precursors for fabrication of rechargeable Li batteries (LI manganates, LIC0O2, LiNio.5Coo.5O2) by sol-gel process. 2526-ERG/TEA Contract with ENEA, Italy principal investigator: Andrzej Deptula, Ph.D. 2. Validation of an immunochemical assay for the detection of DNA damage as a tool for biological dosimetry of human exposure to Ionising radiation. Contract with TNO Prins Maurits, Holland principal investigator: Jolanta Zaim 154 LIST OF THE VISITORS TO THE INCT IN 1996 LIST OF VISITORS TO THE INCT IN 1996 Name Institution Country Period 1. C. Abbruzzese Institute of Mineral Processing CNR Italy two weeks 2. L. Actina Latvian Academy of Sciences, Institute of Inor Latvia one week ganic Chemistry 3. H. Afarideh International Atomic Energy Agency Iran short visit 4. L. Ahmuda Chilean Nuclear Energy Commission Chile about three months 5. H. Al-Kassiri International Atomic Energy Agency Syria short visit 6. M.R. Alkowni International Atomic Energy Agency Jordan short visit 7. A Al-Murshed International Atomic Energy Agency Saudi short visit Arabia 8. Sh. Aoki Ebara Corporation, EBA Engineering Department Japan short visit 9. J. Belloni Universite de Paris XI (Paris Sud) France one week 10. A Borisenko International Atomic Energy Agency Kazakhstan short visit 11. A Borisova University of Chemical Technology and Metallurgy Bulgaria one week 12. Byung-Sun Choi Korea Electric Power Corporation Korea short visit 13. F. Callens University of Ghent Belgium one week 14. A Ciancia ENEA, C.R.E. Italy short visit 15. N. Confuorto Research Comtrell USA short visit 16. S. Czigrinov Sciences and Technical Centre of "Sosny", Aca Byelarus short visit demy of Sciences of Byelarus 17. M.K. Daghash International Atomic Energy Agency Jordan short visit 18. R. Delmas CEA/CNR, Laboratoire Pierre Sue France one month 19. Dong-Wha Kim Korea Electric Power Corporation Korea short visit 20. N. Doronkin Centre of Scientific and Technical Activity and Byelarus short visit Investigations 21. W. Ellison Ellison Consultant's USA one week 22. J. Espinoza Chilean Nuclear Energy Commission Chile one month 23. O.L. Fainchtein ENERGOSTAL Ukraine two weeks 24. ML Ferreira Polonia Technological and Nuclear Institute Portugal one week 25. Genii Li Shanghai Institute of Nuclear Research, Chinese China two weeks Academy of Sciences 26. R. Genuario Virginia Accelarators Corporation USA two short visits 27. L. Giorgi ENEA, C.R.E. Italy short visit 28. A. Habjouqa International Atomic Energy Agency United short visit Nations 29. Haji Azim Atomic Energy Organization of Iran Iran short visit 30. M. Haji-Saeid International Atomic Energy Agency Iran short visit 31. M. HSrkOnen Virginia Accelarators Corporation USA two short visits 32. S. Hashimoto Japan Atomic Energy Research Institute, Takasaki Japan short visit Radiation Chemistry Research Establishment, De partment of Radiation Research for Environment and Research 33. J. Holcman Ris0 National Laboratory Denmark one week LIST OF THE VISITORS TO THE INCT IN 1996 155 34. V. Honkonen University of Kuopio, Department of Applied Finland three months Physics 35. I. Ishigaki Japan Atomic Energy Research Institute, Takasaki Japan short visit Radiation Chemistry Research Establishment 36. Jin Young Boo Samsung Heavy Industries.Co. Korea short visit 37. Jong-Sung Yu Han Nam University Korea two weeks 38. K. Kamishima Ebara Corporation, EBA Engineering Department Japan short visit 39. T.J. Kemp University of Warwick Great two weeks Britain 40. Kihun Job Samsung Heavy Industries Co. Korea short visit 41. M.R. Koltun ENERGOSTAL Ukraine one month 42. J. Laria Menchaca Centro de Estudios Aplicados al Desarrolo Nuclear Cuba three months 43. S. Machi International Atomic Energy Agency United one week Nations 44. A Maezawa Ebara Corporation, EBA Engineering Department Japan two short visits 45. P. Matthys University of Ghent Belgium one week 46. N. MiljeviC Institute of Nuclear Sciences Yugoslavia one week 47. M. Mostafavi Universite de Paris XI (Paris Sud) France one week 48. A Moussa International Atomic Energy Agency Syria short visit 49. G.S. Murthy School of Chemistry, Andhra University, Visa- India short visit khapatnam 50. H. Namba Japan Atomic Energy Research Institute, Takasaki Japan short visit Radiation Chemistiy Research Establishment 51. H. Nichipor Institute of Radiation Physical and Chemical Prob Byelarus four weeks lems, Academy of Sciences of Byelarus 52. H. Norkojouri Atomic Energy Organization of Iran, Nuclear Iran six months (till Research Center 06.03.1997) 53. V. Ohkrimenko International Atomic Energy Agency Austria short visit 54. O.M. Pietruchin Mendeleev University of Chemical Technology Russia short visit 55. V. Piotrovskiy ENERGOSTAL Ukraine two weeks 56. H. Rahimi Atomic Energy Organization of Iran, Nuclear Iran two weeks Research Center 57. Renchang Hou Shanghai Institute of Nuclear Research, Chinese China two weeks Academy of Sciences 58. J.L.S. Romero Advanced Institute of Nuclear Science and Tech Cuba two months nologies 59. M.V. Sagaidak ENERGOSTAL Ukraine one month 60. M. Samiei International Atomic Energy Agency United short visit Nations 61. I. Saphonov International Atomic Energy Agency Kazakhstan short visit 62. J. Satyanarayana School of Chemistry, Andhra University, Visa- India ten months (till khapatnam October 1997) 63. A Sereno University of Porto Portugal one week 64. M.P. Sequeira Esteves Technological and Nuclear Institute Portugal one week 65. Z. Serikbaeva International Atomic Energy Agency Kazakhstan short visit 66. A Shahrokhi Atomic Energy Organization of Iran, Nuclear Iran one month Research Center 67. H. Sunaga Takasaki Radiation Chemistry Research Estab Japan three weeks lishment 156 LIST OF THE VISITORS TO THE INCT IN 1996 68. J. Thereska International Atomic Energy Agency United short visit Nations 69. B. Tronin International Atomic Energy Agency Kazakhstan short visit 70. E. Vansant University of Antwerp Belgium one week 71. L.M. Villanueva Chilean Nuclear Energy Commission Chile about three months 72. Z. Zarina Latvian Academy of Sciences, Institute of Inor Latvia one week ganic Chemistry 73. B.M. Zeliksson OPTIKA - St. Petersburg Russia short visit 74. A. Zhetabev International Atomic Energy Agency Kazakhstan short visit 75. Zhiyuan Zhu Shanghai Institute of Nuclear Research, Chinese China two weeks Academy of Sciences