rth - osti.gov

ISSN 1425-204X

INSTITUTEOF NUCLEAR CHEMISTRYAND TECHNOLOGY

(27/a)

rth

PL9802027

1997

2 9 - 4 3

INSTITUTEOF NUCLEAR CHEMISTRYAND TECHNOLOGY

SiF 1997

EDITORS

Wiktor Smuiek, Ph.D.Ewa Godlewska

PRINTING

Sylwester Wojtas

© Copyright by the Institute of Nuclear Chemistry and Technology, Warszawa 1997All rights reserved

CONTENTS

GENERAL INFORMATION 7

MANAGEMENT OF THE INSTITUTE 9MANAGING STAFF OF THE INSTITUTE 9HEADS OF THE INCT DEPARTMENTS 9

PROFESSORS AND SCIENTIFIC COUNCIL 10PROFESSORS 10ASSOCIATE PROFESSORS 10ASSISTANT PROFESSORS (Ph.D.) 11SCIENTIFIC COUNCIL (1995-1999) 12HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (1995-1999) 14

RADIATION CHEMISTRY AND PHYSICS 15•OH RADICAL INDUCED OXIDATION OF CONFORMATIONALLY CONSTRAINED SULPHUR-CONTAININGAMINO ACIDSD. Pogocki, A. Sci gosz, K. Bobrowski, K.-D. Asmus 17

REACTIONS OF HYDROXYL RADICAL WITH THIOAMIDESP. WiSniowski, K. Bobrowski 19DIRECT EFFECT OF IONISING RADIATION ON DNA, INFLUENCE OF COPPER IONSH.B. Ambroz, E. Komacka, G. Przybytniak 21INFLUENCE OF IRON IONS ON RADIATION-GENERATED DNA RADICALSH.B. Ambroz, E. Kornacka, G. Przybytniak 23CCI4 REMOVAL FROM DRY AIR UNDER INFLUENCE OF ELECTRON BEAMH. Nichipor, E. Dashouk, AG. Chmielewski, Z. Zimek, S. Bulka 24THE REMOVAL OF 2,4-DICHLOROPHENOL FROM AQUEOUS SOLUTIONS USING y-IRRADIATIONM. Trojanowicz, P. Drzewicz, P. Panta, W. Gtuszewski 25ORGANIC RADICALS STABILIZED IN AIPO4 MOLECULAR SIEVESZ. Stuglik, S. Kowalak, A Jankowska, K. Kruszona 27THE EFFECT OF HIGH LET RADIATION ON THE DYNAMICS OF MICROWAVE POWER SATURATIONOF EPR SIGNAL IN ALANINEB. Ciesidski, Z. Stuglik, L. Wielopolski, I. Zvara 28

DIFFERENTIAL ENERGY OF ION PAIR FORMATION IN AIR BOMBARDED WITH 240 MeV Ca-40 IONSZ. Stuglik, P.Yu. Apel 28ESR AND OPTICAL STUDIES OF CATIONIC SILVER CLUSTERS IN ZEOLITE rhoJ. Michalik, J. Sadto, T. Kodaira, S. Shimomura, H. Yamada 30ESR STUDY OF SOLID PEPTIDESG. Strzelczak, K. Bobrowski, J. Michalik 32EPR SPECTRA OFy-IRRADIATED DL-a-ALANINE SUPPORTED ON MOLECULAR SIEVESZ. Stuglik, S. Kowalak, A Jankowska, K. Kruszona 33DIFFERENTIAL SCANNING CALORIMETRY STUDIES OF GAMMA IRRADIATION INFLUENCEON STARCH GELATINIZATIONK. Cie&a, E. Svensson, A.-Ch. Eliasson 34

IONIZATION-INDUCED DAMAGE INCREASE IN As-IMPLANTED GaAsS. Warchol, H. Rzewuski 35HEAVY IONS IRRADIATION EFFECTS IN POLY(BUTYLENETHEREPHTHALATE)K. QeSla, E. Ferain, R. Legras, W. Starosta 37

RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS,CHEMISTRY IN GENERAL 39COMPLEXATION OF f-ELECTRON (3+)IONS WITH PSEUDOHALIDE LIGANDSM. Borkowski, S. Lis, S. Siekierski 44SYNTHESIS AND ION EXCHANGE PROPERTIES OF MANGANESE(IV) DIOXIDE DOPED BY +3 TRANSITIONMETAL CATIONSB. Bartos", A. Bilewicz 41

DENSITY FUNCTIONAL CALCULATIONS ON HYDROGEN-BONDED HYDRATES OF METALACETYLACETONATESJ. Narbutt, M. Czerwirtski 42

ON THE CORRELATION BETWEEN CHEMICAL AND OPTICAL ISOTOPE SHIFTSW. Dembhiski, M. Ponifiski 43

INNER-SPHERE SOLVATION OF SCANDIUM TROPOLONATE AND ETHYLMALTOLATE IN SOLUTIONJ. Narbutt, J. Krejzler, D. Dymecka 44

INVESTIGATION OF THE STABILITY OF VARIOUS MERCURY COMPOUNDS IN SAMPLES OF RIVERWATERS AND MODIFICATION OF THE METHOD OF THEIR DETERMINATIONL. Pszonicki, W. Skwara, J. Dudek, E. Sterlifeka, J. Chwastowska 46

INVESTIGATION OF VARIOUS MODIFIERS AND THEIR BEHAVIOUR AT THE DETERMINATIONOF ARSENIC BY GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROMETRYL. Pszonicki, J. Dudek 47

ASSEMBLING OF LABORATORY EQUIPMENT FOR THE INVESTIGATION OF TEMPERATURE INFLUENCEON THE SEPARATION OF MOST COMMON ANIONS WITH THE USE OF ION CHROMATOGRAPHYK. Kulisa, R. Dybczyrtski, H. Polkowska-Motrenko 47

ELABORATION OF AN IMPROVED VERSION OF A PROGRAM FOR INTERPRETATION OF RESULTSOF INTERLABORATORY COMPARISONS AND ITS USE FOR CERTIFICATION OF A NEW REFERENCEMATERIAL: CTA-VTL-2, AS WELL AS VALIDATION OF SOME DATA BY MEANS OF OUR OWN ACCURATERNAA METHODSR. Dybczyrtski, H. Polkowska-Motrenko, Z. Samczyfiski, Z. Szopa 48

ADAPTATION OF THE RDF METHOD FOR INVESTIGATION OF MEMBRANE-PENETRANT SYSTEMSH. Grigoriew, AG. Chmielewski 50

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS OF HETEROCYCLIC CARBOXYLIC ACIDS.PART XIX. THE CRYSTAL STRUCTURE OF STRONTIUM COMPLEXWITH PYRAZINE-2,5-piCARBOXYLIC ACIDH. Ptasiewicz-Bak, J. Leciejewicz 52

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS OF HETEROCYCLIC CARBOXYLIC ACIDS.PART XX. THE CRYSTAL STRUCTUREOFCIS-TETRAAQUOBIS(PYRAZINE-2-CARBOXYLATO-O,N)STRONTIUM(II)H. Ptasiewicz-Bak, J. Leciejewicz 53

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS OF HETEROCYCLIC CARBOXYLIC ACIDS.PART XXI. THE CRYSTAL STRUCTUREOFTRANS-DIAQUOBIS(5-METHYLPYRAZINE-2-CARBOXYLATO-N,O)NICKEL(II)H. Ptasiewicz-Bak, J. Leciejewicz 53

CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDS OF HETEROCYCLIC CARBOXYLIC ACIDS.PART XXII. THE CRYSTAL STRUCTURE OF COBALT(II) AND ZINC(II) COMPLEXESWITH FURAN-2-CARBOXYLIC ACIDB. Paluchowska, T. Lis, J. Leciejewicz 54

MAGNETIC ORDERING IN LANTHANIDEINTERMETALLIC PHASESJ. Leciejewicz, A. Szytute 54

STRUCTURE, CHARGE AND SPIN DENSITY IN Na2Ni(CN)4 -3H2O AT 295 AND 30 KH. Ptasiewicz-Bak, I. Olovsson, G.M. Mclntyre 57

WHAT RESULTS FROM THE SOLUBILITY DATA IN THE Ce2(SO4)3-H2O SYSTEM?T. Mioduski 58

RADIOBIOLOGY 61DIFFERENTIAL EXPRESSION OF C-MYC PROTEIN IN X-IRRADIATED L5178Y SUBL1NES WITH FUNCTIONALOR DEFECTIVE DNA REPAIRI. Szumiel, M. Kapiszewska, A. John, B. Sochanowicz, A. Jaworska 63

REDOX DEPENDENT ACTIVATION OF NFKB IN X-IRRADIATED OR HYDROGEN PREROXIDE TREATEDL5178Y SUBLINESB. Sochanowicz, I. Grqdzka, E. Przygoda, I. Szumiel 63

INDUCTION AND REPAIR OF DOUBLE-STRAND DNA BREAKS (DSBs) IN 5 CELL LINES AFTER SUBLETHALDOSES OFX-RADIATION - USE OF PULSE-FIELD GEL ELECTROPHORESISI. Gradzka, A. Jaworska, A. Wojcik 65

CELL CYCLE ARRESTS AND APOPTOSIS IN X-IRRADIATED DIFFERENTIALLY RADIOSENSITIVE L5178YSUBLINESI. Gradzka, B. Sochanowicz, A. Jaworska, I. Szumiel 66

DO LOW DOSES OF IONIZING RADIATION INDUCE CHROMOSOMAL REPAIR ACTIVITY? SCREENINGHUMAN T CELL EXTRACTS MICROINJECTED INTO MOUSE EMBRYOSA. Wojcik, J.D. Shadley, Ch. Streffer 67

DNA DAMAGE CAUSED BY Cr(VI) IONS IN TWO L5178Y MOUSE LYMPHOMA SUBLINES WITH VARIOUSANTIOXIDANT ENZYME ACTIVITIESE. Bouzyk, M. Kmszewski 68

EFFECTS OF IRON CHELATOR, DESFERAL AND COPPER CHELATOR, NEOCUPREINE ON MICRONUCLEIFREQUENCY IN L5178Y CELLSE. Bouzyk, P. Fuchs 68

SPONTANEOUS REARRANGEMENTS DURING INCORPORATION OF FOREIGN DNA IN CHO-K1 CELLSDEFECTIVE IN DNA REPAIRM. Kruszewski, I. Buraczewska, M. Trzaska, N. Jarocewicz 69

DIFFERENTIAL INHIBITORY EFFECT OF OK-1035 ON DNA REPAIR IN L5178Y-R AND L5178Y-S SUBL1NESWITH FUNCTIONAL OR DEFECTIVE REPAIR OF DOUBLE STRAND BREAKSM. Kruszewski, T. Iwaneriko, M. Wojew6dzka, I. Szumiel, A. Okuyama 71

DNA REPAIR IN ADAPTED HUMAN LYMPHOCYTES: COMPARISON OF THE COMET AND SANDWICH ELISAMETHODSM. Wojewodzka, A. Szcz^ch, P. Fuchs 72VALIDATION OF AN IMMUNOCHEMICAL ASSAY FOR THE DETECTION OF DNA DAMAGE AS A TOOLFOR BIOLOGICAL DOSIMETRY OF HUMAN EXPOSURE TO IONIZING RADIATIONM. Wojewodzka, G.P. van der Schans, AJ. Timmerman 72

NUCLEAR TECHNOLOGIES AND METHODS 75PROCESS ENGINEERING 77TRACER MEASURMENTS OF EFFLUENT TRANSPORT PARAMETERS ON A SELECTED SECTIONOF THE WKRA RIVERA Owczarczyk, G. Kurzawski 77

A RADIOTRACER STUDY ON THE LOCALIZATION OF FAVOURABLE SEDIMENTATION ZONEIN A BIG INDUSTRIAL SEDIMENTATION BASINA Owczarczyk, J. Palige, AG. Chmielewski 78

EMPIRICAL MODEL EQUATIONS FOR THE REMOVAL EFFICIENCY OF SO2 AND NOX IN A MULTISTAGEE-B SYSTEM OF FLUE GASES PURIFICATIONAG. Chmielewski, A. Dobrowolski, B. Tymiriski, J. Licki, E. Iller 79

PARAMETRISATION AND MODELLING OF LONGSHORE SEDIMENTS TRANSPORT RATES IN THE COASTALZONE OF BALTIC SEAA Owczarczyk, R. Wierzchnicki, Z. Pruszak 80

A TRACER STUDY OF THE CONTACT BETWEEN TWO POPULATIONSA Owczarczyk, J. Palige 81

MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS 83PREPARATION OF Pt-WO3(W)/C CATALYST POWDERS (10 AND 20% Pt) AND THIN COATINGSBY THE COMPLEX SOL-GEL PROCESS (CSGP)A Deptuta, W. Lada, T. Olczak, B. Sartowska, A Ciancia, L. Giorgi, A. Di Bartolomeo 83

SYNTHESIS OF ELECTROCHEMICAL QUALITY LixMn2O4±<$ (x=0.55-l.l) POWDERS BY THE COMPLEXSOL-GEL PROCESS (CSGP)A Deptuta, W. Lada, A. Ciancia, L. Giorgi, F. Aiessandrini 86

SYNTHESIS OF ELECTROCHEMICAL QUALITY LiNio 5C00 5O2 POWDERS BY THE COMPLEX SOL-GELPROCESS (CSGP)A. Deptuta, W. Lada, T. Olczak, A Ciancia, L. Giorgi, F. Aiessandrini 89

AN ATTEMPT TO DETERMINE MAJOR AND TRACE ELEMENTS IN ANCIENT GOLD AND SILVERARTIFACTS OF MATERIAL CULTURE BY REACTOR NEUTRON ACTIVATION ANALYSISL. Rowiriska, E. Paiiczyk, J. Andrzejewski, B. Sartowska, L. WaliS 92

PULSED PLASMA BEAM MIXING OF TITANIUM AND MOLYBDENUM WITH SAPPHIREJ. Piekoszewski, E. Wicser, J. Langner, R. Groetschel, H. Reuter, Z. Werner 94MODIFICATION OF SILICON NITRIDE CERAMICS WITH HIGH INTENSITY ION PULSESF. Brentscheidt, J. Piekoszewski, E. Wieser, J. Langner, R. Groetschel, H. Reuter 95NEW MATERIALS CONTAINING SILVER ON SUPPORT SURFACE AS POTENTIAL CATALYSTSA Lukasiewicz, L. WaliS, J. Michalik, J. Sadto 96POTASSIUM DETERMINATION IN ANCIENT GLASSES BY DETECTION OF ITS NATURAL GAMMA RAYACTIVITYJ J. Kunicki-Goldfinger, J. Kierzek 96

PEN AS MATERIAL FOR PARTICLE TRACK MEMBRANESW. Starosta, D. Wawszczak, M. Buczkowski 98MATERIALS FOR IN-SITU MONITORING OF LIGHT WATER REACTOR (LWR). WATER CHEMISTRYBY OPTICAL METHODSL. Fuks, C. Degueldre, E. Schenker 99

RADIATION TECHNOLOGIES 102HIGH-DOSE DOSIMETRY TECHNIQUES FOR QUALITY ASSURANCE IN RADIATION PROCESSINGZ.P. Zagorski 102RESEARCH ON RADIOLYSIS EFFECTS DURING PAPER DISINFECTION WITH IONIZING RADIATIONA Ldiwa-Kania, P. Rudniewski, P. Panta, W. Gtuszewski 103PRELIMINARY STUDY OF ALANINE-POLYMER RODS, MANUFACTURED IN THE INCT, IRRADIATEDWITH GAMMA RAYSZ. Stuglik, T. Bryl-Sandelewska, K. Mirkowski 104

EFFECT OF STORAGE CONDITIONS AND GAMMA IRRADIATION OF MEAT ON DNA ANALYZEDBY "COMET1 ASSAYZ. Szot, K. Malec-Czechowska, T. Iwanertko, M. Kruszewski, M. Wojew<5dzka, AM. Dancewicz 105

ELECTRON BEAM AS METHOD OF REMOVAL OF VOCs FROM GAS STREAMA Ostapczuk, AG. Chmielewski, V.A Honkonen 107

NUCLEONIC CONTROL SYSTEMS 109CALIBRATION OF 222Rn PROGENY MEASURING INSTRUMENTST. Radoszewski 109MEASURING PROBE FOR MONITORING CONCENTRATION OF RADONJ. Bartak, P. Pierikos 110AGC CONTROLLED SCINTILLATION PROBE FOR INDUSTRIAL APPLICATIONJ. Mirowicz, B. Machaj 111

SHORT LIVED RADON DECAY PRODUCTS IN LUCAS CHAMBERB. Machaj 112ASSESSMENT OF LINEAR REGRESSION MODELS USING THE BOOTSTRAPP. Urbartski, E. Kowalska 114PRELIMINARY RESULTS OF CARBON CONTENT DETERMINATION IN COAL BY XRFJ.L. Parus, J. Kieizek, B. Matozewska-Buflco 116A NEW TOTAL REFLECTION X-RAY FLUORESCENCE SPECTROMETERJ. Kierzek, J.L. Parus, B. Matozewska-Budko, U. Waldschlager 116

THE INCT PUBLICATIONS IN 1997 119

THE INCT REPORTS IN 1997 139

NUKLEONIKA 141

THE INCT PATENTS AND PATENT APPLICATIONS IN 1997 147PATENTS 147

PATENT APPLICATIONS 147

CONFERENCES ORGANIZED BY THE INCT IN 1997 148

COURSES ORGANIZED BY THE INCT IN 1997 153

PhD THESES 157

RESEARCH PROJECTS AND CONTRACTS 159RESEARCH PROJECTS GRANTED BY THE POLISH STATE COMMITTEEFOR SCIENTIFIC RESEARCH IN 1997 AND IN PREVIOUS YEARS 159IMPLEMENTATION PROJECTS GRANTED BY THE POLISH STATE COMMITTEE

FOR SCIENTIFIC RESEARCH IN 1997 160

GOVERNMENT STRATEGIC PROGRAM 160

IAEA RESEARCH CONTRACTS IN 1997 160

IAEA TECHNICAL CONTRACTS IN 1997 161

EUROPEAN COMMISSION RESEARCH PROJECTS IN 1997 161

OTHER FOREIGN CONTRACTS IN 1997 161

LIST OF VISITORS TO THE INCT IN 1997 163

THE INCT SEMINARS IN 1997 166

A COMPUTER NETWORK (LAN) IN THE INCT 167

GENERAL INFORMATION

GENERAL INFORMATION

The Institute of Nuclear Chemistry and Technology (INCT) is one of the successors ofthe Institute of Nuclear Research (INR) which was established in 1955. The latterInstitute, once the biggest Institute in Poland, has exerted a great influence on thescientific and intelectual life in this country.

The INCT came into being as one of the independent units established after thedissolution of the INR in 1983.

The fundamental research on radiobiology, radio- and coordination chemistry andradiation chemistry is continued.

The Institute offers academic and research programmes for Ph.D. and D.Sc. thesis inchemistry.

Institute is one of the most advanced science and technology centres working ondevelopment of technologies and methods in the field of:• radiation chemistry and technology,• application of nuclear methods in material and process engineering,• design and manufacturing of instruments based on nuclear techniques,• trace analysis and radioanalytical techniques,• environmental research.

At this moment, with its nine electron accelerators in operation and with the staffexperienced in the field of electron beam applications, the Institute is one of the mostadvanced centres of science and technology in this domain. The following activity shouldhere be mentioned:• experimental pilot plant for food irradiation,• pilot plant for radiation sterilization of medical devices and transplantations,• pilot plant for radiation modification of polymers,• pilot plant for removal of SO2 and NOx from flue gases.

In 1997 the Institute was the host of the International Symposium on Radiation Tech-nology for Conservation of the Environment with 120 participants and observers from 40countries.

The IAEA Interregional Training Course on Developments in the Application ofElectron Beams in Industry and Environmental Protection was held in Warszawa. Theparticipants of the Course represented 23 national atomic agencies. The experiments anddemonstration were held at irradiation facilities of the Institute.

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 forassessing 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 Eastearn 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

GENERAL INFORMATION

of rechargeable Li batteries (Li manganates, LiCoO2, LiNio.5Coo.5O2) by sol-gelprocess.Two students from Ecole de Mines de Nantes (France), nine fellowship holders from

the IAEA and other six fellows were trained at the Institute.The INCT participates in IAEA technical cooperation programmes and organizes

training courses. The employees of the Institute undertake many expert missions for theIAEA.

The Polish Section of the International Nuclear Information System is situated in theINCT.

The Institute is the editor of NUKLEONIKA - world wide recognized journal fornuclear research.

MANAGEMENT OF THE INSTITUTE

MANAGEMENT OF THE INSTITUTE

MANAGING STAFF OF THE INSTITUTE

DirectorAssocProf. Lech Walis, Ph.D.

Deputy Director for Research and DevelopmentProf. Andrzej G. Chmielewski, Ph.D., D.Sc.

Deputy Director for AdministrationEdmund Freliszka, M.Sc.

Accountant GeneralBarbara Kazmirska

HEADS OF THE INCT DEPARTMENTS

• Department of Nuclear Methods of Material • Department of Radiation Chemistry andEngineering TechnologyAssocProf. Lech WaliS, Ph.D. Zbigniew Ziraek, Ph.D.

• Department of Structural Research • Department of Analytical ChemistryWojciech Starosta, M.Sc. Prof. Rajmund Dybczynski, Ph.D., D.Sc.

• Department of Radioisotope Instruments and • Department of Radiobiology and HealthMethods ProtectionProf. Piotr UrbaAski, Ph.D., D.Sc. Prof. Irena Szumiel, Ph.D., D.Sc.

• Department of Radiochemistry • Pilot Plant for Food IrradiationAssocProf. Jerzy Narbutt, Ph.D., D.Sc. Wojciech Migdal, Ph.D.

• Department of Nuclear Methods of Process • Laboratory for Detection of IrradiatedEngineering FoodstuffsProf. Andrzej G. Chmielewski, Ph.D., D.Sc. Waclaw Stachowicz, Ph.D.

10 PROFESSORS AND SCIENTIFIC COUNCIL

PROFESSORS AND SCIENTIFIC COUNCIL

PROFESSORS

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

2. Dancewicz Antonibiochemistry, radiobiology

3. Dybczyriski Rajmundanalytical chemistry

4. Fidelis Irenaphysical chemistry, coordination chemistry of lanthanides and actinides

5. Leciejewicz Januszcrystallography, solid state physics, material science

6. Lukasiewicz Andrzejmaterial science

7. Piekoszewski Jerzysolid state physics

8. Pszonicki Leonanalytical chemistry

9. Radoszewski Tomaszradiometry

10. Rzewuski Henryksolid state physics

11. Siekierski Siawomirphysical chemistry, inorganic chemistry

12. Szot Zbigniewradiobiology

13. Szumiel Irenacellular radiobiology

14. Trojanowicz Marekanalytical chemistry

15. Urbanski Piotrradiometric methods, industrial measurement equipment, metrology

16. Zagorski Zbigniewphysical chemistry, radiation chemistry, electrochemistry

ASSOCIATE PROFESSORS

1. Ambroz Hannaphysical and radiation chemistry, photochemistry

2. Bobrowski Krzysztofradiation chemistry, photochemistry, biophysics

3. Chwastowska Jadwigaanalytical chemistry

PROFESSORS AND SCIENTIFIC COUNCIL 11

4. Grigoriew Helenasolid state physics, diffraction research of non-crystalline matter

5. Legocka Izabellapolymer technology

6. Michalik Jacekradiation chemistry

7. Mioduski Tomaszlanthanide and actinide chemistry

8. Ostyk-Narbutt Jerzyradiochemistry

9. Parus J6zefanalytical chemistry

lO.WaiiSLechmaterial science, material engineering

11. Zottowski Tadeusznuclear physics

ASSISTANT PROFESSORS (Ph.D.)

1. Bilewicz Aleksanderchemistry

2. Borkowski Marianchemistry

3. Bouzyk Elzbietabiology

4. Bryl-Sandelewska Teresaradiation chemistry

5. Buczkowski Marekphysics

6. Bukowski Piotrmechanics

7. Burzynska-Szyszko Majadosimetry

8. CieSla Krystynachemistry

9. Dembiriski Wojciechchemistry

10. Deptuta Andrzejchemistry

11. Dobrowolski Andrzejchemistry

12. Do Hoang Cuongnuclear physics

13. Dzwigalski Zygmunthigh voltage electronics, electron injectors, gaslasers

14. Fuks Leonchemistry

15. Grodkowski Janradiation chemistry

16. Harasimowicz Mariantechnical nuclear physics, theory of elementaryparticles

17. IHer Edwardchemical and process engineering

18. Jaworska Alicjabiology

19. Kierzek Joachimphysics

20. Kleczkowska Hannabiology

21. Krejzler Jadwigachemistry

22. Kruszewski Marcinbiology

23. Krynicki Januszsolid state physics

24. Machaj Bronisiawelectricity

25.MigdatWojciechchemistry

26. Mirkowski Jaceknuclear and medical electronics

27. Nowicki Andrzejorganic chemistry and technology, high-tem-perature technology

28. Owczarczyk Andrzejchemistry


29. Owczarczyk Hannabiology

30. Palige Jacekmetallurgy

31. Panta Przemysławnuclear chemistry

32. Pogocki Dariuszradiation chemistry, pulse radiolysis

33. Polkowska-Motrenko Halinaanalytical chemistry

34. Przybytniak Grażynaradiation chemistry

35. Ptasiewicz-Bąk Halinaphysics

36. Skwara Witoldanalytical chemistry

37. Smułek Wiktorradiochemistry

38. Sochanowicz Barbarabiology

39. Stachowicz Wacławradiation chemistry, EPR spectroscopy

40. Strzelczak Grażynaradiation chemistry

41. Stuglik Zofiaradiation chemistry

42. Szpilowski Stanisławchemistry

43. Tymiński Bogdanchemistry

44. Urbański Tadeuszchemistry

45. Walicka Małgorzatabiology

46. Warchoł Stanisławsolid state physics

47. Wasek Mareknuclear physics

48. Wąsowicz Tomaszradiation chemistry, molecular spectroscopy

49. Wierzchnicki Ryszardchemical engineering

50. Wojewódzka Mariaradiobiology

51. Wójcik Andrzejcytogenetics

52. Wrońska Teresachemistry

53. Zakrzewska-Trznadel Grażynaprocess and chemical engineering

54. Zimek Zbigniewelectronics, accelerator techniques

55. Żmijewska Wandaanalytical chemistry

SCIENTIFIC COUNCIL (1995-1999)

1. AssocProf. Hanna Ambroż, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technologyphysical and radiation chemistry, photochemi-stry

2. AssocProf. Krzysztof Bobrowski, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technologyradiation chemistry, photochemistry, biophysics

3. Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technologychemical and process engineering, nuclear che-mical engineering, isotope chemistry

4. AssocProf. Jadwiga Chwastów ska, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technologyanalytical chemistry

5. Prof. Rajmund Dybczyński, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technologyanalytical chemistry

6. Żyta GłębowiczInstitute of Nuclear Chemistry and Technologystaff representative

7. Ewa Gniazdowska, M.Sc.Institute of Nuclear Chemistry and Technologyphysical chemistry of solutions

8. Edward Iller, Ph.D.Institute of Nuclear Chemistry and Technologychemical and process engineering

9. Prof. Janusz Jurczak, Ph.D., D.Sc.Polish Academy of Sciences, Institute of OrganicChemistry; University of Warsaworganic chemistry, stereochemistry

10. Antoni Kalicki, M.Sc.Institute of Nuclear Chemistry and Technologyradiometrie methods, industrial measurementequipment, metrology

PROFESSORS AND SCIENTIFIC COUNCIL 13

11. Iwona Katuska, M.Sc.Institute of Nuclear Chemistry and Technologyradiation chemistry

12. Barbara KazmirskaInstitute of Nuclear Chemistry and Technologystaff representative

13. Prof. Kazimierz Korbel, Ph.D., D.Sc.Stanislaw Staszic Academy of Mining and Me-tallurgynuclear electronics, nuclear technical physics

14. Janusz Kra£, M.Sc.Institute of Nuclear Chemistry and Technologyradioisotope diagnostic methods for enginesand industrial installations

15. Gabriel Kuc, M.Sc.Institute of Nuclear Chemistry and Technologyradiation chemistry

16. Prof. Janusz Lipkowski, Ph.D., D.Sc.Polish Academy of Sciences, Institute of PhysicalChemistryphysico-chemical methods of analysis

17. Prof. Andrzej Lukasiewicz, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technologymaterial science

18. Prof. J6zef Mayer, Ph.D., D.Sc.£x3dl Technical Universityphysical and radiation chemistry

19. AssocProf. Jacek Michalik, Ph.D., D.Sc.(Co-chairman)Institute of Nuclear Chemistry and Technologyradiation chemistry

20. AssocProf. Jerzy Narbutt, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technologyradiochemistry

21. Dariusz Pogocki, Ph.D.Institute of Nuclear Chemistry and Technologyradiation chemistry, pulse radiolysis

22. Prof. Jan Przytuski, Ph.D., D.Sc.Warsaw University of Technologychemistry, solid state technology

23. Prof. Leon Pszonicki, Ph.D., D.Sc.(Chairman)Institute of Nuclear Chemistry and Technologyanalytical chemistry

24. Prof. Henryk Rzewuski, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technologysolid state physics

25. Zbigniew Samczyriski, M.Sc.Institute of Nuclear Chemistry and Technologyanalytical chemistry

26. Prof. SJawomir Siekierski, Ph.D.Institute of Nuclear Chemistry and Technologyphysical chemistry, inorganic chemistry

27.JanSkajsterInstitute of Nuclear Chemistry and Technologychemical technology

28. Prof. Irena Szumiel, Ph.D., D.Sc.(Co-chairman)Institute of Nuclear Chemistry and Technologycellular radiobiology

29. Prof. Jan Tacikowski, Ph.D.(Co-chairman)Insitute of Precision Mechanicsphysical metallurgy and heat treatment of me-tals

30. Prof. Marek Trojanowicz, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technologyanalytical chemistry

31. Prof. Piotr Urbariski, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technologyradiometric methods, industrial measurementequipment, metrology

32. AssocProf. Lech Walis", Ph.D.Institute of Nuclear Chemistry and Technologymaterial science, material engineering

33. Prof. Stanislaw Wronski, Ph.D., D.Sc.Warsaw University of Technologychemical engineering

34. Prof. Zbigniew Zagdrski, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technologyphysical chemistry, radiation chemistry, electro-chemistry

35. Wieslaw Zielinski, M.Sc.Institute of Nuclear Chemistry and Technologystaff representative

36. Wanda Zmijewska, Ph.D.Institute of Nuclear Chemistry and Technologyanalytical 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 Technologyhaematology, radiobiology biochemistry, radiobiology

RADIATION CHEMISTRY

AND

PHYSICS

NEXT PAGE(S)left BLANK

RADIATION CHEMISTRY AND PHYSICS 17

•OH RADICAL INDUCED OXIDATION OF CONFORMATIONALLYCONSTRAINED SULPHUR-CONTAINING AMINO ACIDS

D. Pogocki, A. Sci gosz, K. Bobrowski, K.-D. Asmusi;

a/ Radiation Laboratory, University of Notre Dame, USAPL9801980

Studies of various sulphur-containing amino acidsprovide vital information about the mechanisms ofthe oxidative damage of proteins. Such degradationpathway is of general importance for biological sys-tems exposed to conditions of the oxidative stress,because of the high susceptibility of sulphides tooxidation.

The reaction of hydroxyl radicals with sulphur--containing amino acids proceeds via an initial for-mation of a hydroxy sulphuranyl radical >S*-OH.The interaction of such a hydroxy sulphuranylradical with the amino functional group NH2/NHJleads ultimately to the formation of a-aminoalkylradicals with parallel elimination of CO2.

Decarboxylation benefits in particular from sta-bilisation of the arising carbon-centred radical pro-vided by the resonance between the unpaired elec-tron at the a-carbon atom and the free electron pairat the nitrogen atom. a-Aminoalkyl radicals arestrong reductants and can be probed by one-elec-tron reduction of moderately good electron ac-ceptor such as p-nitroacetophenone (PNAP) andmethyl viologen (MV).

a-Aminoalkyl radicals undergo /3-cleavage of C-Sbond, characteristic for the carbon-centred radicalscontaining the sulphur atoms in /3-position, whichleads to the formation of R-S* radicals (probed byTable 1. Radiation chemical yields of CO2 formation, reduction

normalized to the yield of the hydroxy radicals.

one-electron oxidation of ascorbic acid (AH)) andcorresponding vinylamine. Vinylamine tautomerisesto the respective imine that subsequently undergoeshydrolysis to the respective aldehyde [1].

Conformationally constrained sulphur-contain-}ng amino acids (thiaproline derivatives) provideconceptually better models for understandingneighbouring group participation in the oxidationof substituted sulphides than conformationally flex-ible molecules. The larger energetic barriers restrictrotational and translational movements of the func-tional groups. Thus experiments can be designatedto follow the influence of the functional groups dis-tance, position, and orientation on the stabilisationor destabilisation of the oxidised sulphur centre.

Pulse radiolysis experiments were carried out in2-50 mM, N2O saturated, solutions of amino acids(over the pH range 0-10.5) by applying 5-17 ns pulsesof high-energy electrons from the L6d2 TechnicalUniversity linear accelerator.

Gamma radiolysis experiments were carried outin the field of a ^Co y-source in the INCT using adose rate of 7.1 kGy/h.

The quantitative CO2 analysis was achieved us-ing a gas-chromatographic (GC) head space tech-nique. Decarboxylation products (a-aminoalkyl ra-dicals, aN) were identified by way of reduction of

of p-nitroacetophenone and oxidation of ascorbic acid at pH 5.8,

Compound

.co,-

V•HjN 1

-cx^s^ccy

*H3N /

•o .c 'N,^COzCHj

CO£*H2N (

C O J C H Jxs

G(CO2)/G(OH)

0.95

0.61

0.89

0.71

G(PNAP.-)/G(OH)

0.93

0.69

0.64

0.15

0.10

G(AH.-)/G(OH)

0.49

0.16

0.18

0.07

0.16

18 RADIATION CHEMISTRY AND PHYSICS

p-nitroacetophenone(PNAP)(PNAP*~,Amax=350 Hydroxyl radical induced oxidation of thiapro-nm, £=17600 M^cm"1). Fragmentation products line derivatives leads to efficient decarboxylation(thiyl radicals, R-S*) were identified by way of oxi- (Table 1) accompanied by the simultaneous forma-

CO2"

(A)

HO2C

(B)

CO2'

Scheme 1.

dation of ascorbic acid (AH) (AH'~ , Amax=360nm,e=3300M-1cm-1).

All experiments were carried out at room tem-perature, 20 ±3°C.

Semi-empirical calculation: Ionisation potentials(IP), energies of stabilisation (Es) of transients havebeen calculated from proper enthalpies of forma-tion (AHf), computed using an AMI (UHF, SCF)method for molecules in the vapour phase.

All computations have been done using MOPAC7 public domain software.Table 2. AMI calculated stabilisation energies (Es) and ionisa-

tion potentials (IP) of selected radicals.

HO2C'

HN—

[ -H 2 0

ET1

-CQ2

HN

HO2C

Radicals

HN ••

HN 1

p.

AHf(R)[kcal/mol]

21.6

17.6

48.6

Es(otN)

[kcal/mol]

18

22

-9

IP(aN)feVJ

8.3

7.6

8.0

ES(R *)=BDE(CH3-H)-BDE(R-H).IP(R*)=AHf(R+)-AHf(R').

tion of a-aminoalkyl radicals, according to themechanism presented in Scheme 1,

The high yields of a-aminoalkyl radicals inthiaproline derivatives (and their strongly reducingproperties (Table 2) are reflected in high yields ofp-nitroacetophenone radical anions (PNAP*~)(Table 1).

a-Aminoalkyl radicals derived from thiaprolinedecay within milliseconds time region with the rateconstants (~7xlO4 s'1), contrary to a-aminoalkylradicals derived from the alkyl and carboxyalkylS-substituted cysteine derivatives which decay with-in microsecond time region with the rate constants(l-5xlO6 s'1) [1], The thiyl radicals (R-S*) obtainedin the above process are relatively strong oxidantsand were easily probed by one-electron oxidation ofascorbic acid (AH') (Table 1).

The OH-radical oxidation of thiaproline deriva-tives occurs through the sequential formation of ahydroxy sulphuranyl radical, and a sulphur-centredradical cation. The latter decomposes via elimina-tion of CO2 with the simultaneous formation ofa-aminoalkyl radicals (Scheme 1).

Decarboxylation of thiaproline derivatives con-taining the carboxylic group in the position - (4)leads to the simultaneous formation of a-amino-alkyl radicals in the position - (4). They undergoy3-cleavage of the C-S bond, characteristic of thecarbon centred radicals containing a hetero-atom inthe/J position (Scheme 2A).


(A) (B)

HN HN-

PNAP AH" PNAP

PNAP- AH" PNAP-Scheme 2.

Decarboxylation of thiaproline derivatives con- the Ca bond undergoing cleavage) readily achievedtaining the carboxylic group in the position - (2) in the flexible Cys(Me)-like systems (Scheme 3A) do

Scheme 3.

leads to the formation of a-aminoalkyl-a-alkyl-thioalkyl radicals in the position - (2). These radi-cals do not undergo /?-cleavage (Scheme 2B).

The /S-cleavage in thiaproline derivatives is lesseffective than in linear (open chain) amino acidsdue to:(i) the lack of driving force from the entropy in-crease, resulting from the formation of two entitiesfrom one,(ii) the transition complex for the /3-cleavage processinvolving a triangular grouping of reactive centres(generated by interaction of the semi-occupiedorbital p2 on Ca with the a* antibonding orbital of

CH3

not be attained when the radical centre is locatedwithin the thiaproline ring (Scheme 3B). The effec-tive formation of the transition complex is addi-tionally made hard by methylation in the position -(5), (Scheme 3C).

References[l].Pogocki D., Bobrowski K., Asmus K.-D.: INCT Annual Re-

port 1993, p. 21.

* Part of this work was presented at the conference "PulseInvestigation in Chemistry, Physics and Biology, PULS'97",13-19 September 1997, Szczyrk, Poland.

PL9801981

REACTIONS OF HYDROXYL RADICAL WITH THIOAMIDES

P. WiSniowski, K. Bobrowski

Nanosecond pulse radiolysis of nitrogen saturatedaqueous solutions of a-(methyltio)-acetamide (I)and N-acetylo-L-metionine amide (II) over the pHrange 1-12 has been used to generate hydroxy-sulfuranyl radicals.

9CH3C-S-CH2~C-NH2

(I)

H3C-C-NH-CH-C-NH2

CH,(II) CHfS-CH3

A transient absorption band with Amax=340 nm(assigned to the hydroxysulfuranyl radicals) wasobserved immediately after the pulse which wassubsequently converted to an absorption band withAmax=480 nm (assigned to the S.-.S+-three-elec-tron-bonded radical cations) and/or absorptionband Amax=290 nm (assigned to the a-thioalkylradical). Monitoring the pseudo-first-order decayrate of the hydroxysulfuranyl radicals at various H+

and (I) and (II) concentrations, respectively, one


can extract the individual rate constant (k<j) of theirspontaneous dissociation

•S-OH

CH,OH"

CH,n3 ^ r i 3

which are one-order of magnitude lower than the kdfor dimethyl thioether. The high stability of thehydroxysulfuranyl radicals formed in thioamides islikely due to the formation of the internal hydrogenbond between the hydroxyl hydrogen and either theoxygen or the nitrogen located in the adjacentamide group.

Any discussion of the oxidation mechanism ofa-MTA and AMA must take into account the fol-lowing observations:

bon dioxide at low and neutral pH lies in the struc-tures of a-MTA and AMA.

In aqueous neutral solution of «-MTA the stabi-lised hydroxysulfuranyl radical subsequently under-goes water elimination by intramolecular hydrogentransfer via six-membered transition state leadingto the formation of imine radicals (Scheme lb).Intramolecular hydrogen transfer competes withspontaneous dissociation of hydroxysulfuranyl ra-dical. Imine radicals are expected to undergo/3-frag-mentation of carbon-carbon bond leading to a-(al-kyl)tioalkyl radicals Id and isocyanate lc. Inaqueous solution isocyanates undergo well-knownHoffman rearrangement which produces ammoniaand carbon dioxide as shown (Scheme 1). It ratio-nalises the formation of carbon dioxide as a stable

H 3C

"O.C-NH,2

,H>.O

.So

stabilization ofhydroxysulphuranyl radical

X=340nmmix

i -0

» CO2 + NH3

H;c NH,

-H2O

-H ...

S^.^C-O ^90run

cisocyanate

HN-C-O

H3C-S-CH2

k^ 290 nm

Hofmosnrearrangement

H2O

d

[•r I l

[HN-C-OH]

Scheme 1. * OH-induced oxidation of or-(methylthio)acetamide in neutral solution.

(i) for both compounds hydroxyl radicals (*OH) actprimary with the sulfur of the thioether group for-ming hydroxysulfuranyl radical (Scheme la);(ii) the * OH-induced oxidation in a-MTA does notlead at a neutral pH to a stable sulfur-centredradical cation (S '+) , indicated through the lack offormation of the intermolecularly three-electron--bonded (S.-.S)+ radical cations even at high con-centrations of the solute (~ 10"2 M) (Fig.l). On theother hand, * OH-induced oxidation in AMA leadsto the absorption bands similar as in the aliphaticthioether (CH3>2S;(iii) carbon dioxide is a stable product of y-radio-lysis of neutral solutions containing a-MTA and thedecrease in radiation chemical yields of the inter-molecularly three-electron-bonded (S.-.S)+ radicalcations correlates with the parallel increase in ra-diation chemical yields of CO2.

The key to understanding the differences be-tween radiation chemical yields of stable sulfur--centred radical cation (S*+) and formation of car-

product of y-radiolysis of neutral solutions contain-ing a-MTA

In a-MTA specific location of the methylenegroup between the electron-donor sulfur and theelectron-acceptor amide group facilitates hydrogenabstraction from the methylene group. The radical

XO

25

20

IS

10

5

0

[/ \1 . 1

-

-

-

1 , 1

300 400 500 600

Fig.l. Transient absorption spectra observed (a) 500 ns and (b) 7fis after pulse irradiation of an N2O-saturated solutioncontaining 10~2 M a-MTA at pH 6.45.


formed is stabilised by the captodative effect (Sche-me 2a). At high concentration of or-MTA la sub-sequently converts into the dimeric radical cation(>S.-.S<)+ (Scheme 2b) as indicated by the for-mation of the characteristic 480 nm absorptionband.

pathways of a-MTA and AMA originates from theinitial interaction of the oxidising species and thethioether group that leads to the formation ofhydroxysulfuranyl radical and sulfur radical cationand the subsequent interaction of these interme-diates with the neighbouring groups. The key step is

HaC'^CH^-™2

run

a

A 9CHgSCHCT

4Vcaptodativeeffect

lowconcentration

== 480 nm

Scheme 2. *OH-induced oxidation of a-(methylthio)acetamide in acid solution.

In conclusion, the geometric structure of speciesduring oxidation of organic sulfides is of great im-portance. The difference between the oxidation

the intramolecular hydrogen transfer in a six-mem-bered cyclic transition state during decompositionof the hydroxysulfuranyl radical.

DIRECT EFFECT OF IONISING RADIATION ON DNA,INFLUENCE OF COPPER IONS

H.B. Ambroz, E. Kornacka, G. Przybytniak

PL9801982

The presence of additives modifies the yield of par-ticular intermediates to a great extent. This effectfor Cu(II) ions is discussed below. Copper ions ex-hibit the effect of a decrease of the *TH populationin DNA, but to a minor degree than Fe(III) (Fig.l).Even addition of Cu(II) at 5 raM concentration stillleads to the detection of above 7% of remainingpopulation of the protonated thymine base (the* TH concentration in samples without added metalions equals to 22%). This is presumed to be theconsequence of the lower electron-scavenging abi-lity exhibited by Cu(II) in comparison to Fe(III).

Careful analysis of the EPR spectra recorded pre-and post-irradiation at 77 K and upon annealingenables one to conclude that copper ions partici-pate not only in primary but also in secondary pro-cesses. The Cu(II)-DNA complexes have well-de-fined EPR spectral parameters and almost the samesignal is obtained under various conditions [1]. Theparallel component of the spectrum undergoestransformation after exposure to 10 kGy (Fig.2).The additional lines marked (4) (A|| = 15.2 mT,g| | =2.28) for the 2-5 mM concentrations of Cu(II)have been detected in the range of 77-220 K. We


77K 203K

OPPH

B

*—I 2.5 m lFig.l. EPR spectra of DNA without additives (A) and in presence

of 1 mM Cu(II) (B), and 5 mM Cu(II) (C) at 77 K and at203 K.

interpret this according to Symons' suggestion thatpart of the added copper ions is bound to the DNAin the form of a dimer structure Cu(II)-Cu(II),which is EPR silent, and the growing lines (4)might be assigned to conversion of Cu(II)-Cu(lI)pairs into paramagnetic Cu(II)-Cu(I) dimers viaelectron addition [2]. In this case, exchange be-tween the two copper ions in the new dimers pro-duces a new signal. On warming the sample up toabove 220 K, the Cu(II)-Cu(I) feature disappears toleave a spectrum similar to the original. This im-plies the decomposition of Cu(II)-Cu(I) complexes.Because of the low intensities of the associatedlines a quantitative assay is not possible. Regardlessof the exact reaction mechanism, the exposure ofDNA to ionising radiation in the presence of Cu(II)results in lower protection against radical forma-tion via a reductive pathway than that observed foriron ions (Fig.3).

The presence of copper in the radiation-inducedprocess reduces electron gain centres and therebylowers the total level of damage in DNA. Cu(II)ions appear to be weaker electron scavengers thanFe(III) ions in the primary processes, in agreementwith standard electrode potentials at 25°C of 0.153

2 600 2700 2800 2900 3000Fig.2. Parallel features of Cu(II) of samples containing 100 mg/ml

DNA and 5 mM Cu(II) (A) before irradiation, (B) afterirradiation at 77 K, (C) on annealing to 193 K, (D) onannealing to 223 K.

and 0.771 V, respectively. Other factors influencingthis process which can be considered are: the ten-dency of Cu(II) ions towards dimer formationand/or the different distributions of both kinds of

10

in presence of Fe(lll), (mM]in presence of Cu(l I), [mM]

Fig.3. Effect of added metal ions on thymyl radical concentra-tions *TH in the radiolysis of frozen DNA solutions at 77K following annealing to 203 K. Radical concentrationsrefer to the total DNA radical concentrations for everysample at 77 K.

ions along DNA strand chelated at various centres,e.g. in the case of Fe(III) the preferential loca-lisation is at thymine and that of Cu(II) is mostlycomplexed at the DNA helix near guanine baseunits [3].

References[1]. Pezzano H., Podo F.: Chem. Rev., 82,398-401 (1980).[2], Cuilis P.M., McClymont J.D., Bartlett M.N.O., Symons

M.C.R.: J. Chem. Soc, Chem. Commun., 1859-1861 (1987).[3].Zimmer C, Luck G., Fritzsche H., Triebel H.: Biopolymers,

10,441-461(1971).

RADIATION CHEMISTRY AND PHYSICS PL9801983 23

INFLUENCE OF IRON IONS ON RADIATION-GENERATED DNA RADICALS

H.B. Ambroz, E. Kornacka, G. Przybytniak

Iron (III) cations have been considered as electronscavengers which in gamma radiolysis of DNAreduce effectively the number of electron gaincentres. The relative ratio of the nucleotide : cationand the nature of the metal ion determine the yieldof this process. Quantitative analysis indicates thatif for one nucleotide approximately one electronscavenger species is present, then the concentrationof DNA radicals decreases sharply, e.g. even to 30%at 77 K for Fe(III) [1]. Generally, metal ions intheir higher oxidation states can noticeably dimi-nish the formation of radical ions in DNA by thereduction in the yields of DNA radical anions.According to quantum mechanical calculations [2]and experimental observations [3,4] the sites whichare the best for capture of electrons are thymineand cytosine bases, while the best electron donor isguanine. Thus, by the EPR method, the thymineT*~ and cytosine C'~ radical anions and guanineG*+ radical cation are commonly identified as theprimary species detected at 77 K. This is the resultof electron and hole migration first into the baseIl-system and then through stacks. On annealing,the T* ~ centres are converted largely into 5-thymylradical *TH by irreversible protonation at the C-6position which results in arising of the octet in theEPR spectrum [5,6].

The effect of Fe(III) ions on the formation oftransients produced in calf thymus DNA following

77K 203K

DPPH

B

H 2.5 mTFig.l. EPR spectra of DNA without additives (A), in presence of

1 mM Fe(III) (B), and 5 mM Fe(IH) (C) at 77 K and at 203K. The arrows in spectrum (C) at 203 K refer to feature ofthe ally!-type radical derived from thymine.

irradiation is depicted in Fig.l. Two distinct chan-ges were observed with an increase in concen-tration of Fe ions, namely, (i) the relative contribu-tion of the central singlet in the spectrum becameat 77 K more distinct and (ii) the population of theoctet detected at higher temperatures was drasti-cally reduced. In spectrum C in Fig.l recorded for[Fe(III)]=5 mM at 203 K, we can also observefeatures ( | ) attributable to the allyl-type radical ofthymine derived probably by deprotonation ofthymine radical cation from the methyl group [1].

The influence of Fe ions are strong on both thetotal population of radiation-generated DNA radi-cals and the production of *TH. According to ourcalculations of the relative contributions of *TH,we have found that, at low Fe(III) concentration,the decrease of the total DNA radical concentra-tion is comparable to that of the protonated thy-mine anion #TH (Fig.2, 1 mM Fe(III)). The con-sequences of this correlation are crucial. Under ourconditions quantitative analysis clearly testifies that

100-

0 1 2 3 5Fig.2. Effect of added Fe(III) ions on total concentration of DNA

radicals in samples of frozen DNA solutions. Spectra arenormalised to DNA radical concentration in absence ofFe(III) at 77 K.

ejected electrons are captured with high efficiencyby Fe(III) ions and not by thymine. The decrease inyield of thymyl radical in the system is controlled bythe concentration of its precursor. Above 77 Kelectron migration from C*~ to thymine is not ob-served. Electron transfer from cytosine to thymineshould reveal this process in EPR spectra as, forexample, arises the octet intensity, which does nottake place. For the sample containing 1 mMFe(III), the reduction in the total radical and *THconcentrations correspond to each other, and weconclude that the populations of C*~ and T*~ de-pend differently on Fe(III) concentration. Our re-sults demonstrate some selectivity of electron traps.Electrons are localised preferentially on cytosine orcaptured by metal ions at 77 K.

References

[1]. Lage M., Weiland B., HiiUermann X: Int. J. Radiat. Biol., £&,475-486 (1995).


[2], Colson A.O., Sevilla M.D.: Int. J. Radiat. Biol., 6_7_, 627-645(1995).

[3].Weiland B., Huttermann J., van Tol J.: Acta Chem. Scand.,51, 541-546 (1997).

[4]. Sevilla M.D., Becker D., Yan M., Summerfield S.R.: J. Phys.Chem., 2Ł 3409-3415 (1991).

[5]. Wang W., Sevilla M.D.: Radiat. Res., 131, 9-17 (1994).[6].Bernhard W.A.. Patrzałek A.Z.: Radiat. Res., 112, 379-394

(1989).

"3"COO

is00

CC14 REMOVAL FROM DRY AIR UNDER INFLUENCE OF ELECTRON BEAM

H. Nichipora/, E. Dashouk v, A.G. Chmielewski, Z. Zimek, S. Bułka11 Institute of Radiation, Physical and Chemical Problems, Academy of Sciences, Republic of Belarus

Volatile organic compounds (VOC) are emitted intothe atmosphere as a result of many industrial pro-cesses. Removal of these toxic species becomes animportant task to achieve environmentally accepted

a

o

14)U

c

1«016011401M100

60604020

0

I;

V \

* * ?

—•—Tici-m-e—*—T2CI2

*%1. •

Theoretical model of the CCI4 decomposition indry air under the electron beam influence describesthe decay of CCI4 and the formation of severalproducts like: Cl2, CCI2O, CO, CO2, CINO3 and

Dose [MRad] Dose [MRad]

Io

IIoO

TOO,

600

500

400

300

200

1C0

0

V

—•—T1C• F

—A—T2CI2

••_—_20

Dose [MRad]Fig.l. CCI4 decay as a function of electron beam dose with its different initial concentration: a -161 ppm, b - 347 ppm, c - 677 ppm.

levels. Recently new data were published concerningthe CCI4 removal in dry air at atmospheric pressure(P=l at) and at a temperature of 25°C under elec-tron beam influence [1,2]. Decomposition of CCI4was described with relation to the following pro-cesses:O a D + CCI4 => CCI3 + O 2 (k - 1 0 4 0 cm3/molec. s)

O + CCI4 => CCI3 + O 2 (k - 1 0 4 4 cm3/molec. s)e + CCI4 => CCI3+ Cl" (k -10' 7 cm3/molec. s)

A computer simulation was performed to findthe kinetics of CCI4 decomposition in dry air underthe influence of electron beam. The calculationswere performed in agreement with the conditionsof experiments described in the literature [2]. Com-parison of the experimental and theoretical datashows that the reaction:

cat + c r => CCI3 + ci2

may play an important role in the radiolysis of a gasmixture containing CCI4 and dry air.

CIO3. The model is based on 191 reactions of theselected 49 chemical particles.

Primary charged particles in the process are theions N24", O%, N + , O + and termalized electrons.The charge transfer is observed in a gas mixturecontaining N2+O2+CCI4 what leads to positiveions formation like: O%, CCtf, N O + , NO^. Thetermalized electrons react efficiently with CCI4,take part in the CCI2O decomposition and reactwith oxygen according to the following reactions:

e + CCI4 => CCI3 + Cl" (1)k - 2,5 • 10"7 cm3/molec. se + CC12O =* CO + C1J (2)

k -1 • 10'7 cm3/molec. se + O 2 + N 2 =>O2 + N 2 (3)k-l,6-10-3cm6/molec.2se + O 2 + O 2 => O2 + O 2 (4)k-2,5-10-30cm6/rnolec.2sO2 + CCI4 => CCI4- + O 2 (5)


In the recombination process the negative ions likeCl~, CIJ, CCI4" play a principal role.

The radical CCI3 is the most important species inthe formation of the final product of the decompo-

tions, during the CCI4 decomposition process with aninitial CCI4 concentration of 278 ppm, depend on thedose level. The calculations were performed for themixture of pressure P=l at and T=25°C. Experi-

< 10

Dose [MRad]16

.1

8

4E040035030025920016010050

o|

pr

ft A/\I '*Aw

Jk

//'/

• 1TO-CI2

10

Dose [MRad)

a.a.

300

260

ZOO

150

100

50

01

d

_ Fl7

. C0+C02^#-E

co*c02

Doss [MRad] D o s e [MRad]Fig.2. CCI4 and product concentrations as a function of electron beam dose: a - CCI4, b - COCI2, c - CI2, d - CO + CO2-

sition process. Those species are formed mainly inan electron dissociative attachment process withCCI4 (1) and can be formed in the CClJ and Cl~ions recombination process. The radical CCI3 reactsin the following way:

CCI3 + O2 + M =*> CCI3O2+ MCCI3O2+ Cl => CCI3O + CIO

CCI3O => CC12O + OCO and CO2 can also be formed in a dissociative

attachment process with an electron and CCI2Oaccording to formula (2). The calculations were per-formed using a model based on a KINETIC programaccording to experimental conditions described inthe literature [2]. The results of calculations and theexperimental data of CCL» concentration dependingon the delivered dose for different initial CCI4 con-centrations, are shown in Fig.l. Fig.2 shows that CCI4and the product (COC12, Cl2, CO+CO2) concentra-

mental data on the curves are marked by the letter E(Figs. 1 and 2).

The results which were obtained by the compu-tation method with the asumption that the recom-bination of CClt and Cl~ is not the source of theCCI3 radicals (curves marked as 1TC1), and the re-combination process is the source of that radical(curves marked as 2TC12).

Comparison of the results indicates that the re-action:

CClt + c r => CCI3 + Cl2may play an important role in process of CCI4 de-composition in dry air under the influence of elec-tron beam.

References

[}]. Penetrante B.M. et al.: Phys. Lett., A209,69-77 (1995).[2], Coch et al.: Environm. Sci. Technol., V29,2946-2952 (1995).

THE REMOVAL OF 2,4-DICHLOROPHENOL FROM AQUEOUS SOLUTIONSUSING y-IRRADIATION

M. Trojanowicz, P. Drzewicz, P. Panta, W. Ghiszewski

Work on the use of ionising radiation-induced de-gradation of water pollutants has been carried outalready for about 20 years. The state of art in thisfield has been recently reviewed [1]. Chlorophenolsbelong to a very troublesome environmental pollu-tants, which although biodegradable, have been

shown to be self-inhibitory to aerobic and anaero-bic systems. Hence, especially for such compoundsit seems to be especially proper to use radiolyticdegradation. In this field the attention of severalresearch groups was focused so far on monochloro-phenols [2-6], and only very recently two attempts

nCOG)OCOO


on radiolytic degradation of multichlorinated phe-nols were reported [5,7], although the latter aremuch more toxic than monochlorophenols. 2,4-di-chlorophenol (2,4-DCP) is fourth on the list ofmost frequently occurring phenolic pollutants in in-dustrial wastewater from Environmental ProtectionAgency in USA among other 129 pollutants [8].Beside pentachlorophenol and tetrachlorophenols,2,4-DCP belongs to most toxic chlorophenols, how-ever, as we shown already, the larger number ofchlorine atoms in the molecule of chlorophenolsthe lower doses of ionising radiation are needed fordegradation [7]. Due to a large toxicity and frequentoccurrence of 2,4-DCP in environment this com-pound has especially attracted attention in thisstage of studies.

Table. Recovery of preconcetration of 2,4-DCP on various com-mercial sorbents. Preconcentration from 20 ml 1 mg/1analyte solution of pH 2.0 containing 5 g NaCl at flow--rate 5 ml/min. Elution 1 ml methanol (for OASIS andAmberlite XAD-2 2 ml methanol was used).

SorbentAmberlite XAD-2

CyanopropylOASIS HLBa

OctylOctadecyl

Octadecyl, Polar Plusb

Phenyl

ManufacturerSigmaBaker

WatersBakerBakerBakerBaker

Recovery, %35 ±364+871+7

100 ±4

85 ±5108+6101 ±6

a hydrophilic-lipophilic balanced macroporous copolymer [po-ly(diviny!benzene-co-N-vinyl-pyrrolidone." with free silanol groups.

The monitoring of effectiveness of y-irradiation of2,4-DCP in aqueous solutions was carried out usingreversed phase HPLC in conditions reported earlier[7]. Determination of 2,4-DCP concentration invarious irradiation conditions and products of irra-diation, because of limited sensitivity of UV detec-tion, requires a preconcentration of analytes. For thispurpose the solid-phase extraction was used. Theeffectiveness of analyte sorption was compared forvarious commercial sorbents recommended for non--polar species or sorbents with mixed affinity both topolar and non-polar analytes (Table). In all caseselution with methanol was carried out. Satisfactoryresults were obtained for three examined sorbents.For practical determination with preconcentrationthe BAKERBOND sorbent with the phenyl groupswas employed, which was demonstrated earlier alsoas satisfactory sorbent for alkylphenols [9].

Effectiveness of radiolytic decomposition de-pends on many different factors. In our previousstudies it was shown that in aerated solutionsplaced in polyethylene bags 2,4-DCP at 20 mg/1level is practically completely decomposed withabout 1 kGy dose [7], however pH in these experi-ments has not been controlled. Because of acidicproperties of 2,4-DCP (pKa=7.85 [10]), dependingon pH of solution this solute can be present inprotonated, neutral or non-protonated, anionicform, therefore pH of irradiated solution may affecteffectiveness and mechanism of degradation of

2,4-DCP. Such effect was examined earlier for4-chlorophenol, but contradictory results have beenreported by various authors [3,4]. In this study pHeffect was examined in the range from 3.1 to 10,7.Irradiated solutions were aerated, as in severalpapers about irradiation of monochlorophenolsand it was found that dehalogenation is more pro-nounced in the presence of oxygen [1,3,6]. In alka-line solution the decomposition of 2,4-DCP occurswith lower yield than in weakly acidic samples(Fig.l). As it can be observed from recorded chro-

—i-pH=31- • — pH«5.1—4—pH«10.7

0 2CO *00 BOO BOO 1000Dose, Gy

Fig.l.Effect of pH on radiolytic decomposition of 2,4-DCP inaqueous solutions at various radiation doses. Initial con-centration in each solution 20 mg/l. HPLC results obtainedafter 25-fold preconcentration on phenyl sorbents.

matograms pH affects also mechanism of degra-dation. In acidic solutions at doses up to 1 kGy themain products of degradation are monochloro-phenols and unsubstituted phenol, and for doses 10kGy formation of dihydroxybenzenes and otherunidentified products was observed. In alkalinesolution already from 0.1 kGy dose, practically

/Jit11

' . J . I .

—•— pH = 3.1- • - pH » 5.1—*—pH-10.7

. . ... , 1 ..

-•*

2000 8000 100004000 8000

Dose, GyFig.2. Effect of pH on release of chloride ion during radiolytic

degradation of 2,4-DCP at various radiation doses. Resultsobtained from ion-chromatography measurements in su-pressed two column system with conductivity detection.


hydroquinone and catechol are formed only, whichwere also found earlier as products of radiolysis of4-chlorophenol [3,4] and phenol [1,11]- The pro-ducts of radiolysis of 2,4-DCP at pH 10.7 and 10kGy dose were not identified, as yet. In case of 4-CPprolonged radiolysis leads to simple carboxylicacids. In this study, preliminary ion-chromato-graphic measurements were not helpful, so far, inthis identification. These measurements confirmed,however, that in alkaline media degradation of2,4-DCP leads to larger concentrations of releasedchlorides (Fig.2).

References

[1]. Getoff N.: Radiat. Phys. Chem., 41,4, 581-593 (1996).

[2]. Getoff N., Solar S.: Radiat. Phys. Chem., 2§, 5/6, 443-450(1986).

[3]. Getoff N., Solar S.: Radiat. Phys. Chem., 31, 1/3, 121-130(1988).

[4]. Stafford U., Gray K.A., Kamat P.V.: J. Phys. Chem., 25, 25,6343-6351 (1994).

[5]. Taghipour F., Evans GJ.: Radiat. Phys. Chem., 42, 257-264(1997).

[6].Schmid S., Krajnik P., Quint R.M., Solar S.: Radiat. Phys.Chem., 5J}, 5,493-502 (1997).

[7]. Trojanowicz M., Chudziak A., Bryl-Sandelewska T.: J. Ra-dioanal. Nucl. Chem., 224,1/2,131-136 (1997).

[8]. Keith L.H., Telliard W.A.: Environm. Sci. Techno]., 13.,416-425 (1979).

[9], Chudziak A., Trojanowicz M.: Chem. Anal. (Warsaw), 40,39-52 (1995).

[10], Li N , Lee H.K.: Anal. Chem., £2,5193-5199 (1997).[11]. Hashimoto S., Miyata T., Washimo M., Kawakumi W.:

Environm. Sci. Tecnnol., 13,71-78 (1979).

ORGANIC RADICALS STABILIZED IN AIPO4 MOLECULAR SIEVES\M 1/ , 1 /

1/

Z. Stuglik, S. Kowalak1', A. Jankowska", K. Kruszona

Faculty of Chemistry, A. Mickiewicz University, Poznan, Poland

A family of crystalline molecular sieves AIPO4 con-sists of several dozen structures regardless of theirinvariable chemical composition. Some of the struc-tures are analogous to the known zeolite structures,the others present novel, sometimes very interest-ing porous crystalline systems. Despite of the simi-larities between aluminosilicate zeolites and AIPO4molecular sieves the latter lack the ion-exchangeproperties, which result from only weak physicalinteractions between "host" and "guest" molecules.The variety of AIPO4 structures results from a dif-ferent crystallization procedure and mostly fromthe different organic templating agents employedfor syntheses.

Recently we have investigated the y-radiolysis ofa-alanine supported on the AIPO4 molecularsieves. In the case of AIPO4-5 (comprising the poresystem formed by parallel 12-membered ring chan-nels of ~0.8 nm in diameter) a-alanine was in-corporated by impregnation. The molecular sievewas synthesized in the A.Mickiewicz University andthe organic template was removed by the routinecalcination at 500°C before impregnation. It isworth-while mentioning that the calcined samplewas not completely colorless. The alanine imnated samples were exposed to y-radiation ^and then examined by means of EPR spectroscopy.It was very interesting to find that, contrary to azeolite support, the AIPO4-5 with adsorbed alanineshowed a set of very sharp lines and additionally thecommon signals originated from alanine (Fig.la).The experiments with the alanine-free AIPO4-5showed the same set of sharp lines which indicatedthat they result from the paramagnetic species pre-sent in the neat molecular sieve. It is also remark-able that the sharp signals decay after a while andthe alanine radical signals become more distinctive(Fig.lb).

The EPR spectrum of AlPO4-5 shows a septetof lines (Fig.lc) with the respective intensityratio 1:7:10:27:10:7:1 and the peak-to-peak distance

14.5 Gauss. It could be tentatively attributed to theCH3-C*R-CH3 radical. The above results indicate

a

2.053 z.oas a.oos 1.983 i.S

2.053 2.0J9 2.005 1.983 1.9

c

2.053 2.029 2 006 1.983 ! 3IG-VALlf)

Fig.l.EPR signals in v-irradiated. (D=3.7 kGy) AIPO4-5 mole-cular sieve impregnated with DL-or-alanir.e (a and b) andnon-impregnatei (c). Signal (a) was observed just after theirradiation and (b) - after two months.


that the amine template, remaining in the mole-cular sieve after crystallization, undergoes radiolysiswhich results in paramagnetic species. The courseof radiolysis and the products depend not only onthe nature of template molecule but also on theprocedure applied for crystallization and the post--synthesis treatment. It is, however, likely that the

organic compounds applied as templates could beconsidered as potential alternative probe moleculesfor dosimetry.

Our results also show that AIPO4 molecular sievescan be a very promising matrix for stabilisation androom temperature EPR analysis of normally unstableorganic radicals.

r

IIloi 00

THE EFFECT OF HIGH LET RADIATIONON THE DYNAMICS OF MICROWAVE POWER SATURATION

OF EPR SIGNAL IN ALANINE

B. Ciesielski17, Z. Stuglik, L. Wielopolski2/, I. Zvara3/

1/1Department of Physics and Biophysics, Medical University, Gdansk, Poland21 Medical Department, Brookhaven National Laboratory, Upton, USA

3/ Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, Dubna, Russia

Variations in the shape of EPR spectra with in-creasing microwave power are used as an indicatorof the degree of spin saturation in alanine samplesirradiated by low LET gamma radiation, 108 MeV

Fig.l.EPR spectra of alanine samples irradiated with a low-LET1.25 MeV photons from a 6 0 Co source and 108 MeV ^"Feions with doses of 200 Gy and 28 kGy, respectively. The spec-tra were normalized to the same peak-to-peak amplitude.The incident microwave power was 20 mW, modulationamplitude 0.1 mT, and scan width 20 mT. The peak-to-peakamplitudes of the x and y peaks were measured at positionsindicated by dotted and dashed lines, respectively.

Fe ions and 200 MeV Co ions. A ratio of the main(y) and satellite (x) line intensities in the EPRspectra is applied as a quantitative measure of the

spectra shape. The microwave power saturationaffects the xyy ratio in different ways in samplesirradiated by radiation of different LET (Fig.l). It isshown, that the introduced S parameter, reflectingthe sample saturation dynamics relative to the re-ference "low LET' sample, decreases from S=l, forsamples irradiated by low LET gamma radiation, to

1.00

0.80

0.60

0.40

0.20

Gamma

2.5 MeVprotons

thermalneutrons

1.5 MeValpha

108 MeVFe ions

0.000.1 1 10 100 1000 10000

LET [keV/micrometer]Fig.2. The dependence of the saturation parameter S on the ra-

diation LET.

about S=0.5+0.6 for samples exposed to the highLET ions (Fig.2), thus indicating slower saturationdynamics, i.e. more efficient relaxation, in the "highLET" alanine samples. These effects, allowing aqualitative determination of the radiation quality,showed a long term stability over the period ofseveral years.

DIFFERENTIAL ENERGY OF ION PAIR FORMATIONPL9801988 I N MR B 0 M B A R D E D WITH 2 4 0 MeV Ca-40 IONS

Z. Stuglik, P.Yu. Ape!v

11 Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, Dubna, Russia

The energies of ion pair formation in gaseous me-dia irradiated with ionizing radiations (total, W and

differential, w) are of great interest for practicaldosimetry and for the understanding of energy de-


position processes. Both values depend on the typeof ionizing radiation, its energy and the chemicalnature of target gas. The differential energy, w, isthe quotient of dE by dN, where dE is the meanenergy lost by a charged particle of energy E intraversing an absorber of thickness dx, and dN is themean number of ion pairs produced when dE iscompletely dissipated in the gas [1]. Precise ex-perimental data and exact theoretical calculationsof W and w exist for electrons only. Some experi-mental data have been collected for protons and

,40,

The results are presented in Table.An important question is to evaluate the uncer-

tainty of quantities used to wajr calculation accord-ing to equation.

On the basis of our previous experience theuncertainties connected with SSTD detectors (Nevaluation) are estimated to be -10%. The uncer-tainties connected with e, Q and S are much lowerand practically can be neglected.

It was difficult to estimate the uncertainties con-nected with various stopping power data which in-

Table. Energy of ion pair formation in air by 6 MeV/amu Ca ions, calculated on the basis of various sources of stopping power data:Northcliffe and Schilling (N-S) tables [6], the computer program Stoppow 82 [7] and the computer program TRIM [8].

Irradiationtime, s

7

3

6

3

5

average

K, tracks/nC

1.33E+05

1.37E+05

1.23E+05

1.37E+05

1.22E+05

1.30E+05

N, tracks/cm^

3.17E+08

2.02E+08

3.70E+08

9.00E+07

1.67E+08

N*S*e/Q

2.12E-05

2.20E-05

1.97E-05

2.19E-05

1.96E-05

2.09E-05

wair. eV

N-S

37.78

39.09

34.95

38.99

34.77

37.12

STOPPOW

40.76

42.18

37.71

42.07

37.52

40.05

TRIM

39.52

40.89

36.57

40.79

36.37

38.83

a-particles. For fast ions and especially fast heavyions the experimental data are rare and most ofthem concern the tissue equivalent gas mixtures ortheir constituents. To our best knowledge there areonly three works in which W or w-values for heavyions slowing down in air are presented [2-4].

Starting chemical experiments with heavy ions[5] we have to calibrate our thin-walled ionizationchamber (working in current regime) on track de-tectors. Low intensity, strongly defocused Ca-40 ionbeam went through the ionization chamber andbombarded solid state track detectors situated be-low it. The charge Q collected from the signal elec-trode of ionization chamber was measured simulta-neously. Irradiated polyethylene terephthalate trackdetectors were etched in 6N NaOH at 50°C andanalyzed on an electron microscope, JSM-840,JEOL with a magnification of 10000. The trackdensity, N, was measured with a 100% efficiency.

All irradiations were done in Dubna on a KHEPTIfacility situated at the vertical ion pipe of a 4-metercyclotron U-400 [5].

The data collected in the course of such experi-ments allow to calculate wajr-value according to theequation:

wair=AE*N*S*e/Qwhere e is the electron charge and AE - energydeposited between the electrodes of the ionizationchamber.

fluenced the accuracy of AE evaluation. So, wepresent (Table) the results of calculations, based onthree different stopping power data tables andprograms. We prefer the value wair (Ca)=38,8 ±2.0eV obtained on the basis of TRIM program whichis actually considered as the most accurate one.

It is the first attempt to measure the wairvaluefor Ca ions and we were not able to compare ourvalue with other data. However, taking into ac-count the data obtained for another ions: wa;r (

12C,135 MeV/amu)=36,2 ±1.0 eV [4], wair ( f gPb, 3.2

O^U 42MeV/amu)=37.9 ±2.0 eV and wair O^U, 4.2MeV/amu)=37.3 ±2.5 our value obtained for 6MeV/amu 40Ca ions seems to be realistic.

References

[1J. ICRU-report No 31.1979.[2]. Varma M.N., Baum J.W.: Phys. Med. & Biol., 22,1449-1453

(1982).[3]. Liesem H.: Nucl. Instrum. and Meth., 121,443-446 (1981).[4]. Kanai T. et al.: Radiat. Res., 131,293-301 (1993).[5].Stuglik Z., Zvara I., Yakushev A.B., Timokhin S.N.: Radiat.

Res., 43,463-469 (1995).[6], Northcliffe L.C., Schilling R.F.: Nucl. Data Tables, A7,

233-463 (1970).[7].Henninger X, Horibeck B.: JINR-report No 10-83-366. 1982

(in Russian).[8], Ziegler J.F.: TRIM - program.


15

ESR AND OPTICAL STUDIES OF CATIONIC SILVER CLUSTERS IN ZEOLITE rho

J. Michalik, J. Sadto, T. Kodairav, S. Shimomura2/, H. Yamada2/

11 National Institute for Research in Inorganic Materials, Tsukuba, Japan21 National Institute for Advanced Interdisciplinary Research, Tsukuba, Japan

Nanophase chemistry develops rapidly during lastyears. The understanding of quantum effects insmall dimensions is essential for designing new ma-terials for electronics and optics.

Small metal clusters of a few atoms are thermo-dynamically unstable and at room temperature theycan be only characterized by time-resolved methods[1]. By spectroscopic methods small clusters can bestudied only under cryogenic conditions.

Molecular sieves are known as the matriceswhich are able to stabilize cationic metal clusters atroom temperature. In AgNa-A zeolite y-irradiatedat room temperature the ESR spectrum of silverhexamer, Agg+ has been observed for several days[2,3]. More recently we found that zeolite AgCs-rhoshowed unique ability for stabilization of tetramericsilver clusters [4].

The main goal of the studies presented in thisarticle was to correlate the ESR and optical data forsmall silver clusters in zeolites. To achieve this goalclusters have to be relatively stable at room tem-perature because diffuse reflectance measurementscannot be carried out at low temperature. For thisreason we selected zeolite rho, which in the de-hydrated form is able to stabilize Ag^+ clusters at

Fig.l.The framework structure of zeolite rho. The preferentiallocations of exchangeable cations are denoted S.

room temperature for months. The secondary struc-ture of zeolite rho consists of a-cages with a dia-meter of 1.16 nm joint together through a doubleeight-member ring (Fig.l). Exchangeable cationspreferentially are located inside octagonal prismsand in the vicinity of hexagonal windows.

Silver cations were loaded into NaCs-rho zeoliteby cation exchange with AgNC>3 solution at roomtemperature. After drying zeolite samples wereplaced into ESR Spectrosil tubings and then at-tached to a vacuum line. After degassing at roomtemperature or dehydration at gradually increasedtemperature till 130°C the samples were sealed off

and irradiated at room temperature for 5 h using anX-ray tube operating at 50 kV and 100 mA. TheESR spectra were measured at room temperaturewith a Bruker ESP 300 X-band spectrometer. Dif-fuse reflectance measurements were carried out forthe same samples with a home-built optical systemusing a Spectra Pro-150 monochromator, halogenand deuterium lamps for visible and UV region anda Si photodiode arrayed device.

Synthesis of the zeolite rho requires the presenceof Cs+ in the reaction gel. It was found that bulkyCs+ cations play an important role in Ag|+ stabi-lization by blocking entrances to the octagonalprisms where silver tetramers are located [4]. InFig.2 the ESR spectra of dehydrated and hydratedAgCs-rho zeolites y-irradiated at room temperature

dehunirradiated

x500

3000 3250 3500 3750[G]

Fig.2. ESR spectra at room temperature of Ag6Cs-rho zeolite: a)dehydrated form y-irradiated at room temperature, b) hy-drated form y-irradiated at room temperature, c) dehy-drated form non-irradiated.


are shown. The dehydrated sample shows an intenseisotropic pentet with hyperfine splitting AjSO=139Gand gisO=1.973 of Agir clusters and a single narrowline with go=2.OlO assigned to radiation inducedparamagnetic centers in the zeolite framework(Fig.2a). In hydrated AgCs-rho the lines of Ag^+

are barely visible and the dominant ESR signal is asingle line representing framework paramagneticcenters (Fig.2b). The results indicate clearly thatthe silver tetrameric clusters cannot be effectivelystabilized at room temperature in AgCs-rho zeo-lites when water molecules are inside the zeolitecages. In contrast, in the dehydrated samples Ag|+

signals do not show visible changes for months atroom temperature.

In Fig.3 the diffuse reflectance spectra ofAgCs-rho samples in dehydrated and hydratedforms are shown. The Kubelka-Munk function wasused for the transformation of diffuse reflectivityinto absorption coefficient. The spectra are pre-sented in such a way as to make visible the spectralchanges arising after y-irradiation. For dehydratedAgCs-rho zeolite the only radiation effect observedin the diffuse reflectance spectrum is an increase ofthe intensity of the 282 nm absorption. So, it wouldseem obvious that the absorption at 282 nm re-presents the paramagnetic Agf+ cluster because thedehydrated sample shows a strong ESR pentet withA,so=139 G at room temperature. Then however,

AgCs-rhoRT

hydrated zeolile

dehydrated zeolite

450 500300 350 400Wavelength (nm)

Fig.3. Diffuse reflectance spectra of AggCs-rho zeolite in a) de-hydrated and b) hydrated form. Spectra of non-irradiatedsamples - dashed lines; spectra of y-irradiated samples -solids lines.

one could expect, for full correlation betweenmagnetic and optical data, the presence of the ESRpentet also in the unirradiated sample. Till now,ESR was always silent for any type of silver zeolite,in hydrated or dehydrated form, which was notirradiated or not reduced chemically. However,when we very carefully measured the dehydratedAgCs-rho sample by accumulating the ESR spectrafor 36 times we were able to record a weak ESRpentet with the hyperfine splitting, the same as forirradiated sample (Fig.2c). According to our bestknowledge the spectrum presented in Fig.2c is thefirst ESR spectrum ever recorded of paramagneticsilver clusters formed during dehydration of zeolite.

This result encouraged us to assign the 282 nmband to the Ag^+ cluster proving at the same timethat Ag^+ can be produced not only by radiolyticreduction but also by the autoreduction processduring zeolite dehydration. It should be noticedhowever, that concentration of paramagnetic clus-ters in dehydrated only rho zeolite is much less thanin samples exposed to y-radiation.

In hydrated zeolite two peaks with maxima at 270and 310 nm appear after irradiation. It was pos-tulated, basing on pulse radiolysis studies of 0.1AgNC>3 water solution, that in a microsecond timescale diamagnetic Agi+ clusters, characterized by astrong absorption band with a maximum at 275 nmwere formed preferentially {!]. It seems reasonableto assume that also in hydrated zeolites silver ca-tions and atoms are solvated by water molecules ina similar way as in bulk solution, so the agglomera-tion reactions should proceed similarity in bothsystems. Thus, we assigned the absorption band at270 nm to the silver divalent tetramer. The opticalspectrum with two maxima 270 and 310 nm cor-responds to the ESR spectrum shown in Fig.2b.The ESR pentet is very weak but without anydoubts represents Ag|+ clusters whose concentra-tion is lower by about a factor of 20 than in the ir-radiated dehydrated zeolite rho, but much higherthan in the unirradiated dehydrated sample. Theoptical band associated with Ag|+ and Ag|+

clusters, 270 and 282 nm respectively, are veryclose, so for low Ag|+ concentration in hydratedzeolites the 282 nm band is not revealed. Theabsorption band at 310 nm in hydrated zeolite canalso represent only diamagnetic silver cluster. Ten-tatively we assigned that band to the Ag^ cluster.

Earlier ESR results show that Agf* clusters areformed in both, dehydrated and hydrated zeoliteafter y-irradiation at 77 K and subsequent annea-ling at gradually increased temperature [4J. Presentstudies reveal that Agl+ are stable at room tem-perature only in dehydrated zeolites whereas inhydrated samples mostly diamagnetic Ag|+ clustersare trapped at room temperature. The questionarises whether the mechanisms of agglomerationare different in two zeolite forms, or the Agl+ clus-ter in hydrated zeolite is transformed into Ag^+ bythe reaction with water molecules. Although theresults of combine magnetic and optical studies areunable to answer this question univocally, theysuggest that rather the later process is responsiblefor Ag5+ formation. It was postulated that Ag^+

clusters are located inside octagonal prisms ofzeolite structure [4,5], where they are easily access-ible for water molecules through a wide octagonalwindow with a diameter of about 0.36 nm. At roomtemperature when adsorbate molecules becomemobile the contact interaction between Ag|+ andH2O with subsequent electron transfer seems poss-ible. If our hypothesis is correct then it means thatthe AgJ dimerization reaction in which diamag-netic Ag|+ clusters are formed, as proposed byErshov et al. [1], does not proceed effectively insidezeolite channels.


References

[1]. Brshov B.G., Janata E., Henglein A.: J. Phys. Chem., 97, 339(1993).

[2]. Morton J.R., Preston K.F.: J. Magn. Reson., 68,121 (1986).

[3]. Michalik J., Kevan L.: J. Am. Chem. Soc, 108,4247 (1986).[4], Michalik J., Sadto J.,Yu J-S., Kevan L: Colloids and Surface

A: Physicochem. Eng. Aspects, 115,239 (1996).[5].Xu B., Kevan L.: J. Phys. Chem., 95,1147 (1991).

PL9801990ESR STUDY OF SOLID PEPTIDES

G. Strzelczak, K. Bobrowski, J. Michalik

Understanding of the radiation damage of a com-plex biological system, like protein, requires a de-tailed knowledge about the final products andradical reaction mechanisms in model compoundsin the aqueous liquid phase as well as in the solidstate. This is due to the known fact that the state ofproteins in vivo lies very often between the solutionand the solid state.

The gamma irradiated at 77 K. polycrystallinemethionine-containing peptides: type X-Met andMet-X (X - aliphatic aminoacid) were evacuatedand irradiated with a dose of — 5 kGy.

The radicals produced by irradiation were studiedover the temperature range 77-293 K by electron spinresonance spectroscopy. The ESR experiments wereperformed using a Bruker ESP-300 spectrometerwith a variable temperature cavity.

The ESR spectra were analysed by a computersimulation (using EPR Software provided by D.Dulling from NIEHS LMB National Institute ofHealth, USA).

Carbon dioxide analysis was performed by a gaschromatography technique (Perkin Elmer 8700),and analysis of ammonia by using an ion-selectiveammonium electrode (Cole-Parmer).

The aim of this study was the identification ofvarious radical intermediates and final productsformed on gamma radiolysis of the peptides withvarying numbers of methionine residue and theirvarying location with respect to the terminal func-tions (Chart 1).

X-METH.,N-CH-CONH-CH-COO~

IR CH2

CH2

SCHo

X=Gly;Ala;Val;

MET-XHJN-CH-CONH-CH-COO"

CH, RCH2

SCH3

i = CH3

t = CH(CH,)2

Leu; R = CH2CH(CH3)2

Ser; R = CH2OH

Chart 1.

The major radical observed at 77 K in all pep-tides is an anion radical formed by the addition ofan electron to the carbonyl group of the peptidebond (singlet with g=2.0068 and AH=8G). De-amination and decarboxylation radicals were de-tected over the temperature range 150-250 K. H-ab-straction radicals in the side chain of methionineresidue cr(alkylthioalkyl) radicals were observed for

peptides with N-terminal methionine at the sametemperature (Figs. 1 and 2), [1-3],

The efficiency of decarboxylation is 2-3 foldhigher at X-Met peptides as compared with Met-X

a)Ala-Met

77 K

O"-C-NH--

180 K

CH-CONH

C)

293 K

-CONH-C-COO-

CH2

CH2

sCH,

Fig.l.ESR spectra of alanyl-methionine irradiated at 77 K: a)recorded at 77 K - singlet of anion radical, b) 180 K quintet- deamination radical of the alanine residue; c) 293 Ktriplet • H-abstraction radical of the methionine residue.


Met-Met200 K

Table. Radiation yields of decarboxylation and deamination.

Fig.2.The multicomponent of ESR spectra of methionyl-me-thionine irradiated at 77 K and recorded at 200 K. Simu-lation spectra: triplet (middle) - a(alkylthioalkyl) radical ofthe methionine residue; quintet (bottom) - decarboxylationradical of the methionine residue.

peptides. This is probably due to differences in crys-tallographic structure of these two types of pep-tides. The yields of CO2 and NH3 are consistentwith the observation of decarboxylation and de-amination radicals in peptides (Table).

At room temperature (293 K) the most stableradicals are H-abstraction radicals at the a-carbonof the C-terminal amino acid (Fig.3).

The nature and the stability of radical interme-diates generated after gamma irradiation in poly-

PeptideGly-MetAla-MetVal-MetMet-MetMet-GryMet-AlaMet-Val

G(CO2)0.61+0.11.37+0.21.98+0.20.5+0.20.3+0.1

0.28+0.10.95+0.3

G(NH3)5.0+0.64.0+0.6

3.5+0.4

2.7+0.4

Met-Ala293 K

Ala-Met293 K

340 345 350 355 [ml]Fig.3. ESR spectra recorded at 293 K: a) for Met-Ala quartet of

H-abstraction radical of the alanine residue; b) for Ala-Mettriplet of H-abstraction radical of the methionine residue.

crystalline methionine-containing peptides is de-pendent upon the location of the metionine residuewith respect to the terminal functions.

References[1]. BurlifSska G., Michalik J., Bobrowski K.: An electron spin

resonance study of gamma-irradiated polycrystalline methio-nine-containing peptides. Rad. Phys. Chem., 42, 425 (1994).

[2]. Burlinska G., Wasowicz T., Michalik J., Bobrowski K.: Radia-tion induced radicals in solid peptides. Mol. Phys. Rep., &134 (1994).

[3], Strzelczak-Burlinska G., Bobrowski K., Pogocki D., Michalik J.:ESR study of radiation induced radicals in polycrystalime me-thionine and its homopeptides. Nukleonika, 42,333 (1997).

EPR SPECTRA OF y-IRRADIATED DL-a-ALANINESUPPORTED ON MOLECULAR SIEVES

Z. Stuglik, S. Kowalakv, A. Jankowska17, K. Kruszonay

v Faculty of Chemistry, A. Mickiewicz University, Poznan, Poland

PL9801991

a-Alanine is widely applied as a probe molecule indosimetry of ionizing radiation. It is used either as a

neat, polycrystalline powder or with some binders(paraffin, polymers). The matrices affect sometime


the measurement, therefore searching for alterna-tive supports for alanine is quite reasonable. Thecrystalline molecular sieves due to their uniformpore system can be considered as very promisingmatrices that provide well ordered distribution ofalanine molecules within the channel or cavity sys-tems. Some of structures (e.g. sodalite) can provideencapsulation of alanine molecules in separatedcages, which eliminates the interaction between theentrapped molecules. Zeolites due to their ion-ex-change properties and polar nature of the surfacecan interact with the adsorbed alanine and sub-sequently affect its radiolysis. In the case of AIPO4materials only a weak physical interaction can beconsidered.

Up to now we investigate some zeolites (Y,ZSM-5, mordenite, sodalite) and two molecular sievesfrom the A1PO4 group (AlPO4-5 and AIPO4-H).Several cation modifications of zeolite Y were ap-plied.

DL-cc-alanine was usually introduced into themolecular sieves by means of impregnation fromaqueous solution. An attempt to employ ion-ex-change for introducing alanine into zeolite NaYfailed and the whole alanine was removed on wash-ing with water. In the case of sodalite, alanine wasincorporated upon zeolite crystallization (Sodalitewas crystallized at 95°C for 20 h in the presence ofalanine admitted to the initial aluminosilicate gel).

The resulting samples were characterized bymeans of the FTIR and XRD methods. Then thesamples were exposed to y-radiation (Co-60, Isslie-dowatiel, 3.7 kOy) and their EPR spectra were re-corded at room temperature on a Bruker EMS 104apparatus. The free alanine and the supportedsamples did not show any ESR signals before irra-diation.

The EPR spectra of irradiated alanine depend onthe nature of the supporting molecular sieves(Fig.). In the case of NaY, ZSM-5, Na-mordeniteand others, the EPR spectra were very similar tothose observed in polycrystalline alanine. Substan-tial differences were noticed for HY. Also the EPRspectra of the sodalite supported sample differ fromthat of neat alanine. In the AIPO4 samples we ob-served the EPR spectra resulting from alanine butalso from the remainders of amine template applied

for their synthesis. The last one can be observed atroom temperature several days after the irradiation.

mordenit

2. OSS

HY

2.028 2.005 1.SS2 1.9

hydrogen formof zeolite Y

2.051

sodalit

2.027 2.003 1.SB1 1.9

2.052 2.028 2.005 1.962 1.9

IG-VALUEIFig. EPR spectra of y-irradiated (D=3.7 kGy) samples of DL-«-

-alanine supported on molecular sieves.

Although the presented results show only thepreliminary findings and the research is in progresswe believe that the molecular sieve matrices couldbe very useful for dosimetric application.

oIS

DIFFERENTIAL SCANNING CALORIMETRY STUDIESOF GAMMA IRRADIATION INFLUENCE ON STARCH GELATINIZATION

K. CieSla, E. Svensson1', A.-Ch. EIiasson1/

11 Chemical Center, Department of Food Technology, University of Lund, Sweden

Studies of the gelatinization processes, occurringduring heating of water suspensions of nonirradiatedpotato starch and wheat flour and the irradiatedproducts, were carried out by differential scanningcalorimetry (DSC). These studies deal with struc-tural changes occurring in starch under the influenceof gamma irradiation. Since the course of gelatini-

zation depends on the structure of starch granules, itwas expected that the changes occurring after irra-diation will influence the process. Decrease of theorder in starch granules, brought about by degrada-tion was concluded previously on the basis of SAXSand WAXS studies. Moreover, significant differencesbetween the maximum viscosities were detected dur-


ing heating of water suspensions of nonirradiatedand irradiated wheat and rye flour.

Potato starch was irradiated with a dose of 20kGy and wheat flour was irradiated with a dose of30 kGy, applying a dose rate of 1.7 kGy/h. Theinitial samples, irradiated products and potatostarch amorphous standard were examined. DSCmeasurements were performed in the temperaturerange 5-130°C, using heating rates of 10, 5 and2.5°/min for the suspensions having concentrationsca. 20% and 40-50% closed hermetically in Al pans.A Perkin-Elmer DSC2 instrument installed in theUniversity of Lund was used.

The influence of the conditions applied duringDSC measurements on the obtained results waschecked. Single gelatinization endothermal effectwith a maximum at ca. 66°C was observed for sus-pensions of initial starch having concentration ofca. 20%, while for highly concentrated suspensions,apart from the main maximum, the shoulder wasnoticed at higher temperatures. In the case of initialflour the endothermal effect of amylo-lipid complexdecomposition with a maximum at ca. 106°C wasadditionally found.

The differences between the processes occurringduring heating of suspensions of irradiated andnonirradiated starch and flour were observed. Thegelatinization enthalpies were found to be smallerfor all the irradiated samples, as compared with thenonirradiated reference samples. An increase in thepeak and onset temperatures were found for theirradiated starch. These differences were larger inthe case of highly concentrated suspensions (ca.45%) as compared with the suspensions at a con-centration of 20%. Besides that, the inflexion pointbetween the main peak of gelatinization and theshoulder, disappeared for the irradiated sample(Fig.). In the case of amorphous standard, a de-crease in enthalpy accompanied by a rise of peaktemperature but a decrease in the onset tempera-

ture was found after irradiation. For example, when42-45% suspensions were heated with a rate of2.5°/min, the values of gelatinization enthalpy equalto 17.3, 13.9 and 4.5 J/g were determined for theinitial starch sample, the product irradiated with adose of 20 kGy (1.8 kGy/h) and for the amorphousstandard. Simultaneously, peak temperatures equalto 64.3, 66.9 and 68.1°C, and the onset tempera-tures equal to 61.2, 63.9 and 56.9°C were deter-mined for the respective samples.

90Temperature, *C

Fig. DSC curves recorded with a heating rate of 2.5°/min for theconcentrated suspensions of initial starch (45.13%) and theproduct irradiated in the solid state with a dose of 20 kGy(1.8 kGy/h) (45.22%).

In the case of wheat flour, apart from the chan-ges in gelatinization process, a decrease in peaktemperature of amylo-lipid complex decompositionwas found after irradiation.

It can be concluded that the differences occur inthe structure of crystalline and amorphous parts ofwheat and potato starch and in the wheat starch--lipids interactions between irradiated and referencesamples.

IONIZATTON-INDUCED DAMAGE INCREASE IN As-IMPLANTED GaAs

S. Warchot, H. Rzewuski

Ion implantation into semiconductor crystals createsheavily disordered regions which deteriorates physi-cal parameters of a crystal. These post-implantationlattice defects can be removed by thermal treatments,and electron, light or laser beam annealing. Therehave been many reports [1-4] on using this approachshowing the decrease of damage level. One of thepossible ways of enhancing defect annealing consistsin ionization created by electron irradiation in ad-dition to thermal treatment. The important pointhere is that electron irradiation stimulates the annea-ling processes, which take place at elevated tempera-tures.

In this paper we report for the first time the ef-fect opposite to defects annealing, i.e. the increaseof post-implantation damage level in GaAs underionizing radiation of a 300 keV electron beam

irradiation at room temperature. The applied 300keV electron energy is greater than the thresholdenergy for atomic displacements in GaAs ( E T = 2 3 3keV for Ga atoms and E T = 2 5 6 keV for As atoms)[5] and the concentration of simple defects intro-duced by electrons of this energy during 4 h irra-diation is negligible compared to the concentrationof defects produced by ion implantation itself.

Fig.l presents the RBS random and channelingspectra of unimplanted GaAs samples irradiatedwith 300 keV electrons to a dose of lxlO17 cm"2 atRT. It may be noticed that the channeling spectrafor virgin and electron irradiated samples coincidewithin the experimental error. It shows that nodetectable damage was introduced by the 300 keVelectron irradiation at the surface layer of a sam-ple.

loo

i§ioi oo

i3

36

5000

4000

O 30001

2000-

1 0 0 0 -

1 -random2-virgin3 - electron irradiated -

300 350 -too 450 500

CHANNEL NOFig.l.Random and channeling RBS spectra of unimplanted

GaAs before and after irradiation with 300 keV electronsto a dose lxlO17 cm"2 at RT.

For implanted GaAs samples (150 keV As+

ions, dose lxlO13 cm"2 ) the RBS channeling spectra(Fig.2a) show distinct damage peaks for As-im-planted and electron irradiation samples. Thedamage density distributions for these two caseswere calculated using formula given in ref. [6] and

5000'1 - rmdont2 -with electron irradiation3 - without electron irradiation -

3 0 0 350 400 4 5 0

CHANNEL NO

500

50

•3 30-

I 20"10 -

0.0-

b)• - with electron irradiation«- - without electron irradiation

500 1000 1500

DEPTH(A')Fig.2.(a) Random and channeling RBS spectra for GaAs im-

planted with 150 keV A s + ions to a dose 1x10^ cm"2:electron beam irradiation of 300 keV to a dose lxlO^cm"2

at RT. (b) Depth damage distributions for a.2 and a.3.spectra.

RADIATION CHEMISTRY AND PHYSICS

the "Defect" computer program [7]. The results aregiven in Fig.2b and demonstrate the increase ofdamage density distribution for 300 keV electronirradiation compared to the ion-implanted sample.The damage increase varies from the surface of asample towards the bulk and amounts approxima-tely to 100%.

Further increase of the dose of the implantedAs+ ions to 2xlO13 cm"2 resulted in higher damagepeaks for the samples with and without electronirradiation (Fig.3a, curves 2 and 3). The respectivedamage profiles presented in Fig.3b show similarbehaviour to the lower implanted dose samplesgiven in Fig.2b.

The only factor which could influence the sta-bility of these damaged zones created by ion im-plantation is ionization created by 300 keV electronirradiation. As was shown by Corbett and Bourgoin[8] and other authors [9-11] ionization increases de-fect mobility in various ways changing the charge

5000

4000"

3000"

2000"

IOOO-

0 -

a)

2

i - random2 - wiili electron imdiatiou3 - without electron irradiation

1

300 350 400 450CHANNEL NO

500

40"

fc 30-&

s5 20-

10-

0.0-

b)• - witb electron irradiation* - without electron irradiation

1^11500 1000

DEPTH (% )

1500

Fig.3. (a) Random and channeling RBS spectra for GaAsimplanted with 150 keV A s + ions to a dose 2xlO13 cm"2:electron beam irradiation of 300 keV to a dose 1x10*cm"2 at RT. (b) Depth damage distributions for a.2. anda.3 spectra.

state of defects and modifying their energy barrierfor migration. Thus we should expect that under theinfluence of ionization out-diffusion of simple de-fects from a damaged zone will take place. At least


part of them migrating through the sample willmake associations with intrinsic or foreign atoms inthe crystal, increasing in this way a total level ofdamage as recorded by RBS.

References[1]. Gamo K., Inada T., Mayer J.W., Eisen F.H., Rhodes C.G.:

Rad. Effects, 32,85 (1977).[2].Khaibullin IB., Shtyrkov E.I., Zaripov M.M., Bayazitov

R.M., Galjautdinov M.F.: Rad. Effects, M, 225 (1978).[3]. Gyulai J., Revesz P.: Inst. Phys. Conf. Sen, 46,128 (1978).

[4].Suski J., Rzewuski H., Kiynicki J., Groetzschel R.: Inst.Phys. Conf. Ser., 52,485 (1981).

[5]. Bauerlein R.: Z. Naturforsch., 14a, 1069 (1959).[6]. Chu W.K., Mayer J.W., Nicolet M.A.: Backscattering Spec-

troscopy. Academic Press, New York 1978.[7J. Sidor R.: unpublished.[8].Bourgoin J.C., Corbett J.W.: Inst. Phys. Conf. Ser., 23, 149

(1975).[9].Kimerling L.C., Poate J.M.: Inst. Phys. Conf. Ser., 22, 126

(1975).[10]. Palmer D.W.; Inst. Phys. Conf. Ser., 21,144 (1977).[11]. Kimerling, L.C.: Inst. Phys. Conf. Ser. 46., 56 (1979).

HEAVY IONS IRRADIATION EFFECTS IN POLY(BUTYLENETHEREPHTHALATE)

i /

K. Cies'la, E. Ferain17, R. Legrasv, W. Starosta

Laboratory of High Polymers, Catholic University of Louvain, Belgium

Studies of physico-chemical changes occurring inpoly(butylenetherephthalate) (PBT) films underheavy ion irradiation were continued. The work isconnected with the search for new materials forheavy ion detectors and particle track membranes(PTM). The knowledge about the processes oc-curring during irradiation and identification of theresulting products is essential for the selection ofetching conditions and production of PTM.

The series of PBT films (80 nm. thick) were pre-pared by melting of commercial granulate (Jelchem,Poland), moulding the ribbons in calander and sub-sequent annealing in vacuum. The films were pre-pared applying different treatment conditions suchas temperature of melting chamber and calander ortemperatures and time of annealing. WAXS andFTIR results show that the films display differentcrystallinities. Four PBT films were selected andirradiated with Ar ions (5.5 MeV, ca. 5xl010

ions/cm2), one of these films was irradiated withdoses of ca. 108, 109, 1010, 10n ions/cm2. WAXSdiffractogramms of the selected PBT films are

60 5

Fig.l. WAXS diffraction patterns of 4 selected PBT films (80^mthick): curve 1 - melted at 240°C, moulded at 20°C; curve2 - melted at 260°C, moulded at 20°C; curve 3 - melted at260°C, moulded at 20°C, annealed at 150°C for 4 h; curve4 - melted at 260°C, moulded at 20°C, annealed at 200°Cfor 3.5 h. The measurements were done applying CuRaradiation.

presented in Fig.l. Moreover, the films preparedfrom PBT and two co-polymers of PBT witholigo-l,4-oxybutylenediol (PTMEG) [1] (30-50 /um

thick) obtained from Szczecin Technical University-were irradiated with a dose of 7xlOn ions/cm2.

DSC measurements were performed in heat-ing-cooling-heating cycles (2-3 heating courses)with a rate 10-10-10°/min. The differences wereobserved between melting and crystallization pro-cesses occurring in particular PBT films and be-tween these processes occurring in the referenceand irradiated films. In particular, peak and onsettemperatures, shape of thermal effect and enthalpy,calculated for the processes occurring in the irra-diated films differ from those observed for the ini-tial samples. The differences were observed already

Fig.2. Melting endothcrmal effects and exothermal effects ofcrystallization observed during first heating (a) and firstcooling (b) of 50 ftm thick PBT film and the product,irradiated with Ar ions (5.5 meV/amu) applying the fluence7 x l 0 n ions/cm2.

after irradiation with an ion fluence of ca. 108

ions/cm2. The examples of DSC curves of initial andirradiated films are presented in Fig.2.

Decrease in the crystallinity in PBT andPBT-PTMEG films after irradiation can be con-cluded not only from the DSC results, but also onthe basis of WAXS diifractogramms and FTIRpatterns. In the case of PBT-PTMEG films signifi-cant chemical changes can be also concluded fromthe FFIR pattern.

References[1].E1 Fray M., Stonecki J.: Multiblock co-polymers consisting of

polyester and poh/aliphatic blocks. Angew. Makromol. Chem.,234,103-117(1996).

ren

o

S3


RADIOCHEMISTRY

STABLE ISOTOPES

NUCLEAR ANALYTICAL METHODS

CHEMISTRY IN GENERAL


RADIOCHEMISTRY, STABLE ISOTOPES,NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL 41

COMPLEXATION OF f-ELECTRON (3+)IONS WITH PSEUDOHALIDE LIGANDS

M. Borkowski, S. Lis1', S. Siekierski11 Faculty of Chemistry, A. Mickievvicz University, Poznan, Poland

It has been known for a long time that with respectto solvent extraction from thiocyanate solutions,contrary to nitrate solutions, yttrium behaves as alight lanthanide, while actinides(III) turn to be si-milar to heavy pseudolanthanides [1-3]. This be-havior is a basis for group separation of yttriumfrom lanthanides and of actinides from lanthanides.it is interesting to know whether other pseudo-halide ligands (NCSe~, NCO~, and NJ) behave ina similar way. For that purpose a comparativesolvent extraction of Y(HI), Am(III) and selectedlanthanides into tri-n-buthyl phosphate, TBP, waspreviously studied [4] and high distribution ratiosfor NCS" and NCSe" and very small distributionratios for NCO~ and NJ were found. Because ofhigher pKa values of HN3 and HNCO than ofHNCS and HNCSe, i.e. higher capability to formcomplexes by the NJ and NCO" than by the NCS"and NCSe" anions, and because of almost the samepartition coefficients of HNCS, HNCO and HN3acids [5], extraction of lanthanides from azide andcyanate solutions should be similar to that fromthiocyanates. We have assumed that partition ofHNCS, HNCO and HN3 acids into TBP can serveas a model for partition of the respective complexesof tervalent cations i.e. that each pseudohalide li-gand bonded to the metal interacts equally stronglywith water molecules. The disagreement betweenexperiment and expected behavior can be due to thefact that the NJ and NCO" ions prefer formationof unextractable outer-sphere complexes, while theNCS" and NCSe~ ions form extractable inner--sphere complexes. Another explanation is that themetal-bonded NJ and NCO" ligands interact muchmore strongly with water than the NCS" andNCSe" ligands.

To decide between the two possibilities, it is ne-cessary to study both the coordination sphere of thelanthanide(III) ion and partition of the LJ1X3 com-plexes as a function of the pseudohalide ligand X. Itis well known that the luminescence spectroscopyof Eu(III) ion is a useful tool in studying theprimary coordination sphere of the cation whilehypersensitive absorption band of Nd(III) 4l9/2 •*4Gs/2 (at ~ 576 nm) is widely used in the study ofmetal-ligand interaction. Therefore, both these me-thods have been used in this work. Unfortunatelly.there is no method which makes it possible todetermine the partition constants of the TBP ex-

tractable LJ1X3 complexes (X=NT3, NCO , NCSand NCSe~). Instead of lanthanide complexes wehave, therefore, studied partition between waterand TBP of the tetrahedral [Co(NCS)4]

2~ and[Co(N3)4]2~ complexes. Partition constants of thetetrahedral Co (II) complexes can be, under certainconditions, determined directly by the spectro-photometric method.

Studies on intensity of the hypersensitive tran-sition band of Nd(III) as a function of the ligandhave shown that, contrary to our previous assump-tion [4], the cyanate and azide ions form inner--sphere complexes with lanthanide ions. The ten-dency to form inner-sphere complexes increases inthe order:

NCSe" < NCS~ < NJ < NCO"This conclusion is supported by the study of the

luminescence lifetimes of Eu(III) in cyanate com-plexes. It follows from this study that already in 0.6M NaNCO solution there are two cyanate ligandsin the inner coordination sphere of the Eu(III) ion.The decrease in the luminescence lifetimes ofEu(III) in azide complexes can also be explained byformation of inner-sphere complexes, assumingthat the NJ ligand is even a better quencher thanthe water molecule.

Because, as demonstrated by spectral results, lan-thanides form inner-sphere complexes with NCO"and NJ anions more readily than with NCS" anion,a much better extraction of lanthanides fromthiocyanates must originate in much higher transfer(partition) constant of the Ln(NCS)3 complex. Thisconlusion has been indirectly confirmed by thestudy of extraction of the tetrahedral complexes ofCo(II) with NJ and NCS" ligands, which hasshown that the distribution ratio of [Co(NCS)4]2~is about 6 orders of magnitude higher than that of[Co(N3)4]2". That means that NJ metal bondedligands interact with water molecules much morestrongly than NCS" metal bonded ligands.

References[1]. Siekierski S.: Radiochem. Radioanal. Lett., 48,169 (1981).[2]. Borkowski M., Siekierski S.: Radiochim. Acta, 56,31 (1992).[3]. Choppin G.R., Barber D.W.: J. Less-Common Met., 149,231

(1989).[4]. Borkowski M., Krejzler J., Siekierski S.: Radiochim. Acta, 65,

99 (1994).[5]. Krejzler J., Siekierski S.: J. Solution Chem., 24,253 (1995).

oCO

i Oi

!a!

SYNTHESIS AND ION EXCHANGE PROPERTIESOF MANGANESE(IV) DIOXIDE DOPED BY +3 TRANSITION METAL CATIONS

B. Barto£, A. Bilewicz

Manganese oxides in a-crystalline form are known have been shown to exhibit unusued ion selectivitiesto possess interesting ion exchange properties and [1,2]. The crystal structure of a-MnO2 is a 2x2 tun-

42RADIOCHEMISTRY, STABLE ISOTOPES,

NUCLEAR ANALYTICAL METHODS, CHEMISTRY IN GENERAL

nel-framed structure with exchangeable alkali oralkali earth cations. a-MnC>2 in the H+ form hasbeen demonstrated to show excellent ion-exchangeselectivity towards cations with crystal ionic radii(rj) of 130-150 pm, e.g. K+, NH^, Ba2+ and Ra2+.The selectivity of a-MnC>2 is related to the stericeffect in the tunnel structure. The presence of ex-changeable ions in the tunnels requires that someof the manganese atoms be present in oxidationstates lower than 4. The formulae could be repre-sented by K^Mn^Mn'toie as postulated by Tsujiand Abe [3] or KMn^vMnIIIOi6 as described byYuan-Gen Yin et al. [4].

By redox (I2) and complexing (EDTA) titrationof the same samples of a-MnC>2 we found thata-MnO2 contains Mn(IV) and Mn(III) cations.Because capacity of the sorbent is related to theMn(III)/Mn(IV) ratio we tried to increase the con-centration of M3+ cations in the sorbent by insert-ing various +3 transition metal cations. The sam-ples of mixed Mn-M oxides (M - transition metal)were synthesized by redox reaction of KMnC>4 andMJ1SO4 in the presence of Co2+ and Fe2+ cations.Under the synthesis conditions the Co2+ and Fe2+

were oxidized to Co3+ and Fe3+ of similar ionicradii to Mn3+ and the M3+ ions were incorporatedin the MnO2 structure. The obtained sorbent sam-ples have higher capacity than pure a-MnO2 and, asshown in Fig., exhibit very high affinity to heavyalkali earth cations, especially for Ra . The ob-tained Mn-Fe and Mn-Co oxides could have prac-tical application for developing a new effective

10000

1000;

140 150130Ionic radius (pm)

Fig. K<i values of alkaline earth metal cations in 1 M HNO3 solu-tion as a function of ionic radii of the studied elements formixed Mn-Fe and Mn-Co oxides, a-MnO2 and sulphonic ionexchange resin. The data for AG-50x8 are for 1 M HC1 weretaken from [5].

procedure for preconcentration and determinationof radium isotopes in natural water at very low con-centration.

References

[1]. Tsuji M., Abe M.: Radioisotopes, 33,210 (1984).[2]. BartoS B., Bilewicz A., Deltnas R., Neskovic C : Solv. Extr.

Ion Exch., IS, 533 (1997).[3]. Tsuji M., Abe M.: Bull. Chem. Soc. Jpn., £8,1109 (1985).[4], Yuan-Gen Yin, Wen-Quing Xu, DeGuzman R., Suib S.L.,

O'Young C.I.: Inorg. Chem., 22,4384 (1994).[5]. Marhol M.: Ion Exchangers in Analytical Chemistry. Acade-

mia Prague, 1982.

DENSITY FUNCTIONAL CALCULATIONS ON HYDROGEN-BONDED HYDRATESOF METAL ACETYLACETONATES

1/

J. Narbutt, M. Czerwiriski1/

Chemistry Institute, Pedagogical University, Cze.stochowa, Poland

Quantum-mechanical calculations based on the den-sity functional theory (DFT) were carried out inorder to find theoretical evidence for experimentaldata which indicate that hydrogen bond is formedbetween water molecules and donor oxygen atoms ofacetylacetonate ligands in metal chelates [1,2], Wealso tried to explain why the strength of this outer--sphere hydration of chelate molecules depends onthe central metal ion [3,4].

Full optimization of the geometry of ML3 che-lates and ML3-H2O adducts was performed fortrivalent Sc, Ti, V, Cr, Mn(HS), Co(LS) and Gacations, and a simplified model of the acetylaceto-nate ligand: L= [H-CO-CH-CO-H]". DMol packagewith DFT numerical functions and the DNP func-tions with VWN potentials were used, as well asGAUSSIAN 94 package. The latter made possiblecalculation of the energy of hydrogen bond, cor-rected for the basis superposition error. Vibrationalfrequencies of free and bonded water moleculeshave been computed by determining the secondderivatives of the energy. The obtained number of

3n-6 positive frequency values indicates that thesystem is in the global minimum.

Fig. Molecular orbital in the VL3-H2O adduct, of the energy-0.5303 a.u., corresponding to the hydrogen-bond, calculatedwith the use of GAUSSIAN 94 (B3LYP with the Lanl2dzbasis).


The energy minimum in the ML3-H2O systemshas been obtained for the case when the watermolecule is directed towards the lone electron pairof one of the oxygen atoms (OL) in the ML3 mole-cule and the distance OL-OW is close to 280 pm,which is evidence for the formation of theOL-..H-OW hydrogen bond. The bond is, however,not exactly linear - small deviations of theOL-H-OW angle from 180° depend on the metal ion.The optimized geometry of the adducts indicatestheir additional stabilization due to weak bondingbetween the second proton of the water moleculeand another ligand in ML3.

The experimental sequence of outer-sphere hyd-ration energies of the metal acetylacetonates, whichincreases from Sc to Co [3], has been reproduced inthe calculations. Molecular orbitals correspondingto the hydrogen bond have been found for theadducts (Fig.). The energies of these orbitals are inagreement with the theoretical and experimental

data on the hydrogen bond in the adducts. It hasbeen also shown that the calculated changes in bothcharge density on the water proton and the stretch-ing frequency of water molecule in the adductscorrespond with the experimental NMR and IRdata for the Co(acac)3-H20 adduct [2]. The contri-butions from electrostatic, exchange and chargetransfer energy to the energy of hydrogen bond inthe adducts were discussed.

The research was supported by a grant (3 T09A016 09) from the Polish State Committee for Scien-tific Research. The calculations were performed ona CRAY-YMP computer at the ICM, University ofWarsaw.

References[1]. Narbutt X: J. Phys. Chem., 213432 (1991).[2]. Moore P., Narbutt J.: J. Sohit. Chem., 20,1227 (1991).[3]. Narbutt J., BartoS B., Siekierski S.: Solv. Extr. Ion Exch., 12,

1001 (1994).[4], Narbutt J., Fuks L.: Radiochim. Acta, 2S, 27 (1997).

ON THE CORRELATION BETWEEN CHEMICAL AND OPTICAL ISOTOPE SHIFTS

W. Dembinski, M. Poninski

I 238/236£ I = | 238/234£ . = 1.0.00037 I < 10.00043 I =238/235

New very accurate separation data obtained in thecourse of studies on the so called "even-odd" effectrevealed that the chemical isotope effect mirroredthe isotope shifts in atomic spectra. Data for theseries of barium isotope pairs: 138/137, 138/136.138/135 and 138/134 may serve as a spectacularexample. The mirroring is visible when one comparesthe values of enrichment gains, ln(q), measured in adicyclohexano-18-crown-6/HCl separation system(Fig.l, [1]) with the optical isotope shifts (Fig.2). The

1.5

« 0.52~ 0

-0.5

-1134 135 136 137 138

Fig.l. Ba chemical isotope shifts; *™Ba as reference.

later are expressed by the changes in the nuclearmean square charge radius, <5(r2)fm2, derived fromthe field shift fraction in the total optical isotopeshift [2]. The same correlation between chemical andoptical isotope shifts have been found for uranium[3] and recently studied ytterbium [4]. In fact, for aseries of uranium isotopes in the separation system,U(IV)/U(VI),wehave:

\

\

\ \

\

j238/235£|

where e = ln(q)/Am, and

[(l/2)(5<r2)]238,236=[(l/2)<5<r2)]238,236=0.5<0.56=

[(l/3)<5<r2>]238,235For a series of ytterbium isotopes in the separa-

tion system, Yb(Hg)/Yb(III)-acetate, we have:176/174 j = j .0.00069! > | -0.000541 = j 176 '1

0.025

0.051-

0.075

0.1

0.125134 135 136 137 138

Fig.2. Ba opiical isotope shifts;' ^Ba as reference,

(these data are illustrated in Fig.3; the straight lineextrapolation gives the hypothetical mass number172 for the isotope 171Yb to fulfill the condition

• \

\ /

-

•

/

/

| | | , ) l ]

[(l/2)(5{r2)]176,i74= i -0.00451 > | -0,00401 =

[(l/5)E<5<r2)]176,i7iIt is here to point out that in both the series of

data (chemical and optical) the direction of "even--odd" effect of ytterbium is opposite to the direc-tion of "even-odd" effect of uranium, e.g. the even-

! O)

io!



•0.3

-0.25 -

-0.2

f-0.15

•0.1

-0.05

1

//

r

9

/ sV

172? ,

/

/

i

176 175 174 173 172 171 MFig.3. "Even-odd" effect of ytterbium isotopes.

-even isotope pair, 176/174Yb, is separated more ef-ficiently (by a factor of 1.27) than the eventope pair 176/171Yb, whereas the even-even

-odd iso-uranium

isotope pairs, ^ s ^ u and 238i/234u, are separatedless efficiently (by a factor of 1.16) than the even--odd isotope pair, 238/235u.

Theoretical explanation of this phenomenonneeds further studies and a better understanding ofthe nature of mass independent constituent in theoverall chemical isotope effect. In fact, the totalseparation gain, ln(q), in the light of new experi-mental data, should be broken into two terms: thevibration one, ln(q0), and the term, ln(KSf), which istold to be sensitive to the nuclear field.

References[1]. Nishisawa K., Nakamura K., Yamamoto T., Masuda T.: Solv.

Extr. Ion. Exch., 12,1073 (1994).[2]. King W.H.: Isotope Shifts in Atomic Spectra. Pergamon

Press, New York and London 1984, p.12.[3]. Bigeleisen J.: J. Am. Chem. Soc., 118,3676-3680 (1996).(4). Dembiriski W., Poninski M., Fiedler R.: Separation Science

and Technology, 3_L August (1998), in press.[5]. King W.H.: Isotope Shifts in Atomic Spectra. Pergamon

Press, New York and London 1984, pp.142-143.

INNER-SPHERE SOLVATTONOF SCANDIUM TROPOLONATE AND ETHYLMALTOLATE IN SOLUTION

J. Narbutt, J. Krejzler, D. Dymecka

Scandium(III) ion of the radius of 73 pm is on theborderline of coordination number (CN) six andseven. Its typical CN with monodentate ligands is 6although CN 7 has also been proposed [1]. GreaterCN are met in scandium chelates with bidentateligands which form five- or six-membered rings withthe ion. For example, for scandium tropolonatestwo different coordination environments of the cen-tral metal ion are known: with CN 6 in the neutralSc(trop)3 chelate and with CN 8 in the anionicH[Sc(trop)4J [2], Anionic chelates and adducts withtrioctylphosphine oxide (TOPO) in chloroformsolution have also been reported for scandiumhexafluoroacetylacetonate [3]. Strong tendency toform inner-sphere adducts by weak chelates is inline with the prevalent opinion that the weaker ischelate the stronger its adduct [4]. According to thisrule, a more basic acetylacetonate ligand does notform anionic octa-coordinate forms with scandium,and only the neutral Sc(acac)3 chelate with CN 6 isknown [5]. In this work we examined the ability ofscandium(III) ion to increase its CN in chelateswith acetylacetone, tropolone and ethylmaltol. Thelatter two are formally a-diketones in the enol

\CH3

form. Different geometry of the ligands (Scheme)causes significant differences in the structure oftheir scandium chelates, influencing in that way theCN of scandium(III) ion.

The values of formation constant of the inner--sphere adducts with TOPO, determined from thesynergistic effect in liquid-liquid distribution of thechelates labelled with 46Sc, were considered as ameasure of the tendency to increase CN of scan-dium ion in a given chelate. Liquid-liquid partitionof the chelates was also studied in order to getinformation on their aqueous-phase hydration andon the ability of scandium to increase CN by thecoordination of water ligand(s). Stablility constantsof scandium tropolonates (log/3i=7.5; log /?2=15.7;log 03=21.6) and ethylmaltolates (9.1; 17.4; 23.3)have been determined using the solvent extractionmethod (I-»0, 25°C). Both chelates are thus of acomparable stability or stronger than Sc(acac)3 [6].

Fig. shows that the presence of carefully purifiedTOPO, even at high concentration, has practically noeffect on the distribution of Sc(acac)3 between hep-tane and water, therefore no Sc(acac)3-TOPO adductis formed in the organic phase. To be sure, formation

3

M(acac)3 M(trop)3 M(etmal)3

Scheme.


-0.5

-1 1-4 -3 -2iog [TOPO]

Fig. The effect of molar concentration of TOPO on the distribu-tion of scandium chelates between water and toluene:Sc(trop)3, (1); Sc(etmal)3 (2); and between water and hep-tane: Sc(acac)3 (3); at 25°C.

of a strong Sc(acac)3-TOPO adduct in benzene wasreported [7], but basing on our further experimentswe attribute that result to impurities present in theTOPO samples. On the contrary, transfer of scand-ium tropolonate from water to toluene is strongly en-hanced by TOPO, even at relatively low concentra-tions. The relationship

log (D/P -1) = Iog/S3,n + n log tTOPO]orgwhere D denotes the distribution ratio of a metal ion,defined as the ratio of total molar concentration ofthe metal in the organic to that in the aqueous phase;P is the partition constant of the chelate; and /^n -formation constant of the n-th SCL3-TOPO adduct;was fitted by the weighted least-squares proceduregiving n=0.95 ±0.02 and log £3,1=4.07 ±0.05. Theenhancement of Sc(etmal)3 transfer was observed athigher TOPO concentrations, with downward devia-tions from the linear relationship observed above101 moldm"3 TOPO (due to association betweenTOPO and ethylmaltol). The formation constant ofthe Sc(etmal)3-TOPO adduct has been calculatedfrom the data points corresponding to [TOPO]org<0.7-104 moldm"3, giving n=0.97 ±0.02 andlog #3,1 = 1-69 ±0.03.

The analysis of thermodynamic functions ofchelate partition leads to similar conclusions: bothscandium a-diketonates in aqueous solution arehydrated in the inner-sphere of scandium ion, whileSc(acac)3 is coordinatively saturated in respect towater [8].

Different abilities of the metal chelates, ML3, toincrease CN of the metal ion by coordination ofadditional ligand(s), B, may be discussed in terms ofbalance between the energy of M-O(B) bond(s) form-ation and the energy required to change the coordi-nation environment of the metal ion. This includeselongation of the six M-OQJ bonds: the strongerM-O(L) bond the greater energy required for theprocess. This is the case of e.g. the Sc(acac)3-Sc(hfa)3pair. Strong electron withdrawing CFJ substituentsweaken the M-O bonds in hexafluoroacetylacetonate[3] so much that the chelate rings are flexible andreadily adapt their geometry to the stereochemicalrequirements of the central metal ion. Thus, the

octahedral environment of Sc(hfa)3 can easily bedistorted in the process of coordinating furtherligand(s), contrary to Sc(acac)3 which is coordina-tively saturated, because of more stable chelate rings.

However, the reverse relationship between thestabilities of the chelate and its adduct is not obeyedin the case of very stable scandium a-diketonateswhich form quite strong adducts with TOPO. To ex-plain this unexpected observation which is at vari-ance with the generally accepted rule, we analyzedliterature data on the molecular structure of scand-ium chelates. Because of rigid structure of the five--membered chelate ring in Sc(trop)3, additionallystabilized with the ^-electron system of the ligand,and a short distance between the two donatingoxygen atoms ("bite"), the coordination environmentof the metal ion is strongly distorted from idealizedoctahedron toward trigonal prism which has twoquite open triangular faces [2], contrary to onlyslightly distorted Sc(acac)3 [5], Unavailable structureof Sc(etmal)3 may be estimated from the literaturedata, giving moderate trigonal distortion, interme-diate between those for Sc(acac)3 and Sc(trop)3.

Basing on the above considerations we assumethat two different mechanisms are responsible formaking room in the first coordination sphere of theM3+ ion in a chelate complex, necessary to coordi-nate a seventh ligand:- In weak octahedral complexes with flexible che-

late rings, formed by bidentate ligands of lowpKa values, the "bite" angles (O-M-O) in thethree chelate rings decrease with adduct forma-tion. This mechanism is energetically unfavour-able in the case of strong octahedral chelateswith rigid rings.

- In strong complexes with rigid chelate rings andsmall "bite" angles, where the octahedral envi-ronment of the metal ion is significantly distort-ed toward trigonal prismatic, additional ligand(s)may coordinate the ion through open triangularfaces without a significant distortion of the che-late rings.The results of the present work show that the

coordination number of Sc3+ ion in neutral chelatecomplexes can be increased by formation of inner--sphere adducts with a neutral molecule of distinctelectron-donor properties. The ability of a metalion to increase CN depends not only on the stabilityof the chelate but also on its structure controlled bythe bidentate ligand. The high CN is promotedeither by low pKa of the ligand, which brings aboutthe formation of weak octahedral complexes withflexible chelate rings, or short by "bite" of theligand, which results in small "bite" angles in thechelate rings and in a distinct distortion of thecoordination environment. The trigonally distortedconfiguration allows ligand(s) to enter the innercoordination sphere of the metal ion without sig-nificant changes in geometry of the rings, even instable chelate complexes.

The work was supported by a grant (3 T09A 016 09)from the Polish State Committee for Scientific Re-search.



References[1]. Hart F.A.: In: Comprehensive Coordination Chemistry. Ed.

G. Wilkinson. Pergamon Press, 1987, vol.3, pp. 1060-1065.[2]. Anderson T.J., Neuman M.A, Melson G.A.: Inorg. Chem.,

12,158,1884 (1974).[3], Nora X, Sefcine T.: Bull. Chem. Soc. Jpn, 66, 3516 (1993).[4].Sekine T., Hasegawa Y.: Solvent Extraction Chemistry.

Marcel Dekker, 1977, p. 209.

[5], Anderson T.J., Neuman M.A., Melson G.A.: Inorg. Chem.,12, 927 (1973).

[6], Stary J., Liljenzin J.O.: Pure Appl. Chem., £4_,2557 (1982).[7].Shigematsu T., Wake R., Honjyo T., Matsui M.: Bull. Inst.

Chem. Res., Kyoto Univ., 4£, 269 (1968).[8]. Narbutt J., Bartos B., Siekierski S.: Sotv. Extr. Ion Exch., 12,

1001 (1994).

INVESTIGATION OF THE STABILITY OF VARIOUS MERCURY COMPOUNDSIN SAMPLES OF RIVER WATERS AND MODIFICATION

OF THE METHOD OF THEIR DETERMINATION

L. Pszonicki, W. Skwara, J. Dudek, E. Sterlinska, J. Chwastowska

In the natural waters the equilibrium among thevarious chemical forms of mercury may depend onthe composition of water to be analized and can varywith the changes of physical or chemical conditionsas temperature, pH, etc. Such processes as biodegra-dation and complex formation can also play a sig-nificant role. At the estimation of speciation a veryserious problem is to keep the natural compositionof the investigated material in the analytical sampleand during its reprocessing to the final measurementof the analytical signal. The forms most commonlydetermined in river waters are inorganic mercury andalkylmercury (methylmercury and ethylmercury). Inthe literature may be found only the data concern-ing the stability of different forms of inorganic mer-cury [1] in various waters and methylmercury in thesee water [2]. These data suggest that the speciationof mercury can be deformed during the storage ofanalytical samples. Therefore, two tests of stabilityof inorganic and alkylmercury compounds in theriver water were performed. Since the mercury con-centration in river waters is very low it was sep-arated and preconcentrated on the thionalide-load-ed Bio-Beads SM-7 [3] and inorganic and alkylmer-cury were successively determined from the samesample by cold vapour atomic absorption spectro-metry [4].

In the first test the effect of time on the concen-tration of inorganic and methylmercury in the sampleof river water was tested. Since this test was carriedout without preliminary separation and preconcen-tration, relatively large and known amounts of inor-ganic and methylmercury (10 ng • ml""1 of each) wereadded to the sample of river water (without filtrationand acidification), in which mercury was not de-tected. The sample was left for 14 days at roomtemperature and periodically 5 ml analytical sampleswere taken and both forms of mercury were deter-mined. After three days the formation of a greensuspension was observed in the sample. It indicatedthat the biological processes were running. Theresults of the determination of individual forms ofmercury indicated unambiguously that the concen-tration of both forms of mercury was not changedsignificantly during two weeks.

In the second test the stability in time of inor-ganic, methyl and ethylmercury in the samples of

filtered and acidified natural water and also theirstability during the separation and preconcentra-tion process was checked. Since methylmercury andethylmercury can be determined only as the sum ofalkylmercury two separate samples were prepared:one of them containing inorganic and methyl-mercury each at a concentration of 50 ng-1"1, andthe second one containing only 50 ng-l~* of ethyl-mercury. These samples were filtered, acidified topH=2 and left for two weeks. From both samplesone litre of analytical samples were taken periodi-cally. These analytical samples were processed andanalyzed in the normal way according to theaccepted analytical procedure [3,4]. Results of thetest prove that inorganic mercury and both formsof alkylmercury are stable not only in the acidifiedwater at pH=2 during two weeks, but also duringtheir preconcentration by sorption and elution.

The sample, preconcentrated by sorption, con-tains the total mercury, therefore, its speciationrequires a separate determination of the individualchemical forms using a proper analytical method.The cold vapour atomic absorption method pro-posed by Magos [4], that enables the sequential in-organic and alkylmercury determination from thesame sample, was used. At first the inorganic mer-cury is determined after its reduction in a strongalkaline solution by tin(II) chloride added in an ex-cess. Then, without opening of the reaction vessel,cadmium chloride is added and cadmium replacesmercury in the alky! compounds. The dislodgedmercury is reduced by the excess of tin(II) to theelemental form and determined again by the coldvapour AAS procedure. It was found, however, thatat the series analysis the obtained results were verydispersed and too low.

The exact investigation of the problem showedthat some amount of tin(II) is adsorbed on the wallsof the reaction vessel. It reduces the mercury imme-diately after putting a sample into the vessel andcauses losses of mercury with the purging gas. Thisadsorbed tin compound cannot be removed bycleaning the vessel even with very aggressive agentsas concentrated acids or alkaline solutions, withorganic solvents or with oxidizing agents. The onlyeffective treatment was to leave the vessel empty forthree days. After this period the result of mercury


determination was correct again, but only for thefirst sample.

In this situation it was necessary to modify theapplied analytical procedure. Only the basic solu-tion (30% potassium hydroxide) was placed in thereaction vessel, then the vessel was closed and purg-ed with a stream of argon. The analytical samplewas injected into the vessel at the same time whenthe tin chloride was added. This modification im-proves the results in a radical way.

References

[l].Christmann D.R., Ingle Jr. J.D.: Anal. Chim. Acta, 86, 53(1976).

[2]. Ahmed R., Stoeppler M.: ibid., 122,109 (1987).[3]. Chwastowska I , Skwara W., Sterlirtska E., Dudek I , Pszoni-

cki L.: Oznaczanie i specjacja rte,ci w wodach naturalnych wzakresie stezeri ponizej 1 ng/ml. Raporty IChTJ, Sena B nr3/97. Institute of Nuclear Chemistry and Technology, War-szawa 1997.

[4], Magos L.: Analyst, 96,847 (1971).

INVESTIGATION OF VARIOUS MODIFIERS AND THEIR BEHAVIOURAT THE DETERMINATION OF ARSENIC

BY GRAPHITE FURNACE ATOMIC ABSORPTION SPECTROMETRY

L. Pszonicki, J. Dudek

We have found recently that palladium, mentionedin the literature as a versatile modifier for graphitefurnace atomic absorption spectrometry and recom-mended also for arsenic determination [1,2], workscorrectly only in the nitric acid medium. In the pre-sence of even small amount of hydrochloric acidone observes significant losses of arsenic and, undersome conditions, palladium becomes itself a stronginterferent. The losses of arsenic occur in two steps:during drying of the sample at 110°C and duringpyrolysis stage when palladium chloride is decom-posed at the temperature above 400°C. Theseshortcomings may be eliminated by the applicationof a mixed palladium nitrate - magnesium nitratemodifier. In the present investigations the applica-tion of iron and magnesium as modifiers and theirbehaviour was tested.

Iron nitrate used as modifier in the nitric acidmedium works very well and its effectiveness iscomparable to that of palladium, however, in thepresence of some amount of hydrochloric acid oneobserves again significant losses of arsenic that canbe eliminated by the addition of magnesium nitrate.When a mixture of iron and palladium nitrates isapplied in the nitric acid solution one observes asuppression of the analytical signal of arsenic andthis suppression is proportional to the iron concen-tration. At a concentration of about 1 mg Fe/ml inthe sample the arsenic signal is suppressed com-pletely. Addition of magnesium nitrate does not im-prove the situation. This suppression may be elimi-nated by the enhancement of atomization tempera-ture from 2100 to 2500°C, however, the obtained

signal peaks are then diffused in time and badlyformed. Similar effects are observed when cobalt ornickel are used instead of iron. This indicates thatthe metals of the iron group form with palladiumand arsenic triple compounds that are significant-ly more refractory than arsenic-palladium com-pounds.

The best modifier for arsenic determination ismagnesium nitrate alone. It saves arsenic againstlosses very effectively during the drying and pyro-lysis stages even when a large amount of hydro-chloric acid is present in the sample. It is ineffectiveonly in the pure hydrochloric acid medium. When asufficient amount of nitrate ions is present, mag-nesium forms with arsenic, most probably, mag-nesium arsenite or arsenate that during the pyro-lysis stage are transformed into mixed magnesiumarsenic oxides that are stable up to 900°C. Theexcess of magnesium nitrate decomposes to mag-nesium oxide that bonds the chloride ions or freechlorine atoms, generated by the pyrolysis of somechlorides, and saving in this way arsenic.

Preliminary investigations indicated that the ef-fect of all tested modifiers on antimony determina-tion is the same as that on arsenic with one ex-ception. The losses of antimony are not observedduring the drying stage in the presence of hydro-chloric acid and the palladium or iron modifiers.

References

[1). Welz B., Schlemmer G., Mukadavit J.R.: J. Anal. At. Spectr.,2,93-97 (1988).

[2], idem: ibid., 2,695-701 (1988).

ASSEMBLING OF LABORATORY EQUIPMENT FOR THE INVESTIGATIONOF TEMPERATURE INFLUENCE ON THE SEPARATION

OF MOST COMMON ANIONS WITH THE USE OF ION CHROMATOGRAPHY

K. Kulisa, R. Dybczynski, H. Polkowska-Motrenko

Temperature is an important factor influencing ionexchange and separation processes and hence thequality of chromatographic separations [1-6]. In thecase of HPLC there are only few papers devoted to

the above problems [7]. Temperature may influenceboth retention times and column efficiency. Thevalues of retention times of particular anions may bevery close, which makes qualitative and quantitative



analysis of multicomponent anionic mixtures difficultor impossible. The change of temperature may thenresult in better separation of many ion pairs.

The effect of temperature on HPLC anion sep-arations was examined using two anion exchangecolumns, i.e. Ion Pac AS5 and Ion Pac AS9SC. Thecolumns were filled with ion exchange resins of thetype of "agglomerates" with functional groups ofdifferent hydrophobicity and ion exchange capacity.The analytical columns together with guard columns(Ion Pac AG5 and Ion Pac AG9SC) were placed in awater jacket (made of glass tube) connected to athermostat. The thermostat enabled to maintain con-stant temperature (±0.5°C). The investigations werecarried out in the temperature range 10-55°C. Toobtain reproducible results the columns were main-tained at constant temperature for about 1 h beforechromatographic separations. It was experimentallyestablished that in these conditions the thermalequilibrium was reached. A commercially availableion chromatograph Dionex 2000i/SP equipped with asuppressor ASRS-1 and a conductivity detectorCDM II with a temperature compensation systemwas used in this work. Solutions of 1.5 mM NaHCC>3(pH=8.15), 10 mM NaHCO3 and buffer solution 1.7mM NaHCO3/1.8 mM Na2CO3 (pH=9.97) wereapplied as eluents. The signals from the detector

3.00

2.S3

2.«5

^ 2.48

O) 2.30

o_ | 2.13

1.96

1 . "

1/T<E.2)

Fig. 1. Dependence of selectivity coefficients on temperature; co-lumn Ion Pac AS9SC, eluent 1.5 mM NaHCO3.

were processed using a computer program AI-450.The following inorganic anions: F~, Cl~, IOT, 104",BOJ, Br~, NOJ, NOJ, H P O i h I", S O r andSO? were investigated. Basic chromatographic pa-rameters as retention time, capacity factor, separa-tion factor, selectivity coefficient, resolution andtheoretical plate number were measured at tem-peratures of 10, 25, 35, 45 and 55°, respectively. Anexample of selectivity coefficients for the investigated

anions as a function of temperature is shown in Fig.l.As one can see in some cases (e.g. Br~ and NOJ") thechange of temperature may enable separation ofanions which is impossible at room temperature. Insome cases selectivity inversion was observed, i.e. thechange of elution order of several ions due to thechange of selectivity coefficient values.

No. of heating cyclesFig.2. Effect of temperature on ion exchange resin capacity: co-

lumn Ion Pac AS9SC.

Considerable influence of temperature on columnefficiency was noted. The temperature range 35-45°Cseemed to be the best from the point of view ofcolumn efficiency. In this range the theoretical platenumber and peak symmetry reached optimum valuesimproving column resolution. Unexpectedly poorthermal resistance of an ion exchange resin bed ofIon Pac AS9SC column was observed as monitoredby checking ion exchange capacity after each heatingcycle. The breakthrough curves of the ion exchangeresin bed were determined by passing of 5 mg/1 Cl~solution through the column. The results are pre-sented in Fig.2.

The changes of thermodynamic functions i.e.AG, AH and AS for the respective ion exchangereactions in the temperature range 10-55°C, werecomputed.

References[1]. Dybczynski R.: J. Chromatogr., 14,79-96 (1964).[2]. Dybczynski R., Wodkiewicz L.: J. Inorg. Nucl. Chem., 21,

1.495-1506 (1969).[3]. Dybczynski R.: J. Chromatogr., 21,507-522 (1972).[4J. Ahuja S.: Trace and Ultratrace Analysis by HPLC. J.Wiley

Inc., New York 1992,419 p.[5]. Meyer V.R.: Practical High-Performance Liquid Chromato-

graphy. J.Wiiey, Chichester 1996,376 p.[6]. Harland C.E.: Ion Exchange Theory and Practice. The Royal

Society of Chemistry, Cambridge 1994, 285 p.[7].Baba Y., Yoza N., Ohashi S.: J. Chromatogr., 348, 27-37

(1985).

; C D! CJ)

iooo

ELABORATION OF AN IMPROVED VERSION OF A PROGRAMFOR INTERPRETATION OF RESULTS OF INTERLABORATORY COMPARISONS

AND ITS USE FOR CERTIFICATION OF A NEW REFERENCE MATERIAL:CTA-VTL-2 , AS WELL AS VALIDATION OF SOME DATA BY MEANS

OF OUR OWN ACCURATE RNAA METHODS

R. Dybczynski, H. Polkowska-Motrenko, Z. Samczynski, Z. Szopa

Certified reference materials (CRMs) play an im-portant role in quality assurance of chemical analysis,

especially in trace analysis. Their use is essential forachieving comparability of results on a global scale.


Preparation and certification of a CRM is a long andcomplex process consisting of several stages; eachstage must be executed accurately according to thestate of art knowledge if the final outcome is to be asuccess [1].

When the certification is based on results of in-terlaboratory comparison, one of the very import-ant stages is evaluation of results, and assigning"recommended" (certified, attested) values and "in-formation" values.

The program for evaluation of results of an inter-laboratory comparison [2] was further improved andused for the certification of a new Polish CRM:Virginia Tobacco Leaves (CTA-VTL-2). The presentversion of a program written for the use with apersonal computer (PC) is based on a general ap-proach described earlier [2], but with several im-provements introduced as a result of our experiencegained during certification of former CRMs issued bythis Laboratory. The program rejects outlying resultsby the concurrent use of four criteria namely those ofDixon, Grubbs, coefficient of skewness, and coeffi-cient of kurtosis at significance level of 0.05, followed

Table. Certified and "information" values for CTA-VTL-2.

The values that did not fulfil this condition, butfulfilled a less stringent criterion were granted thename "information" value, which is quoted as anumber only (without confidence interval). Thevalues obtained as a result of evaluation of inter-comparison results which did not fulfil even thisless stringent criterion were considered to be out-side of any classification.

The computer program has been devised for theuse with PC under DOS operating system, and viaits input/output can cooperate with statistical/gra-phical packages like Excel, Quattro Pro, Statgra-phics, dBASE etc. This fact enables also the possi-bility of graphical presentation of results.

Table presents certified and "information" valuesfor Virginia Tobacco Leaves CRM obtained by theprocedure described above. CTA-VTL-2 with its 33certified and 10 "information" values ranks amongbest characterized biological CRM ever producedworldwide. It is worth emphasizing that it waspossible to certify such elements like: Ce, Cs, La, Li,Sm, Tb, Th and U for which only few biologicalCRMs seem to exist.

CERTIFIED VALUES FOR CTA-VTL-2Major elements

Element

Ca

Cl

K

Mg

Concentration,wt%

3.60 ±0.150.743 ±0.0281.03 ±0.04

0.510 ±0.023

Trace elements

Element

As

BaBr

Cd

Ce

CoCr

Cs

Cu

FeHf

HgLa

Li

Mn

Concentration,ft%lg (ppm)0.969 ±0.072

42.7 ±6.614.3 ±1.41.52 ±0.171.91 ±0.29

0.429 ±0.0261.87 ±0.16

0.515 ±0.04618.2 ±0.9

1083 ±330.118 ±0.0220.048 ±0.0091.01 ±0.1023.0 ±1.979.7 ±2.6

Element

MoNi

P

Pb

Rb

Sb

Sm

Sr

Tb

Th

U

V

wZn

Concentration,(«g/g (PPm)

2.01 ±0.151.98 ±0.21

2204 ±7822.1 ±1.248.6 ±2.3

0.312 ±0.0250.157 ±0.022

110 ±120.022 ±0.005

0.378 ±0.0310.163 ±0.0084.00 ±0.42

0.233 ±0.06343.3 ±2.1

"INFORMATION" VALUES FOR CTA-VTL-2Major elements

Element

S

Concentration,wt%0.669

Trace elements

Element

Al

EuNa

Sc

Se

Concentration,figli (ppm)

16820.033312

0.2680.188

Element

Si

Ta

Ti

Yb

Concentration,^g/g (ppm)

45900.03376.30.080

by calculation of overall mean, standard deviation,standard error, confidence intervals etc. This methodof evaluation of results is however not of purely sta-tistical character, because the inseparable part of it isa set of four classification criteria, which must besimultaneously fulfilled in order to assign the name"certified" to a value.

The particle size distribution of CTA-VTL-2 wascomprehensively studied by optical microscopy,laser diffraction and scanning electron microscopymethods. Homogeneity of the material was checkedby INAA and PIXE etc. Good homogeneity ofCTA-VTL-2 was confirmed and the CRM can berecommended for microchemical methods i.e. those



that use sample masses of ca. 1 mg or even slightlylower.

The reliability of the values obtained in our certi-fication process was confirmed by the "definitive"and "very accurate methods" developed in this Lab-oratory for selected trace elements namely: cobalt[3], cadmium [4], nickel [5], molybdenum and uran-ium [6]. In all cases there was a good agreementbetween the certified values and those obtained by"very accurate methods".

References[1]. Dybczyiiski R.: Materiafy odniesienia i ich rola w zapew-

nieniu jakoSti w nieorganicznej analizie Sladowej. In: Proble-

my jakoSci Sladowej analizy w badaniach Srodowiska przyrod-niczego. Eds. A. Kabata-Pendias, B. Szteke. Palistwowa Ins-pekcja Ochrony Srodowiska, Warszawa 1996.

[2]. Dybczynski R.: Anal. Chim. Acta., HZ, 53-70 (1980).[3]. Dybczyriski R., Danko B.: J. Radioanal. Nucl. Chem., 1S1,

43-59 (1994).[4]. Samczyiiski Z., Dybczyrtski R.: unpublished results.[5].Polkowska-Motrenko H., Dybczynski R., Danko B., Becker

D.A.: J. Radioanal. Nucl. Chem., 202,401-412 (1996).[6]. Danko B., Dybczynski R.: J. Radioanal. Nucl. Chem., 216,1,

51-57 (1997).

ADAPTATION OF THE RDF METHOD FOR INVESTIGATIONOF MEMBRANE-PENETRANT SYSTEMS

H. Grigoriew, A.G. Chmielewski

A typical method in structural studies of amor-phous materials is Radial Distribution Function(RDF). In this method I(k) measurements shouldbe carried out in specific conditions that ensurehigh accuracy, because the effects measured aremuch weaker than for crystals. Classical mathema-tical treatment of measuring data i.e. of the inten-sity function I(k), obtained in a large wave vectorrange k (k=4;rsin0/A) consists in calculating theradial distribution function of atoms (RDF) or therelated atom pair distribution function P(r). This iscarried out by passing from reciprocal to directspace by means of Fourier's transform. As a result afunction of the interatomic distances and frequencyof their occurrence is attained. In addition, this me-thod is very susceptible to the presence of areas ofcrystal order.

First, we studied a dry cellulose Tomophanmembrane using RDF.

Measurements of I(k) up to k=170 nm"1 bymeans of URD-6 diffractometer, provided with asemiconductor Si(Li) detector, using a IQjMo radia-tion and step-scanning were carried out. For eachmeasuring point 20000 pulses were accumulated.From these measurements the interference func-tion, F(k) was calculated:

F(k) = k{In(k) - <f2(k)» <f(k)>"2

followed by the pair distribution function P(r):P(r)= Ircrpo + / k F(k) sin(kr)dk

where: In(k) - is the intensity function obtained byintroducing suitable corrections (material andinstrumental ones) to the I(k) function followed byits normalization, f - is the atomic scattering factor,po - is the average atomic density, r - the distance(nm) in direct space. The calculations were carriedout using a modified Kaplov's program.

The function P(r) includes only three maxima, upto the distance about 0.3 nm corresponding to threedistances within the cellulose ring: interatomic dis-tance and small and large diagonal. This result meansthat the short range order, with respect to RDFstudies, is very limited in this material. This is evi-

dent, because around the O and C atoms there existmany various surroundings. They are composed ofvarious neighbouring atoms of various distances andthe effects for pair distribution function are additive.This result can only be considered as evidence thatthis material does not contain areas of crystal orderdespite the fact that on I(k) two distinct maxima,typical for polymers, are shown. The distances d,calculated from the positions of those maxima are 0.7and 0.42 nm, respectively.

The preliminary studies of cellulose have shownthat this material is entirely amorphous, what shouldbe expected because crystalline phase brings abouteffects in the whole range of the intensity function.As the scattering angle (or k) increases they becomeweaker and weaker, particularly for small crystals.Precise I(k) measurements are needed to prove theirexistence. Even formation of so small species asnanocrystals is evidently registered in the whole I(k)range. The P(r) function obtained by Fourier trans-formation of I(k) provides information not onlyabout the existence but also about the structure ofcrystalline phase. Single maxima that are not reflect-ed in the further I(k) course, indicate the existence ofa priviledged distance in the structure. This is thecase for our samples and the distance 0.42 nm can beassigned to that between polymer chains, while thedistance 0.7 nm to that between chains-second neigh-bours.

Further RDF studies were not carried out sincethey could only prove the exsistence of crystalli-zation. An adaptation of the used method wasneeded.

For further study of the cellulose - water system4 samples were prepared: 2 water-vapor treated and2 soaked in liquid ones, applying in all cases lightand heavy water. As reference samples, a dry mem-brane and water were used.

Analysis of the precise I (k) measurements hasshown that on I(k) curves detectable changes arevisible in the k-range 15-40 nm"1, apart from twodistinct maxima. In this range the I(k) curves have a


different course for each sample and can be used forcomparative studies.

Next, a mathematical treatment of I(k) curveswas carried out using the applied RDF program forcalculation of interference functions F(k). In com-parison to I(k), the F(k) function is more pointeddue to the subtraction of atomic scattering f2(k)from I(k) and then its multiplication by k thatenhances the effects for larger k. F(k) functions arecalculated using RDF program in a large measuringrange (e.g. to k=170 nm'1) in order to carry outtheir Fourier transformation. However, in this casethey were calculated for a short range, up to k=40nm'1, using the integral method for normalization.The normalization constants calculated in a sosmall k-range are less precise, but in this case this isof minor importance.

The F(k) functions for the examined and refer-ence samples are shown in Fig.l. As one can see, onthe F(k) of dry cellulose (Fig.la) are visible twotypical maxima, for k=9.6 and k=14.4 followed bythe next two in the interesting range, for k=28.7and k=31.7 nm"1. They change after vaporizing thecellulose (Fig.lb,c).

On F(k) of the soaked samples (Fig.le,f) a distinctband centered of about k=20.7 nm , identical withthe main band of bulk water can be seen (Fig.ld).The next maximum, at k=28.7 is very spread.

After the H20-vapor treatment of cellulose, thefirst maximum (distance d of about 0.23-0.24 nm) sig-nificantly increases (Fig.lb). After the D20-vaportreatment of cellulose the F(k) is only slightlychanged in comparison with F(k) of dry cellulose(Fig.lc). This means that the H2O-vapor modifiesthe cellulose structure much more strongly than theD20-vapor. The distance d of that maximum corres-ponds to the distance of the second neighbours of theC and/or O atoms, e.g. it can be the distance from theO atom in a water molecule attached to an activecellulose center by means of hydrogen bonding to 2carbon atoms in the cellulose ring (the secondneighbours with respect to that of oxygen atom). Ad-ditionally, F(k) will be affected by the pairs of Oatoms from the neighbouring water molecules and allthe distances will be modified as a result of limitedspace between the molecular chains. Hence univocalinterpretation of that effect is difficult.

The weaker interaction of D2O with cellulosecorresponds to its lower permeation rate throughcellulose membrane. This phenomenon was a sub-ject to patents and publications. Of course, it is notthe sole reason of permeation and there is at least asecond one, namely diffusion, which also can bevarious for each kind of water. An open question isthe cause of the differences in the interaction oflight and heavy water vapor with cellulose.

It follows from the analysis of F(k) curves of thewater vapor treated samples that no bulk waterthere exists since for k corresponding to the watermain maximum (k=20.7 nm"1), (Fig.lb,c,d) a mini-mum is observed for both water vapor treatedsamples.

F(k) curves of the cellulose samples soaked inliquid H2O and D2O show a significant change inthe range examined (Fig.le,f). By comparing themwith the respective curves of the reference sample-

15.S0 31,60

k(nm')

15,80 31,60

k(nm-')

Fig.l. Interference function F(k) in the selected k range, for a -dry cellulose, b - H2O-vapor-treated one, c - D2O-vaportreated one, d - water, e - cellulose soaked in liquid H2O, f -cellulose soaked in liquid D2O.

-water (Fig.ld) one can see that there appears bulkwater in considerable amounts. For both the sam-ples the main water maximum has a similar shape.On the other hand the maximum at k=28.7 nm"1,which changes after water vapor treatment, also inthe case of soaked samples exhibits differences inthe height, in the same way (Fig.le.f). It means thatindependently of the existence of bulk water, in thesoaked samples the differences at the molecularstructure level, similar to those observed for watervapor treated samples, are retained.

References[1]. Grigoriew H., Chmielewski A.G.: .f. Mat. Sci. Lett., 16,

1945-1947 (1997).[2]. Grigoriew H., Chmielewski A.G.: J. Membr. Sci., 142, 87-95

(1998).



SCO

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CRYSTAL CHEMISTRY OF COORDINATION COMPOUNDSOF HETEROCYCLIC CARBOXYLIC ACIDS.

PART XIX. THE CRYSTAL STRUCTURE OF STRONTIUM COMPLEXWITH PYRAZINE-2,5-DICARBOXYLIC ACID

H. Ptasiewicz-Bqk, J. Leciejewicz

In the structure of strontium(II) complex with pyra-zine-2,3-dicarboxylic acid (2,3-PZDC) the stront-ium ion has been found to be coordinated by only

021

C21022'

Fig.l.A fragment of the structure of Sr(2,5-PZDC)(H2O)3showing the bridging of two Sr ions by the molecule of2,5-PZDC.

one (N,O)-bonding moiety of the 2,3-PZDC mole-cule and by four oxygen atoms donated by the car-boxylic groups of three adjacent ligand molecules

Fig.2. Packing diagram of the structure of Sr(2,5-PZDC)(H2O)3.

forming a two dimensional pattern. In addition,each Sr+2 ion is chelated by the oxygen atoms ofthree water molecules which complete the nine-fold coordination around the metal ion. It becametherefore interesting to find how the different con-

figuration of carboxylic groups in pyrazine-2,5-di-carboxylic acid (2,5-PZDC) will affect the mole-cular pattern in the crystals of its complex withstrontium.

The molecular pattern of Sr(2,5-PZDC)(H2O)3has been found to be polymeric. Strontium ions arebridged by the acid molecules which use both their(N,0)-bonding moieties [mean Sr-O 2.567(3) A,mean Sr-N 2.826(3) A] (Fig.l). The bridging is alsoaccomplished by two water molecules [mean Sr-O2.681(3) A and bidentate carboxylic oxygen atoms[Sr-O 2.697(3) A] giving rise to a three - dimen-sional molecular framework. The coordination ofthe Sr ion is ninefold: seven oxygen and two nitro-gen atoms form a distorted, monocapped squareantiprism. Two water molecules per unit cell locat-ed in the holes of this framework take part in anextended hydrogen bond scheme. Fig.2 shows thepacking diagram of this structure.

X-ray data collection was done using a KUMAKM4 four circle diffractometer at this Institute.Data processing, structure solution and refinementwas carried out using the SHELXL 93 programpackage.

References

[1]. Part X. Paluchowska B., Maurin J.K., Leciejewicz J.: Hete-ro-ring oxygen coordination to strontium in the crystal struc-ture of strontium bis(2-furanocarboxylate). Acta Cryst., C53.287 (1997).

[2]. Part XI. Ptasiewicz-Bqk H., Leciejewicz J.: A pyrazine--bridged chain structure of magnesium complex with pyra-zine-2,3-dicarboxylicacid. Polish J. Chem., 21,493 (1997).

[3], Part XII. Paluchowska B., Maurin J.K., Leciejewicz J.: Directand outer-sphere coordination of the magnesium ions in thecrystal structures of complexes with 2-furancarboxylic acid(I) and 3-furancarboxylic acid (II). J. Chem. Cryst., 22, 177(1997).

[4]. Part XIII. Ptasiewicz-Bajc H., Leciejewicz J.: The crystalstructures of diaquobis(3-aminopyrazine-2-carboxylato-N,0)magnesium(II) monohydrate and 3-amino-2-pyrazine carbo-xylic acid. Polish J. Chem., 21,1350 (1997).

[5]. Part XIV. Leciejewicz J., Ptasiewicz-Ba.k H., Paluchowska B.:Molecular ribbons composed of calcium atoms bridged bycarboxylate oxygens in the X-ray structure of calcium com-plex with 3-aminopyrazine-2-carboxylic acid. Polish J. Chem.,21,1359(1997).

[6]. Part XV. Ptasiewicz-Ba.k H., Leciejewicz J.: Two-dimensionaimolecular layers in the crystals of calcium complex with pyra-zine-2,3-dicarboxylic acid! Polish J. Chem., 21,1603 (1997).

[7]. Ptasiewicz-Bqk H., Leciejewicz J.: Part XVI. Polymeric crys-tal structure of trisaquoGu-pyrazine-2,3-dicarboxylato)stron-tium(Il). Polish J. Chem., 22,627 (1998).

[8]. Part XVII. Paiuchowska B., Maurin J.K., Leciejewicz J.:Dinuclear copper(II) complexes with 3-furancarboxylic acidand 2-thiophencarboxylic acid. J. Coord. Chem., in press.

[9]. Part XVIII. Ptasiewicz-Bqk H., Leciejewicz J.: X-ray diffrac-tion study of the crystal structures of pyrazine-2,5-dicarbo-xylic acid dihydrate and its magnesium complex. J. Coord.Chem., in press.



PART XX. THE CRYSTAL STRUCTUREOF CIS-TETRAAQUOBIS(PYRAZINE-2-CARBOXYLATO-O,N) STRONTIUM(II)

H. Ptasiewkz-Bqk, J. Leciejewicz

The crystal structures of pyrazine-2-carboxylic acid(PZCA) complexes with a number of divalent metalions show the same molecular pattern: monomericmolecules composed of a metal ion chelated by twoPZCA ligands via their (N.O)-bonding moieties con-sisting of one heteroring nitrogen atom and thenearest to it carboxylate oxygen. The second nitrogenatom of the pyrazine ring does not take part inbonding. The characteristic for each particular metalion coordination is completed by oxygen atoms ofwater molecules. X-ray diffraction study of the crystalstructure of strontium complex with PZCA (mono-clinic, space group P2i/n) has revealed that itcontains also monomeric molecules. The strontiumion is coordinated by eight atoms at the apices of anirregular decahedron with two rectangular and eighttriangular faces: two nitrogen atoms [mean Sr-N2.751(4) A], two oxygen atoms from monodentatecarboxylic groups [mean Sr-O 2.588(4) A] and fourwater molecules [mean Sr-O 2.572(4) A]. A moleculeof Sr(PZCA)2(H2O)4 is displayed in Fig. Thiscompound provides the first example of eightfold

! CDiCD

Fig. The molecule of Sr(PZDC)2(H2O)4.

coordination of strontium ion in its complexes withpyridine and pyrazine carboxylic acids and is isostruc-tural with Ca(PZCA)2(H2O)4.

X-ray measurements were carried out using aKUMA KM4 four circle diffractometer at this Insti-tute. Data processing, structure solution and refine-ment were performed using the SHELXL 93 prog-ram package.

CRYSTAL CHEMISTRY OF COOORDINATION COMPOUNDSOF HETEROCYCLIC CARBOXYLIC ACIDS.

PART XXI. THE CRYSTAL STRUCTUREOFTRANSDIAQUOBIS(5-METHYLPYRAZINE-2.CARBOXYLATO-N,O)NICKEL(II)

H. Ptasiewicz-Bqk, J. Leciejewicz

Continuing our studies on the crystal chemistry ofdivalent metal complexes with pyrazinic acids wehave decided to investigate whether the chelatingactivity of the second nitrogen atom in the pyrazinering will be enhanced if the methyl group will be

H3HI

H2

02H31

Fig. The molecule of Ni(5-MPZA)2(H2O)2.

present in its neighbourhood. A nickel(II) complexwith 5-methylpyrazine-2-carboxylic acid (5-MPZA)has been chosen as the first object these studies.

The crystals of the title compound are triclinic,space group PI. The structure contains monomericmolecules Ni(5-MPZA)2(H2O)2. The coordinationaround the nickel ion is octahedral consisting oftwo (N,O) bonding moieties from two ligand mole-cules in trans configuration and two oxygen atomsdonated by two water molecules (Fig.). The Ni-Nand Ni-O mean bond distances are 2.070(3) A and2.043(3) A respectively and compare well withthose found in the monomeric molecule of thenickel(II) complex with pyrazine-2-carboxylic acid.The molecules of the title compound are held to-gether by hydrogen bonds operating between thewater molecules and methyl groups of adjacentcomplex molecules.

X-ray data collection was performed using aKUMA KM4 four circle diffractometer at this Insti-tute. Data processing, structure solution and refine-ment were carried out using the SHELXL93 prog-ram package.

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8


PART XXII. THE CRYSTAL STRUCTUREOF COBALT(II) AND ZINC(II) COMPLEXES WITH FURAN-2-CARBOXYLIC ACID

B. Paluchowska1', T. Us2', J. Leciejewicz11 Institute of Atomic Energy, Otwock-Swierk

21 Department of Chemistry, University of Wroclaw, Poland

In the complexes of divalent cations with furan--2-carboxylic acid (2-FA) the carboxylate group do-nates its oxygen atoms to the coordination sphereof the central ion acting as a bridging ligand andgiving rise to a variety of coordination schemes. Inthe complexes with magnesium, calcium, strontiumand barium also the furan ring oxygen has beenfound to take part in the chelating the central ion.Polymeric molecular patterns have been detected inthe structures of calcium, strontium and bariumcompounds. In the uranyl furoate hydroxy-bridgeddimers linked via carboxylate ligands form infinitemolecular chains. On the other hand, in the struc-ture of nickel furoate the Ni ion is coordinated byfive oxygen atoms from water molecules and oneoxygen atom donated by the carboxylate group ofaone furoate ligand acting in monodentate mode.The Ni[(H2O)5 (2-FA)]+ cation is linked to the(2-FA)" anion by hydrogen bonds only. In the cop-per furoate two Cu2+ cations make a dimer bridgedby oxygen atoms donated by four bidentate furoateanions.

The crystals of cobalt and zinc furoates are iso-structural. They belong to the triclinic system, spacegroup PT. The metal ions in the dimer have dif-ferent environments (Fig.). The furoate ligand Fulis monodentally bonded to the Col (Znl) ion. TheFu2 and Fu4 ligands bridge the cations using theircarboxylic groups acting in the bidentate mode(O,O) while the Fu3 ligand bridges in the (O:O,O)mode. The Co-O bond distances range from2.037(3) to 2.296(3) A and the Zn-O from 2.003(3)to 2.221(3) A. They are typical for the coordination

Fig. The molecule of Zn2(2-Fu)4(H2O)4.

compounds of respective metals. Each metal ion isalso chelated by two water molecules. In this way,the coordination polyhedron in both compounds isrepresented by a distorted octahedron. Only carbo-xylate oxygen atoms are bonded to metal ions; thefuran ring oxygen atoms participate in a network ofhydrogen bonds which are also active betweencarboxylate oxygen atoms and water molecules.

X-ray diffraction data were collected at 120 Kusing a KUMA KM4 instrument at the Departmentof Chemistry, University of Wroclaw. Data process-ing, structure solution and refinement were carriedout using SHELXL 93 program package.

CMo

l oiCM! O

MAGNETIC ORDERING IN LANTHANIDEINTERMETALLIC PHASES

J. Leciejewicz, A. Szytula1^11 Institute of Physics, Jagiellonian University, Krak6w, Poland

Antiferromagnetic ordering schemes in ternaryRNiSi (R=Tb - Er) compounds

Ternary lanthanide nickel silicides crystallize inthe orthorhombic TiNiSi-type of structure and ex-hibit antiferromagnetic properties at low tempera-tures. A neutron diffraction study has been carriedout on the following compounds:- TbNiSi: a square modulated magnetic order has

been found at 1.5 K. It is described by the propa-gation vector k=[0.710(1), 0.315(1), 0] and 3kwith magnetic moment of 9.06(9) Bohr mag-netons localized on the Tb+ 3 ion. A magneticphase transition to a sine modulated antiferro-

magnetic structure occurs at 9 K. The magneticmoment of 8.28(9) Bohr magnetons is directedalong the b-axis. The Neel point is at 16 K.

- DyNiSi: the magnetic structure at 1.5 K is square--modulated antiferromagnetic, with k=[0.698(8),0.318(6), 0] and 3k. The magnetic momentlocalized on the Dy+3 ion amounts to 9.15(21)Bohr magnetons and is parallel to the c-axis. Thisstructure transforms at 3 K into an antiferro-magnetic, sine-modulated described by the wavevector k= [0.708(5), 0.314(4), 0]. The magnitude ofmagnetic moment at 5 K is 8.86(3) Bohr magne-tons. The Neel point is at 9 K. A schematic


• 4

' 4• 4

4' 4

4• 4

4

444•t

f4444444

+4

44444

4 •4 «4 •f .i4 -4 •4 •

b)

• :12 I1 i 3

•ff 'i i

{

<

I

r"( • •

h-t

a)

Fig. 1. Schematic representation of magnetic structures observedin TbNiSi and DyNiSi: (a) the low temperature phase and(b) the high temperature phase.

representation of the low and high temperaturemagnetic structures is shown in Fig.l.

- HoNiSi: the magnetic structure at 1.6 K is col-linear, antiferromagnetic given by the wave vectork=[l/2,0,1/2]. The magnetic moment localized onthe Ho ion is 9.08(7) Bohr magnetons and isaligned along the b-axis. This structure is illus-

-»- aFig.2. The low temperature magnetic structure of HoNiSi pro-

jected on the (a-c) plane. The + and - signs indicate thedirection of the magnetic moments along and opposite theb-axis, respectively.

trated in Fig.2. A magnetic phase transition into asine-modulated structure characterized by athree-component wave vector k=[ki, k2, k3] takesplace at 3.2 K. The Neel point is at 4.1 K.

- ErNiSi: a collinear antiferromagnetic structurewith the wave vector k=[0, 1/2, 1/2] present at1.5 K transforms at 2.2 K into an antiferro-magnetic, sine-modulated order described by athree component wave vector. The Neel point is

at 3.3 K. In the low temperature phase the mag-netic moment of 8.68(11) Bohr magnetons loca-lized on the Dy+ 3 ion is aligned along the a-axis.

The magnetic phase diagramof the HoRh2-xRuxSi2 solid solution

Continuing our investigations of the magnetic pro-perties of lanthanide ternary phases with ThCr2Si2--type crystal structure and their solid solutions [1,2]we have made a neutron diffraction study of theHoRh2-xRuxSi2 system. Its boundary compounds ex-hibit different magnetic structures: in HoRh2Si2 it iscollinear antiferromagnetic [3]; HoRu2Si2 shows amodulated antiferromagnetic structure [4]. The ana-lysis of the positions and intensities of magnetic re-flections observed at low temperatures on the neutrondiffraction patterns of all studied compositions re-vealed the presence of a variety of magnetic orderingschemes appearing successively as Ru content x in-creases.

x=0.25: two collinear antiferromagnetic phasesdescribed by the wave vectors k=[0, 0, 1] andk=[l/2, 1/2, 1/2] are observed at 1.6 K. The lattervanishes at 28.5 K, the former at 20 K. A newantiferromagnetic phase with k=[l/2, 1/2, 1/2] issetting up at 5 K and vanishes at 28 K - the Neelpoint. Fig.3 shows the variation with temperature

T(K)Fig.3. HoRhi.75Ruo.25Si2 - temperature variation of magnetic

peak intensities of colinear antiferromagnetic structuresdescribed by the wave-vectors k=[l, 0, 0], k=[l/2,1/2, 1/2]and k= [1/2,1/2,0].



Jli1 1 1"521

H*i i i H!100-1 101*

i It 101- 110" iio-'

^ ^ ^ ^ ^

H°R h1.5R U0.5S i2

Fig.4. Neutron diffractograms of HoRh1.5Ruo.5Si2. The inset shows how the intensities of magnetic peaks characteristic for eachmagnetic phase change with temperature.

of the intergrated intensities of magnetic reflectionscharacteristic for each structure.

Fig.5. Schematic representation of the sine-modulated antiferro-magnetic structure of HoRh1.5Ruo.5Si2-

x=0.50: the antiferromagnetic structure withk=[l/2, 1/2, 1/2] appears in the temperature range

30001 •

from 1.5 K to the Neel point at 6.5 K. A sine-mo-dulated antiferromagnetic order has been also de-tected in the temperature range between 1.6 and 3.5K. It is represented by a three-component wavevector k= [0.150(1), 0.150(1), 0.473(1)]. Neutrondiffractograms are shown in Fig.4, the magneticstructure is illustrated schematically in Fig.5.

x=0.75: the collinear antiferromagnetic structurewith k=[l/2, 1/2, 1/2] is observed in the tempe-rature range between 1.6 K and the Neel point at4.8 K. A sine-modulated antiferromagnetic phasedescribed by a pair of wave vectors has been alsofound in this temperature range.

x=1.00: the above mentioned sine-modulatedorder has been found to be present between 1.6 Kand the Neel point at 5.5 K.

x=1.25: it is also observed for this composition.Its temperature stability range is 1.6-5.8 K - theNeel point.

x=1.50: a collinear ferromagnetic structure withmoments along the tetragonal axis transforms at 7

KoRh08RulsSij

T=8K• Yobs- -Ycnl— Yobs-Yea!

20 30 60 8040 ao

2ThataFig.6. Neutron diffraction pattern of HoRho.5Ru1.5Si2 recorded at 8 K. The inset shows the temperature variation of the magnetic

peaks characteristic for each magnetic phase observed below the Neel point. F - ferromagnetic phase, SMI and SM2 -sine-modulated antiferromagnetic phases.


aI

b

^

-iX

Fig.7. Schematic representation of the sine-modulated antiferro-magnetic structures: a - SMI, b - SM2 observed inHoRho.5Ru1.5Si2.

K into two sine-modulated antiferromagnetic struc-tures which coexist up to the Neel point at 12 K.Fig.6 shows the diffractogram recorded at 8 K. Theinset contains the variation with temperature of themagnetic peaks characteristic for each magneticphase. The respective magnetic structures are sche-matically illustrated in Fig.7.

x=1.75: a single sine modulated antiferromag-netic structure with the wave vector k=[0.252(1), 0,0] is operating between 1.6 and 15.5 K (the Neelpoint).

J Jt J it

if

C- • r i -

Fig.8. Magnetic structure of HoRu2Si2-

x=2: HoRu2Si2 shows a sine-modulated antifer-romagnetic structure with k=[0.22(1), 0, 0] stablebetween 4.2 and 19 K (the Neel point). This struc-ture is displayed in Fig.8.

Fig.9. Magnetic phase diagram of the HoRh2-xR"xSi2 system.

The magnetic phase diagram based on the aboveneutron diffraction data is shown in Fig.9.

References[l].Jaworska T., Szytula A., Ptasiewicz-Bak H., Leciejewicz J.:

Solid State Comm., 61,261 (1988).[2]. Jaworska T., Szytuta A., Leciejewicz J., Ptasiewicz-Bajc H.: J.

Magn. Magn. Mat., 82,313 (1989).[3]. Slaski M., Leciejewicz J., Szytula A.: J. Magn. Magn. Mat., 22,

268 (1983).[4], Slaski M., Szytuia A., Leciejewicz J., Zygmunt A.: J. Magn.

Magn. Mat., 46,114 (1984).

STRUCTURE, CHARGE AND SPIN DENSITYIN Na2Ni(CN)4 3H2O AT 295 AND 30 K

H, Ptasiewicz-Bqk, I. Olovsson17, G.J. Mclniyre2/

11 Inorganic Chemistry, Angstrom Laboratory, University of Uppsala, Sweden21 Institute Laue-Langevin, Grenoble, France

PL9802003

The earlier-reported structure of the title compoundhas been found to be incorrect and has now been re-determined. The charge distribution has been deter-mined by multipole refinements against single-crystalX-ray diffraction data. In the refinement at 30 K acomparison was made between the results obtainedusing hydrogen positions and displacement parame-ters from X-rays with those using the values deter-mined by neutron diffraction. The spin density hasbeen investigated by polarized neutron diffraction at1.6 K.

Due to the strong ligand field of the cyanide ions,the common octahedral coordination of nickel isvery much distorted and the structure containspractically square planar Ni(CN)3~ ions, which arestacked on top of each other in almost linear chainsalong the a - direction. The separation between the

Ni(CN)5 planes is rather large, with Ni-Ni dis-tances around 3.7 A. The six crystallographically

30 K 295 K

Fig.l. Deformation densities at 30 and 295 K in the plane definedby Nil, Cl and C2; only deformation functions centred onNil included (partial deformation maps). Contours aredrawn at intervals of 0.05 eA . Negative contours aredashed; the zero contour is omitted.



Ni2* Nil

ii2w

Fig.2. Three projections of the nickel-nickel arrangement in Na2Ni(CN)4 • 3H2O (the y axes are not in the plane of the paper).

independent water molecules are each coordinatedto two sodium ions, approximately in the tetra-hedral (lone-pair) directions, and the polarizing in-fluence of these sodium ions also appears to be re-flected in the deformation density in the lone-pairplane. All water molecules, except one, donate twohydrogen bonds to nitrogen of the cyanide ions, butthe distances O—N are quite long, 2.9-3.4 A. Oneof the hydrogen atoms is involved in a bifurcatedhydrogen bond.

The charge density based on the deformationfunctions of all atoms in the structure is comparedwith the individual densities calculated from the de-formation functions of only nickel or the separatewater molecules. In this way the effects of simplesuperposition of the individual densities have beenstudied [1-4]. In the planar Ni(CN)l~ ion the indi-vidual deformation density of nickel is in qualitativeagreement with that expected from crystal-fieldtheory: excess deformation density in the diagonaldirections and deficiencies in the ligand directions(Fig.l). As the repulsion from the electrons is muchweaker perpendicular to the Ni(CN)|~ plane thanwithin this plane (due to the long distance tonearest neighbours, 3.7 A) the deformation densityis considerably larger in the perpendicular direc-tion. However, the largest maxima in the individualdeformation density around nickel are not foundprecisely in the planes defined by nickel and thefour cyanide ligands or in the perpendicular direc-

tion just mentioned, but in the planes defined byNi-Ni sublattice (Figs. 2 and 3), which illustrates

30 K 295 K

Fig.3. Partial deformation maps in plane through nickel, whichdo not involve the (CN)' ligands, at 30 and 295 K. Theplane defined by Ni-Ni sublattice illustrated in Fig.2. Nil1,Nilv , Ni l^ , ^ 2 ^ and Ni2 iv denote the equivalent posi-tions.

that it is necessary to consider the crystal field dueto the whole crystalline environment.

References

[1]. Mclntyre G.J., Ptasiewicz-Bqk H., Olovsson I.: Acta Cryst.,B46,27-39 (1990).

[2]. Olovsson I., Ptasiewicz-Bqk H., Mclntyre G.J.: Z. Natur-forschung, 48a, 3-11 (1993).

[3].Ptasiewicz-Bak H., Olovsson I., Mclntyre G.J.: Acta Cryst.,B49,192-201 (1993).

[4]. Ptasiewicz-Bqk H., Olovsson I., Mclntyre G.3.: Acta Cryst.,B51,325-336 (1997).

PL9802004

VHAT RESULTS FROM THE SOLUBILITY DATAIN THE Ce2(SO4)3-H2O SYSTEM?

T. Mioduski

Analyses of the solubility data for the aqueous rareearth sulphate systems in the IUPAC 8.V. Com-mission have brought some interesting results forSc(III) [1], Eu(II) [2] and Ln(III) [3] where Ln standsfor all lanthanides except cerium. This report, whichis an extended abstract of publication [4], concernsthe last and the most entangled Ce2(SC>4)3-H2O sys-tem with 39 source papers and divergencies in thesolubility data reaching up to 185%. The criticalevaluation was performed as previously [1], and its

theoretical basis was the same as described in ref.[1,3]. Over the temperature range 273-373 K, thesaturating solid phases, Ce2(SO4)3-hH2O, of thehydrate number h equal to 12, 9, 8, 5, 4 and 2, havebeen identified. The solubility smoothing equations,transition points and solution enthalpy estimatorsAHfofn [3] of the identified hydrates are given inTable. The solubility in the Ce2(SO4)3-H2O systemis illustrated in Fig. It results from this evaluationthat the stable equilibrium solid phases are only:


Table. Solubility smoothing equations in the Ce2(SO4)3-H2O system over the 273-373 K temperature range.

Ce2(SO4)3hH2O

Phase A; h=9Phase B; h=8

Phase C;h=12Phase D;h=2Phase E;h=5Phase F;h=4

Solubility equations*: In m = a + b/Tm in moles of anhyd.salt/kg H2O and T(K)

In m = (-9.166+0.118) + (2163±36)/Tlnm = (-9.951 ±0.101) + (2419±30)/TIn m = (-4.365 ±0.344) + (926+100)/TIn m = (-30.70±0.93) + (9627±332)/TIn m <= (-16.52±1.25) + (4553±418)/TIn m = (-16.92+1.03) + (4567±342)/T

AHf§ln,kJ/mol-9O±1.5

-1OO.5±1.5-38.5+4-400±14-189±17-190+14

• By definition [1,3], AHs$ln=[5RT2Ti/(T2-Ti)/(T2-Ti)ln(m2/mi)].

Ce2(SO4)3 • 9H2O at 273-310 K, Ce2(SO4)3 • 4H2O at310-367 K and Ce2(SO4)3 • 2H2O at 367-373 K. Thus,

Inm m/molkg'1

-1.2

Fig. Solubility in the Ce2(SO4)3-H2O system as In molality vs.1/T(K). The hydrate phases: A, B, C, D, E and F are speci-fied in Table.

divergencies in the reported solubility data aremainly due to the variety of metastable equilibria

involved in close crystallization fields and incorrectassignements of the saturating solid phases by theauthors of the source papers [4]. Since a similarvariety of the hydrate numbers exists for theanalogous La(III) system [3], it must occur also forthe respective Pu2(SO4)3hH2O, Np2(SO4)3 • hH2Oand U2(SO4)3-hH2O aqueous systems [4] over thetemperature range 273-373 K.

The above conclusion may be of interest fortreatment of lanthanide and actinde fission pro-ducts as well as for analytical chemistry and tech-nology of rare earths.

The uncertainties in the a, b and AHfoln valuesare given at the confidence level /S=0.95. The majortransition points, as calculated from the respectivesolubility smoothing equations, are as follows:AoB at 327 K, BoC at 267 K, AoE at 324 K, AoFat310KandDoFat367K.

References

[1]. Mioduski T.: J. Radioanal. Nucl. Chem., Lett., 165,9 (1992).[2]. Mioduski T.: Comments Inorg. Chem., 19,231 (1997).[3]. Mioduski T.: Identification of saturating solid phases in

aqueous solutions of lanthanide(III) sulfates from the solu-bility data. Chem. Ana!., in press.

[4]. Mioduski T.: Identification of saturating solid phases in theCe2(SO4)3-H2O system from the solubility data. Submittedfor publication in J. Thermal Anal.

NEXT PAQE(S)toft BLANK

RADIOBIOLOGY


RADIOBIOLOGY 63

DIFFERENTIAL EXPRESSION OF C-MYC PROTEININ X-IRRADIATED L5178Y SUBLINES

WITH FUNCTIONAL OR DEFECTIVE DNA REPAIR

I. Szumiel, M. Kapiszewska1/, A. John1', B. Sochanowicz, A. Jaworska2/

v Department of Biochemistry, University of Al-Ain, United Arab Emirates^Norwegian Radioprotection Authority, Oslo, Norway

We examined the expression of c-MYC protein intwo L5178Y (LY) murine lymphoma sublines, LY-Rand LY-S. They differ in radiation sensitivity; slowerdouble strand break (DSB) rejoining in LY-S(radiation sensitive) cells is paralleled by slowerchromatid break repair estimated from PCC [1]. Themolecular defect in LY-S cells remains undefined.Both sublines carry a mutation in codon 170 of p53[2]. In this report we show that the differentialexpression of c-MYC protein is related to the cellularresponse of LY sublines to X-irradiation.

c-MYC is constitutively expressed in both LYsublines; the ratio LY-R/LY-S is 0.71 ±0.13 (meanresult from densitometric analysis of Western blot

UJa:

800

700

600

500

3 400

300

200

100

- • - LY-R.2Gy••*.- LY-R.5Qy-O- LY-S,2Sy"A- LY-S, SQy

^ •

/ \

A

1 100010 100

TIME AFTER IRRADIATIONFig. Expression of c-MYC in X-irradiated LY cells (60 fig pro-

tein per lane); results of densitometry from a representativeWestern blot chosen among 2-3 repeats. Relative amount isobtained by densitometric volume integration of the chosenblot region.

±standard deviation). After X-irradiation (5 Gy)c-MYC expression is very strongly enhanced in

LY-R cells (Fig.), whereas in LY-S cells it increases2-3 times (Fig.) and the differences between cellsirradiated with the two indicated doses are small.

So, upregulation of c-MYC is pronounced inLY-R cells and very low in LY-S cells. A high levelof this protein in the absence of survival factors isthought to be related to apoptosis in a variety ofcell lines (e.g. [3]). However, in the presence ofserum in the culture medium, apoptosis is accom-panied by a decrease in c-MYC [4]. Furthermore,when the supply of survival factors is adequate,c-MYC promotes proliferation [3]. Increase inc-MYC after irradiation in lymphoid cell lines haspreviously been reported, but not in breast tumorcell lines. So, it should be expected that in LY-Rcells, in contrast with LY-S cells, there is an in-crease in c-MYC expression which supports post-irradiation recovery.

The work was supported by the Polish StateCommittee for Scientific Research, and grants fromthe United Arab Emirates University and the Re-search Council of Norway.

References[l].Wtodek D., Hittelman W.N.: The relationship of DNA and

chromosome damage to survival of synchronized X-irradiatedL5178Y cells. H.Repair. Radiat. Res., US, 566-575 (1988).

[2].Storer R.D., Kranyak AR., McKelvey T.W., E!ia H.C.,Goodrow T.L., Deluca J.G.: The mouse lymphoma L5178YTK+/-cell line is heterozygous for a codon 170 mutation inthe p53 tumor suppressor gene. Mutat. Res., 222, 157-165(1997).

[3]. Askew D.S., Ashmun R.A., Simmons B.C., Cleveland J.L.:Constitutive c-myc expression in an IL-3-dependent myeloidcell line suppresses cell cycle arrest and accelerates apop-tosis. Oncogene, &1915-1922 (1991).

[4].Suminatani K., Kamijo R., Naguaio M.: Cytotoxic effect ofsodium nitroprusside on cancer cells: involvement of apoptosisand suppression of c-MYC and c-MYB protooncogene ex-pression. Anticancer Res,, 12,865-872 (1996).

REDOX DEPENDENT ACTIVATION OF NF/cB IN X-IRRADIATEDOR HYDROGEN PEROXIDE TREATED L5178Y SUBLINES

B. Sochanowicz, I. Gradzka, E. Przygoda, I. Szumiel

The relations between antioxidant efficiency andlocalization of the "protective" enzymes, content oftransition metal ions and relative sensitivity ofDNA and membranes as targets for oxidative da-mage remain largely undefined in mammalian cells.Also, the role of transcription factor NF/cB, inducedby reactive oxygen species [1], in intrinsic cellularsensitivity to oxidants has not yet been established.Therefore, we characterize the activation of NF/cB

in L5178Y (LY) sublines, which are inversely cross--sensitive to hydrogen peroxide [2,3] and X-rays:LY-R cells are radioresistant and oxidant-sensitive,whereas LY-S cells are radiosensitive and oxidant--resistant.

X irradiation (1 Gy) activated NFKB in LY-Rcells 1 h after exposure with an increase until 6 h;24 h after exposure the level was equal to thecontrol one. There was a weaker activation in LY-S

64 RAD1OB1OLOGY

cells (Fig.lA). Hydrogen peroxide induced NF/cB inboth sublines in a concentration related manner;the effect was considerably more pronounced inLY-R than LY-S (Fig.2A). On the contrary, inhibi-A. X-irradiationlGyXTIME, h

lGyXTIME, h

) 24

'V 'A

+24

+1 2 4 6

LY-R

B.NAC+X-irradiation

lGyX,3h - + •

0 1 2 4

LY-S

+6

LY-R

C. Selenium pretreatment

LY-S

IGyXTIME, h 0 1 2 4 6 0 1 2 4 6

LY-SLY-R

D. ATM pretreatment

lGyXAMT 4

3h 6h 3h 6h

LY-R LY-S

Fig.l. Activation of NFKB by X-irradiation (1 Gy ) in LY cells(A) and the effect of 1 h pretreatment with 300 /M NAC(B), selenium pretreatment (C), and AMT (D; 5mM -LY-R, 10 mM - LY-S). Western blots of protein from thenuclear extracts.

tory kB protein, which when released, inducesNF/cB activation, was not present in untreated cells;A. NF/cBH2O2,mM 0 0.25 0.501.0 2.0 0 0.25 0.501.0 2.0

LY-R LY-S

B.I/cBH2O2, mM

C. NF/cB

0 0.25 0.501.0 2.0 0 0.25 0.501.0 2.0

LY-R LY-S

2 3 4 5 1 2 3 4 5

LY-R LY-S

Lanesl-control,2-NAq3-NAC+H2O2,4-H2O2,5-H2O2+NAC

Fig.2. Activation of NFKB (A) and IKB (B) by hydrogen peroxide(1 h, 37°C) in LY cells and the modifying effect of 300 MN-acetylcysteine (NAC) given before or after 1 mM hydro-gen peroxide (C). Western blots of proteins from thenuclear (NFKB) or cytoplasmic (IKB) extracts.

hydrogen peroxide treatment induced it in LY-Rcells very strongly, in LY-S cells kB was constitu-tively expressed and the induction was less marked(Fig.2B).

By manipulating the antioxidant defense status[4] (treatment with antioxidant, N-acetylcysteine(NAC), catalase inhibitor, aminotriazol (AMT), in-duction of glutathione peroxidase by cell culture ina selenium-supplemented medium) we obtained analteration in NFKB activation in LY cells. NACpretreatment counteracted activation of NFKB byirradiation in LY-R cells (Fig.lB) with a weakeffect in LY-S cells, as in the case of hydrogen per-oxide treatment (Fig.2C). 300 fiM NAC counter-acted the activation of NF/cB only when givenbefore hydrogen peroxide (Fig.2C). AMT enhancedNFKB activation in untreated LY-R cells (Figs.IDand 3A). The concentration of AMT was chosenaccording to its effect on 80% reduction in catalaseactivity. Irradiation or hydrogen peroxide did not

A. ATM treatmentATMH2O2, mM 0 0 0 0

ATMH2O2, mM 0 0.25 0.501.0 2.0 0 0.25 0.501.0 2.0

LY-R LY-S

B. Selenium pretreatment

0 0.25 0.501.02.0 0 0.25 0.501.0 2.0ATMH2O2, mM

LY-R LY-S

Fig.3.The effect of AMT treatment: 5 mM - LY-R, 10 mM -LY-S (A), or activation of glutathione peroxidase (4-6 daycell culture in selenium supplemented medium) (B) onNFKB induction by hydrogen peroxide.

change the activation of NF/cB in AMT pretreat-ment LY-R and LY-S cells (Figs.lD and 3A). Cellskept in the selenium-supplement medium for 4-6days show an increase in glutathione peroxidaseactivity (LY-R cells: 15.6 times; LY-S 1.7 times) [4];in this cells the activation of NF/cB by irradiation orhydrogen peroxide is markedly lower, especially inLY-R cells (Figs.lC and 3B, respectively).

We conclude that the differential activation ofNF/cB in LY sublines is not related to the lethaleffect of the activating, damaging agent, since theactivation is stronger in LY-R cells, more radiore-sistant than LY-S cells but also more sensitive tohydrogen peroxide; rather, the difference is due tothe more efficient antioxidant defense in LY-S thanin LY-R cells. An additional feature of the studiedcellular model is a marked dependence of NFKBactivation on the p21ras controlled cellular redoxstatus.

RADIOBIOLOGY 65

The work was supported by the Polish State Com-mittee for Scientific Research - grant 3T09A 03209.

References[1]. Schreck, R., Albermann K, Bauerle P.A.: Nuclear factor «B: an

oxidative stress-responsive transcription factor of eukaryoticcells (a review). Free Rad. Res. Comm., IX 221-237 (1992).

[2]. Kruszewski M., Green M.H.L., Lowe J.B., Szumiel I.: DNAbreakage, cytotoxicity and mutagenicity of hydrogen peroxide

treatment at 4°C and 37°C in L5178Y sublines. Mutat. Res.,308,233-241 (1994).

[3], Kruszewski M., Green M.H.L., Lowe J.E., Szumiel I.:Comparison of effect of iron and calcium chelators on theresponse of L5178Y sublines to X-rays and H2O2- Mutat.Res., 226,155-163 (1995).

[4], Bouzyk, B., Iwanenko T., Jarocewicz N., Kruszewski M.,Sochanowicz B., Szumiel I.: Antioxidant defense system indifferentially hydrogen peroxide sensitive L5178Y sublines.Free Rad. Biol. Med., 2,697-704 (1997).

INDUCTION AND REPAIR OF DOUBLE-STRAND DNA BREAKS (DSBs)IN 5 CELL LINES AFTER SUBLETHAL DOSES OF X-RADIATION

- USE OF PULSE-FIELD GEL ELECTROPHORESIS

I. Grqdzka, A. Jaworska17, A. Wdjcikl/ Norwegian Radiation Protection Authority, Oslo, Norway

Among DNA lesions induced in cells by ionizingradiation, DSBs appear with the lowest frequency -approx. 20-30 DSBs per cell per Gy of X rays [1,2].Nevertheless, this type of DNA damage has a majorrole in radiation-induced cell killing [3,4].

Methods previously used for measurement ofDSBs, i.e. neutral filter elution, neutral sedimenta-tion or conventional electrophoresis, required veryhigh doses (102-103 Gy), far above the dose rangewhere cell survival is measurable. The developmentof pulse-field electrophoresis enabled separation ofvery high molecular weight double-strand DNAmolecules [5,6] and thus, quantification of DSBsresulting from sublethal (<10 Gy, [7]) radiationdoses [8-10].

We used a new generation pulse-field electro-phoresis system, CHEF-DR III (Bio-Rad). In a pre-liminary study, we estimated DSBs resulting from0.1 to 10 Gy of X-radiation and compared the effi-ciency of DSBs repair in 5 lymphoid cell lines: Reh,human acute lymphoblastoid leukemia (B-lineage);

A B RehReh

GM00717C and GM00736A, transformed humanlymphoblasts derived from ataxia telangiectasia pa-tients, homozygous and heterozygous respectively;L5178Y-R (LY-R) and L5178Y-S (LY-S), mouselymphoma (T-lineage), resistant and sensitive toX-radiation respectively.

The cells were irradiated at 0°C (initial damage)or at 37°C (repair experiments), embedded inagarose and lysed. The resulting nucleoids inagarose plugs were then placed into wells in 1%agarose gel and subjected to electrophoresis in 0.5 xTBE buffer, at pH=8.0, at 6 V/cm, for 24 h, at14°C. The angle between two current directions was120° with initial and final switch times 60 s and120 s respectively. After the electrophoresis, DNAin the gel was stained with ethidium bromide andphotographed under UV light (Fig.l). With equaldensities of the cells in the agarose plugs, the levelsof DSBs were reflected by the quantity of DNAentering the gel and distribution of DNA fragments(Fig.lA). The dose of 2 Gy induced a distinct

GOO17JC GOO736A C LY-R LV-S

Fig.l.Pulse-field gel electrophoresis of DNA; gels stained with ethidium bromide. Results of three different experiments withX-irradiation are shown: A - DSBs induction in Reh cells irradiated with increasing doses of X-rays at 0°C (ca. 0.5x10cells/lane); B and C - DSBs repair after 2 Gy of X-rays in 5 lymphoid cell lines (ca. 1.5xlO6 cells/lane). Control - unirradiatedcells; 2 Gy - cells irradiated at 0°C with the dosis of 2 Gy; 2 Gy + 15(30) min - cells irradiated with the dosis of 2 Gy at 37°C andthen let to repair the damage for 15(30) min at the same temperature; S.cerevisiae - Saccharomyces cerevisiae artificialchromosomes used as molecular weight markers, range 240-2200 kb.

66 RAD1OB1OLOGY

increase in DSBs over unirradiated control and waschosen for the repair experiments (Fig.IB and C).

Of the cell lines examined, LY-R and GM00736Ashowed a substantial decrease in the level of DNAdamage 30 min after irradiation. In the case of LY-S,GM00717C, and Reh cells no apparent differencewas seen between the initial (time "0") DSBs and theDSBs 30 min after irradiation (Fig.lB and C). DSBsrepair deficiency in LY-S cells and homozygousatcoda telangiectasia cells was in agreement with theprevious reports [11,12]. A defect in DSBs repairafter X-irradiation in human Reh cell line has, to ourknowledge, not yet been described.

The results presented here are a pilot study. Toenable studying DSBs repair after biologicallyrelevant doses, sensitivity of the method has to befurther improved. This can be achieved by adjustingelectrophoretic conditions and enhancing the DNAdetection efficiency. There is a possibility to use anew DNA dye with fluorescence much exceedingthat of ethidium bromide (e.g. GeiStar, FMCBioproducts, USA) - for direct staining of DNA inthe gel, or DNA transfer from the gel to a nylonmembrane (Southern blotting) and subsequentidentification of the bands with a specific digoxy-genine-labelled DNA probe and immunoenzymatic,signal amplificating reaction.

The work was performed in the laboratory ofNorwegian Radiation Protection Authority and wassupported by the grant 113339/720 from the Re-search Council of Norway. I. Gra.dzka was a reci-pient of a 3-week scholarship from the ResearchCouncil of Norway under the Specialists ExchangeProgramme 1997.

References[l].Ward J.F.: Prog. Nucl. Acid Res. Mol. Biol., 35, 95-125

(1988).[2]. Nevaldine B., Longo J., King G.A, Vilenchik M., Sagerman

R.H., Hahn P.J.: Radiat. Res., 133,370-374 (1993).[3]. Frankenberg-Schwager M.: Radiat. Environ. Biophys., 29,

273-292 (1990).[4]. Uiakis G.: Bioessays, 13,641-648 (1991).15]. Stamato T.D., Denko N.: Radiat. Res., 121,196-205 (1990).[6].Sestili P., Cattabeni F., Cantoni O.: Carcinogenesis, 16,

703-706 (1995).[7]. Bedford J.S., Phil D.: Int. J. Radiat. Oncol. Biol. Phys., 21,

1457-1469 (1991).[8]. Longo J.A., Nevaldine B., Longo S.L., Winfield J.A., Hahn

PJ.: Radiat. Res., 147,35-40 (1997).[9].Kysela B.P., Michael B.D., Arrand J.F.: Radiat. Res., 134,

107-111 (1993).[10]. Erixon K., Cedervall B.: Radiat. Res., 142,153-162 (1995).[11]. Wlodek D., Hittelman W.N.: Radiat. Res., 112, 146-155

(1987).[12]. Pandita T.K., Hittelman W.N.: Radiat. Res., 131, 214-223

(1992).

CELL CYCLE ARRESTS AND APOPTOSISIN X-IRRADIATED DIFFERENTIALLY RADIOSENSITIVE L5178Y SUBLINES

I, Grqdzka, B. Sochanowicz, A. Jaworska1', I. Szumiel

^Norwegian Radiation Protection Authority, Oslo, Norway

We examined the cell cycle arrest, apoptosis andexpression of BAX and BCL2 proteins in twoL5178Y (LY) murine lymphoma sublines, LY-Rand LY-S. They differ in radiation sensitivity slowerdouble strand break (DSB) rejoining is seen inLY-S (radiation sensitive). Both sublines carry amutation in codon 170 of p53 [1], LY-R cells do notconstitutively express BCL2, whereas both sublinesshow high BAX content. The levels of theseproteins do not change after irradiation. There isno Gl arrest and a difference in G2 arrest, short inLY-R cells and long in LY-S cells. Radiationinduces delayed apoptosis to a greater extent inLY-S than in LY-R cells; it can be seen 24 h after

irradiation (2 Gy) of LY-S cells, with a maximum at48 h; LY-R cells need 5 Gy and 72 h to showmarked apoptosis (identified by the flow cytometryTUNEL method (Fig.lA) and the "ladder" patternof DNA electrophoresis (Fig. IB)). The effectrevealed by both methods was considerably morepronounced in LY-S cells than in LY-R cells.

In the TUNEL method apoptotic LY-S cellswere seen 24 h after irradiation and the maximumwas reached at 48 h. The electrophoretic pattern forLY-S irradiated with 5 Gy was closer to a smearthan to ladder pattern at 72 h after irradiation(Fig.lB), indicating late necrosis. Apoptotic LY-Rcells could be found at later time intervals and

34 a 72

TIME AFTER IRRADIATION, h

STANDARDCONTROL 48 hCONTROL 72 h2GyX 48 h2GyX 72 h

GyX 48hISGyX 72 hCONTROL 48 hCONTROL72h

<2GyX 48 h2GyX 72 h5GyX 48 h

}SGyX 72 h

B

LY-R

LY-S

Fig.l. Apoptosis in X-irradiated LY cells. A - % of apoptotic cells determined by flow cytometry-TUNEL in cell cultures X-irradiatedwith 1,2 or 5 Gy; B - patterns of DNA electrophoresis (standard - DNA from apoptotic, heat-treated LY-S cells).

RADIOBIOLOGY

higher doses. This could be clearly seen also on dotplots of TUNEL-stained cells (not shown).

The delayed apoptosis is much more frequent inLY-S than in LY-R cells, even at a roughly com-parable survival level (2 Gy for LY-S cells, survivingfraction (SF)=ca 0.04; 5 Gy for LY-R cells, SF=ca0.02. However, it is impossible to predict the celltendency to undergo apoptosis judging from theexpression of p53, bcl-2, bax, c-myc and bcl-x2 [2];clearly, more information is needed on the func-tioning and cross-talks of signalling pathways. Also,apoptosis is not always a reliable indicator of radia-tion sensitivity, as recently reviewed by Hendry andWest [3].

The work was supported by the Polish StateCommittee for Scientific Research, and grants from

the United Arab Emirates University and the Re-search Council of Norway.

References

[l].Storer R.D., Kranyak A.R., McKelvey T.W., Elia H.C.,Goodrow T.L., Deluca J.G.: The mouse lymphoma L5178YTK+/-ce!I line is heterozygous for a codon 170 mutation inthe p53 tumor suppressor gene. Mutat. Res., 222, 157-165(1997).

[2].Khanna K.K., Wie T., Song O., Burrows S.R., Moss D.J.,Krajewski S., Reed J.C., Lavin M.F.: Expression of p53, bct-2,bax, bcl-x2 and c-myc in radiation-induced apoptosis inBurldtt's lymphoma cells. Cell Death Different., 2, 315-322(1996).

[3], Hendry J.H., West C.M.L.: Apoptosis and mitotic cell death:their relative contributions to normal-tissue and tumourradiation response. Int. J. Radiat. Biol., 21,709-719 (1997).

DO LOW DOSES OF IONIZING RADIATION INDUCECHROMOSOMAL REPAIR ACTIVITY?

SCREENING HUMAN T CELL EXTRACTS MICROINJECTEDINTO MOUSE EMBRYOS

A. W6jcik, J.D. Shadley17, Ch. Streffer2'

^Department of Radiation Oncology, Medical College of Wisconsin, Milwaukee, USA^Institute of Radiation Biology, University Clinics, Essen, Germany

The adaptive response of human lymphocytes toionizing radiation has been proposed to involve achromosomal repair activity [1]. Several reports haveappeared in support of low dose induction of newproteins in human lymphocytes. Youngblom et al. [2]have found that the presence of the protein syn-thesis inhibitor cycloheximide between the adaptingand challenging doses prevented the detection of anadaptive response. Wolff et al. [3] have reported onthe identification of new proteins induced by lowdoses of X-rays.

The observations of low dose induced geneproducts in human lymphocytes, while intriguing,remain associations, and not identification ofmolecular factors responsible for the adaptive res-ponse. We chose alternate approaches, by searchingfor a chromosomal repair activity present in ex-tracts from low dose exposed human T cells. Theactivity was screened in mouse embryos that, them-selves, fail to exhibit an adaptive response and thusprovided a background free from this variable [4].Embryos were microinjected with the whole cellextracts from the same human T cell populationthat exhibited an adaptive response for micronuc-leus induction. Chromatid aberrations were scoredin microinjected embryos challenged with 0.5 Gy ofX-rays in G^ phase.

Mouse embryos microinjected with the wholecell extracts from low dose exposed Jurkat cells hadfewer aberrations than those microinjected withcontrol extracts (Fig.). These extracts came fromthe same population of Jurkat cell that exhibited anadaptive response to micronucleus induction. It istempting to conclude that some component(s) ofthe extracts was responsible for the reduced

cytogenetic damage in both human and mouse cells.However, the reduction in 0.5 Gy-induced aberra-tions in the mouse embryos was not at the levelobserved for micronuclei in the Jurkat cells (25 vs

Control AD AD+CD upected

Fig. Chromosomal aberrations in embryos microinjeced with ex-tracts from Jurkat celis. AD - adapting dose, CD - challeng-ing dose.

40%), nor was the reduction in aberrations statis-tically significant. Thus, this result strongly indi-cates that the adaptive response in Jurkat cells iseither not due to the inducible chromosomal repairactivity or that the activity responsible is not com-mon to the human and mouse cell types tested.

References[1]. Wojcik A,, Streffer C : Adaptive response to ionizing radia-

tion in mammalian cells: a review. Bio!. Zent. bl., 113,417-434 (1994).

[2]. Youngblom J.H., Wiencke J.K., Wolff S.: Inhibition of theadaptive response of human lymphocytes to very low doses ofionizing radiation by the protein synthesis inhibitor cyclo-heximide. Mutat. Res., 227,257-261 (1989).

[3]. Wolff, S., Wiencke J.K., Afea! V., Youngblom J.H., Cortes F.:The adaptive response of human lymphocytes to very low dosesof ionizing radiation: a case of induced chromosomal repairwith the induction of specific proteins. In: Low Dose Radiation:Biological Bases of Risk Assessment. Eds. K.F. Baverstock,J.W. Stather. Taylor and Francis, London 1989, pp. 446-454.

68 RAD1OBIOLOGY

[4]. Wojcik, A., Bonk K., Miiller W.-U., Streffer C , WeissenbornU., Obe G.: Absence of adaptive response to low doses ofX-rays in preimplantation embryos and spleen lymphocytes

of an inbred mouse strain as compared to human peripherallymphocytes: a cytogenetic study. Int. J. Radiat. Biol., 62,177-185 (1992).

DNA DAMAGE CAUSED BY Cr(VI) IONSIN TWO L5178Y MOUSE LYMPHOMA SUBLINES

WITH VARIOUS ANTIOXIDANT ENZYME ACTIVITIES

£. Bouzyk, M. Kruszewski

Chromium is a well established human carcinogen.Individuals with occupational exposure to specificsalts of chromium and other metals are at anincreased risk of developing lung, nasal and skincancer [1]. Chromium has been shown to be carcino-genic in animal models and also has carcinogenic andmutagenic activities in vitro in mammalian cell assaysystems [1].

Carcinogenic and toxic chromium (VI) com-pounds have been shown to produce a variety ofDNA lesions such as DNA single-strand breaks,alkali-labile sites and DNA-protein crosslinks invivo and in cell cultures [2].

DNA damage caused by Cr(VI) ions (0.1-100 fiM)in two L5178Y lymphoma sublines with variousantioxidant defense systems has been studied by thesingle-cell gel electrophoresis method. Both transi-tion metal ion content and antioxidant enzyme acti-vities are responsible for the differential sensitivitiesof these sublines to oxidative stress [3]. DNA damagedue to Cr(VI) ions was found to be dose dependent(Figs.l and 2). DNA breaks in L5178Y-R (LY-R)

0 0,1 I 10

K2CrO4 CONCENTRATION l«M)

Fig.l.DNA damage expressed as tail moment in LY-R cellsfollowing treatment (1 h, 37°) with K2&O4 preceeded ornot with incubation in 100 nM Na2SeO3 supplementedmedium.

subline appeared in a greater number than those inL5178-S (LY-S) subline; the latter subline has 2times higher catalase activity and 2 times lower gluta-thione peroxide (G-Px) activity than the L5178-R

subline. Both sublines were cultured in 100 nMNa2SeC>3 supplemented Fischer's medium in orderto investigate how G-Px activity affects theCr(VI)-induced DNA damage. G-Px activity in LY-Rand LY-S cells was increased 15 and 50 times,respectively; this resulted in a decreased yield ofDNA breaks induced by Cr(VI). The attenuation ofDNA breaks by the factor of 2.4 was observed forLY-R cells (Fig.l) and by the factor of 1.4 for LY-Scells (Fig.2). The role of the enzymes that remove

10K2CrO4 CONCENTRATION |uM|

100

Fig.2. DNA damage expressed as tail moment in LY-S cellsfollowing treatment (1 h, 37°) with K2CrO4 preceeded ornot with incubation in 100 nM Na2SeO3 supplementedmedium.

H2O2 is obvious, as H2O2 reduces Cr(VI) to Cr(V)(Fenton reaction) [4] and subsequently to Cr(III);this contributes to Cr(VI) genotoxicity. Nevertheless,there are no sufficient reasons, so far, to imply thecontribution of a particular enzyme in the physiologi-cal processes that take place upon Cr(IV) exposurein vivo.

References[1]. Cohen M.D., Kargacin B., Klein C.B., Costa M.: Crit. Rev.

Toxicol., 23,255-281 (1993).[2].De Flora S., Bagnasco M., Serra D., Zanacchi P.: Mutat.

Res., 238, 99-172 (1990).[3]. Bouzyk E., Iwanefiko T., Jarocewicz N., Kruszewski M,

Sochanowicz B., Szumiel 1.: Free Radical Biol. & Med., 22, 4,697-704 (1997).

[4j. Shi X., Dalai N.S.: Arch. Biochem. Biophys., 281,90-95 (1990).

EFFECTS OF IRON CHELATOR, DESFERAL AND COPPER CHELATOR,NEOCUPREINE ON MICRONUCLEI FREQUENCY IN L5178Y CELLS

E. Bouzyk, P. Fuchs

We have previously found different proportions ofiron and copper in nuclei of two sublines of murinelymphoma L5178Y (LY) and proposed a model ofchromatin organization with these metal ions at theDNA attachment sites [1].

L5178Y-R (LY-R) cells, more sensitive tohydrogen peroxide and more radioresistant than

L5178Y-S (LY-S) cells, contain more iron and lesscopper in the nuclei than the radiosensitive, oxidantresistant counterpart of cellular model, LY-S.

In the present study we examined the effect of ironion chelator, desferal (DFO) and copper ion chelator,neocupreine (NEO) on LY-R and LY-S cells, usingboth micronuclei frequency and cell growth tests.

RADIOBIOLOGY 69

0.1

1

4="Ck LY-S

"•s . LY-R

—" _

0.1 0.1 1 5DFO CONCENTRATION |mMl

10

Fig.l. Relative cell numbers in LY cells cultures treated withvarious concentrations of DFO for 48 h at 37°.

Relative cell numbers after 48 h growth periodwere measured in cell cultures treated with DFOand plotted against DFO concentration. The effectsestimated for both sublines were similar; however,LY-R cells appeared to be slightly more sensitive toDFO than LY-S cells (Fig.l). Nevertheless, therewere no statistically significant differences in themicronuclei frequencies in both LY lines treated byDFO (Fig.2).

0 0.01 005 0.1 0.5 1 10NEO CONCENTRATION (uMJ

Fig.2. Micronuclei frequency in LY cells after 48 h NEO treat-ment.

Copper ion chelator, NEO, acted differentlyfrom DFO: LY-R cells showed a greater sensitivityto NEO than LY-S cells. This was reflected in therelative cell number - NEO concentration plots for

both sublines [2] and in micronuclei frequenciesshown in Fig.3. This difference was particularly ap-parent at the lower concentration range, in agree-ment with the lower copper content in the nuclei ofLY-R cells. The results also were consistent with

0 0.01 0.1 5DPO CONCENTRATION |mM]

Fig.3. Micronuclei frequency in LY cells after 48 h DFO treat-ment.

those obtained using the comet assay for investi-gation of the effects of DFO and NEO on DNAintegrity [3].

Altogther, the effects of chelator treatmentspeak for the differences in chromatin architectureof LY-S and LY-R cells due to the different ironand copper ion contribution to the maintenance ofDNA superstructure.

References[lj.Szumiel I., Kapiszewska M., Kruszewski M., Iwanenko T.,

Lange C.S.: Content of iron and copper in the nuclei andinduction of pH 9-labile lesions in L5178Y sublines inverselycross-sensitive to H2O2 and X-rays. Radiat. Environ.Biophys., 24,113-119 (1995).

[2]. Bouzyk E., Iwaneliko T., Kruszewski M.: Effect of copperchelator, neocupreine, on L5178Y cells. Annual Report1996. Institute of Nuclear Chemistry and Technology, War-szawa 1997, p.70.

[3]. Bouzyk E., Iwanenko T.. Kruszewski M.: Ion chelator,desferal, differentially affects nucleoid DNA in two sublinesof L5178Y murine lymphoma. Annual Report 1996. Instituteof Nuclear Chemistry and Technology, Warszawa 1997, p.70.

SPONTANEOUS REARRANGEMENTS DURING INCORPORATIONOF FOREIGN DNA IN CHO-Kl CELLS DEFECTIVE IN DNA REPAIR

M. Kruszewski, I. Buraczewska, M. Trzaska, N. Jarocewicz

Transfection of DNA into mammalian cells is awidely used technique nowadays, however, littleinformation is available about actual events in-volved in the DNA integration and factors that mayinfluence the integration fidelity. Several studieshave demonstrated that foreign DNA incorporatedinto mammalian genome is highly unstable andmany rearrangements may occur in the intergratedDNA as well as in the surrounding cell DNA [1,2],On the other hand, one study indicated thatincorporation of viral DNA into mouse cell DNAcan occur directly without additional rearrange-ments [3]. It was also found that incorporation ofplasmid DNA into the genome of primary humanfibroblasts occurred without major rearrangements,although rearrangements of the cell DNA at theintegration site was found in one clone [4].

In the current study plasmid DNA was intro-duced into three hamster lines defective in DNAdamage repair and the parental CHO-Kl cell line.Defective in DNA double strand break (dsb) repairxrs6 mutant cell line is deficient in DNA-dependentprotein kinase (DNA-PK) activity due to mutationin the XRCC5 gene (Ku 86) [5]. Pal3 and Pb4mutant cell lines were isolated on the basis of sensi-tivity to reactive oxygen species (ROS) generatingagent plumbagin [6]. During further characteriza-tion it was found that these cell lines were alsosensitive to another ROS generating agent, X-raysand DNA crosslinking agent. Although the natureof Pal3 and Pb4 cells sensitivity to DNA damagingagents is under investigation, it is speculated thatPb4 cells are exclusively defective in some pathwayof DNA crosslink repair, whereas Pal3 may be

70 RADIOBIOLOGY

defective in a DNA repair step that is sharedbetween DNA dsb and crosslink repair [6].

pLrec plasmid used in this study was originallydeveloped by Mayne [7]. The plasmid consists oftwo trunctated tandem copies of bacterial LacZgene separated by a mammalian selective marker -neo gene (Fig.l), as well as pBR332 ori and amp se-quences, HSV tk promoter and SV40 promo-ter/enhancer and poly(A) signal.

Seal linearized pLrec plasmid was used fortransfection. Transfected clones were isolated byliquid or soft agar selection with 500,«g/ml of G418as a selective agent. Isolated clones were main-tained in selective medium to prevent spontaneousplasmid deletion. After transfected clone selection,integrity of the incorporated plasmid was checkedusing appropriate PCR primers specific for plasmid

I Copies of LacZ gensI both "HIST Bright Dnen*

100M

y LicZ arntaat Nao ! « • •

Fig.l.Schematic diagram of Seal linearized pLrec plasmid. Ver-tical black bar corresponds to the position of Xho I linkerthat makes 3' LacZ gene copy non-functional. Horizontalbars correspond to the approximate position of AC and BCPCR products.

DNA at left and right site of the selective marker(as indicated in Fig.l).

Fig.2 shows the frequency of rearrangementsduring incorporation of plasmid DNA in CHO-Klcell lines. 16, 18, 14, 13 and 49 independent cloneswere isolated from Pal3, Pb4, xrs6, CHO-Kl(J) andCKO-K1(A) cell lines, respectively, transfectedwith pLrec plasmid. Intact pLrec plasmid was foundin only 4 (6.4%) single copy clones from 62 isolatedclones of CHO-Kl parental cell line (pooledCHO-Kl (J) and CHO-Kl (A)). On the contrary,intact plasmid was found in 11 (68.8%), 9 (50%), 5(35.7%) clones of Pa 13, Pb4 and xrs6 cell linesrespectively (Fig.2).

Events leading to the integration of nonhomo-logous plasmid DNA into a mammalian host chro-mosomal DNA are not well understood. Usually,supercoiled plasmid used for transfection has to belinearized by nuclease activity within the cell. Toprevent random linearization previously linearizedplasmid can be used. Linearized plasmid moleculeis susceptible to further attack of nucleases thatmay degrade most of plasmid molecules before theyhave opportunity to integrate into the genome.Another cellular enzymatic activity that is involvedin foreign DNA integration into host cell genome isnuclear ligase. A number of DNA ligases are in-volved in maintaining of genome integrity. Sincemammalian cells have end-joining capabilities it islikely that these enzymatic activities would act onall DNA molecules with "free ends", including li-near plasmid molecules.

In this study we found a lower frequency ofintrachromosomal rearrangements in cell linesdefective in DNA damage repair. It seems thatsome malformation of DNA structure, e.g. DNAdsb may promote the integration of foreign DNAinto the genome. Presence of the more persistent

xr*6

Fig.2. Rearrangement frequency in CHO-Kl cell lines transfectedwith pLrec plasmid. CHO-K1(J) indicates CHO-Kl strainparental for Pal3 and Pb4 mutant cell lines; CHO-Kl(A)stands for parental strain for xrs6 mutant cell line.

"free DNA ends" in cells defective in DNA damagerepair may speed up foreign DNA integration, andprevents the introduced DNA from degradation byexonucleases. This is essential in the case of xrs6mutant cell line, as these cells (deficient in Ku80end-binding activity) exhibit excess degradation ofextrachromosomal DNA [8]. Indeed, we needed5-times higher DNA concentration during electro-poration to get transfected xrs6 clones, as comparedto the parental cell line.

An assumption that malformations of DNAstructure may promote foreign DNA integration issupported by the fact that nonhomologous DNAintroduced to the normal mammalian cells is prefe-rentially integrated into the chromosomal fragilesites [9] or into repetitive DNA elements [10]. Inte-gration of foreign DNA into these sites usually isaccompanied by high frequency of rearrangementsand chromosome instability [1,11]. However, it is notclear whether genomic instability and high frequencyof rearrangements are associated with the integrationevent itself or concern the specific structure of theseregions, as it is well known that DNA of theseregions is highly unstable. High frequency of DNArearrangements was found in mouse satelite DNA [2]and in fragile sites [12].

References[lJ.Heartlein M.W., Knoll J.H., Latt S.A.: Chromosome insta-

bility associated with human alphoid DNA transfected intothe Chinese hamster genome. Mol. Cell. Biol., 8, 3611-3618(1988).

[2].Butner K.A., Lo C.W.: High frequency DNA rearrange-ments associated with mouse centromeric satellite DNA J.Mol. Biol., 187,547-556 (1986).

[3]. Gahlmann R., Doerfier W.: Integration of viral DNA intothe genome of the adenovirus type 2-transformed hamstercell line HES without loss or alternation of cellular nuc-leoides. Nucl. Acid. Res., 11,7347-7361 (1983).

[4].Murnane J.P., Yezzi MJ., Young B.R.: Recombinationevents during integration of transfected DNA into normalhuman cells. Nucleic Acids Res., 18,2733-2738 (1990).

[5]. Chen F., Peterson S.R., Story M.D., Chen D.J.: Disruptionof DNA-PK in Ku80 mutant xrs-6 and the implications inDNA double-strand break repair. Mutat. Res., 362, 9-19(1996).

RADIOBIOLOGY

[6]. Hama-Inaba H., Shimazu Y., Takusagawa M., Sato K.,Morimyo M.: CHO-K1 cell mutants sensitive to active oxy-gen-generating agents. I. Isolation and genetic studies.Mutat. Res., 311,95-102 (1994).

[7].Herzing L.B., Meyn M.S.: Novel lacZ-based recombinationvectors for mammalian cells. Gene, 137,163-169 (1993).

[8]. Liang F., Jasin M.: Ku80-deficient cells exhibit excess de-gradation of extrachromosomal DNA. J. Biol. Chem., 271,14405-14411 (1996).

[9].Rassool F.V., McKeithan T.W., Neilly M.E., van Melle E.,Espinosa R., LeBeau M.M.: Preferential integration ofmarker DNA into the chromosomal fragile site at 3pl4: anapproach to cloning fragile sites. Proc. Natl. Acad. Sci.USA, 88,6657-6661 (1991).

[10].Kato S., Anderson R.A., Camerini-Otero R.D.: ForeignDNA introduced by calcium phosphate is integrated intorepetitive DNA elements of the mouse L cell genome. Mol.Cell. Biol., 6,1787-1795 (1986).

[ll].Rassool F.V., Le Beau M.M., Neiiiy M.E., van Melle E.,Espinosa R.: Increased genetic instability of the commonfragile site at 3pl4 after integration of exogenous DNA.Am. J. Hum. Genet., 50,1243-1251 (1992).

[12]. Glover T.W., Stein C X : Chromosome breakage and re-combination at fragile sites. Am. J. Hum. Genet., 41,882-890 (1988).

DIFFERENTIAL INHIBITORY EFFECT OF OK-1035 ON DNA REPAIRIN L5178Y-R AND L5178Y-S SUBLINES

WITH FUNCTIONAL OR DEFECTIVE REPAIR OF DOUBLE STRAND BREAKS,1/M. Kraszewski, T. Iwaneńko, M. Wojewódzka, I. Szumie!, A. Okuyama1

11 Banyu Research Institute and Mrerck Research Laboratories, Tsukuba, Japan

Radiosensitive L5178Y-S subline and its parental,more radioresistant L5178Y-R subline differ inDNA double strand break (DSB) rejoining [1].DSB rejoining is impaired both in Gl and G2 LY-Scells [1], as determined by non-denaturing filterelution; the slow DSB rejoining is paralleled byslow chromatid break repair estimated from PCC.According to [2] in Gl phase the repair is carriedout by a DNA-PK-dependent system. The mole-cular defect in LY-S cells remains undefined; it isalso possible that there is an auxiliary to DNA-PKprotein factor indispensable for the repair activitythat is lacking in this cell subline.

OK-1035, 3-cyano-5-(-4-pyridyl)-6-hydrazono-methyl-2-pyridone, has been characterized as aspecific inhibitor of DNA-dependent proteinkinase, DNA-PK [3]. It caused a 50% inhibition ofDNA-PK activity at S^M, a concentration about 50times lower than those required for inhibition ofother kinases.

We applied the comet assay, a sensitive methodof DNA damage determination allowing to examine

120

100

80

eo40

20

, LY-S

V-O- -OK-1035

-•- +OK-1035

20 40 eoTIME AFTER X-1RRADIATION, MIN

Fig.l.DNA repair measured with the comet assay (tail momentas damage measure) in the absence or presence ofDNA-PK inhibitor, OK-1035 (2 nsM), in X-irradiated with8 Gy LY-S (radiosensitive) cells.

its distribution in the cell population subjected tothe damaging agent. At alkaline pH the effect ofboth single and double strand breaks on tail mo-

ment value is estimated. The level of initial DNAdamage measured at DNA-denaturing pH is thesame in both LY sublines: the mean tail momentvalues ±SD, are 92.93 ±10.39 for LY-R cells and94.93 ±12.94 for LY-S cells. The control cellsdiffer: the respective values for LY-R and LY-Scells are 9.62 ±2.84 and 3.52 ±0.1, reflecting thesusceptibility to lysis conditions as well as possibleendogenous (oxidative) damage level.

As shown in Fig.1, in LY-S cells the repair ofX-ray-induced damage proceed identically in thepresence or absence of 2 mM OK-1035. In contrast,the inhibitor considerably slows the repair in LY-Rcells (Fig.2). These results support the assumption,that the DSB repair defect identified by Włodekand Hittelman [1] is due to a lack of function of

120

100 LY-R-O- -OK-1035-•- +OK-I035

20 40TIME AFTER X-IRHADIAT1ON, MIN

80

Fig.2. DNA repair measured with the comet assay in the absenceor presence of DNA-PK inhibitor, OK-1035 (2 mM), inX-irradiated (8 Gy) LY-R (radioresistant) cells.

DNA-PK in X-irradiated LY-S cells. Since thepresence of the Ku subunits of the enzyme in LY-Scell extracts has been confirmed (D. Włodek, P.Jeggo, private communications) it is possible thatthe defect lays in its activation in the irradiatedcells, due to lack of an auxiliary protein or the DNAdamage sensor.

The work was supported by the Polish StateCommittee for Scientific Research.

72 RADIOBIOLOGY

References

[1]. Wlodek, D., Hittelman W.N.: The relationship of DNA andchromosome damage to survival of synchronized X-irradiatedL5178Y cells. ILRepair. Radiat. Res., 115,566-575 (1988).

[2]. Lee S.E., Mitchell R A , Cheng A., Hendrickson E A : Evidencefor DNA-PK-dependent and -independent DNA double-strand

break repair pathways in mammalian cells as a function of thecell cycle. Mol Cell. Biol., 17,1425-1433 (1997).

[3]. Take Y., Kumano M., Hamano Y., Fukatsu H., Teraoka H.,Nishimura S., Okuyama A : OK-1035, a selective inhibitor ofDNA dependent protein kinase. Biocheai. Biophys. Res.Comm., 215,41-47 (1995).

DNA REPAIR IN ADAPTED HUMAN LYMPHOCYTES:COMPARISON OF THE COMET AND SANDWICH ELISA METHODS

M. Wojew6dzka, A. Szczech, P. Fuchs

We have previously described the role of calciumions in the induction of the adaptive response [1]and assumed that the adaptation is dependent ontransduction of intracellular signal(s). We haveattempted to find correlation between DNA repairkinetics and adaptive response estimated frommicronuclei frequency.

Incubation of human lymphocytes in hydrogenperoxide (10 /uM H2O2, 30 min) evoked a ca 30%decrease in the frequency of micronuclei upon sub-

0 10 20 30 40 SO 60 70 80 90 100 110 120

Tlme(min)

Fig.l.DNA damage repair measured by the comet assay inadapted (10 /*M H2O2) and non-adapted human lympho-cytes. Data computer-fitted (least square method) to theequation y=a*exp(-bt)+c, where a is the initial repairabledamage, b is reciprocal of the time constant and c is theresidual damage. Bars denote standard deviation.

sequent X-irradiation (2 Gy). The response wasreflected in a lower micronuclei frequency but nochange in DNA repair rate was observed as measuredby the comet assay directly after the challenge dose.Initial DNA damage and its repair were measuredwith alkaline comet assay immediately after givingthe challenge dose (on ice). Lower damage revealedat the chromosomal level in the adapted lymphocyteswas unrelated to DNA repair rate. The kinetics of

DNA repair in the lymphocytes adapted by 10 ,wMH2O2 treatment and non-adapted cells were similar(Fig.l). We applied also sandwich ELISA [2,3] for

0 tO 10 M 40 SO tt 70 SO 90 100 110 CO

Time (mln)

Fig.2. Repair of DNA damage measured by sandwich ELISA inhuman blood lymphocytes adapted (10/<M H2O2, 30 min)and non-adapted. % ssDNA in X-irradiated (2 Gy) lym-phocytes detected after 6-min alkali treatment (pH 12.4).The data represent mean results for 2 blood samples, splitfrom the same donor and divided over 4 microtiter plates.The error bars represent the SEM.

DNA strand breaks to study radio-adaptation ofhuman lymphocytes. Preliminary results show nodifferences in repair kinetics between the adaptedand non-adapted cells (Fig.2). These results point tothe need of a different approach to solve theproblem: a very sensitive method specific for doublestrand breaks should be applied.

References[1]. Wojewodzka M., Kruszewski M., Szumiel I.: Int. J. Radiat,

Biol., 21,245-252 (1997).[2J. van der Schans G.P., van Loon AAW.M., Groenendijk R.H.,

Baan R.A.: Int. J. Radiat. Biol., 51,747-760 (1989).[3]. Timmerman A.J., Groenendijk R.H., van der Schans G.P.,

Baan R.A.: Mutat. Res., 2M, 347-356 (1995).

VALIDATION OF AN IMMUNOCHEMICAL ASSAY FOR THE DETECTIONOF DNA DAMAGE AS A TOOL FOR BIOLOGICAL DOSIMETRY

OF HUMAN EXPOSURE TO IONIZING RADIATION

M. Wojew6dzka, G.P. van der Schansx/, A.J. Timmerman1/

11 Prins Maurits Laboratory, Nutrition and Food Research Institute, Rijswijk, the Netherlands

For an accurate assessment of the extent of damage,induced by exposure to ionizing radiation, a comple-mentary approach that combines physical dosimetry

and biological indicators of damage is necessary. Tothis purpose the Nutrition and Food Research Insti-tute (TNO, Rijswijk, the Netherlands) is developing

RADIOBIOLOGY 73

•/isiDNANL TU} 00%+normTNO)

iO.CH

1

0.1

- • - tg 12.4 NL

0 J 2 3 4 5 6 7 8 9 10 I I i2

personFig.l. Inter-individua! variation in background level, expressed as %

ssDNA, in blood of 11 individuals. The data are calculatedwith the 100%-ssDNA fluorescence values, determined atthe TNO, and with the TNO plate-to-plate normalization.NL and PL denote results obtained at the TNO and theINCT, respectively.

a method for biological dosimetry based on theimmunochemical detection of DNA damage in

%ssDNA 5Gy (100%+norm TNO)lOO-i

M

£10-

- D " 11.4 PL- • - 12.4 NX- * - 12.3 NL•f- 12.3 PL

O.O 2.S 5.0 7.5 10.0 12.5

personFig.2. Inter-individual variation in the % ssDNA after irradiation

with a dose of 5 Gy, in blood of 11 individuals. The data arecalculated with the 100%-ssDNA fluorescence values,determined at the TNO, and the TNO plate-to-plate nor-malization.

human white blood cells [1,2]. A rapid immuno-chemical assay, the sandwich ELISA, has been de-veloped. With this technique the extent of radia-tion-induced single-strandedness in DNA is assessed,which results from the partial unwinding of DNAcontaining single-strand breaks. Because directly in-duced single-strand breaks are rather rapidly repair-ed, this dosimetry method should be applied within ashort period after exposure.

Blood samples of 11 individuals were irradiatedwith 0 or 5 Gy of 170-kV X-rays at this Instituteand analysed both at the INCT and the TNO(Figs.l and 2). It appeared that in both Labora-tories damage could be detected to the same extent.

Gy-eq NL PL (norm TNO)

10.0-,

$I 1.0-

tu

- * - p H 1 2 . 4 N L•-D-- pH 11.4 PL••*•- pH n* PL

0 1 2 3 S 6 7 8 9 10 II 12

personFig.3. Inter-individua! variation in background level, expressed as

Gy-eq, in blood of 11 individuals.

The average background level of DNA damageamounted to 1.0 Gy-eq with an inter-individualstandard deviation of 0.25 Gy (Fig.3). The contri-bution of the sample variance to the total variancewas only 14%. The radiosensitivity showed only avariation of about 10% and can, therefore, beneglected in estimating the radiation dose from theamount of.DNA damage detected.

References[1], van der Schans G.P., van Loon A.A.W.M., Groenendijk R.H.,

Baan R.A.: Int. J. Radiat. Biol., 55,747-760 (1989).[2J. Timmerman A.J., Groenendijk R.H., van der Schans G.P.,

Baan R.A.: Mutat. Res., 2M, 347-356 (1995).

NEXT PAQE(S)left BLANK

NUCLEAR TECHNOLOGIES

AND

METHODS

NEXT PAQE(S)toft BLANK

NUCLEAR TECHNOLOGIES AND METHODS 77

PROCESS ENGINEERING

TRACER MEASUREMENTS OF EFFLUENT TRANSPORT PARAMETERSON A SELECTED SECTION OF THE WKRA RIVER

A. Owczarczyk, G. Kurzawski1'lf Warsaw Agricultural University, Poland

Theoretical description of effluent transport proof natural hydrological conditions and the river bedcesses in rivers is still open to satisfactory solution, morfology additionally complicate any approach toThe gravity driving force and complex dispersion mathematical description.Table. Parameters of tracer concentration distribution at the Wkra River; experimental course.

Measurement no.Profile no.

p l lp21p31

p!2P22p32

P13p23P33

pl4p24p34

P15p25p35

Time[min]

30.8830.5429.10

54.2154.4653.95

90.4091.5489.78

130.96132.38129.78

175.97177.17179.26

Variance[min2]

25.8225.3627.83

55.7042.9947.21

102.78138.50104.12

163.86160.95149.03

230.08165.88212.85

Time of appearinga maximum on

curve [min]

28.128.126.3

51.950.851.4

86.186.785.4

126.1127.1125.2

171.1171.0174.0

Mean velocityof water flow

[m/s]

0.360.360.38

0.470.480.47

0.470.470.48

0.460.460.46

0.470.470.46

Dispersioncoefficient

[m2/s]

3.183.154.15

6.785.435.88

7.6710.077.95

7.947.607.39

8.506.107.47

Symmetrycoeffcient

1.271.181.14

0.760.930.79

0.791.150.99

0.550.630.73

0.540.410.59

phenomena decide on the effluent distribution down-stream the discharge point. Moreover the influence

The modelling of transport in rivers very oftenbases on the dispersion equation, using various

profile Iprofile 2profile 3

- profile 4piofite 5

IK' 120 130

Fig. Tracer concentration distribution measured at 1 ->-5 profiles. Residence time distribi; tion (RTD) curves.

78 PROCESS ENGINEERING

simplifications and corrections needed to avoidmathematical difficulties and approximation of realconditions as close as possible.

Such approach needs experimental determinationof the basic model parameters (velocities, dispersioncoefficients and others) in natural field conditions.This can be made by means of the tracer method. Theradioisotopes ^Br, 31J as well as the fluorescent dyesRhodamine B and fluorescein can be used as tracers.

Experiments of this type were carried out at aselected section of the Wkra River in June 1997.The water-alcohol Rhodamine B solution was usedas a tracer.

Five cross-sections, in approximately every 2 kmof the river course, have been established for mea-surements of the tracer concentration distribution.The continuous measurements of the tracer fluore-scence have been carried out by means of Turner

10-105 fluorometers localized in each cross-section.The river bed bathymetry and hydrometric mea-surements of the river flow conditions have beenalso measured in every cross-section during thecourse of experiment.

Because the first cross-section has been localizedat the distance longer than needed for completemixing in vertical and transverse directions of thestream, the problem has been simplified to the one--dimensional dispersion phenomena. Thus, only thelongitudinal dispersion coefficient was determined.All experimental results are presented in Table.

Obtained parameters will be used for the rivertransport modelling.

The experimental results of time and spatial dis-tribution of effluent concentration (typical set ofRTD curves presents Fig.) can be used for modelvalidity verification.

PL9802005

A RADIOTRACER STUDY ON THE LOCALIZATIONOF FAVOURABLE SEDIMENTATION ZONE

IN A BIG INDUSTRIAL SEDIMENTATION BASIN

A. Owczarczyk, J. Palige, A.G. Chmielewski

Removal of suspended matter from sewage is oneof the stages of sewage purification, especially inbiological treatment where the activated sludge isadded to the system and should be removed fromthe sewage before its discharge into the natural re-ceiver.

2500

2000

i.1500

from the basin after its filling during the exploita-tion period. At that moment the parallel techno-logical line should be ready to work.

It is technologically resonable to prolongate thesedimentation compain time as much as possible.For this reason the sludge transport and sedimen-

500

I

/

11

\\

\

/

\ -

1

/

/

/

j(

A1

I}

//I

\

r

1\Jto 1

K\V

\\

. . . \

\

......

_A_ metsutemest 1

-o- measurement 2

1 v23 B3 83 103 123 143 163 183 203 223

Distance from inlet M

Fig.l. Sediment transport diagram session 1.

The process is usually realized in two steps. Pre-liminary sedimentation with recirculation of thebiological sludge and secondary step where thesewage are finally clarified in a big settling basin.The accumulated sediment is periodically removed

tation mechanism should be known in detail. Be-fore designing any technical solution for partial re-moval of the accumulated sludge during the com-pain, its best localization in the sedimantation basinshould be find out.


50000

4S0G0

40000

35000

30000

25000

20000

15030

100301

I/M

/

A/

i\\Vk1\ (

tV

>j i—i '—1 NK-—^

= ;

1—i•~—i

1

_a_ mcasuicaia

~°~me»surero«

I HH

—H i

It 2

23 43 43 103 123 193 203 S23 243 263

Disunce from mid [m]

Fig.2. Sediment transport diagram session 2.

Two series of experiments were carried out in abig settling basin (340x60x3 m) of the biologicalsewage treatment plant in a petrochemical factory.

The tracer method was used for that purpose.The region of the favourable sedimentation was de-termined in two stages of the basin rilling: the firstjust after the beginning of the compain (filling withsediment about 15%), the second in the middle ofthe compain (filling about 45%).

As a tracer for sediment, the gamma-radioactiveLa-140 was chosen. The isotope has been permanent-ly sorbed on the activated sludge grains taken fromthe inlet system. The labelled sediment bottom dis-

EMPIRICAL MODEL EQUATIONSFOR THE REMOVAL EFFICIENCY OF SO2 AND NOX

IN A MULTISTAGE E-B SYSTEM OF FLUE GASES PURIFICATION

A.G. Chmielewski, A. Dobrowolski, B. Tyminski, J. Licki17, E. Iller11 Institute of Nuclear Energy, Otwock-Swierk, Poland

tribution as well as its bathymetry were measured bymeans of a specially equipped boat. The residencetime distribution of the sewage was also measured.The fluorescein was used as a tracer for the aqueousphase.

It was proved that the localization of the mostfavourable sedimentation region is independent ofthe sediment accumulation in the basin. The cross--section most convenient for the deposition of anysludge removing system without interuption of thecompain was determined basing on the localizationof the tracer cloud of center gravity (Figs. 1 and 2).

PL9802006

On the basis of the results of experimental workcarried out in an e-b pilot plant, the differences inthe influence of the process parameters on the re-moval efficiency of SO2 and NOX have been ob-served. In the case of multistage e-b treatment offlue gases the following process parameters shouldbe taken into consideration in the determination ofthe removal efficiency of SO2 and NOX [1-4].- absorbed dose of e-b irradation [D],- initial concentration of NOx [NOx]o,- temperature of flue gases in the entrance to the

reaction vessel [Tpn],- humidity of flue gases after conditioning process

[H].- residence time of flue gases inside the reaction

vessel [r].The listed above parameters have an unequal in-

fluence on the e-b removal process of SO2 and

NOX. The absorbed dose and the initial NOX con-centration in flue gases indicate a major influenceon the removal efficiency of NOX. An increase ofabsorbed dose and a decrease of initial concentra-tion of NOX leads to increasing removal efficiencyof these compounds.

In the case of SO2 we observe a strong influenceof temperature and humidity of flue gases on itsremoval degree. A decrease of temperature and anincrease of water vapour content in flue gases com-ing to the reaction vessel, cause an increase of re-moval efficiency of SO2.

The different influence of the process parame-ters on the e-b simultaneous removal of SO2 andNOX can be explained by the difference in thechemical paths of both reactions (Fig.l). The elimi-nation of NOX occurs through a radiochemical reac-tion while the elimination of SO2 is realised mainly


NOx removal

HO2NO2

>C/NOi

NO d H ^ N 0 2 0H '• HNO3 - - - - • NH4NO3N O,HO2 /NHNHa

IN

N2

/NHJNH2 O \ \

N2O NO3\** N2O5

SO2 removal

SO2- -H^-* H2SO41

i NH3

HSO3

NV.. O5H5O

* (NH3)2SO2 - " - — • (NH4)2SO4Fig.l. Main reaction paths to remove NOx and SO2.

by a thermochemical reaction. To determine modelequations for the approximation of experimentaldata of the removal degree of NOX and SO2, theHook Jeevs [5] optimization method and the multi-dimensional regression method [6] have been used.The data of 64 experiments carried out at the KA-

Fig.2. Arrangements scheme of accelerators and irradiationchamber.

W^CZYN e-b pilot plant have been selected formathematical treatment (Fig.2). Each of them ful-filled the following requirements; equal dose de-livery ratio at each irradation stage, and ammoniastoichiometry in the range 0.87+0.93.

The process parameters were in the ranges:- temperature of flue gases enterning into the re-

action vessel Tpn (53.67- 103.2°C),- per cent of water vapour contained in flue gases

H (5.13-12.39% vol.),- absorbed dose of e-b energy D (2.89-14.65 kGy),- initial concentration of NOx [NOx]o (119-253

ppmv),- mean residence time of flue gases inside the re-

action vessel T (3.56-14.43 s).

The following empirical equations have been ob-tained:- for removal efficiency of NOx [%]

NOx = 80.417[l-exp(-0.25876D)] (1)(1.03495 - 0.00007[NOx]o)

- for removal efficiency of SO2

tjS02 = 0.96(144.9787 - 1.12341Tpn + (2)

0.00267T^n) -(0.85732 + 0.01423H)

(0.98528 + 0.00226D) • (1.1777 - °-7^092)The values of removal efficiencies of SO2 and

NOX evaluated basing on equations (1), (2) havebeen compared with experimental data. A measureof the discrepancy between the model and experi-mental data are related as follows:

-100%

in which: r^ - experimental efficiency removal of agiven compound, J7P1 - modelled removal efficiencyof a given compound.

The experimental and model data show a satis-factory conformity, therefore the obtained modelequations can be used for the prediction of removalefficiency of SO2 and NOx in the e-b process duringtwo stages irradiation of flue gases particulary inthe case of scale up.

References[1]. Electron beam flue gas treatment. Research cooperation

among JAERI, IAEA and INCT, October 1996. JAERI -Research 96-053.

[2).Wittig S., Spiegel G., Platzer K.H., Willibald V.: ProjektEuropaisches fur Massnahmen zur Luftreinhaltung. Simul-tane Rauchgasreinigung durch Elektronenstrahl. KfK, Karls-ruhe 1988.

[3]. Namba H., Tokunaga O., Hashimoto S., Tanaka T., Ogura Y.,Doi Y., Aoki S., Izutsu M.: Pilot - scale test for electron beampurification of Due gas from coal - combustion boiler. 9th Inter-national Meeting on Radiation Processing (IMRAP), 11-16September 1994, Istambul, Turkey.

[4]. Chmielewski A.G., Tymiliski B., Licki J., Iller E., Zimek Z.,Dobrowolski A : Pilot plant for flue gas treatment with elec-tron beam start up and two stage irradiation tests. Rad. Phys.Chem, 42, 4-6, 663-668 (1993).

[5]. Findeisen W., Szymanowski J., Wierzbicki A.: Teoria i meto-dy obliczeniowe optymalizacji. WNT, 1977.

[6]. Kafarow W.W.: Metody cybernetyki w chemii i technologiichemicznej. WNT, 1979.

PL9802007

PARAMETRISATION AND MODELLING)F LONGSHORE SEDIMENTS TRANSPORT RATES

IN THE COASTAL ZONE OF BALTIC SEA

A. Owczarczyk, R. Wierzchnfcld, Z. Pruszak1'

Institute of Hydroengineering, Polish Academy of Sciences, Gdafisk, Poland

The near-shore zone is the most interesting sea reg-ion for coastal engineering. In this region the mosteffective changes in the coastal morphodynamicstakes place due to intensive sediment transportgenerated by waves and currents. The processes

occurring in this zone are of great importance forcoast protection and hydrotechnic activities as wellas recreation. They are extremely complicated dueto their stochastic character in the time and spacedomain.


0.02

Fig. The global sediment transport Q vs. angle of breaking waves a% for different values of breaking waves height Hz-

The most valuable information concerning thedynamics of bedload transport and its local cha-racter is provided by field surveys. Such investi-gations are carried out under natural conditionsand take into account characteristic properties ofthe region.

The subject of the work was a study of bedloadmovement for the multibar conditions. The generalaim was the determination of longshore sedimenttransport rate.

The field study was carried out in a multibar (4-5bars) coastal zone 700 m long and about 1000 m wideat the Coastal Laboratory near Lubiatowo (southerncoast of Baltic Sea). Sediment transport in this reg-ion was the object of intensive and complex fieldstudies by the use of radiotracer method [1].

The most effective way to investigate the sedi-ment transport processes under natural conditionsis a tracer technique. The characteristic advantageof this technique is noninvasive observation andmeasurement of parameters of the bedload orpollutant transport in the sea bed floor. Especiallythe radioactive tracers provide the most reliableinformation concerning the examined process dueto the measurement of nuclear radiation (conti-nuous detection, no sampling necessity). The iso-tope 192Ir was used as a radiotracer in the work.192Ir was a component of specially prepared glassgrains of diameter 0.020-0.025 cm and density of2668 kg/m3. The tracer was introduced at selected

points of the coastal zone in order to cover its mostinteresting regions. As a result of interaction ofwaves and currents on the sea bottom, the bedloadmotion was evaluated on the basis of the measuredtracer distribution within the region under test [2].

The results obtained give the possibility to elabo-rate an empirical model of the global sedimenttransport rate for the multibar conditions:

Q=0.015- kv • (H^s)?5 • sin2az (1)

sin2«z (2)

v ( ^ )for ( H L S ) Z - V L < 0.15

(2=0.00225+0.0052• kvfor (HLS)Z • VL > 0.15

where: ky - regional factor; V - velocity of long-shore sediment transport; H, a - height, angle ofbreaking waves.

The solution of the model for the different condi-tions has been presented in the form of nomograms[3]. An example of nomogram is shown in Fig.References[1], Owczarczyk A., Strzelecki M., Szpilowski S., Wierzchnicki R.,

Basiftski T.: New application of radioactive tracer method forthe sediment movement measurements in the near-shorezone. Isotopenpraxis, 25, 8, 330-340 (1989).

[2]. Owczarczyk A., Pruszak Z., Szpiiowski S., Wierzchnicki R.,Zeidler R.: Badanie ruchu osadow w morskiej strefie brzego-wej metoda^ radioznacznikowa.. Rozprawy Hydrotechniczne,54,55-69 (1991).

[3]. Wierzchnicki R.: Charakterystyki i parametryzacja ruchuosadow dennych dla warunk6w wielorewowej strefy brzego-wej na podstawie badaift terenowych (PhD thesis in Polish).Polish Academy of Sciences - Institute of Hydroengineering,Gdansk.

A TRACER STUDY OF THE CONTACT BETWEEN TWO POPULATIONS

A. Owczarczyk, J. Palige

One of the principal and first application of thetracer method was the determination of connecting

links existing between two or more populations. Apopulation can be defined as a set of members having


0

Fig.l.Scheme of system: 1 - channel of heating water, 2 - wastewater channel.

a common characteristics [1]. Good examples of po-pulations are the phases (liquid, solid, gas), differentsorts of chemical compounds, parts of a system etc. Apopulation can change in time and space and caninteract with other populations.

35

heating water net. The water balance in the heatingwater net indicated the "suspicious" region. Thetracer experiment had to confirm or to deny theexistence of water leakage in the waste watersewage system and its penetration into other net.

The fluorescent tracer, Rhodamine B, was inject-ed continuously with a constant flow rate to wastewater (duration of injection -1 h). During the next3 days, after injection, the samples of water fromthe heating water net were withdrawn. The resultsof tracer concentration measurement by a Turnerfluoremeter are presented in Fig.2.

The data obtained indicate that there is a directcontact between the two mentioned water nets. Theshape of the curve observed proves that the contact

20

15

10

till Ij

riV '"•Ufa ' v

A-/ V/ \ \

\• — • —

Fig.2. Tracer concentration vs. time in heating water.

The most important problem solved by the tracermethod is the so called "yes-no" information i.e. theinformation indicating that between two popula-tions exist a contact.

One of the problem solved in the INCT by appli-cation of this method was the determination of thecontact between two independents water systems: achannel of the municipal central heating water andthe net of the waste water sewage system in thePruszk6w city.

A scheme of the system under investigation ispresented in Fig.l.

A long time of observations suggests that somequantity of the waste water penetrates into the

has the character of hydraulic break down as well asthe infiltration flow. The waste water from thesewage system penetrates through the soil into theheating water channel.

The analysis of the obtained results allowed tolocalize a leakage point and to minimize the cost ofnecessary repaires.

References[1]. Guidebook on Radioisotope Tracers in Industry. IAEA,

Vienna 1990.


PL9802008

MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS

PREPARATION OF Pt-WO3(W)/C CATALYST POWDERS (10 and 20% Pt)AND THIN COATINGS BY THE COMPLEX SOL-GEL PROCESS (CSGP)

A. Deptula, W. fcada, T. Olczak, B. Sartowska, A. Ciancia17, L. Giorgi17, A. Di Bartolomeo1/

17 ENEA-CRE-Casaccia, Rome, Italy

Direct Methanol Fuel Cells (DMFC) have been Os, Ir, Pd, Sn, Pb, Bi, Cr, Cu, Fe and W) on carbonrecognized as one of the most promising systems of black support [1]. For preparation of similar typeenergy sources for automotive area [1], Oxidation catalysts the method of impregnation has beenof methanol in these cells is catalyzed by Pt (often widely used. However there is no information on itsmixed with other metals or/and oxides e.g. Ru, Au, application to the preparation of catalyst for

200g/ dm320g/dnr ASC solution

<- (NH,)»W5Oi72.5H2O ->

HjPtCIs

\ carbon /N black ' CjHsOH->

Gelation by evaporation under IR and at 110°C

Air400'C

Argon900°C

Hydrogen700T

/

Blending

Immersion of Ag orTi substrate

Gelation by evaporationat b.p.

Gelation at R.T. and than at 200°C

Thermal treatment at 700°C

Pt-W<VC Pt-W<VC Pt-W/CC A T A L Y S T S

Pt/WO,COATING on Ag or Ti

PtAVOj

POWDERS

Fig.l. Experimental procedure for preparation Pt-WOx/C catalysts and Pt/WO3 coatings on Ag; and Ti.

84 MATERIAL ENGINEERING, STRUCTURAL STUDIES, DIAGNOSTICS

DMFC. There are two main advantages of the im-pregnation process: the relative simplicity and pos-sibility of precisely obtaining materials with thedesired composition.

The goal of the present work was the applicationof this method for the preparation of Pt-WOxcatalysts on carbon black. Sols prepared with a veryTable. Weight changes (Am) and leaching results.

The results of thermal analysis of the samplesdried at 110°C as well as of the carbon black areshown in Fig.l.

Weight losses of impregnated samples start earlier(150°C) than pure carbon black due to losses of vola-tiles (H2O, ammonia and Cl"). Decomposition ofASC begins at 400°C and is accompanied by a large

Sample No, %Pt+W

and impregnation method used

Kl-10(onlyW)-l

K2-10-IM-1

K3-10-IM-2

K4-20-IM-1

K5-20-IM-2

Am, % (+ in the case of weight increase); in ( ) % of leached Cl' and inorganic species(calcined at 400°C)

Air

110°C,24h»

(0;0.5)

(2.5;1.4)

(3.4;0.7)

(0.3;5.1)

(0.3;5.6)

400°C, 0.5 h,Am after 1 h

9(0.3;0.16);12

ll(0.4;0.13);12

10(0.1;0.14);12

10(0.1;0.16);12

900°C, 10 h

90

87

82

82

Ar

9 0 0 ° C , l h "

10(0;0)

12 (0;0)

14(0;0)

IS (0;0)

H2

700°C, 1 h

+ 15

+9

+ 13

+7

* - starting samples for treatment at higher temperature in air and argon.* * - after these experiments parts of the samples were heated in hydrogen.

strong complexing agent (ascorbic acid-ASC) wereused as impregnating solutions. The application ofASC to sol preparation by the Complex Sol GelProcess (CSGP) has been patented by the INCT(Poland) and the ANL (USA) teams [2].

The starting saturated tungsten solutions wereprepared by dissolving (NH^WsOn • 2.5 H2O inconcentrated aqueous solution of ASC containing200 g/dm3, (solution No I) or in the solution diluted10 times (solution No II). In both cases the concen-tration of W (0.15 M) was similar. To both solu-tions an aqueous solution of HkPtCl,; (11 gPt/dm3)was added to the molar ratio of Pt:W=l:l. The re-sulting products were denoted I+Pt and Il+Pt,respectively.

Solution No Il+Pt (after dilution with water to atotal volume of ~ 170 cm3 per 10 g of carbon blackwas used for impregnation (method IM-2) of car-bon black Vulcan XC-72 (Carbochrom, Milan,Italy). Amounts of the starting sols were calculatedas to obtain 10 and 20% of Pt+W in the final pro-duct. Dilution of the starting solutions with waterwas necessary for complete wetting of the carbonblack. The impregnation was carried out in anultrasonic bath supported by mechanical stirringuntil black, creamy, homogeneous, very viscous slipwas obtained. In some experiments (denoted me-thod IM-1) W-ASC solution (II) diluted with waterwas added first to the carbon black followed by theaddition of respective Pt solutions. The obtainedslips were initially dried under an infrared lamp andthen at 110°C for 24 h. The thermal treatment athigher temperatures was carried out in an air, argonand hydrogen atmosphere.

It has been observed that in contrast to water theascorbate sols perfectly wet the carbon black. Nocrystallization of the added metallic compounds wasobserved. Consequently the slips were perfectlyhomogeneous.

exothermic effect in the region 400-700°C. Theshoulder on the DTA curve near 700°C correspondsto the final oxidation of pure carbon black.

The results of the calcination experiments atvarious temperatures and atmospheres and theleaching experiments of the dry residues are sum-marized in Table. At a temperature of 110°C a partof the compounds added during the impregnation

20

30

40

50

60

70

80

90

—w

> 7

i — ^ _

\

k t

1

1I

\

*

\

\

\\

V \ /X,V

1

i

A

t

1

too 300 500 700 900temperature, *C

Fig.2. Thermal analysis of carbon black (- - -) and catalyst (—)and 20% Pt+W (xxx) dried at 110°C.


process is loosely bonded and is easily leached withwater. Unexpectedly after leaching of the 20% Pt-Wcatalyst the extracted amounts of chlorides were 10times lower than for the 10% Pt-W catalysts.

In contrast to chlorides solid elements pass towater in amounts several times higher (approxi-mately 25% of the added amounts). After heating at400°C for 0.5 h the leached amounts of solid species

are significantly lower (<0.2%) and similar for alltypes of catalysts. Since further heating in air(Fig.2) is connected with high carbon losses thefinal thermal treatment of the catalysts was carriedout in an argon atmosphere at 900°C. In theseconditions only a limited weight loss is observedand no substances are leached. This indicates thatthe bonding of catalytic elements on carbon is ef-

black carbonVULCAN XC-72

air400°C -1h

Pt-WOx/C10% ]£ Me

argon900°C -1 h

hydrogen700°C -1h

Pt-WOx/C10% £ Me

Fig.3. SEM of carbon black and Pt-WOx/C catalysts prepared under various conditions (2Q*EL y


fective. Unexpected weight increases were alwaysobserved after heating the catalyst in a hydrogenatmosphere at 700°C. Since the only possible reac-tion is that with carbon black it means that ap-proximately 0.5 and 1 mole of H2 per mole of C,respectively for IM-2 and IM-1 technique, reactswith carbon. This suggests that in the latter tech-nique the activity of the catalyst is higher presum-

H I

568

« 9

It?

%

•wo, I

1 '»•

/[ ON A ixJl JI ^ *

FigAXRD patterns of Pt/WO3 powders prepared by CSGP.

ably due to the deposition of Pt on the surface ofthe formed tungsten species.

SEM micrographs of the carbon black and cata-lysts are shown in Fig.3.

In contrast to flocky surface of the carbon blackthe catalyst surfaces are relatively smooth. No signi-ficant differences were observed between the sam-ples prepared under various conditions.

Thin films on Ag and Ti substrate were preparedfrom solution (I-f-Pt) using the method elaboratedin the INCT [3]. It can be observed that after thethermal treatment (Fig.l) at coatings are very ad-herent and their cross-sections show that the layershave a uniform thickness.

Also Pt-WC>3 powders were prepared usingCSGP (Fig.l). Their XRD patterns, shown in Fig.4,indicate that Pt is homogeneously distributed inWO3.

References[1]. Giorgi L., Pozio A: Celle a combustibile ad elettrolita poli-

raerico solido. ENEA, Rome 1995, RT/ERG/95/0S.[2]. Deptuia A, tada W., Olczak T., Lanagan M., Dorris S.E.,

Goretta K.C., Poeppel R.B.: Method for preparing of hightemperature superconductors. Polish Patent No 172618, 2June 1997.

13]. Deptuia A, Lada W., Olczak T., LeGeros R.Z., LeGerosJ.P.: Preparation of Calcium Phosphate Coatings by ComplexSol-Gel Process (CSGP), Bioceramics. Vol. 9. Pergamon,Cambridge 1996, p. 313; Lamy C, Leger J.-M.: ibid, p. 477.

PL9802009

SYNTHESIS OF ELECTROCHEMICAL QUALITYLixMn2O4±<5 (x=0.55-l.l) POWDERS

BY THE COMPLEX SOL-GEL PROCESS (CSGP)

A. Deptuia, W. fcada, A. Ciancia17, L. Giorgi1'', F. Alessandrini1/

^ENEA-CRE-Casaccia, Rome, Italy

Spinels of LiMn2O4 type are currently used aspreferred cathodic materials for Li rechargeablebatteries. This type of batteries are frequently usedfor many applications due to several times higherenergy density e.g. than ordinary lead/acid battery.For this reason they are also very promising forelectric vehicles [1], The most frequently used waysfor preparation of these compounds for batteriesare solid state reactions of Li and Mn oxides, car-bonates, acetates, and nitrates. The main disadvan-tages of the solid state reactions are high tempera-ture and long time, generally higher that 700°C andseveral tens of hours, respectively. Also seriousproblems with scaling up from 10 to 200 g associat-ed with the LiMn2C>4 synthesis have been recentlyreported [2] for solid state reactions of Li and Mnoxides or carbonates, the most frequently used pro-cess.

The goal of the present study was elaboration ofa method for LiMn2C>4 synthesis using ComplexSol-Gel Process (CSGP) patented by the INCT(Poland) and the ANL (USA) teams [3] and suc-cessfully applied to the synthesis of high tempera-ture superconductors.

The starting aqueous solutions of molar concen-trations: acetates Li - 3.68, Mn - 1.57; hydroxidesNHt -12,1, Li+ - 3.9; were prepared. The startingsol-solutions were prepared in two different ways: I,in which ascorbic acid (ASC) was added to the

t

SgZ3DTA

iTG

% A m10

20

30

40

50

60

70

80

ff\tj * i

sQ^/} V\_,

FVj\ \

\\

100 300 500 700 900Temperature, *C

Fig.l. Thermal analysis of Li-Mn gels dried at 100°C for 48 h:AC (—) and AC+ASC (—); (MR ASC: 2Me=0.22:l).


20ouc, 2 h , i

+ 3(X!0C,2h>l+ UMn2O4

- U 2 C O 34. 0 Mn2O3| • M11O2

1 +

200°C, 2h,I

200°C, 24h,II

1

J+ 300°C, 2 h, 1

10 802-Theta 8010 2-thetaAC get ASCgei

Fig.2.XRD patterns of Li-Mn AC and ASC (MR ASC: 2Me=0.22:l) gels calcined in various conditions.

starting solution of Li and Mn acetate (AC) whose ammonia and II, in which LiOH was added to apH was adjusted to alkaline values with aqueous solution of Mn and NH4 acetates containing ascor-

1

100°C,48h,I

1 awe, 2 h, ]

Tr

«it< 1000 MOO

1 1

- ^ ^ \ r

300°C, 2h,l1600 1500 K»

1 1

IOO°C,«Ji,I

2<XfC, 2 h, 1

V 20Oc'C, 24 h, tl

1

Sr*/ VXPC, 2 h, I3000 ICOO 1600 1200 SCO1 1 I 1 1

AC gel ASC gelWivenumber, cm"'

Fig.3. Infrared spectra of Li-Mn AC and ASC gels (MR ASC: 2Me=0.22:l) calcined in various conditions.


bic acid. For evaluation of the CSGP results someexperiments, without the addition of ascorbic acid,were carried out. It has been observed that additionof ASC to the above starting solutions results inslower hydrolysis kinetics and completely preventsprecipitation, due to the strong bidentate networkof ascorbic acid. After several days, monolithic andhomogeneous, beige colored gels, were alwaysobtained from the starting ASC sols.

The results of thermal analysis of AC andAC+ASC gels are shown in Fig.l.

In AC gels, the thermal transformations are verydistinct. The first endothermic peak associated withthe elimination of water, some parts of ammoniaand acetates, appears in the region 150-200°C. Thelast sharp exotherm 380°C is associated with thedecomposition of lithium acetate. After this peakthe mass of the sample is constant from 400 to950°C. The thermal decomposition of AC+ASCgels is more complex. The main differences, as com-pared to the above described AC gels, are:- lower endothermic first effects, indicated by a

stronger bonding of volatile;- regular weight losses typical for amorphous ma-

terials;

Li Ac •Mn Ac2 —ASC —

- >->

NH4OH >

DissolvingH2O

j complex solution

Solformation

(complex

Evaporation undevacuum

r

sol

1 concentrated sol4-

Gelationand drying 8O-20O°C

4- dried gel, shard

Self-ignition240-280°C

4.Grinding

4-gelp

Calcination400°C- 8 h

1owd ers

4-calcined powders

Grinding

4-LiMn2O4

Irregularly shaped powders

- higher exothermic effects and mass losses due tohigher organic content;

- higher temperature of the end of the exothermictransformation (= 700°C).Moreover, it was observed that the main exo-

therm is larger for gels prepared with higher ASCcontent.

The differences between AC and ASC gels canbe seen from XRD studies (Fig.2).

The first one dried at 200°C for 2 h is a mixtureof crystalline Li and Mn acetates and their com-plexes with H2O and Am. ASC gel prepared byvariant II and calcined at 200°C for 24 h iscompletely amorphous. In the amorphous ASC gelprepared by variant I and dried at 200°C only for 2h formation of LiMn2C>4 starts. For a 2 h calcina-tion at 300°C, this process is very advanced. AC gelfired similarly shows XRD-structure of LiMn2O4accompanied by the admixtures of MnC>2+Mn2O3and U2CO3. The presence of CO3 in this sample isconfirmed by an IR spectrum (Fig.3).

In ASC gel calcined identically, only a very weakband of molecular water (3440 cm'1) and verystrong Me-O bands (520 and 620 cm'1) exist. Theabsence of CO3 bands for ASC gels confirms the

Mn Acj-ASC -

NHOH—>NH4AC—>Li OH >

Dissolving<-H2O

I complex solution

Solformation

complex sol

Evaporation undervacuum

4- concentrated sol

Gelation and drying80-200°C

I dried gel, shard

Self-ignition240-310°C

Grinding4- gel powders

Calcination400"C- 8 h

4-calcined powders

Grinding

4-LiMn2O4

Irregularly shaped powders

Variant J " Variant ,,II"

Fig.4. Experimental procedure for preparation of 1 kg batch of LiMn2O4 irregularly shaped powders by CSGP.

NUCLEAR TECHNOLOGIES AND METHODS

suggestion of the present authors [3,4] that duringthermal treatment in the presence of ASC, COinstead of CO2 is formed in the gels.

On the basis of the results we scaled up bothvariants to 1 kg of the final product in a run. Solswere concentrated under vacuum and gelled atelevated temperatures up to 135°G However, duringthe preliminary experiments it was observed that thethermal treatment of the resulting homogeneous gelto the desired temperature of several hundred °Cresults in very intensive foaming (the volume in-creases several times). This phenomenon negative -for a scaling up - can be avoided by introducing along duration preheating procedure followed by aself-ignition step. After self-ignition the sampleconsisted of loosely agglomerated powders, onlyslightly sintered on the surface. SEM analysis of thefinal powders has shown that the mean particleradius ranged from 1 to 10 /urn. The detailed experi-mental procedures are shown in Fig.4.

89

It seems that scaling up to a higher industrialscale should not face with difficulties.

Results of preliminary electrochemical propertiesof prepared materials are described in [5]. The over-all result of this preliminary electrochemical charac-terization can be considered as good.

References

[1]. Brousseley M., Planchat J.P., Rigobert G.F Virey D., SarreG.: J. Power Sources, 68,8 (1997).

[2].Manev V., Momochilov A., Nassalevska A., Sato A.: ibid, 54,323 (1995).

[3].Deptuta A., Lada W., Olczak T., Lanagan M., Dorris S.E.,Goretta K.C., Poeppel R.B.: Method for preparing of hightemperature superconductors. Polish Patent No 172618, 2June 1997.

[4].Deptuta A., Olczak T., Lada W., Goretta K.C., Di Bartolo-meo A., Brignocchi A.: J. Mater. Res., 11,1 (1996).

[5].Deptuia A, Lada W., Croce F., Appetecchi G.B., Ciancia A.,Giorgi L., Brignocchi A., Di Bartolomeo A.: In: New Ma-terials for Fuel Cell and Modern Battery Systems II. Eds. O.Savadogo, P.R. Roberge. Montreal 1997, p. 732.

SYNTHESIS OF ELECTROCHEMICAL QUALITY LiNio.5Coo.sO2 POWDERSBY THE COMPLEX SOL-GEL PROCESS (CSGP)

A. Deptuta, W. l^da, T. Olczak, A. Ciancia17, L. Giorgi17, F. Alessandrini1'

^ENEA-CRE-Casaccia, Rome, ItalyPL9802010

Lithiated transition metal oxides having a layeredstructure and the general formula LJMO2, havebeen extensively studied as positive electrode activematerials for lithium or lithium-ion batteries. Re-cently LiNixCoi.x02, especially at x=0.5, is beingconsidered for such applications because of itshigher capacity and lower material cost as com-pared to LiCoO2 [1]. LiNio.5Coo.5O2 is generallyprepared by solid state processes in which longtimes, high temperatures and an oxygen atmo-sphere are applied [1]. According to the best know-ledge of the present authors it has never been syn-thesized by the sol-gel process. The goal of thepresent study was the application of the ComplexSol-Gel Process (CSGP) patented by the INCT(Poland) and the ANL (USA) teams [2] to the fab-rication of high temperature superconductors. Theprocess has also been successfully applied to thesynthesis of LixMn2O4±<5 [3].

The starting sol-solutions were prepared in twodifferent ways: I, in which aqueous ammonia (Am)was added to the starting solution of Li+-Ni2+-Co2^acetate (AC)-ascorbate (ASC), and II in which LiOHwas added to the solution of Ni2+-Co2+ and NHtacetate-ascorbate. For evaluation of the CSGPresults some experiments, without the addition ofascorbic acid were carried out. Molar concentrationsof the starting solutions were: LiAC - 3.42 M; MAC2- 0.64 M; CoAC2 - 1.16 M, NH4OH - 12,1; LiOH -4.25 M. Solid ascorbic acid was added to the acetatesolutions.

Potentiometric titrations of the Li-Ni-Co(pH=6.5) with aqueous ammonia (to final pH=9,variant I) as well as of the Ni-Co-NH4 (pH=4.7)

acetate solution with LiOH (to pH=4.8) and Am(to final pH=8, variant II) indicate relatively quickhydrolysis (no inflection point on the. potentio-metric curve). In variant I the addition of NH4OHto acetate starting solution or in the presence of asmall amount of ASC (less than corresponding tothe molar ratio (MR) ASC:£Li+Ni+Co=0.15 re-

t11

SSZQDTAendo

iTG

'/.Am10

20

30

40

50

60

70

80

- •1

* i\

' H i

• - - ,- - -

100 300 500 700 900temperature, C

Fig.l. Thermal analysis of Li-Ni-Co gels dried at 140°C for 48 h:AC (- -) and AC+ASC, variants: I (—), II (xxx).


suits in the formation of a green precipitate (Ni2+

species) at pH=8. Larger amounts of ASC inhibitsthe precipitation due to the strong complexing ofthe cations by ascorbic acid. After several days ofgelation to violet, monolithic gels were observed forboth variants. It was due to the solvent evaporation;in a closed recipient the sols were liquid for severalmonths.

The gels prepared above (on the scale ~ 10 g ofoxides) were dried for 48 h at 140°C. Intensive foa-ming, especially for the gels of type I was observed.The results of thermal analysis of these dried gelsare shown in Fig.l.

Thermal analysis of the acetate precursor showsone exothermic effect at ~400°C which can beattributed to the decomposition of acetates. Thethermal decomposition of both types of theAC+ASC precursors is more complex. It seemsthat the first exotherm at ~ 350°C is connected withthe decomposition of the metal acetates. Thesecond one, composed of many superimposed ef-fects, observed in the temperature range 460-700°C,is mainly caused by the oxidation of complexcompounds formed by ASC decomposition. On thebasis of IR spectra (Fig.2) it can be supposed thatalso in this step carbonates are formed and partiallydecomposed.

For the temperature region 540-800°C weightlosses <15% were observed. During prolonged cal-cination in stationary conditions (Fig.2) weightlosses were 20-40%. It means that the amounts ofcarbonates formed in dynamic conditions duringthe thermal analysis were significantly lower thanduring the prolonged calcination. However, evenafter firing for 1 h at 800°C traces of carbonates are

°C h %CO3 d

140 24 0

300 1 32380 1 32 2.97

500 1 31 3.90500 10 20 4.48540 1 40 4.18

700 1 7 4.78700 10 2 4.70700 40 2 4.63

800 1 1 4.951000 1600 1200

Fig.2. Infrared spectra, % CO3 and density (d, g/cm^) of Li-Ni-CoASC gels (I) calcined in various conditions.

present. As follows from IR spectra distinct tracesof water exist after calcination at 600°C.

Fig.3 shows XRD patterns of the ASC gels cal-cined at various temperatures in air for 1 h. It can be

noted that the final LiNio.5Coo.5O2 structure occursfor samples fired for 1 h at 800°C.

A»i

r >o r•HOT,.. ID

1[I 800°C

f\ 700°C

rv• l a1 vNho, , 0 540'C

t i 440°C

| | 300°C

140°C

10 20 30 40 50 60 70 802 - Theta

Fig.3. XRD patterns of Li-Ni-Co gels ASC (I) calcined for 1 h atvarious temperatures.

The formation of a unique phase with the expect-ed layered (SG=R3m) structure in these conditionsindicates the advantage of CSGP over the solid

10 20 30 60 70 B040 502-Theta

FigAXRD patterns of Li-Ni-Co gels ASC (I) calcined at 700°Cfor various times (h).


state processes in which longer times, higher tem-peratures and an oxygen atmosphere are commonlyused [1]. The XRD patterns shown in Fig.4 indicatethat a similar effect can be obtained for samplesheated for a longer time at 700°C.

However, the shape of the peak at 2 6 - 3 9suggests the presence of small amounts of unre-acted NiO. However, even a prolonged heating (upto 40 h) does not lead to positive results at 500°C.

On the basis of the results we scaled up bothvariants to 200 g of the final product in a run.However, during the preliminary experiments it wasobserved that the thermal treatment of the resultinghomogeneous gel to the desired temperature of

The foaming was not observed only for very thicklayers (several tens of ^m) prepared on metallicsubstrates (Al, Ag and Ti) from concentrated sols(diluted with ethanol) by the technique described in[4]-

Apparent densities of many samples were mea-sured. They are shown in Fig.3. The materials pro-duced on a large scale, heated for 1 h at 800°C hadlower densities (I - 4.78 g/cm3 and II - 4.83 g/cm3)than those obtained on a laboratory scale. Furtherheating increases the density to a similar value (4.94g/cm3).

Results of preliminary electrochemical proper-ties of the prepared materials are described in [5J.

Li Ac (5.1 M)~>Ni Ac2 (0.64M)-CoAc2(1.2M)-

Dissolving,& Blending

ASC:£MeMR-0.5

NH«0H(11.8M)-*topH=9

I complex solutionSol

formation

4- complex sol,Evaporation under

vacuum

I concentratedI >2M£Mesol,4-viscosity 912 cSt

Gelation and Drying60DC,4h-80,48-100,24-125,24-150*.144-

170,24-200,100;solidification

i dried gel, shardGrinding

in agate mortar

i gel powdersself-ignition step, 390°C, than firing for

13hat8OOeC

*- limited foaming (..balloon" formation, 2times increasing in volume)

Ni Acj(0.64 M) •CoAcj(1.2M) HASC:2MeMR=-=0.5

Dissolving& Blending *-HjO

I complex solutionI pH= 4.3

to pH=4.74Li OH (4M)[ to MRLi:(Ni Co>= 0.5] | complex sol

i pH=4.86

Acidic solformation

NH4OH(11 8M)->Alkali- Solformation

I complex soL pH=8Evaporation undervacuum

I concentrated sol.I ~2M ZMe in sot•Iviscosity 1360 cSt

Gelation and Drying60"C,4h-80,48-100,24-125.24-150,144-170.24-200.100;iolidification

4 dried gel, shard

Grindingin agate mortar

gel powdersself-ignition step, 390"C, than firing for

!3hat8OO'C

Variant I Variant IIFig.5. Experimental procedure for preparation of irregularly shaped powders LiNio.5Coo.5O2 (0.2 kg/batch) by Complex Sol-Gel

Process.

several hundred °C results in a very intensive foam-ing (the volume increases several times). Therefore,similarly as in our former work [3] concerned withthe fabrication of LiMn2C>4 a long duration pre-heating procedure followed by a self-ignition step (at>400°C) were applied. The detailed experimentalprocedures are shown in Fig.5.

It was observed that for this scale a longer heat-ing time was necessary for obtaining the desiredfinal product. SEM analysis of the final powders hasshown that the mean particle radius ranged from 1to 10 ftm. It seems that further scaling up to theindustrial scale should not face with serious dif-ficulties.

The overall result of this preliminary electroche-mical characterization can be considered as good.

References[1]. Li C.W., Currie J.C.: J. Electrochem. Soc., 144,2773 (1997).[2]. Deptula A., fcada W., Olczak T., Lanagan M., Dorris S.E.,

Goretta K.C., Poeppel R.B.: Method for preparing of hightemperature superconductors. Polish Patent No 172618, 2June 1997.

[3]. Deptula A., Lada W., Croce F., Appetecchi G.B., Ciancia A,Giorgi L., Brignocchi A., Di Bartolomeo A.: Synthesis andpreliminary electrochemical characterization of LixMn2O4(x=0.55-l.l) powders obtained by the Complex Sol GelProcess (CSGP). Second International Symposium on NewMaterials for Fuel Cell and Modern Battery Systems, 29June-3 July 1997. Proceedings, New Materials for Fuel Cell


and Modern Battery Systems II. Eds. O. Savadogo, P.R.Roberge. Montreal 1997, p. 732.

[4]. Lada W., Deptuła A , Olczak T., Torbicz W., Pijanowska D.,Di Bartolomeo A : Preparation of Thin SnO2 Layers by Inor-ganic Sol-gel Process. J. of Sol-Gel Sci. and Technol., 2, 551(1994).

[5]. Croce F., Deptuła A, Lada W., Marassi R., Olczak T., RonciF.: Electrochemical Characterization of Lithiated MixedNickel-Cobalt Oxides (LiNixCoi-xO2) Prepared by Sol-gelProcess. 4th Euroconference on Solid State Ionics - RenvyleHouse Hotel Connemara, Co. Galway, Ireland, 13-19 Sep-tember 1997 (to be published in "Ionics").

AN ATTEMPT TO DETERMINE MAJOR AND TRACE ELEMENTSIN ANCIENT GOLD AND SILVER ARTIFACTS OF MATERIAL CULTURE

BY REACTOR NEUTRON ACTIVATION ANALYSIS

PL9802011L. Rowińska, E. Pańczyk, J. Andrzejewski1/, B. Sartowska, L. Waliś

11 National Archeological Museum, Warszawa, Poland

In the Department of Nuclear Methods of MaterialEngineering of this Institute in collaboration withthe Academy of Fine Arts and the National Museumin Warszawa and recently also with the National Ar-cheological Museum in Warszawa, systematic stud-ies of art objects are carried out using nuclear me-thods. The high sensitivity of these methods makes itpossible to determine trace elements present in e.g.pigments (lead white, yellow-white tin-lead smalt) aswell as in ceramic and geological materials at ex-tremely low concentration levels. The content oftrace elements is a "fingerprint" of lead ores, claydeposits, marble or alabaster and is characteristic ofthe mineral and its geological history.

For this purpose mainly two methods were used:- instrumental neutron activation analysis,- X-ray fluorescence analysis.

These techniques have also been used for theexamination of archeological objects. The maingoal of such studies is to determine the age andplace of origin of the examined art object or objectof daily use and identify the material from whichthe object was made.

Preliminary studies were devoted to four silverand gold artifacts from the collections of the De-partment of Iron Age of the National ArcheologicalMusem in Warszawa dated from the 1st century B.Cto the Vth century AD. So far the material ofwhich the objects were made was determined on thebasis of the silvery or golden colour of the metal.Table 1. Description of the samples examined.

No ofsample

1

2

3

4

Object examined

Brooch-Nadkole, stand 2, tomb 51, inventoryNoIV/8283/POL440

Pendant- Nadkole, stand 2, tomb 44 b, inventoryNoIV/8283/POL410

A fragment of ornament - Nadkole, stand 2, tomb58b, inventory No IV/8283/POL 889

Pin-Nadkole, stand 2, tomb 114, inventoryNo IV/8283/POL889

The purpose of these studies was to obtain infor-mation, enabling further studies on ancient tech-nologies and goldsmith techniques, on the locationand range of the activities of goldsmith workshops,on the creation and adaptation of new decorationstyles as well as on the commercial links within the

territory inhabited by barbarian tribes and theirconnections with the Roman Empire.

Bearing in mind the character of the artifacts,studies should be carried out by nondestructivemethods or using very small samples .

Preliminary analyses of the samples supplied bythe National Archeological Museum and describedin Table 1 were carried out by instrumental neutronactivation analysis (INAA). The analysis has yieldedvaluable data on the contents of Ag, Cu and Au.

However, the determination of trace elements inthese materials by the INAA method is difficult be-cause of the Compton continuum, generated by themajor elements and resulting in a decrease in theaccuracy of the measurement of the photopeakstrace elements [1-4].

Samples of 0.02 g and smaller were irradiated ina nuclear reactor at a thermal neutron flux of8xlO13 n-cm"2-s4 for 0.5 h. Standards of Au, Cuand Ag of known weights were irradiated under thesame conditions in order to establish the relation-ship between the mass of the element examined andthe radioactivity of the radioisotope formed.

The measurement of radioactivity of the obtainedradioisotopes were carried out using a CANBERRAS-100 multichannel analyser with an HPGe detector.

The studies have shown that all the samples exa-mined contain gold and silver. Samples 3 and 4contain also copper. Sample 2, in addition to goldand silver, contains an element which does not formradioactive isotopes under the applied conditions ofirradiation; this may be lead. The precision of themeasurements in terms of the coefficient of varia-tion V=100% S/X (where S-standard deviation,X-mean) is 3-8%. The quantitative composition ofthe samples is given in Table 2.Table 2. Mean contents of silver, copper and gold in the samples

examined.

No of sample

1

2

3

4

Ag[%]

26.9

26.8

95.4

93.2

Cu [%]

-

-

2

4.14

Au [%]

75.04

48.4

0.28

0.3

The results obtained by INAA were not consis-tent. This suggests that the samples were not repre-sentative due to the heterogeneity of their composi-


tion. Therefore additional studies were carried outusing a scanning microscope SEM DSM942 (ZEISS)and an X-ray microprobe (LINK).

The examination was carried out for samples 2and 4 for which the results of INAA were not uni-vocal. Photographic documentation was preparedand characteristic X-ray spectra of the samples weremesured and analysed.

Phot.1 shows the shape and dimensions of sample2. Phot.2 shows the surface of sample 2. Craters ofvarious shape and dimensions can be seen.

analysis for the porous spot gave the followingresults: Ag - 48.09%, Cu - 23.825, O - 20.53% S -4.90%, C -1.67%, Si - 0.99%. For the second spot,

Phot.l.

Using the Link system, characteristic X-ray spec-tra were obtained for the two spots seen in Phot.l,the dark and the light one.

The quantitative analysis carried out for the lightspot yielded the following results: Au - 68.67% Ag -25.59%, Fe - 4% Mg -1.21% and Zn - 0.52%.

For the dark spot the following results were ob-tained: Au - 74.77%, Ag - 25.49%. The content ofadmixtures was below the determination limit. Forboth spots Pb, Bi and Sn were not found.

Phot.3.

the smooth one, the following results were ob-tained: Ag - 90.96%, O - 7.43%, Cu - 1.33%, Si -0,345%, S - 0.02%, C - 0.08%.

The studies of the monuments made of gold andsilver have shown that univocal results can beobtained only by the application of complementarymethods. Neutron activation analysis yields reliableresults only in the case of samples taken from spotswhere the material is homogeneous and represen-tative for the whole object. Therefore preliminaryanalysis by means of a microscope is necessarry.However, preliminary analyses carried out so farhave shown that the material examined is relativelyless contaminated. This may suggest that the orewas obtained by the ancient jewellers from nuggetsof local deposits.

Phot.2.

The shape and dimensions of sample 4 are shownin Phot.3. Its surface is shown in Phot.4. The porousstructure of the examined material can be seen.

Analysis of the characteristic X-radiation wascarried out for the two spots seen in Phot.3, thevery porous one and the very smooth one. The

Most of the objects to be examined is made fromdelicate filigree and granulation and belongs to thetop class of goldsmith works. From some of theobjects small samples of the order of hundreds ofmicrogrammes can be taken and activation analysis(with the above mentioned limitations) can be usedfor quantitive analysis. In order to apply the ac-tivation method to the determination of trace


elements it is necessary to separate the majorelements [2-4].

However, a great deal of the objects examinedconsist of appliqu6 and incrustations on the artif-acts made from other metals (bronze, brass, iron)from which samples cannot be taken. In such casethe elemental composition of the sample can bedetermined and semiquantitative analysis carriedout by the X-ray fluorescence method.

References[1]. Meyers P., van Zelst L., Sayre E.V.: Determination of Major

Components and Trace Elements in Ancient Silver by Ther-

mal Neutron Activation Analysis. J. Radioanal. Chem., 16,67-78 (1973).

[2].Schubiger P.A., Muller O.: Trace Elements in Ancient SilverCoins by Neutron Activation and Solvent Extraction withBismuth Diethyldithiocarbamate. Radiochem. Radioanal.Lett., 24, 353-362 (1976).

[3]. van Dalen A , Das H.A., Zonderhaus J.: Non-DestructiveExamination of Roman Silver Coins by Neutron ActivationAnalysis. J. Radioanal. Chem., 1 1 143-149 (1973).

[4]. Hancock R.G.V., Farquhar R.M., Pavlish L.A., FinlaysonW.D.: Chemical Analysis of Copper and Brass Samples fromChristian Island, Georgian Bay, Ontario. J. Radioanal. andNucl. Chem., 126,255-266 (1995).

PL9802012PULSED PLASMA BEAM MIXING

OF TITANIUM AND MOLYBDENUM WITH SAPPHIRE

J. Piekoszewski, E. Wieser1', J. Langner27, R. Groetschel17, H. Reuter17, Z. Werner27

Forschungszentrum Rossendorf, Institut fur Ionenstrahlphysik und Materialforschung, Dresden,Germany

27 Sottan Institute for Nuclear Studies, Otwock-Swierk, Poland

A wealth of information was published in the lastdecade on the results of experiments on the forma-tion of alloys and chemical compounds on the sur-faces of materials by means of ion beams (ion im-plantation and ion mixing techniques) and laserbeams.

In the former case mixing of an alloyed consti-tuent (most often metallic) with a substrate appearsas a result of superposition of the three followingprocesses: displacing impacted atoms (ballistic mix-ing, BM); diffusion through radiation-generateddefects (radiation enhanced diffusion, RED); anddiffusion caused by a chemical potential gradient,leading to the formation of a new phase or newphases. The first process is a short-range one (be-low < 100 am). The other two may lead to a long--range mixing (several micrometers).

In case of laser techniques, the near-surface layerof a metallic film-substrate structure is molten by acontinuously scanned or a pulsed laser beam ofpower in the range lO^lO8 W/cm2. Since migrationof atoms in the liquid phase is by 7 orders ofmagnitude (or even more) higher than that in thesolid phase, an effective mixing of a film-substratestructure may take place in time as short as severaltens of nanoseconds; it is a consequence of a veryeffective diffusion of both structure constituents.

As was shown in our previous works devoted tometal-metal structures, the Deposition by PulsedErosion (DPE) version of intense plasma pulsestechnique (under development in the Softan In-stitute for Nuclear Studies at Otwock-Swierk) ispotentially capable of alloying (mixing) also the ce-ramic-metal structures. The method exhibits somefeatures of both the above mentioned techniques(ion beams and laser beams). During the DPEprocess, a plasma pulse containing ions of a select-ed metal (e.g. Al, Cu, Ti, Ni, Mo) and ions of aworking gas in which the discharge takes place (e.g.

N, Ar, H, Xe) supplies to the substrate a portion ofenergy sufficient to melt its near-surface layeranalo-gously as in the case of a laser beam treatment.However, the transport of mass takes place simulta-neously, as in the case of an ion beam treatment.

A series of experiments aiming at determiningthe efficiency of metallization of AI2O3 (sapphire)and polycrystalline Si3N4 ceramics by the DPEmethod has been conducted within the reportedperiod. The main difference between both the men-tioned materials - from the DPE application pointof view - lies in the fact, that the former ceramicmelts in 2030°C (in normal conditions), whereasthe latter one does not exhibit any liquid phase, andat a temperature of 1900°C decomposes or inten-sely evaporates. Some results obtained for AI2O3samples irradiated with Mo-N and Ti-N plasmapulses are briefly discussed below.

Experimental conditions: mean energy density ofpulses generated in the rod-type plasma generatorIBIS: 5.5 J/cm2; delay times: t=160,180 and 200 s(for 160 fis plasma is rich in metal ions, poor innitrogen ions, on the contrary for 200 ps); numberof subsequent pulses: 5. The irradiated sampleshave been characterized in FZR by the followingmethods; secondary and back-scattered electronimages observed in SEM, EDX microprobe analy-sis, RBS spectra, AES measurements.

Computer simulation of thermal evolution in sap-phire irradiated with pulses of plasma lasting morethan 1 s, and carrying energy densities of the order ofthe experimentally encountered ones, showed thatduration of the molten phase does not depend on theenergy level; it amounts to about 10 ,MS. On the otherhand, the melted depth for pulses of duration 5-1 samounts to 0.7 to 1.7 pm.. Therefore one can easilyestimate that during the melt time (50 <s at 5 pulses)the diffusion range is approximately 0.5 /*m (takinginto account a typical value of diffusion constant for

NUCLEAR TECHNOLOGIES AND METHODS

impurities in molten phase D=5xlO"5 cm2/s). Onecan then expect that mixing in AI2O3 might occur atthe depth of a fraction of micrometer provided othernecessary conditions are met.

A detailed analysis of the results of sample cha-racterization provided the following observationsand conclusions. There is a very pronounced dif-ference in the topology of samples irradiated withthe Mo-N and Ti-N plasma.

In the former case one can see microdroplets, netof microcracks and gaps on the surface. Number anddimensions of microdroplets are the largest fort=160 ^s and diminish with increasing t. Microdrop-lets consist mainly of Mo. Between them there existsa thin layer also containing Mo with surface concen-trations Ns=1.6xlO17, 4xlO16 and 2xlO15 cm"2 fort=160,180 i 200^, respectively. The Ns value doesnot vary between gaps and outside of them.

In the latter case (Ti-N) there appears a homo-geneous layer without microdroplets and with notvery abundant gaps, but with a visible net of micro-cracks. A sub-layer of Ti-N appears down to a depth5 nm; the deeper layer is composed of metallic

95

titanium. The surface concentrations of Ti amountto 1.8xlO17, 3.2xlO16 and 3.2xlO16 cm'2 for t=160,180 and 200 s, respectively.

In case of Ti a distinct mixing of deposit withsubstrate takes place up to a depth of about 0.5 pm.It is not yet clear whether the mixing is connectedwith the formation of titanium-oxygen and/or tita-nium-aluminum compounds or alloys, or if tita-nium is an impurity dissolved in sapphire.

Conclusions drawn from the above reported re-sults:- A capability of the DPE version of the intense plas-

ma pulse technique to perform a long-range mixingof deposit with substrate in the Ti/Al2O3 structureshas been proved. Previous attempts of other au-thors aiming at obtaining mixing in this structureby means of ion and laser beams have failed.

- Further experiments are required in order todetermine the chemical state of titanium alloyedinto a sapphire substrate and to clarify the ques-tion whether the thin metal (Mo, Ti) layer ob-served on the substrate is formed cumulatively oronly during the last pulse.

MODIFICATION OF SILICON NITRIDE CERAMICSWITH HIGH INTENSITY ION PULSES

PL9802013

F. Brentscheidt1', J. Piekoszewski, E. Wieser17, J. Langner27, R. Groetschel17, H. Reuterv

11 Forschungszentrum Rossendorf, Institut fur Ionenstrahlphysik und Materialforschung, Dresden,Germany

21 The Andrzej Soitan Institute for Nuclear Studies, Otwock-Swierk, Poland

Samples were irradiated and characterized similarlyas in the previous task, except that the number ofpulses was 10, and the mean energy density wasabout 6.5 J/cm2. Additionally some tribologicaltests were performed during characterization. Theresults allow to make the following statements.

Ni-rich microdroplets are the more abundant inNi/Si3NT4 structures the shorter the delay time t. Athin layer exhibiting a strong 1617 eV line in theAES spectra covers the area between the micro-droplets; the line is characteristic for nickelsilicides. This can be understood by taking intoconsideration the fact that the substrate materialdecomposes, providing a source of silicon forformation of silicides. The outer sub-layer consistsmainly of pure nickel. Because of presence of themicrodroplets, broadening of the main line in thelow-energy part of the RBS spectra may not, in anycase, be interpreted as a result of mixing.

Long-range mixing does not take place also inthe Ti/Si3N4 structures. Some narrow surface peaksappear in RBS spectra in case of these structures,whereas the low-energy part of the spectra is even.The Ti presence only on the surface is confirmed bya sequence of shifts of Si edges; the sequencedepends - in agreement with expectations - on thevalue of time t. Surface concentrations Ns oftitanium amount to lxlO17 and 2.4xlO16 cm'2, for160 and 170 ^s, respectively. For larger delays theconcentration falls below the detection limit of the

RBS method. The surface layer consists of a mix-ture of Ti, TiSi and TiNx. Presence of the latter isconfirmed by the 416 eV line that appears next tothe 419 eV line in AES spectra, whereas presenceof TiSi - by the 1617 eV line that appears next tothe 1612 eV SiaN4 line. Differences in the morpho-logy of surfaces of the samples bombarded by Niand Ti plasma may be explained by a larger surfacetension of the liquid Ni phase (1.74 N/m) than thatof Ti (1.57).

In spite of lack of a long-range mixing, structuresof both types exhibited in the "ball-on-disk" test(10 000 cycles) about a tenfold increase of the wearresistance. A similar result may be brought about bysome conventional ion implantation (according toinvestigations performed earlier in FZR). Improve-ment of the wear resistance did not clearly dependon the amount of deposit in the delay time ranget=160-200 ^s. The improvement was attributed tothe following factors:- melting and distributing the binding component

over the microcracks,- formation of new phases generating a squeezing

strain that restrains propagation of microcracks,- ablation of the surface-defected material.

The above results were presented on the "Mo-dification of ceramics and semiconductors by ionbombardment" International Conference held onMay 19-23,1997 in II Ciocco, Italy, and accepted forpublication in "Materials Science and Engineering".


NEW MATERIALS CONTAINING SILVERON SUPPORT SURFACE AS POTENTIAL CATALYSTS

A. Lukasiewicz, L. Walls', J. Michalik, J. Sadto

Interest in the supported silver catalysts, e.g. onzeolites, is growing continuously [1,2]. It has beenfound earlier [3] that the thermal decomposition invacuo of polymerized aminotriazole complexes withsilver acetate on a mineral support leads to sup-ported free silver agglomerates.

The polymerized aminotriazole complexes withtransition metals are investigated at this Institute forseveral potential applications [3-5]. They have a ge-neral formula M Anatr2(p), where M - transition me-tal (Cu2+, Co2 + , Ni2 + , Ag+) or two different metals,A - CH3COO, n = l or 2, atr - 3-amino-l,2,4-triazole,(p) stands for the complex polycondensed withformaldehyde. They are denoted further by MAXp(X=atr). MAXp complexes bind effectively fromaqueons solutions to mineral supports (silica, clays,zeolites). Thermal decomposition of MAXp comp-lexes in vacuo leads to a free metal [3] or to a mixtureof free metal and metal carbides [6].

Supported (Ag++M2) AXp complexes containingsilver and metal M2 (Cu2+, Co2+ , Ni2+) have beenprepared by quantitative binding of complexes (10 cm3

of 1% solution) to the support (1 g of 4 A zeolite).Supported complexes (for various Ag+/M2 pro-

portion) were decomposed by heating (500°C ) invacuo and the materials obtained were analyzed byESR spectroscopy. Shape of the ESR signal (freeAg) depended on the M2 metal and was more

narrow for M2=Co2 + and Ni 2 + as compared withSilver alone [3]. It suggests the formation of smallersilver agglomerates in presence of a second metal.For M 2=Cu 2 + the shape of ESR signal (AgCu) de-pended strongly on the Ag+/Cu+proportion andsuggested the formation of a complicated AgCucombination. This combination is analyzed.

New supported {Ag AXp+nCu (OAc)2> comp-lexes have been also obtained (n is molar propor-tion of copper acetate to Ag and maximally n=4)and were decomposed thermally to s-Ag.nCu ma-terials. These materials are being still investigated.

The {Ag AXp+nCu (OAc)2> complexes belongto a new group of MAX complexes combined withsome metal salts [7].

Supported s-Ag/M2 and s-Ag.nCu materials areinterested as a new type of potential silver catalysts.

References[1]. Sun T., Seff K.: Chem. Rev., 94,857 (1994).[2]. Bousgard P J.E., Siegbahn P.E.M., Svensson M : Chem. Phys.

Lett., 231,337 (1994).[3]. Lukasiewicz A., WaliS L., Michalik J., Sadlo X: Mater. Lett.,

29,149 (1996).[4]. Lukasiewicz A , WaliS L.: Mater. Lett., 30,249 (1997).[5].Najer A., Parnowska W., Lukasiewicz A : Acta Polon.

Pharm., 54,203 (1997).[6]. Lukasiewicz A , WaliS L, Grigoriew H., Kaszuwara W.,

Leonowicz M.: Mater. Lett., 30,83 (1997).[7]. Lukasiewicz A., Walis" L., Panasiewicz J.: in press.

lo

POTASSIUM DETERMINATION IN ANCIENT GLASSESBY DETECTION OF ITS NATURAL GAMMA RAY ACTIVITY

J.J. Kunicki-Go!dfinger1/, J. Kierzek11 Institute for Conservation and Restoration of Cultural Property, Nicholas Copernicus University

of Torun, Poland

Potassium is one of the most important ingre-dients of historical glass objects from the earlymedieval period till the end of the 18th century. Adecrease in its concentration in corroded surfacelayers is a limiting factor for the use of numerousmethods of surface analysis. The fully non-destruc-tive gamma ray spectrometry method is free ofthese limitations. Till now the problem of utilizingthe natural radioactivity of historical glass has re-ceived little attention. Only a few communicationsare reported in the literature. Murray and Haggith[1] and later Festag, Gentner and Miiller [2] exa-mined the uranium content. Hudson and Newton[3] used radiation monitoring films to determinethe amounts of potassium in medieval glass by mea-suring beta activity. Their results have been verifiedby Cox and Gillies [4]. The glasses produced beforethe end of the 18th century contained only radio-active nuclide, 40K. Uranium may be found in glassmade later (19th century). Rubidium, the thirdradioactive element which may appear in old glass,

may be ignored because of its trace content and avery low radioactivity.

The purpose of this study was to find the possi-bility of measuring the potassium content of histo-rical glass objects by gamma ray spectrometry.

The measurement of 1460.8 keV gamma radiationfrom the radioisotope **K was performed by a gammaray spectrometric system containing an HPGe detectorwith the resolution of 1.91 keV and a relative detectionefficiency of 92.4% for the 133 MeV gamma line. Theabundances of the natural isotopes of potassium are asfollows: 39K - 93.08%, K - 0.0119%, * K - 6.91%. Theradioisotope 40K decays with a half-life of 1.28-109

years. The radiation emitted are beta particles with 1314keV endpoint energy (89.3% yield), gamma rays of1460.8 keV energy (10.5%) and characteristic Ar X-raysfollowing the electron capture (EC).

The natural background spectrum contains a1460.8 keV peak and it was reduced by the use of 10cm passive lead shield lined with 0.5 cm cadmiumand 0.5 cm copper. The reduction factor was 274.


In order to determine the content of potassiumin objects of irregular geometry it was necessary tomake moulds corresponding to shape of the speci-mens to be analysed.

Three measurements were made in each case inthe initial part of experiment:(a) on an empty mould (the background),(b) on a mould with the glass object inside,(c) on a mould filled with a potassium sulphatepowder which was used as a reference source.

As the natural background radiation did not varyduring the course of the analysis, subsequent testswere carried out on (b) and (c) only.

We found that a silicon rubber (RTV) was thebest material for the moulds. However, an alumi-nium foil and a dental wax are also suitable. Thetype of material for the moulds is not significantprovided that it does not contain potassium.

To increase the accuracy, the measurement timeswere in the range from 10000s to 120000s. The ap-proximate statistical error was about ±6%.

The K2O content in the glass was calculated fromthe results obtained by the measurement of the glassobjects and the mould filled with potassium sulphatehaving the same shape as the measured objectTable 2. Gamma spectrometry result of glass objects analysis.

Table 1. Comparison of gamma spectrometry and AAS results ofglass plates.

Glass plates

No

1

2

3

4

5

6

AAS'

K2O,%

19.7

15.7

11.5

9.57

5.15

1.09

Gammaspectrometry

K2O, %

20.0

16.1

11.6

9.2

5.04

1.04

• AAS analysis of samples conducted by the Polish GeologicalInstitute (PIG) in Warszawa.

The results of potassium content in 11 glassobjects with their description and the place oforigin are presented in Table 2. In all objects thepotassium content was also determined using othermethods. Some of reference methods were appliedonly for the surface analysis (e.g. scanning electronmicroscopy - samples 4 and 5). In atomic absorp-tion spectrometry to avoid the damage to the object

No

1

2

3

4

5

6

7

8

9

10

11

Glass object

Body and neck of bottle. Greenish. Weathered. 1 half of 18th c. (Royal Castle,Warszawa [ZK/95/6/98])

Stem of goblet. Colourless. Unweathered with the naked eye. Around 1730/Lubaczow?/ (National Museum, Warszawa [SZS mag. 486])

Foot of glass. Green glass. Weathered. 18th c. (Royal Castle, Warszawa[ZK/95/23/0])

Fragment of bracelet. Dark brown. Weathered. K2O-PbO-SiO2 type.12th/13th c. /?/. (PMA, Warszawa [V/VI/1235, no 4])

Fragment of bracelet. Dark brown. Weathered. K2O-PbO-SiO2 type.12th/13th c. /?/. (PMA, Warszawa [V/VI/1235, no 2])

Fragment of glass. Weathered. (J6zwik6w, district Radoszyce, voiv. Kielce[inv. no 56/94/17])

Fragment of greenish glass. Weathered. (Biaia Glina; district Mni6w,voiv. Kielce [inv. no 2c/94/7])

Fragment of colourless glass. Weathered. (Nowa WieS, district Strawczyn,voiv. Kielce [inv. no lc/94/3])

Fragment of greenish glass. Weathered. (Widetki, district Daleszyce,voiv. Kielce [inv. no 13/94/6])

Fragment of green glass. Weathered. (Cisow, district Daleszyce, voiv. Kielce[placel.inv.no 7/94/8])

Goblet. Colourless. Unweathered with the naked eye. Naliboki, 18th c.(National Museum, Warszawa [SZS mag. 446])

Weight, g

80.8

252.0

25.7

3.3

2.562

8.98

21.06

14.59

15.72

11.742

73.440

K2O,%

Gammaspectrometry

13.4

14.9

6.3

18.6

16.5

9.0

7.1

11.4

15.7

6.01

20.0

Comparativeresults

14.69

14.82

6.33

15.8

17.0

8.0

6.2

11.4

14.4

6.0

18.6

The performance of the measurement methodwas tested using a set of 6 glass plates (35x35x5mm) with a variable potassium content. The mouldof the same shape filled with K2SO4 was used as astandard. The potassium content in glass plates wasdetermined by atomic absorption spectrometry. Theresults of comparison are shown in Table 1. Theagreement of results was acceptable.

only a very small amount of glass was used foranalysis. In gamma spectrometry measurements theresults represent the bulk content of potassium andare therefore more representative. In this way theinfluence of glass weathering is also avoided. Onthe other hand, the use of mould for each measuredobject eliminates the influence of the shape of theobject.


References[1]. Murray S., Haggith J.: The estimation of uranium in colored

glasses. J. Glass Stud., 15,184-186 (1973).[2], Festag J.G., Gentner W., Miiller O.: Search for uranium and

chemical constituents in ancient roman glass mosaics. In:Applications of nuclear methods in the field of works of art.International Congress, 24-29 May 1973, Rome-Venice.Accademia Nazionale Dei Lincei, Rome 1973, pp. 493-503.

[3]. Hudson AP., Newton R.: A means for the in-situ identifica-tion of medieval glass by detection of its natural radioactivity.Archaeometry, IS (2), 229-232 (1976).

[4]. Cox G.A, Gillies K.J.S.: The X-ray fluorescence analysis ofmedieval durable blue soda glass from York Minster. Ar-chaeometry, 28 (1), 57-68 (1986).

!S100i CD

PEN AS A MATERIAL FOR PARTICLE TRACK MEMBRANES

W. Starosta, D. Wawszczak, M. Buczkowski

Polyethylene naphthalate (PEN) is chemically re-lated to commonly applied polyethylene terephtha-late (PET) but its mechanical, thermal and gasbarrier properties are much better in comparisonwith the PET ones. PEN is made by a processsimilar to that one used for making PET, startingwith ethylene glycol and dimethyl 2,6,naphthalendi-carboxylate. The structure of a PEN monomer unitis shown in Fig.l.

aD / = \ II

Fig.l. The scheme of PEN monomer unit.

PEN biaxially oriented films are commerciallyavailable at present (the thinnest - 25 m) and sup-plied by ICI Polyester and DuPont. Some of physi-cal an chemical properties of PEN and PET poly-mers are shown in Table [1],Table. Comparison of some of PEN and PET properties.

Parameter

Glass transition temperature

Continuous use of temperature

Shrinkage (190°C, 5 min, MD)

Tensile strength (MD)

Hydrolysis resistance (retentionof tensile strength, 90°C, 1689 h)

Water vapour transmission

Weathering resistance (time to50% reduction in tensile strength)

Young's modulus

PEN value

120°C

180°C

<0.8%

200 MPa

90%

3.6 g/m2/day

1500 h

5000 MPa

PET value

78°C

130°C

>2%

195 MPa

30%

20 g/m2/day

500 h

4000 MPa

For many years PET films have been used forParticle Track Membranes (PTMs) manufacturing.PTMs, having fine cylindrical pores and smoothsurface, are advanced technology material for use inmicrofiltration processes. The maximum thicknessof a PET film used for PTM preparation was 20 m[2],

Considering the better properties of PEN as apolymeric material it is interesting from the scien-tific and technical point of view to investigate thepossibility of PTM preparation using PEN films.

Two sorts of PEN films (25 fim in thickness)Kaladex™ by ICI Polyester and by DuPont wereused in experiments. The samples were irradiated ina heavy ion cyclotron at the Florov Laboratory of

Nuclear Reactions, JINR in Dubna. The fluence ofheavy ions beam was equal to 3 108 ions/cm2^"1.The samples, irradiated with heavy ions, were sen-sitized with UV radiation and then chemically etch-

Fig.2.The fracture of PEN (Kaladex™ ICI Polyesters) trackmembrane with mean value of pore size - 0.50 ftm (SEMphotograph).

ed with a 6N NaOH solution, using a standard pro-cedure elaborated for PET and as a result particletrack membranes with PEN films have been ob-tained. Their properties have been investigated byusing a SEM and Coulter® Porometer II instru-ment. A general view of fractures of above mem-brans are shown in SEM photos (Figs. 2 and 3).

Results from Coulter Porometer II instrument:differential flow distribution and pore numberdistribution are given in Fig.4. Narrow distributions

Fig.3.The fracture of PEN (DuPont) track membrane with amean value of pore size - 0.14 pm (SEM photograph).


S.00

DiffFlow(14)

2.50

— DIFFERENTIAL JU5W WSTMBUTON -

Min u t 0.142MM. u e 0 575MHP. B » 0.504

• DDTERENTVAL PORE NUMBER DISTMBUtTON —

100 EOS

Min. ate 0.412Mn. i t s 0.575MFT.as 0.5W

No. ofForaper cm1

50.0 £06

1.000 Pure Size (Jim)

Size M cursor 0.3O4 pxaPiffcrgrtul Flow 3.U %

0.100 1.000 Pore Sizt (Mm)

Size * curaor 0.5O* paNumber of Peru 13.0 KU6 per cm'

0.100

a/ b/Fig.4. Results of PEN track membrane investigation by using Coulter® Porometer II instrument (mean value of pore size - 0.50 ftm):

a) differential flow distribution, b) pore number distribution.

curves with a mean value of pore size - 0.50 fim areseen.

The dynamics of pore creation is shown in Fig.5.Higher velocities of bulk track etching were foundin the case of Kaladex films. Many factors can beresponsible for such behaviour (molecular mass dis-

(.00

300 •

S 200

£ 100

1 1 >-•- , . . . . . , . . . ,

Kaladex

6N Na0H,50"C

r 1 - *^J_ l ._ . i L

/

Du

-

•

POftt

.J !

20 80 10040 60Etching time, min

Fig.5. The dynamics of pores creation during etching of irradiat-ed with heavy ions PEN films.

tribution, morphology of polymer, crystallinity in-dex etc.). We have concentrated on the investiga-

tion of the crystallinity changes after irradiationwith heavy ions. The detailed studies of crystallinityof virgin and irradiated with heavy ions PEN poly-mers were undertaken using a HZG4c diffracto-meter and CuKa monochromatic radiation.Aknowledgements

The authors are grateful to the research stafffrom the Florov Laboratory of Nuclear Reactions,JINR, Dubna (in alphabetic order): P.Yu. Apel,A.Yu. Didyk, O.L. Orelovich, L.I. Samoilova fortheir help in PEN samples irradiation in a cyclo-tron, photo-chemical treatment of irradiated sam-ples, SEM investigations and fruitful discussions.

We would also like to thank the ICI Polyester andthe DuPont Companies for obtaining samples ofPEN films and catalogue information about them.

References[1], Information Note KX IN 004, ICI Polyester, UK, Imperial

Chem. Ind. PLC. (1997).[2]. Apel P.Yu., Didyk A.Yu., Larionova I.E., Mamonova T.I.:

Properties of PETP Track Membranes of Different Thick-nesses, Proceedings of the 3rd Conference on Particle TrackMembranes and Their Applications, 26-28 October 1993, Ja-chranka, Poland. Eds. W. Starosta, M. Buczkowski. Instituteof Nuclear Chemistry and Technology, Warszawa 1995, p. 51.

MATERIALS FOR IN-SITU MONITORINGOF LIGHT WATER REACTOR (LWR).

WATER CHEMISTRY BY OPTICAL METHODS*

L. Fuks, C. Degueldre1', E. Schenker1/

X/Paul Scherrer Institute, Villigen, Switzerland

PL9802016

Optical methods permit continuous, noninvasive mo-nitoring of numerous technlogical processes. Amongthese methods, Diffuse Reflection Spectroscopy(DRS), which was used off-line up-to-day, seems tobe among the most attractive techniques for investi-gation of the formation of corrosion layers in thenuclear reactor operating conditions [1-12]. The useof optical interferometric techniques for off-line

measurements of the thickness of oxide films onzirconium, started about 35 years ago [1-3] and wasrapidly abandoned. It was reported that these films,especially thermal ones, after reaching a certainthickness, absorbed too much light at UV-Vis rangeto allow for precise measurements. Also, early at-tempts to measure corrosion films by infrared inter-ference methods gave very limited success. However,


a great progress was achieved due to the introductionof Fourier Transform Infrared Reflection (FTIR)spectroscopy. This technique was successfully used todetermine the thickness of Zicaloy oxide layer form-ed in a CANDU reactor pool [4]. Meanwhile, directmeaurements of the properties and thickness of an

Fig.l.Main optical phenomena appearing in optical investiga-tions of the metal oxide layer.

oxide layer on zirconium alloys were also performedby FTIR reflection spectroscopy [5,6]. However, onlya few studies concern application of this method inthe in-situ manner [7-12].

Numerous substances in their natural state (e.g.solids with rough surfaces, colloidal solutions), whenilluminated, generate diffused reflections (DR). Theabove name describes a phenomenon in which incidentlight is scattered in all directions, contrary to specular(mirror-like) reflection where the angle of incidence is

equal to the angle of reflection. The phenomena occur-ring in DR the oxide layer covering metal surface de-pend mainly on the following (Fig.l), [10-12]:- chemical composition of the layer, which influ-

ences absorption propeties of the material;- thickness of the layer and roughness of its sur-

face, which affect the inteferometric signal caus-ed by reflections produced by two parallel metal--oxide and oxide-water interfaces;

- the chemistry of the circulating water;- optical and geometrical parameters of the ex-

perimental system.The last two terms influence both absorption and

reflection of light.In laboratory investigations metal samples were

corroded in water under BWR conditions (i.e.about 550 K (about 280°C), 92 kg-cm"2 (90 bar),400 ppm of O2 in the water, conductivity <0.1^S-cm"1) directly in a spectrophotometric cell (flowrate about 550 dm3^"1) which was connected tothe nuclear reactor test loop in the Paul ScherrerInstitute [10-12].

The spectrophotometric cell (Fig.2) was equippedwith an optical window, till now manufactured froman artificial sapphire (single-crystal material consist-ing of about 99.9 wt% of AI2O3; prod, commerciallyfor the watch industry by Saphirwerk, Bnigg/Biel,Switzerland). Tests were also performed with Vycor7913® (Corning Glass Works, New York, USA),glassy material of the reduced boron content (about97 wt% of S1O2,2.5% of B2O3, and 0.5% of A12O3).It appeared, however, that under the BWR condi-tions the latter material is too fragile and too soluble.Relevant values of the corrosion rate for the syn-thetic sapphire and Vycor® glass, determined aftertheir long-term exposition to BWR-like water con-

Table. Main properties of the materials proposed for the optical windows.

Property

Producer

Price

Formula

Structure

Purity

Transparency

Density

Hardness

Pressure strength

Impulse strength

Specific heat

Thermal expansion

Refractive index, n o

Maximum temperatureapplication

Corrosion ratea

Acid resistance8

Base resistance3

Unit

US $/ piece(prod, scale)

%

nm

gem ' 3

kg • mm"2

kg • mm"2

k-gmm"2

Jkg-i-K"1

ppm

(")K(°C)

mg-cm"2-h"l

Synthetic sapphire

Saphirwerk (CH)

40(commercial scale)

AI2O3

single-crystal

99.99

200-4,500

3.98

1,900

210

38.5

755

67

1.761

2,073 (1,800)

0.0071

high

high

Vycor 7913®

Corning (USA)

20(laboratory scale)

SiO2/B2O3/Al2O3

amorphous

230-3,400

2.18

600

788

7.5

1.458

1,173 (900)

0.0310

high

high

Zirconium oxide

MaTecK(D)

130(laboratory scale)

ZrO2

single-crystal

95

300-?

6.0

1,100-1,500

640

69-105

500

103

2.20

2,773 (2,500)

0.00009

extremely high

extremely high

Calcium fluoride

Beijing GlassResearch Institute (TJ)

to be established(laboratory scale)

CaF2

single-crystal

130-12,000

3.18

170

911

18.9

1.39

1,573 (1,300)

to be determined

high

high

a measured for the BWR conditions.


ditions in an autoclave, are 0.0071 and 0.0310mg-cm^h*1, respectively. Hardness of the investi-gated materials, in term, is 1,900 kg-mm*2 for

probe

water

sample^holder

Fig.2. In-line experimental arrangement.

sapphire vs. 600 kg- mm*2 for Vycor®. Because it hasbeen experimentally found that optical windows pro-duced from Vycor® glass are too fragile to be ap-plied in the nuclear installations and pressurestrength of the material has not been established.The corresponding value for the artificial sapphire is210 kg-mm-2.

Considering the main requirements of measure-ments (thermo-mechanical stress, optical transpa-rency and commercial availability), yttrium stabi-

200 400 600 1000

Fig.3.wavelengths (nm)

Optical transparency of the potential materials for thespectrophotometric windows: (1) - artificial sapphire, (2) -Vycor 7913®, (3) - zirconia.

lized zirconia (single-crystal material with about 95wt% of ZrO2; prod. e.g. by MaTecK GmbH, Julich,Germany, at present on a laboratory scale only)seems to offer an important improvement over theartificial sapphire. Extremely small weight loss(0.0001 mg-cm^-h'1, literature data) and highpressure strength (640 kg-mm'2, literature data) of

zirconia are not balanced, however, by the lowerlimit of its optical transparency compared to thisfor synthetic sapphire (400 nm for zirconia vs. 200nm for sapphire, Fig.3). As a result, the properchoice of optical window material is dictated byboth mentioned above factors, which act oppositely.

Finally, unit price of the material must be alsotaken into account. Nevertheless we expect that ifthe sapphire windows (of low unit price) are chang-ed every 1000 h of operation (i.e. about every 40days) because of loosing their transparency, zirco-nia windows (much more expensive) should run atleast one year (i.e. more than 8600 h).

Laboratory investigations have been just ini-tiated to test the possibility of replacing artificialsapphire by zirconia optical windows.

References[1]. Wilkins N.J.: Infra-Red Interference Measurements on Oxi-

de Films on Zirconium. Corros. Sci., 4,17-24 (1964).[2]. Wilkins N.J.: Optical Measurements of Oxide Films on

Zirconium in the Range of Wavelengths from 2000 A to 2.5ft. Corros. Sci., 5_,3-18 (1965).

[3j. Cox B.: Low Temperature (<300°C) Oxidation of Zirc-aloy-2 in Water. J. Nucl. Mat., 21,310-321 (1968).

[4].Ramasubramanian N., Ling V.C.: Fourier Transform Infra-red Reflection (FTIR) Spectroscopy of Corrosion Films onZirconium Alloys. J. Nucl. Mat., 17_5_, 237-243 (1990).

[5]. Cox B., Won Y.M.: Direct Measurements of the Thicknessand Optical Properties of Zirconia Corrosion Films. J.Nucl. Mat., 122,258-271 (1993).

[6]. Cox B., Yamaguchi Y.: The Development of Porosity inThick Zirconia Films. J. Nucl. Mat., 21& 303-317 (1994).

[7], Alder H.P., Schenker E.: Advanced Analytical Techniquesfor Boiling Water Reactor Chemistry Control. In: Proc.IAEA Technical Committee Meeting "Influence of WaterChemistry on Fuel Cladding Behaviour", 4-8 October 1993,Rez, Czech Republic. IAEA-TECDOC-927 Report. 1997,pp. 391-406.

[8]. Alder H.P., Degueldre C, Schenker E.: Non-invasive Moni-toring of Corrosion in the Light Water Reactor by OpticalMethods. In: Proceedings of the VII International Con-ference on Water Chemistry of Nuclear Reactor Systems,13-17 October 1996, Bournemouth, England; vol. 1, pp.272-276.

[9]. Degueldre C, Dran J.C., Schenker E.: Study of the Oxi-dation of a Stainless Steel under BWR Conditions by Ad-vanced Analytical Techniques. J. Nucl. Mat, 1£8, 255-257(1992).

[10]. Degueldre C, O'Prey S., Francioni W.: An In-Line DiffuseReflection Spectroscopy Study of the Oxidation of StainlessSteel under Boiling Water Reactor Conditions. Corros. Sci.,38,1763-1782 (1996).

[11]. Degueldre C, Fuks L., Schenker E.: In-Line Measurementof the Oxide Layer Build-up on Zircaloy under BoilingWater Reactor (BWR) Conditions Using Diffuse Reflec-tion Spectroscopy. Meas. Sci. Technol., accepted for publi-cation.

[12]. Degueldre C, Fuks L., Schenker E,: Pre-Oxidation of Stain-less Steel, a Study by Diffuse Reflection Spectroscopy.Appl. Surface Sci., accepted for publication.

• Performed under the IAEA Research Contract NoPOL/8426/RB.

102 RADIATION TECHNOLOGIES

RADIATION TECHNOLOGIESPL9802017

HIGH-DOSE DOSIMETRY TECHNIQUES FOR QUALITY ASSURANCEIN RADIATION PROCESSING

Z.P. Zag6rski

Several decades of research and applications of highdose dosimetry for radiation processing in the De-partment of Radiation Chemistry of this Institute(first paper [1] and international review [2]) re-sulted in elaboration of techniques appropriate toparticular tasks. As the high-dose dosimetry is theintegral part of efficient radiation processing, thedosimetric work was always confronted with inter-national progress in the field. Our participation inthe Subcommittee E10.01 in the American Societyfor Testing and Materials contributed to the im-provement of standards connected with dosimetryand radiation processing.

In recent years the collaboration has extended tothe participation in the co-ordinated research prog-ramme (CRP) on characterization and evaluationof high-dose dosimetry techniques for quality assur-ance in radiation processing, organized by the In-ternational Atomic Energy Agency. In many IAEA--member states the use of gamma and electron faci-lities for industrial processing continues to grow.With these processes, quality assurance should beachieved by applying well established dosimetrysystems and procedures. This is especially the casefor health regulated processes, as in radiation steri-lization of health care products, food irradiation toeliminate pathogenic organisms or for pest control,and waste treatment. Standardized dosimetry is alsovaluable in the radiation processing of polymers,which are in the centre of interest also of ourInstitute.

Several years ago we have been invited by theInternational Atomic Energy Agency to participatein the International Dose Assurance Service (IDAS)provided by the Agency. The meetings, exchange ofpublications, reports and not published informationshas been recorded and documented in IAEA prints.The most important initiative of the Agency in 1997has been the High-Dose Intercomparison in which 10laboratories from the world have participated (Cana-da, China, Denmark, France, Hungary, India, Japan,Poland, Thailand and USA). The intercomparisonconsisted in y-irradiation of three solid dosimeterssupplied by the IAEA to the dose in the range of 15±3 kGy, with the documented laboratory statementof the value of dose, confidence level, field uniformityetc. and the conditions of irradiation - temperatureand date. The dosimeters with the number notrevealing the laboratory, were analyzed by the EPRmethod in the IAEA-Seibersdorf Laboratory for the

real dose obtained by the sample. The results werecollected by an independent officer in the IAEA andpresented in the Fig. The Agency has restricted therevealing the identity of all participants in the inter-comparison in publications, except of authors them-selve, presenting their results. Polish result is No 8,confined in acceptable limits of confidence. In thepreparation to the intercomparison, P.P. Panta and

-40%

1 2 3 4 5 6 7 8 9 10

Institute No

Fig. Results of intercomparison of dosimetry 1997. Explanationsand comments in the text.

W. Ghiszewski have taken part. Discussions amongparticipants of the intercomparison in Vienna, 6-10October 1997 helped to improve their own tech-niques, as concerns the accuracy and precision.

The collaboration with the IAEA will continuein two directions. The first one will concentrate onintercomparison of dosimetry of electron beamirradiation, which is more difficult than dosimetryof gamma or bremstrahlung fields. Irradiated dosi-meter body not resemble a sample of a standardused for chemical analysis by participating labo-ratories. In such case the samples are perfectlyhomogeneous. On the contrary, an irradiated objectcontains always the inhomogeneously distributednew compound to be determined. The heteroge-neity in gamma irradiations is not very critical andmay be controlled. However, in EB irradiations theisodose curves are more congested because ofshorter ranges of electrons in the dosimeter body incomparison to gammas. The congestion of dosesrequires a thin geometry of dosimeters and thatcondition eliminates many dosimeters otherwiseexcellent in gamma-dosimetry.

The second line of coordinated research is theimprovement of existing dosimetric materials, e.g.


the alanine dosimeter. The latter shows some incon-venient properties. Their explanations is difficult,because the radiation-chemical basis is not fullyunderstood yet. For instance, the temperature-of--irradiation coefficient of response (+0.23%/°C) israther high and there is no explanation of the originof the phenomenon. Our basic research on themechanism of radiation chemistry of solid crystallinealanine [3], especially on short living intermediates,as seen in solid state pulse radiolysis [4] starts to givea clue to the origin of the high temperature co-

efficient of radical anion formation by deaminationof alanine.

References

[1], Zag6rski Z.P.: Nukleonika, 5,253-260 (1960).[2]. Holm N.W., Zag6rski Z.P.: Aqueous chemical dosimetry. In:

Manual on Radiation Dosimetry. Marcell Dekker Inc., NewYork 1970, pp. 83-104.

[3].Zag6rski Z.P., Pnzybytniak G.K.: Nukleonika, 42, 373-378(1997).

[4).Zag6rski Z.P., Sehested K.: accepted for print in Int. J.Radioanal. Nud. Chem., 232, (1-2), (1998).

RESEARCH ON RADIOLYSIS EFFECTS DURING PAPER DISINFECTIONWITH IONIZING RADIATION

A. Leliwa-Kania1', P. Rudniewski17, P. Panta, W. Ghiszewski11 Academy of Fine Arts in Warsaw, Poland

PL9802018

The paper matter is a subject to degradation due tonatural processes of ageing as well as the degrada-tion caused by physico-chemical, mechanical andmicrobiological factors like fungi, mould and in-sects. The microorganisms, part of them pathoge-nic, negatively affect books. The destruction offungi and mould is the first and most basic interven-tion before further processes of conservation ofbooks and old prints can take place. The fungi andmould are resistant to high and low temperatures,they need little moisture and their resistance tochemical substances increases with time whichcreates problems in the fight against them.

Methods of disinfection applied by the paperconservators usually narrow down to chemicalmeans. The agent applied is usually in the liquidform (bath, spray or tissue-paper saturated with afungicide and inserted among the infected pages),or gas [1]. These methods are time-consuming andlaborious. They are not friendly to the people andenvironment. The chemical means are insufficientwhen we deal with large collections infected withmicroorganisms. While the disinfection of one partof the books takes place, the fungi freely develop,infecting other volumes.

This situation occurred in Leipzig in 1992 where15000-20000 books were infected with a fungus dueto the inadequate storage in humidified crypts. Adisinfection on a large scale became necessary and adecision was made to irradiate the books with ^Coy-rays. According to the published report [2] theintervention was successful and led to rescue of thecollection.

In the year 1995, the Facility of Art Conservationat the Academy of Fine Art in Warsaw, in coopera-tion with this Institute and the Warsaw Universityof Technology and the National Library undertooka research dealing with the effect of ionizingradiation that is 60Co y-radiation and fast electronradiation (accelerator generated) on paper matter[3]. The mechanical (double fold number, tear re-sistance, breaking length), physico-chemical (cop-per-number, pH-water extract) properties, as well

as the degree of whiteness in paper (Whatman'spaper No 1 and wood pulp paper) were investi-gated (Table).Table. Dependence of whitening and yellowing of Whatman's

paper on dose and kind of radiation. Ageing time - 6months [4].

Dose [kGy]

0

1

5

10

20

Whitening R457 [%]

EB

91.34

91.44

90.56

88.69

87.01

y

91.34

90.97

89.49

87.79

86.55

Yellowing [%]

EB

4.27

4.26

4.81

6.06

7.95

y

4.27

4.39

5.55

6.54

8.53

Part of the samples was studied for a secondtime, after six months of natural and 25 years ofartificial ageing process [5], to determine the effectof radiation on the process of ageing. The studyconfirmed a slight influence of radiation on thestrength of paper (2% at the rate of 20 kGy, thusthe dose three times greater than the "mortalityrate" for most microorganisms). The chemical re-sults, picturing the radiolysis state proved the elec-tron beam radiation to be more beneficial.

It is of interest to determine which radiation ismore effective. The microbiological studies carriedout on two strains of fungi (Aspergillus niger andCharetomium globosum, both grown in the Agri-culture University, Faculty of Wood Protection)proved that both types of radiation are similarly ef-fective.

The care of our cultural heritage leads to asearch for supreme means and methods of conser-vation. A wide selection of methods permits a selec-tion of an optimal approach for each particularcase. Radiation, when an adequate dose is adapted,widens the spectrum of methods of disinfection. Itsadditional values is the elimination of chemicals,saving of time and the fact that invention can becarried out on a large scale.


References[1]. Idurski J.: Kryteria zdrowotne środowiska. T. 55. Tlenek ety-

lenu. Łódź 1992.[2]. Mann J., Wildfuhr W., Langguth H., Teichert E.: Gammastrah-

len zur Schimmelbekampfung bei Bilchern: Veisuche an derUniversitatsbibliothekzu Leipzig. Restauro, 2,114-119 (1992).

[3]. Zimek Z., Panta P., Kowalewski R., Głuszewski W.: Badaniadozymetryczne Stacji Sterylizacji Radiacyjnej Sprzętu Me-

dycznego i Przeszczepów. Zjazd Naukowy Polskiego Towa-rzystwa Chemicznego, Warszawa 1994.

[4].Leliwa-Kania A., Gradoń L.: Badania efektów radiolizy za-chodzących przy dezynfekcji papieru promieniowaniem joni-zującym. Prace Wydziału Inżynierii Chemicznej i ProcesowejPolitechniki Warszawskiej, XXIII 3-4,63-79 (1996).

(5J.PN-93-P50174/01.

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PRELIMINARY STUDY OF ALANINE-POLYMER RODS,MANUFACTURED IN THE INCT, IRRADIATED WITH GAMMA RAYS

Z. Stuglik, T. Bryl-Sandelewska, K. Mirkowski

Irradiation of crystalline aminoacids generates pa-ramagnetic centres which can be detected by theelectron paramagnetic resonance (EPR) method atroom temperature. Paramagnetic centres generatedin a-alanine are extremely stable.

In the early sixties the a-alanine/EPR system wasinvestigated and suggested as a new type of relativedosimeter. In the eighties the a-alanine/EPR dosi-meter was carefully reinvestigated and proposed fortransfer dosimetry. The International Dose Assu-rance Service (IDAS) initiated in 1985 by the Inter-national Atomic Energy Agency is based on an ala-nine/EPR dosimeter [1]. ASTM and ISO standardsdealing with alanine/EPR dosimetry were publishedlately [2,3].

In this paper we present first results obtained forone of our compositions of alanine-polymer rods, inwhich a very low concentration of the cheap racemicform of a-alanine was used. This composition hasmuch better mechanistic properties than the pre-viously used alanine/escoren system. It enables us toobtain rods with the same (3 mm ±2%) diameter

and good homogeneity of constituents. These twofactors are important if we want to use all the cavitylength and abandon weighing procedure. 3 mm dia-meter of the rods fits the dimentions of our EMS-104spectrometer tubes. (Smaller diameters are also ac-ceptable.) The EPR signals do not depend on thelength, 1, of the rods for 1>35 mm (whole cavitylength is utilized) and on their rotation around theaxis, if irradiated in homogeneous field.

The EPR signal of irradiated a-alanine is shownin Fig.l. It is a little different from that observed inneat microcrystalline alaninę. The reason of the dif-ferences is actually investigated. The amplitude ofthe central peak is taken for the dose evaluation.

Our rods, containing few per cents of D,L-a-ala-nine in a polymer mixture, 3 mm in diameter, 40mm long, were irradiated at room temperature in aCo-60 gamma source ISSLEDOVATIEL at thedoses of: 1.3; 2.7; 4.1 and 12.2 kGy. The EPRsignals were measured on an EMS-104 Bruker EPRspectrometer - a device specially dedicated to dosi-metric applications. The signals were measured im-

E M S 1 O 4 EPR ANALYZER

BRUKER" d e f a u l t "

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PARAMETERSPOHES) (KM)SWEEP tllOTH (0)N00U.ATION 10)SWEEP TIME Is)F R I E R T.C. lira)flECEIVER 6»1N (OSIRECEIVER OFFSETRECEIVER PHASEFIELO OFFSET (E)NUMBER OT SKEEPSSAMPLE HEIGHT lull

COMMENTS :

1.25500.00

2.0141 .94

163.0450

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DATETIKEOPERATORSAMPLEUNITSCOMMENTFRE0 (GHZ)

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Fig.l. EPR signal of gamma irradiated a-alanine - polymer rods. The samples were irradiated with Co-60 gamma rays at 298 K andmeasured on EMS-104 Bruker EPR spectrometer at room temperature. The measurements were done in the INCT.


g

100

90

80

70

60

50

40

30

20

10

010 20 30 40 50 60 70 80 90 100 110

Storage time [hours]Fig.2. Dependence of EPR signal of D.L-a-alanine - polymer rods irradiated in Co-60 gamma source, on the storage time, for various

doses.

mediately after irradiation, as well as during thestorage time up to 72 h (one sample - up to 94 h).The influence of the storage time on the amplitudeof EPR signals is shown in Fig.2.

It can be seen from Fig.2, that the signals de-crease somewhat during the first few hours after ir-radiation, especially those in the samples irradiatedwith higher doses, and then they are stable for along time. We suppose, that the decay is connectedmainly with unstable polymer radicals created in

the alanine-polymer mixture or alanine originatedradicals situated on the grain boundaries.

References[1]. Nam J.W.: Radiat. Phys. Chem., 21,3999 (1989).[2]. ASTM Standard E 1607-94: Standard Practice for Use of the

Alanine-EPR Dosimetry System. ASTM, 1994.[3]. Draft International Standard ISO/DIS 15566: Use of an Ala-

nine-Electron Paramagnetic Resonance Dosimetry System.ISO 1997.

EFFECT OF STORAGE CONDITIONS AND GAMMA IRRADIATION OF MEATON DNA ANALYZED BY "COMET" ASSAY

Z. Szot, K. Malec-Czechowska, T. Iwaneiiko, M. Kruszewski, M. Wojew6dzka, A.M. Dancewicz

DNA "comet" assay has been developed to analyzethe extent of DNA damage in irradiated cells, main-ly single and double strand breakage [1,2]. Cellsembedded in agarose on microscopic slides weresubjected to lysis and electrophoresis. Upon stain-ing this technique enables visualization of DNAfragmentation in single cell. Hence, it was namedSingle Cell Gel Electrophoresis (SCGE) [3]. Thistechnique found its practical application in toxico-logy, cancer research, radiobiology, genetics, bio-monitoring and detection of irradiated food [2,4].Fragmentation of DNA cannot be ascribed solely tothe effect of radiation. Other factors like heat,enzyme action, repeated freezing and thawing play arole in this event.

Here we present results showing that storageconditions can have a significant effect on the out-come of DNA "comet" assay used for detection ofirradiated meat. The method used in this inves-tigation was adopted from that described in theliterature [2-4] and in many aspects was identicalwith that proposed recently in a procedure for

screening of irradiated food [5]. It will be publishedelsewhere [6].

Visual evaluation of cells was made using a com-mon transmission microscope for slides stained witha silver or fluorescent microscope for slides stainedwith 4,6-diamidino~2-phenylindole (DAPI). Accord-ing to the shape and stain intensity, DNA "comets"were classified arbitrarily to 4 classes (Fig.). Class I:images of apparently unchanged cells; class II: cellswith a dye expanded slightly beyond the core (nuc-leous) border; class III: classic "comet" image, andclass IV: almost all dye in the tail of the "comet".Objective evaluation of "comet" images stained withDAPI was made using an automatic scanning devicecontrolled by a computer program (Comet V3). Asmost suitable for this investigation a tail moment waschosen, which is a product of "comet" tail length andDNA content (stain intensity) in the tail.

The results obtained are summarised in Tables.Table 1 shows that in the beef fresh and stored upto 48 h at 4°C or up to 4 days at -21°C the cells withimages of class I and II are within the range of

i o

ISis15


Fig. The class of DNA "comets" from beef and pork. A - fluorescent staining with DAPI, B - silver staining (x 200).

-21°C it still amounts to roughly 50%. Correspon-dingly the number of "comets" classified as III and

75-96%. After prolonged storage the per cent ofthese cells decreases, though after 2 months atTable 1. Influence of storage conditions on DNA in beef and pork assayed by the single cell gel electrophoresis (SCGE) method (DNA

"comet" assay). The range of mean values of visual evaluations and tail moment measurements are given.

Storage conditions

Fresh meat

20 h at 4°C

48 h at 4°C

72 h at 4°C

140 h at 4°C

20 h at -21°C

4 days at-21 °C

2weeksat-21°C

2 months at-21 °C

Beef

Tail moment

10-24

9-11

9-22

34-44

16-33

39-76

86-90

102-108

Visual scoring

class 1+II

85-91

88-91

79-86

57-81

class IH+rV

9-15

9-12

14-21

20-43

Pork

Tail moment

20-26

31-37

24-54

35-48

Visual scoring

class 1+II

88-94

76-83

56-85

56-82

beyond the sensitivity of computer system

88-96

77-89

63-66

52-64

4-12

11-23

25-37

48-36

12-20

30-38

52-77

37-59

89-97

86-89

38-57

62-64

class III+IV

6-12

18-24

15-44

18-43

3-11

11-14

43-62

36-38


IV class increases with storage time. After 3 days at4°C it may reach up to 40% and after 2 weeks at-21°C almost 40% of these "comets" were found inthe analyzed beef samples.

More susceptible to detoriation during storageseems to be pork. At least our figures for the porkare higher than that obtained for the beef. This sub-jectively made scoring of "comet" images was con-firmed by the tail moment analysis of the samemicroscopic slides scanned. The data obtained in-dicate that the value of tail moment measured insamples from the fresh meat increased with storagetime. It doubled in the meat stored 3 days at 4°Cand more than trippled after 2 months storage at-21°C, both in the beef and pork.Table 2. Visual evaluation of "comet" in irradiated beef and pork.

The ranges of mean values are given as per cent scored24 h after exposure.

Dose, kGy

01.53.0

Beef

class I+II

87-91

67-74

54-71

classIII+IV

9-13

26-33

29-46

Pork

class I+II

88-93

74-76

13-23

classm+rv

7-12

24-26

87-77

Data in Table 2 show that the appearance of"comet" in the meat irradiated with gamma raj's issignificantly higher than in an unirradiated sample.Dose of 1.5 kGy caused an increase from 11% forthe unirradiated beef to 29.5% for the irradiatedand scored 24 h later. The respective figures for thepork were 9.1% and 24.7%. A higher irradiationdose (3.0 kGy) resulted in a more pronounced in-crease in the number of "comets" class III and IV(37.3% in beef and 83% in pork).

From the data presented in Tables 1 and 2 it isapparent that the doses of ionizing radiation usedfor meat irradiation cause an extensive increase inthe number of "comets" which indicates extensivedamage (fragmentation) of DNA. However, such"comets" (class III and IV) also appear in the unir-radiated meat and their number increases withstorage time and conditions. After 2 weeks at -21°Cthe number of "comets" scored in the unirradiatedmeat is roughly the same as found in the meat irra-diated with a 1.5 kGy dose. This leads to the con-clusion that although DNA "comet" assay can beused, as recommended [5] for rapid screening offood irradiation, one should take into account theprobability that positive evaluation can be erro-neous owing to the action of other factors besideradiation. Improper or/and prolonged storage ofmeat is just one of such factors.

References[1]. Ostling O., Johanson KJ.: Biochem. Biophys. Res. Commun.,

123,291-298(1984).[2].Kruszewski M., Wojewodzka M., Iwanenko T.: Test komet-

kowy. Teoria i praktyka. Institute of Nuclear Chemistry andTechnology. Warszawa 1996. Raporty IChTJ, Seria B nr1/96.

[3]. McKelvey-Martin J., Green M.H.L., SchmeUer P., Pool-Zo-bei N.L., deMeo M.P., Collins A : Mutat. Res., 2S& 47-63(1993).

[4].Cerda H., Hofsten B., Johanson K.J.: EUR 14315, 401-405(1993).

[5]. Cerda H., Delincee H., Heine R , Rupp H.: Mutat. Res., 225.,167-181 (1997).

[6], Kruszewski M., Malec-Czechowska K., Dancewicz AM.,Iwaneriko T., Szot Z., Wojewodzka M.: submitted for publi-cation in "Nukleonika" (1998).

ELECTRON BEAM AS METHOD OF REMOVAL OF VOCs FROM GAS STREAM

A. Ostapczuk, A.G. Chmielewski, V.A. Honkonen17

Xl University of Kuopio, Finland

Volatile organic compounds (VOCs) are releasedinto the atmosphere from various industrial pro-cesses. A lot of compounds from this group areharmful to human health and produce toxic sub-stances by photo-chemical processes in the atmo-sphere. Industrial off-gasses have been cleaned byseveral conventional methods (incineration, ad-sorption, condensation, biofiltration). New techno-logies are being developed for finding an alternativemethod with higher efficiency and lower costs.Electron beam treatment seems to be promisingtechnology for VOCs reduction.

Decomposition of many VOCs has been inves-tigated using electron beam treatment. The processhas been used for aromatic hydrocarbons. Benzeneand toluene at an initial concentration of 50-100ppm in the air were irradiated. The removal effi-ciency of these compounds from the gas phaseranged from 90 to 98%, the dose used being 3-10kGy. The irradiation in this case results in coagula-tion of the compound into clusters which can be

collected on the surface of a filtration material. Asthe products aerosols are obtained. When trichloro-ethylene was irradiated, only gaseous were obtained[1]. Numerous investigations have been done forchlorinated aliphatic compounds from the VOCsgroup. The removal efficiency by electron beamtreatment for these compounds were higher than90% with CO2, HC1 and Cl as the final products[2-5]. Irradiation of tetrachloroethylene was per-formed with the aim to determine the dose necess-ary to decompose 90% of the initial concentration.The dose ranged from 2.1 kGy for 300 ppm to 5.4kGy for 1800 ppm [2]. For xylene the clean-upefficiency by electron beam treatment at 10 kGydose was nearly 90%, but only 50% for butylacetate.

Generally, electron beam treatment is an oxida-tion process. The efficiency of this reaction and thekind of products depend on the kind of irradiatedcompounds, their initial concentration and the doseof irradiation. The quality and concentration of theproducts are mostly followed by gas chromato-

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CompundsStyrene

BenzaldehydePhenol

# Ret Time7.94310.4411.336

Area3826639574320191

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Fig. Results of analysis of the products from the irradiated air with styrene.

graphy and mass spectrometry. Our investigationhas began with styrene and phenol as the com-pounds from the VOCs group. First experiment wasmade to check the usefulness of the electron beammethod as the first step in the cleaning processfollowed by biofiltration. The products of irradia-tion like: aldehydes, esters, ketons are known asbiodegradable [6]. The next experiment was madewith styrene. Two kinds of sample were prepared:dry and wet in continuous conditions - the technicalair flowed through a dryer (or humidifier), a styrenesource and sample boxes, which were closed whilethe concentration of styrene and humidity becamestable. The samples were irradiated inside steelboxes with a titanium window. Products of the pro-cess were analyzed in the gas and aerosol phases.The analyses were made by a tandem gas chromato-graph-mass spectrometer system and examples ofthe results are shown in Fig. The results show thatthe main products of irradiation of styrene arephenol and benzaldehyde. The removal efficiency of

styrene from the gas phase ranged from 83 to 95%.Results of the last experiment on the decomposi-tion of styrene by electron beam treatment is pre-pared for publication.

References

[1], MakelS J. et al.: Aerosol particle formation by irradiation ofbenzene... Proceedings of the 10th Symposium on AerosolScience and Technology, Mururoran, Japan, 1993.

[2). Hakoda T. et al.: Decomposition of tetrachloroethylene byionizing radiation. International Symposium on RadiationTechnology for Conservation of Environment, 8-12 Septem-ber 1997, Zakopane, Poland.

[3], Vitale S.A. et al.: Decomposing VOCs with an electron-beamplasma reactor. Chemtech, 1996, pp. 58-63.

[4]. Penetrante B.M. et al.: Electron beam and pulsed coronaprocessing... Pure & Appl. Chem., £&, 5,1083-1087 (1996).

[5]. Hirota K. et al.: Removal of butylacetate and xylene from airby electron beam. A product study. Rad. Phys. Chem., 46,4-61,093-1097 (1995).

[6], Honkonen V.A et al.: VOCs removal by simultaneous elec-tron beam treatment and biofilter application. InternationalSymposim on Radiation Technology for Conservation ofEnvironment, 8-12 September 1997, Zakopane, Poland.


NUCLEONIC CONTROL SYSTEMSPL9802022

CALIBRATION OF 222Rn PROGENY MEASURING INSTRUMENTS

T. Radoszewski

Calibration of any instrument for measuring 222Rnor its progeny needs a standard to be comparedwith. As standard of 222Rn, or its progeny does notexist, the only standard to be used in this case isradium, a 226Ra source. The activity of 226Ra sourcecan be measured in an exact way and thereforeamount of 222Rn and its progeny can be also deter-mined.

In most cases the 226Ra source is used to pro-duce so called "standard atmosphere" of radon, thatmeans a well-known amount of radon to be intro-duced to the detector of measuring instrument. Inthe case of 222Rn progeny however, where a paperfilter is used to absorb aerosols with the active222Rn progeny, 226Ra in a rather specific form canbe used to a more direct calibration of the instru-ment. A radiometer, type RGR-40 [1], may serve asan example of such a way of calibration (1). In thiscase the primary standard source is prepared from a226Ra standard solution in the form of a flat discfirmly closed in a plexiglass capsule. The cavity inthe plexiglass container should have the same dia-meter as the active surface of the filter (e.g. <I>20mm). The thickness of the cavity should be kept assmall as possible, so that the geometry of thestandard source is as close as possible to that of afilter sample. The closed 226Ra source is in equili-brium with 222Rn and its short-lived progeny [2].

Apart from the primary standard, a secondarystandard for 222Rn progeny is needed. The secon-dary standard is prepared from the filter paper usedin RGR-40, basing on the collection of 222Rnprogeny on it. The filter paper must be put in aplexiglass container of the same construction as thecontainer used for the primary standard. Only thecavity for the filter is open, to make a-particlesemission from the filter possible [2].

To make the calibration process possible, twodetectors are needed; one scintillation counter witha Nal (Tl) scintillator for y-radiation measure-ments, and one surface barrier detector for a-par-ticles counting. Both detectors should cooperatewith a multichannel analyser.

Having all the equipment mentioned above, thecalibration process can be done according to thefollowing principle. The primary standards is usedto establish the counting efficiency of the y-scin-tillation counter for y-radiation emitted from 224Bi(0.609 MeV, 44.8%). Afterwards the secondaryfilter standard (after 222Rn progeny collection bypumping it in the RGR-40 radiometer) is put be-tween the y-scintillation counter, and the o-particle

(surface barrier) detector to count y-photons of214Bi and a-particles from 214Po (7.678 MeV,100%) simultaneously. This means that the surfacebarrier detector will be calibrated for counting ef-ficiency a-particles from 214Po after the second-ary standards. This indicates that by the doubley-counting (first from the primary standard, andthen from the secondary standard) calibration ofthe a-particle surface barrier detector by the pri-mary ^ R a standard can by done indirectly. As thehalf life time of 214Po is very short (1.64 • 10"4 s) onecan take that the activities of 214Po and 214Bi are inequilibrium.

Calculation of the surface barrier a-detector effi-ciency for counting a-particles of 214Po can be ob-tained from the equation:

and after transformation:

Ea = ^ X Ey (2)

where: E« - counting efficiency of a-detector fora-particles of 214Po, Ey - counting efficiency ofy-detector for y-photons of 214Bi, Na - net countingrate of a-particles from the filter, Ny - net countingrate of y-photons from the filter [2].

As a consequence of the counting and calcula-tions, a calibration possibility of the RGR-40 radio-meter has been obtained by comparing the instru-ment indication with the surface barrier a-detectorwhich was calibrated indirectly by the primary 226Rastandard. The process of RGR-40 radiometer cali-bration is associated with several sources of error.First, is an uncertainty of primary 226Ra standardpreparation. Taking the uncertainty given by the^ R a standard supplier - 1.4% and the uncertaintycombined with the preparation process, the overalluncertainty may by taken as ±2%. The secondarystandard (filter paper with collected 222Rn progeny)does not introduce an uncertainty, as the velocity ofgas and collection time do not change the ratiobetween the activity of 214Bi and 214Po.

The second part of uncertainty is due to the cali-bration processes of the scintillation counter fory-photons from 214Bi, and the surface barrier detec-tor for a-particles from 214Po. This first process isassumed to be ±0.5%, and the second ±1%. Thismeans that altogether the uncertainty of the wholeprocess of calibration, including the measurementof a given filter, may by estimated as ±4%.

It should be emplasized that the proposed me-thod of calibration does not operate with gaseous

110222Rn and that it refers to a calibration factor of agiven instrument. It does not concern the methodof measurement of 222Rn progeny as well as 222Rnand its progeny concentration calculation [3].

References

[1]. Gierdalski X, Bartak J., Urbafiski P.: New generation of themining radiometer for determination of radon and its decay

NUCLEONIC CONTROL SYSTEMS

products in the air of underground mines. Nukleonika, 2Si 4,27-32 (1993).

[2J. Radoszewski T.: Metoda wzorcowania radiometru typ RGR-40zrodtem radu 2 2 6Ra. Institute of Nuclear Chemistry and Tech-noloy, Warszawa 1997. Raporty IChTJ, Seria B nr 1/97.

[3].Falk R., Hagberg N., Mjones L., More H., Nyblom L.,Smedjemark G.A.: Standards calibration and quality assur-ance of *^2Rn measurements in Sweden. Nucl. Inst. andMeth. in Phys. Res., A 339,254-263 (1994).

MEASURING PROBE FOR MONITORING CONCENTRATION OF RADON

J. Bartak, P. PienkosiooISIS!8

Radon, Rn-222, a noble radioactive gas, that can befound in mines presents a serious hazard to thehealth of miners. Both radon and its short lived de-cay products emit alpha radiation that by irradiat-ing respiration system tissues can cause a lungcancer [1]. The emission of radon in excavations iscaused by the variation of stress in geological layersfrom which coal or other minerals are obtained [2].Investigations of the variation of radon concentra-tion is carried out in Poland, employing trace detec-tors (laboratory method) or imported instruments.In 1996 technical requirements were elaborated forthe construction of a probe for measurement ofradon concentration and in 1997 the probe was pro-duced. Development of the probe was carried out inthe frame of a contract with the Central MiningInstitute in Katowice. In the scope of activities ofthe contract a model of the measuring probe wasproduced and examined for the determination ofradon concentration in bore-holes in coal mines orin mines of other minerals. The probe can also byused to foresee "bumps" in the mines.

The probe is constructed in the form of a cylin-der. Electronically, the probe operates together witha modified mine radiometer RGR-40 [3]. The probecan measure the radon concentration in two ways inrespect to the air flow through the probe:1) a natural diffusion air flow through the probe,2) a forced air flow through the probe by means of amembrane air pump powered from a battery andcontrolled by a rotameter.The second way of measurement speeds up the ex-change of air in the probe and consequently speedsup the response of the probe to radon concentra-

AIRINLET

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Fig. Block diagram of SRDN-1 probe for radon concentrationmeasurement: FP - air filter, D - semiconductor Si detector,KP - measuring chamber, WI - pulse amplifier, DYS - pulsediscriminator, USISI - pulse separation and standardizationcircuits, PP - air pump, UPISN - processing and voltage sta-bilization circuits, ZS - probe connector for RGR-40 connec-tion.

tion variations. Block diagram of the probe, typeSRDN-1, is shown in Fig.

The air sample containing radon is introducedinto the measuring chamber of the probe through aspecial air filter FP on which decay products ofradon are deposited. A high quality low backgroundsemiconductor Si detector is used to detect alphaparticles produced by radon and its daughters in themeasuring chamber. Output pulses from the detec-tor after amplification in a Wl amplifier and afterdiscrimination by a DYS pulse discriminator arestandardized in USISI circuit. The probe is con-nected by a ZS cable with a modified radiometerRGR-40 that serves as a probe controller, process-ing and display unit.

The air pump of the probe is powered though acable and a ZS connector from the internal batteryof RGR-40 radiometer. A fully charged battery al-lows for 5 days of continuous operation of theprobe when the measuring cycle is 59 min and thepumping interval lasts 1 min at a 2 1/min air flow(LED display switched on). If longer period of timeof continuous operation of the probe is required,the probe can be powered from a low voltage powersupply that is delivered with the RGR-40 radio-meter, connected to 220 V/50 Hz. The electroniccircuits of the probe are supplied from an internalNi-Cd battery specially made in the INCT. Whenfully charged, the battery is sufficient for threemonths of continuous operation of the probe.

The probe can operate in four basic operationmodes: Measurement (poM), Date (Dat), Check-up(Kon), Transmission (Trans):

poM Dat Kon Transrodzaj pracy: -

The mode of operation is selected from the mainmenu by pressing the capital letter character of thekeyboard, describing the mode. The keyboard em-ployed is a foil keyboard situated at the front panelof the RGR-40 radiometer. After the basic mode ofoperation poM (Measurement) is selected the ope-rator is requested to set up a number of measure-ment in the range 01-99 (or to accept successivenumber displayed by the radiometer), and to set theair pumping interval in the range 0.0-10 min. Thedisplay after the measuring cycle is finished a shownbelow.


ckO5*3O min <>. ?N=000000741 pom 05

The presented probe with a modified RGR-40radiometer is an up-to-day construction instrumentpermitting to make experimental measurements ofradon concentration in the mine environment. Ser-vicing of the instrument is fully automated. Theinstrument allows to keep the measuring results inmemory and to transmit them by a serial port to anexternal computer for further processing and forarchive purposes. The final construction of the probehas to observe sharp spark-proof requirements [4].

First measurements of radon concentration em-ploying the model of the probe were carried out ina radon chamber in the Department of Radioiso-tope Instruments and Methods of the INCT. Thevolume of the chamber is 0.8 m3. Before measure-ments a proper activity of radon was introducedinto the chamber, then the investigated probeSRDN-1 with the modified RGR-40 radiometerwas introduced into the chamber and measure-ments were carried out. The measurements wereperformed in two ways, i.e. with a natural diffusionof air through the measuring chamber of the probeand with a forced air flow through the probe. Fromthe measurements it results that a radon concentra-tion of 20 Bq/m3 produces 1 count/h.

Other measurements were carried out in a 7.5 m3

volume radon chamber of the Central Mining Insti-tute in Katowice (CMI). The Ra-226 source, locatedinside the chamber, permitted to obtain a high radonconcentration, more than 35 kBq/m3. It can be con-cluded from the performed measurements that when

the air is forced through the probe by an air pump,the calibration coefficient depends on the countingperiod and is different for short and long countingintervals. Operation with a short measuring cycleincreases the sensitivity of the probe and for thecycle: for 1 min pumping and 5 min counting intervalthe sensitivity was 3 c/(3.5 Bq h) and the detectionlimit was lower than 30 Bq/m3.

The measurements carried out indicate that it isadvisable to employ a forced flow of air through themeasuring chamber of the probe. To obtain a cor-rect calibration coefficient, a radon concentration inthe chamber has to be kept constant (Ra-226 sourcein radiation equilibrium with radon). If the countingtime is long, e.g. 60 min the calibration coefficient issimilar to that achieved at the forced air flow and thenatural diffusion flow through the probe.

The measurements of the probe, model SRDN-1,are preliminary ones and further investigations inthis field are necessary. Such investigations will beperformed by the CMI.

References[l].Domartski T., ChruScielewski W., Kluczyliski D., Olszewski

J.: Zagrozenia radiacyjne zatog g6rniczych powodowane na-turalnym radioaktywnym skazeniem powietrza w kopalniach.Raport IMP-ZOR-079/90.

[2]. Lebecka J., Skubacz K., Chatupnik S., Michalik B., Skow-ronek J.: Metody kontroli zagrozenia radiacyjnego w kopal-niach w^gla kamiennego. Og61nopoiskie seminarium, 25-26luty 1993, Warszawa.

[3], Gierdalski J., Bartak J., Urbartski P.: Radiometr gdrniczy dopomiarow chwilowych stc.zeri produktow rozpadu radonu wpowietrzu. PTJ, 3/4 (1993).

[4]. Fraczak J.: Aparatura przeciwwybuchowa w wykonaniu iskro-bezpiecznym. Podre,cznik akademicki. Slaskie WydawnictwoTechniczne, Katowice 1995.

AGC CONTROLLED SCINTILLATION PROBE FOR INDUSTRIAL APPLICATION

J. Mirowicz, B. Machaj

A scintillation probe with a photomultiplier tube(PM) is a very sensitive detector of ionization radia-tion especially of gamma radiation but it exhibitsone serious drawback: the gain of such a probe isunstable resulting in considerable errors of countrate and consequently in the measured quantity.The instability of gain of the scintillation probewith the PM tube is a subject mainly to the instabi-lity of PM gain due to the ambient temperaturevariations, ageing of the PM tube, instability of PMplate voltage and statistical variation of gain. Theageing effect alone can result in a 10-20% gainvariation within a few months. If the scintillationprobe is to be employed in the heavy industrial en-vironment an automatic gain control circuit (AGC)is obligatory. To meet this requirements of a scin-tillation probe for industrial application, the AGCcircuit should ensure a proper operation of theprobe in a wide range of PM gain variations, notless than ±50% from the nominal one, and, whatmore, the AGC should recover and start automati-cally operation of the probe when the mains isswitched on after a failure of the mains even when

prior to the failure the gain of PM differed by±50% from the nominal one. The AGC circuit em-ploying the principle of comparison of count rate attwo discrimination levels can meet these require-ments [1]. Such AGC circuit was selected for con-struction of an instrument for simultaneous re-gistration of the radiation from Cs-137 and Am-241in an industrial gauge for continuous measure-ment of ash in coal transported by a conveyor belt

At nominal PM gain the output currents fromthe frequency-to-current converters FCC1 andFCC2 at the discrimination levels E4 and E5 areequal and of opposite direction (polarity). No cur-rent error is produced and no voltage error issuperimposed on the plate high voltage of PM tubederived from HV power supply. If PM gain deviatesfrom the nominal one, a current error is producedat the output of FCC1 and FCC2 converters,voltage error is generated of such a polarity as tocompensate the deviation of PM gain. To ensurewide "catching" range (to start operation aftermains failure at ±50% gain deviation) the E5 dis-

3CNOCMOCO

112 NUCLEONIC CONTROL SYSTEMS

w^ ^ ^ ^ w^Wf vll^nvl^V

» . 1100V

LV

Fig.l. Functional diagram of measuring channel and AGC circuit: SP - scintillation probe; RS - radiation source Am-241 and Cs-137; A- pulse amplifier; E l , E2 - lower and upper discrimination level of single channel analyzer; SCA - single channel analyzer forAm-241; E3 - pulse discrimination level from Cs-137; E4, E5 - lower and upper pulse discrimination level for AGC; FCC1 -frequency-to-current converter"+"; FCC2 - frequency-to-current converter"-"; I/U - current-to-voltage converter; HV - PM highvoltage power supply 900-1100 V/100^A; LV - low voltage power supply +5 V, ±15 V; nl - pulse count rate from Am-241source; n2 - pulse count rate from Cs-137 source; n4 - pulse count rate from Cs-137 at lower AGC discrimination level; nS - pulsecount rate from Cs-137 at upper AGC discrimination level; Rf- coaxial cable characteristic impedance.

crimination level (upper) is set at 660 keV, and theE4 level (lower) at approximately 420 keV.

Investigations of the circuit showed [2] that thestabilization coefficient is >100 at n5=50OO p/s, ef-

4400

4000

35O0 '

3000 '

2000 '

2000 -

1900 -

1000 '

500 -

i

0 90

AGC on and offAm-241 • Cs-137

1Avidbla (MTarMViM J 1

1 1

—vj \100 150 200 250 300 350 «

olwinib» 450 tin 550

Fig.2. Two differential spectra superimposed when the AGCcircuit was switched on and off. Channel 43 corresponds tothe 60 keV photopeak from Am-241, channel 362 corre-sponds to the 662 keV photopeak from Cs-137.

fective time constant is <1 s. No measurable increaseof FWHM was detected when the AGC loop wasclosed (AGC on) or open (AGC off), (Fig.2). Gain

variation of the PM tube by ±50% resulted in thevariation of count rate in the measuring channelfrom Am-241 and Cs-137 less than 0.15%. An ave-rage count rate of 10000 s (100 readings 100 s each)counting time within 17 h of continuous operationresulted in a minimum reading of 5570.4 ±1.22 p/s, amaximum reading of 5576.3 ±0.72 p/s from Am-241and a minimum reading of 2289.6 ±0.98 p/s, amaximum reading of 2291.4 ±0.42 p/s from Cs-137.Investigations of the influence of ambient tempera-ture variation on the electronic circuits show thatwhen the ambient temperature varies by 14.5°C thepulse count rate from Am-241 source varies by 1 p/s(0.025%) and from Cs-137 by 4 p/s (0.4%).

The work has been carried out in the frame ofthe IAEA Purchase Order No. IRA8012-190Cdated 4 September 19%.

References[l].Machaj B.: Automatic gain control circuit for scintillation

probe with plastic scintillator. Nucl. Instr. and Meth., 118,231-235 (1974).

[2]. Mirowicz J., Machaj B.: Sonda scyntylacyjna do zastosowanprzemystowych stabilizowana ukladem ARW. Institute ofNuclear Chemistry and Technology, Warszawa 1997. Rapor-ty IChTJ, Seria B nr 8/97.

i m• C M

IS

SHORT LIVED RADON DECAY PRODUCTS IN LUCAS CHAMBER

B. Machaj

The standard procedure of radon concentration mea-surement consists in introducing air into a measuringchamber, in this case the Lucas chamber, through anair filter. Thus the short lived decay products of

radon are deposited on the filter and pure radonenters the chamber. Immediately after the radon isintroduced into the chamber short lived decay pro-ducts are generated, in a radioactive series decay.


Employing known relations for radioactive seriesdecay A-»B-»C-».... [1] the increasing concentration(activity) of radon daughters in the Lucas chambercan be computed [2]. Fig.l. shows a simulated (com-puted) variation of total alpha radiation activityRn-222+Po-218+Po-214 when at time t=0 a radonconcentration of 1000 dis/min (16.7 Bq) is intro-duced into the chamber.

Fig.l. Simulated increase of total alpha activity of radon andradon daughters against time Rn-222+Po-218+Po-214when at time t=0 radon at a concentration of 1000 dis/minwas introduced into the chamber.

If in instant time t=240 min (radiation equili-brium between radon and radon daughters con-centration is achieved) only radon is removedfrom the chamber, i.e. the activity of Po-218, Pb-214and Bi-214 (Po-214) is equal to 1000*exp(-0.693/(3.982*24)*4)=970 dis/min and radon activityequals to 0, the total alpha activity of Po-218 andPo-214 decreases as shown in Fig.2. It correspondsto a hypothetical situation when the chamber is

Fig.2. Activity of alpha radiation of radon daughters from Fig.lagainst time. The time instant t=0 on the diagram cor-responds to t=240 min in Fig.l.

flushed with a clean air removing radon from thechamber and all the radon daughters are attachedto the internal walls of the Lucas chamber and re-main in the chamber. From the properties of radondaughters [3] one can expect that the radon daught-ers can attach to the walls of Lucas chamber. To seewhat part of the radon daughters attach to the wallsof Lucas chamber and remain inside the chamberafter it is flushed with the clean air, measurementswere carried out in the following way. The Lucaschamber, having dimensions 4>54x74 mm (0.17 1),

was filled with radon and was left for a time untilradiation equilibrium between the radon and itsdaughters was established. Count rate from alphaparticles (Po-218+Po-214) was measured at radia-tion equilibrium. The chamber was then flushedwith a 1.7 1 clean (ambient) air within 2 min and

(•/nw.

24009

22000

200CC

IKCO

IWOO

1*000 -

12O00 -

10000'

MOD'

6000

WOO

2000

0t

Count r x * btton «nd after flushing ttw ehwnb«r

1IM9dkMl

, . "? M .?^. . .

xSO 100 l i o ado 2SC 300 3S0 400

Fig.3. Count rate measured before and after flushing Lucas cham-ber.

count rate measurements were continued withinfurther 250 min. The results of measurements areshown in Fig.3.

A fast decrease of the alpha activity of radonchamber after the flushing indicates on the origin ofshort lived decay products of radon. The count rateratio after and before the flushing of the chamberequals to 11292/19245=0.58. Simulation computa-tions show that within the first 2 min from the startof flushing the chamber, the activity of alpha radia-tion decreases by the coefficient 0.82 which gives thecorrected ratio as 0.58/082=0.70. The expected ratio,if all the radon daughters remain inside the chamber,is 2/3=0.67 (lower than 0.70). The measurements,repeated four times, gave an average corrected ratioequal to 0.69. Taking into consideration errors of themeasurements, it can be concluded that all the shortlived decay products of radon are attached to theinternal walls of the Lucas chamber. Similar resultswere achieved (all the produced radon daughtersattached to the walls of the chamber) for the casewhen the chamber was flushed after 15 min since theradon was introduced into the chamber - no radia-tion equilibrium in the chamber. Another conclusionis that such a situation exists in other measuringchambers (semiconductor, ionization chamber) withthe dimensions similar or lower than that of theinvestigated Lucas chamber, and it must be consi-dered when continuous measurement with shortsampling time is planned.

References

[lj.The atomic nucleus. Ed. R.D. Evans. McGraw-Hill Company,1970.

[2]. Machaj B. Computations of concentration of radon and itsdecay products against time. Computer program. Institute ofNuclear Chemistry and Technology, Warszawa 1996. Rapor-ty IChTJ, Seria B nr 6/96.

[3]. Nazaroff W.W., Nero A.V.: Radon and its decay products inindoor air. John Wiley & Sons, 1988.


ASSESSMENT OF LINEAR REGRESSION MODELS USING THE BOOTSTRAP

P. Urbariski, E. Kowalska

The bootstrap is one of the computer intensivemethods, which emerged in the past decade as auseful tool for constructing inferential procedures inmodern statistical data analysis. The mathematicalprinciples of the bootstrap are presented in theliterature [1-3] and examples of its application fordata analysis are also widely considered [4-6]. Thebootstrap technology is very useful when used for de-termination of the confidence limits of the estimatedparameters of the regression models. Conventionalmethods of the confidence limits estimation dependon normality assumption for the error distributionand can be applied only for the least squares method[3-4].

(a)

3 5 0

3 0 0

2S0

200

150

100

SO

•50

0 9990 99?

0.95fj'90

f OSQ

0. 025

0.05mQ.0P3

. ...

'jA

".1

; ; }

c/Lz.'fy «jh «...

Considering a linear regression modely = bo + bix + ej (1)

where x is an independent variable (e.g. intensity ofmeasured radiation), and y is a dependent variable(e.g. concentration of an element in a sample), weassume, that ej is independent, identically distributed(i.i.d.) random variable of distribution F.

ei,£2, . . . , £ j , . . . , en ~ F (2)The estimate of the parameters bo and bi can be

obtained using, for example, the least squares prin-ciple:

2, 9 (3)(yj-bo-biXj)

350

300

280

200

(b)

1S0

too

•0.0S

(d)

Norrrnf Probtbtlity Plot

0.9990.997

0,003

amy - i . , . ; . . , : .:...

•40 -50 0 20 4>84&& ^ 0.020.040OStO** hO ti* - *1

Fig.l. Distribution functions of the regression coefficients bo (a) and t>i (b) and their normal probability plots (c)-(d).


The bootstrap algorithm for estimation of thestatistical distribution of these parameters can besummarised as follows:(i) It is assumed that the probability mass of eachobserved residual ej is 1/n.(ii) A bootstrap data set is constructed:

yf = b0 + + ef (4)fwhere ef are drawn independently of F, whereas boand bf are calculated using least square constraint:

n . (5)b&bf:min2 <yf - bfl - bjks)2

i = l

(iii) The step (ii) is repeated B times yielding boot-strap replications:

b51,b52)...)b5J)...,b5B (6)

bf.bf2 bjl bfB

The calculated replicates can be used for deter-mination of the empirical distribution of predictionerror D*nv:

D^v = yp* - yp = (bo - b5) + (7)+ (bx - b|)xp + 4

where: xp - a value of the independent variable x forwhich corresponding value yp of dependent variabley is determined using equation (1); e£ - vector ofresiduals.

An alternative to resampling residuals could beto perform resampling vector of the observationpairs (XJ, yi). Such procedure is preferred in the casewhen residuals are correlated.Table. Moments of the distribution function of the regression

coefficients bo and bi .

Moment

bobl

E(b&" - b0)

E(bl - bi)

«GX»«0>l)Kt>0)y(bl)

Classicalregression

theory

-111.67

1.0156

0

0

7.6989

0.0134

0

0

Bootstrap

Resampledvariables

-112.24

1.0162

-0.5713

0.0006

6.9101

0.0118

-1.1185

0.5584

Resampledresiduals

-111.55

1.0154

-0.1170

0.0002

7.2513

0.0134

-0.0978

0.0978

E - mean values.a - standard deviations.y - skewness.

The bootstrap method was applied for assess-ment of the estimated parameters of the calibrationmodel of the radiometric sulphuric acid concen-tration gauge MSK-6 [7-8]. The numerical values ofthe first three moments of the estimated parame-ters bo and bi distribution are presented in Table.Fig.l shows diagrams of the distributions of thisparameters together with their normal probabilityplots. The distribution of the prediction errors forthe inverse approach Djnv and for the classicalapproach Dci are shown in Fig.2.

•ED

2DD

100

n

JjkJIIL

-50 90 -63

Fig.2. Distribution function of prediction errors for inverse (a)and classical (b) approach for three different values of xp.

The obtained results show that although thedifferences in the numerical values of the estimatedparameters determined with classical and bootstrapmethods are relatively small, their distribution de-termined using bootstrap shows some asymmetry.Also the distribution function of the predictionerror is asymmetrical but differs considerably fromthe normal plot. It can be concluded that the boot-strap methodology can be very useful for detailedanalysis of the calibration models parameters.

References[1], Hall P.: The Bootstrap and Edgeworth Expanision. Springer-

-Verlag, New York 1992.[2], Efron B., Gong G.: A Leistureh/ Look at the Bootstrap, the

Jackknife and Cross-Validation. Am. Statistician, 52, 36-8(1983).

[3]. Leger Ch., Politis O.N., Romano J.P.: Bootstrap Technologyand Applications. Technometrics, 34,378-397 (1992).

[4]. Roy T.: Bootstrap Accuracy for Non-Linear RegressionModels. J. of Chemometrics, g, 37-44 (1994).

[5].Bonate P.: Approximate Confidence Intervals in CalibrationUsing the Bootstrap. Analyt. Chem., £5_,1367-1372 (1993).

[6].Jones G., Wontberg M., Kreissig S.B., Hammock B.D.,Rocke D.M.: Application of the Bootstrap to Calibration Ex-periments. AnaJyt. Chem., 6j$, 763-70 (1996).

[7].Mirowicz J.: Zastosowanie przemystowych radioizotopowychmiernikow ste^ert kwasu siarkowego i oleum. Materiafy Krajo-wego Sympozjum 'Technika Jadrowa w Przemysle, Medycynie,Roinictwie i Ochronie Srodowiska", Warszawa 24-27.04.1995,pp. 297-300.

[8]. Urbariski P., Kowalska E.: Zastosowanie metody bootstrapdo badania liniowych modeli regresyjnych. Institute of Nuc-lear Chemistry and Technology, Warszawa 1997. RaportyIChTJ. Seria B nr 10/97.


PRELIMINARY RESULTS OF CARBON CONTENT DETERMINATIONINCOALBYXRF

J.L. Parus, J. Kierzek, B. Maiozewska-Buc'ko

Modern XRF spectrometers enable the determi-nation of light chemical elements. We have tried todetermine the carbon content in hard coals burnt inthe coal fired power stations producing hot waterand electricity. The main difficulty in XRF analysisof carbon, resulting from the basic physics, is a verylow X-ray fluorescence yield for this element. Itamounts to 0.0026 only [1]. The K absorption edgefor carbon is 283 eV and, on other hand, the cut-offenergy of X-ray tube is about 2 keV. It is a ratherwide energy- gap between the available tube radia-tion and the carbon K edge that, in consequence,decreases the overall excitation efficiency.

It was shown that the photoelectrons ejected fromthe K-shell of carbon atoms contribute significantlyto the excitation of CKa X-rays. Due to this effectthe CK# counts of pure carbon are increased by afactor of 2.5 to 3 and the count rate ratios in an Fe-Cbinary system increase by a factor of 5 to 10 [2].

It is surprising for us that till now nobody at-tempted to use this technique for direct carbon de-termination in coals. We are aware that a very lowenergy of CKa X-rays makes available for analysisonly a few micrometers layer of analyzed sampleand this, in turn, increases the requirements con-cerning its homogeneity.

Measurements were carried out using a PhilipsPW-1480 sequential spectrometer equipped with arodium side window X-ray tube operated at 40 kVand 70 mA. A PX4 multilayer structure with a 122nm 2d spacing was used as an analyzing crystal.CKa X-rays were measured at 42.77° 2 Q angle andthe background channels were ±5.1° on both sidesof the CKa. A coarse collimator and a flow propor-tional counter with a 1 m polypropylene windowwere used. The measurement time was 60 and 20 sfor a line and background intensity measurement,respectively.

The samples for measurements were prepared in apellet icrrri. One gram of finely powdered coal was

uniformely spread as a disk of 28 mm diameter in a40 mm diameter pellet die, covered with 6 g of aboric acid powder and a pellet was fabricated in thedie under a pressure of 230 MPa.

The relationship between the CKa line intensityand the carbon content for several samples of thehard coal is shown in Fig. This is a linear functionwith a coefficient of correlation above 0.99. Usingthis function, the carbon content in a referencesample, containing 66.7%, was found to be 63.8%.This significant difference may be caused by theerrors of carbon determination in the samples usedfor preparaton of the regression line. The analytical

o •

5-

IIO 2-

1 •

0

y «O.I21x-3.%WR3 - 0.9914

1 1 1 —i 1

50 m 70 75 SO60 65Cartxm content, %

Fig. CKcr intensity vs. carbon content.

sensitivity for carbon is about 120 counts s'1%'1.This means that the counting error in a countingtime of 60 s will be negligible. This sensitivityshould also be sufficient for the determination ofcarbon content in the ash after burning of coal,which is usually a few per cent. More detailedstudies are continued.

References

[1]. Vrebos B.A.R., Kuiperes O.TJ.: Adv. in X-ray Anal, 26, 73(1993).

[2]. Manlier M: Adv. in X-ray Ana!., 3& 27 (1993).

SCO

ISIS'8

A NEW TOTAL REFLECTION X-RAY FLUORESCENCE SPECTROMETER

J. Kierzek, J.L. Parus, B. Maiozewska-Budko, U. Waldscbiager1'x/ Institute of Enviromental Technology, Berlin, Germany

The continuous progress in XRF analytical applica-tions is achieved through the analysis of new ma-terials, progress in instrumentation and improvementof analytical procedures. Multielement capability, re-latively simple sample preparation and short analysistime render the XRF a very suitable technique formonitoring the environment pollution with inorganicconstituents. For this purpose a high detectability isrequired. A relatively new total reflection X-ray fluo-rescence (TXRF) spectrometry seems to be here a

method of choice. The first paper on this techniqueappeared in 1971 [1]. Detailed description of thismethod can be found in a book [2]. The TXRF, basedon the total reflection of exciting radiation from avery smooth sample support shows a very high re-duction of scattered radiation, usually about threeorders of magnitude, in comparison to conventionalXRF. The main features of TXRF are [3]:1) a beam of exciting radiation strikes the analyzedsample under an angle smaller than the critical


angle for which a total reflection is effected,2) an exciting beam strikes a very flat surface whichis a support for a very thin sample deposited on itor is itself an object of analysis (surface analysis).

The TXRF has been used for trace element ana-lysis in many fields, e.g. in water, soil and atmo-spheric air for environmental protection [4,5], inblood, body fluids and tissues [6,7], in food andplant materials [8,9], in ultrapure water, chemicalreagents, metals in chemical industry products[10,11], in minerals and geological samples [12,13],in semiconducting materials [14], in thin layers ofmultilayered structures [15]. Capabilities and com-parison of TXRF with other analytical methods canbe found in [2,16].

The TXRF spectrometer described below hadbeen designed and constructed at the Institute of En-vironmental Technology in Berlin. The design guide-lines were consulted with the Laboratory of Micro-and Trace Analysis of University in Antwerp. Theinstrument was installed and put into operation atthe Department of Structural Research in December1997.

A diagram of the spectrometer is shown in Fig.As can be seen in this Fig. a primary excitationbeam from a fine focus (focal spot area 0.4x8 mm2)molybdenum anode of diffraction X-ray tube (Sei-fert FK-61-04) of 2 KW power is partly mono-X-RayTubc Double Reflector Sample Carrier

with Sample Rim

Filter

Si(Li) Detector

Fig. Schematic picture of the TXRF spectrometer.

chromatized by a filter and a double reflector. The50 fim Mo filter minimizes the background level inthe low energy region of an X-ray spectrum. Thedouble reflection block made of quartz glass is 100mm long and is fixed together with two spacers (50fim thick) between the reflector blocks. Such adouble reflection block is acting as a low-pass orcutoff filter. It transmits the low-energy part of theprimary beam and eliminates the high-energy part[2]. This arrangement is adjusted to cutoff energy ofabout 20 keV. The highly energetic bremsstrahlungprimary spectrum is eliminated by scattering orabsorption. The shape and intensity of the beam isoptically checked by the Zn-S screen. The doublereflection block directs the X-ray beam towards thesample placed on the support and it is totally re-flected at this sample carrier at the grazing incid-ence. A small amount of sample placed on the car-rier is excited and the characteristic X-ray radiationpartly enters a Si(Li) detector. Due to the smallincidence angle and the collimation to a narrowbeam, the detector entrance window is situatedclose to the sample (a distance of a few mm).

Several materials have been used as samplecarriers: especially quarz glass, polymethyl metha-crylate (Plexiglass), glassy carbon, boron nitride,silicon and germanium. Usually the sample carriersare in the form of circular disks with a diameter of30 mm and a thickness of 2 to 3 mm. The criticalangle of total reflection for this materials andMo-Ka tube radiation amounts to about 0.1°.

The samples should be available in the form ofaqueous or organic solutions, emulsions, suspen-sions. Aliquots from 1 to 100/d are pipetted on thecenter of the sample carrier and allowed to dry to athin film with a diameter of 5-8 mm.

A Si(Li) detector of 80 mm2 area, 5.5 mm thick-ness and 180 eV energy resolution for MnKa line isused. The spectra are stored in a multichannel ana-lyzer (MCA) memory. The raw data are processedby a personal computer using the QXAS programs.

The described TXRF spectrometer offers ad-vanced methods of trace element analysis in a vari-ous type of samples. Due to a compact geometry ofmeasurement and a very high reduction of the scat-tered radiation intensity the very low detectionlimits in a few picogram range for about 60 ele-ments are achieved. This corresponds to concentra-tion in solution at 10 ppb level. With the use ofenrichment in the sample preparation procedurethe detection limit can be lowered below 1 ppb.This is valid for elements with atomic numbersZ>19 (potassium). A very important application ofTXRF is the analysis of surfaces in the semicon-ductor industry. In case of the polished siliconplates the detection limit for heavy elements islower than 109 atoms/cm2.

References

[1]. Yoneda Y., Horiuchi T.: Optical Flats for Use in X-ray Spec-trochemical Microanalysis. Rev. Sci. Instr., 42,1069 (1971).

[2]. Klockenkamper R.: Total-Reflection X-Ray FluorescenceAnalysis. John Wiley & Sons, Inc., New York 1997.

[3]. Schwenke H., Knoth X: Total Reflection XRF. In: Hand-book of X-Ray Spectrometry, Methods and Techniques.Eds. R.E. van Grieken, A.A Markowicz. Marcel Dekker,Inc., New York 1993.

[4].Koopmann C , Prange A : Multielement determination insediments from the German Wadden Sea-investigations onsample preparation techniques. Spectrocbim, Acta, 46E,1395 (1991).

[5]. Schneider B.: The determination of atmospheric trace metalconcentrations by collection of aerosol particles on sampleholders for total-reflection X-ray fluorescence. Spectro-chim. Acta, 44B, 519 (1989).

[6].Ayala R.E., Alvarez E.M., Wobrauschek P.: Direct deter-mination of lead in whole human blood by total reflectionX-ray fluorescence spectrometry. Spectrochim. Acta, 46B,1429 (1991).

[7]. Klockenkamper R., von Bohlen A., Wiechen B.: Quanti-fication in total reflection X-ray fluorescence analysis ofmicrotome sections. Spectrochim. Acta, 44B, 511 (1989).

[8]. Wobrauschek P., Streli C , G6rgl R., Ladisich W.: TotalReflection X-Ray Fluorescence Analysis and Its VersatileApplicability to Environmental Samples. In: Proceedings ofthe Symposim on Applications of Isotopes and Radiation inConservation of the Environment, Karlsruhe, 9-13 March1992. IAEA, Vienna 1992.

[9]. Giinther K., von Bohlen A.: Multielement speciation in vege-table foodstuffs by gel permeation chromatography (GPC)and total reflection X-ray fluorescence (TXRF). Spectro-chim. Acta, 4j£B, 1413 (1991).


[10]. Prange A., Kramer K., Reus U.: Determination of traceelement impurities in ultrapure reagent by total reflectionX-ray spectrometry. Spectrochim. Acta, 46H, 1385 (1991).

[llJ.Bilbrey D.B., Leland D.J., Leyden D., Wobrauschek P.,Aiginger H.: Determination of metals in oil using total re-flection X-ray fluorescence spectrometry. X-Ray Spectrom.,16,161 (1987).

[12]. Michaelis W., Prange A,: Trace analysis of geological andenvironmental samples by total-reflection X-ray fluorescencespectrometry. Nud. Geophys., 2,231 (1988).

[13]. Muia L., van Grieken R.: Determination of rare earth ele-ments in geological materials by total reflection X-ray fluo-rescence. Anal. Chim. Acta, 251,177 (1991).

[14]. Penka V., Hub W.: Application of total reflection X-rayfluorescence in semiconductor surface analysis. Spectro-chim. Acta, 44R, 483 (1989).

[15]. De Boer D.K.G., van den Hoogenhof W.W.: Total re-flection X-ray fluorescence of single and multiple thin-layersamples. Spectrochim. Acta, 46R, 1323 (1991).*

[16]. Tolg G., Klockenkamper R.: The role of total-reflectionX-Ray fluorescence in atomic spectroscopy. Spectrochim.Acta,4£B_, 111(1993).


THE INCT PUBLICATIONS IN 1997

1. Althaus F.R., Kleczkowska H.E., Malanga M., Miintener C, Pleschke J.M.Poly ADP-ribosylation: A DNA damage signal mechanism?The 12th International Symposium on ADP-ribosylation Reactions. From Bacterial Pathogenesis toCancer. Cancun, Mexico, 10-14.05.1997, p. 90.

2. Ambroz H.B., Kemp T.J., Kornacka E.M., Przybytniak G.K.Damages or protections of DNA following irradiation.International Conference of PhD Students. Section proceeding. Medical Science. Book of Abstracts.Miskolc, Hungary, 11-17.08.1997.

3. Ambroz H.B., Kemp T.J., Kornacka E.M., Przybytniak G.K.Effects of transition metals ions on radiation-induced damage to DNA.Third European ESR Meeting on Modern Aspects of Structure and Dynamic Investigations of Para-magnetic Systems by EPR. Book of Abstracts. Leipzig, Germany, 25-28.08.1997, p. P54.

4. Ambroz H.B., Kemp T.J., Kornacka E.M., Przybytniak G.K.Radiation-induced damage to DNA. The influence of copper and iron ions.XVII Conference on Radio- and Microwave Spectroscopy. Poznan, Poland, 22-25.04.1997, p. P-85.

5. Ambroz H.B., Kemp T.J., Przybytniak G.K.Unusual features in the triplet state EPR spectrum of 3,5-dichloro-4-aminophenyl cation.Journal of Photochemistry and Photobiology. A: Chemistry, 108,149-153 (1997).

6. Ambroz H.B., Kemp T.J., Przybytniak G.K., Sevilla M.D.The matrix effect in EPR spectroscopy of aryl cations of strong dipolar interaction.Third European ESR Meeting on Modern Aspects of Structure and Dynamic Investigations of Para-magnetic Systems by EPR. Book of Abstracts. Leipzig, Germany, 25-28.08.1997, p. L8.

7. Ambroz H.B., Kornacka E., Przybytniak G.K., Wronska T.Radiation-induced damage to DNA30th Annual International Meeting: ESR Spectroscopy of Radicals in Organic and Biological Sys-tems. Lancaster, England, 6-10.04.1997.

8. Ambroz H.B., Przybytniak G.K., Kappl R.Proton hyperfine splittings in aryl cations 3Ar+, an ENDOR study.Third European ESR Meeting on Modern Aspects of Structure and Dynamic Investigations of Para-magnetic Systems by EPR. Book of Abstracts. Leipzig, Germany, 25-28.08.1997, p. P67.

9. Balanda M., Hofmann M., Kolenda M., Leciejewicz J., Penc B., Szytuta A., Zygmunt A.Struktury magnetyczne zwia_zkow miedzymetalicznych RNiSi (R=Tb-Er) (Magnetic structures ofintermetallic compounds RNiSi (R=Tb-Er).Og61nopolskie Seminarium Rozpraszania Neutron6w. Streszczenia. Chlewiska k/Siedlec, Poland,26-28.11.1997, p. 30.

10. Baran S., Hofmann M., Leciejewicz J., Slaski M., Szytuta A., Zygmunt A,Antiferromagnetism of ternary lanthanide stannides RAuSn (R=Pr, Nd, Gd-Er).Journal of Physics: Condensed Matter, 9,9053-9063 (1997).

11. Baran S., Leciejewicz J., Hofmann M., Stiisser N., Szytula A.Systematyka struktur magnetycznych zwia,zk6w miedzymetalicznych RTSn (T=Cu, Ag, Au) (Syste-matics of magnetic structures of intermetallic compounds RTSn (T=Cu, Ag, Au).Og61nopolskie Seminarium Rozpraszania Neutronow. Streszczenia. Chlewiska k/Siedlec, Poland,26-28.11.1997, p. 29.

12. Baran S., Leciejewicz J., Stiisser N., Ding Y., Szytuta A.Magnetic structures of HoRh2-xRuxSi2 compunds.

120 THE INCT PUBLICATIONS IN 1997

Journal of Alloys and Componds, 262-263,225-228 (1997).

13. Baran S., Leciejewicz J., Stusser N., Dong Y,, Szytuła A., Zygmunt A.Magnetic structures of HoRh2-xRuxSi2 compounds.Seminarium "Nieuporządkowane struktury krystaliczne" i XXXIX Konwersatorium Krystalograficz-ne. Wrocław, Poland, 25-27.06.1997, p. 111.

14. Baran S., Leciejewicz J., Stusser N., Szytuła A., Tomkowicz Z.Incommensurate-commensurate magnetic phase transition in TbCuSn.Solid State Communications, 101,8,631-634 (1997).

15. Baran S., Leciejewicz J., Stusser N., Szytuła A., Zygmunt A., Ding Y.Neutron diffraction study of magnetic ordering in RAgSn (R=Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er) com-pounds.Journal of Magnetism and Magnetic Materials, 170,143-154 (1997).

16. Baran S., Leciejewicz J., Śląski M., Szytuła A., Penc B., Ding Y., Stusser N.Spin glass behaviour observed in the RGauNio.3 (R=Gd-Ho) and RGai.sCuo.5 (R=Gd, Tb) phases.Journal of Alloys and Compounds. Letter, 256, L18-L21 (1997).

17. Baran S., Szytuła A., Leciejewicz J., Stusser N., Zygmunt A., Tomkowicz Z,, Guillot M.Magnetic structures of RCuGe (R=rare earth) compounds.Physica B. Condensed Matter, 234-236,656-658 (1997).

18. Bartoś B., Bilewicz A., Delmas R., Loos-Neskovic C.Synthesis and ion exchange properties of various forms of manganese dioxide for cations of the I andII groups.Solvent Extraction and Ion Exchange, 15,3,533-546 (1997).

19. Bażela W., Baran S., Leciejewicz J., Szytuła A., Ding Y.Magnetic structures of TbPd2Si2 and TbPd2Ge2 a redetermination.Journal of Physics: Condensed Matter, 9,2267-2273 (1997).

20. Biesaga M., Kwiatkowska M., Trojanowicz M.Separation of chlorine-containing anions by ion chromatography and capillary electrophoresis.Journal of Chromatography A, 777,375-381 (1997).

21. Bilewicz A.Solvent extraction of groups 4 and 14 metal chelate complexes: Model experiments for chemicalstudies on coordination number of element 104.Journal of Radioanalytical and Nuclear Chemistry, 221,1-2,19-22 (1997),

22. Bobrowski K., Holcman J., Poznański J., Wierzchowski K.L.Pulse radiolysis studies of intramolecular electron transfer in model peptides and proteins. 7.Trp-»TyrO* radical transformation in hen egg-white lysozyme effects of pH, temperature, Trp62oxidation and inhibitor binding.Biophysical Chemistry, 63,153-166 (1997).

23. Bobrowski K., Hug G.L., Marciniak B., MiiSer B., Schoneich Ch.Catalysis through intramolecular proton transfer and sulfur-oxygen-bond formation during photo-oxidation of hydroxyalkyl sulfides.XVIIIth International Conference on Photochemistry. Book of Abstracts. Warszawa, Poland,3-8.08.1997, p. IP6.

24. Bobrowski K., Hug G.L., Marciniak B., Miller B., Schoneich Ch.Mechanism of one-electron oxidation of /?-, -/-, and <5-hydroxyalkyl sulfides. Catalysis through intra-molecular proton transfer and sulfur-oxygen-bond formation.Proceedings of the Twenty-First Doe Solar Photochemistry Research Conference. Book of Abstracts.Copper Mountain, Colorado, USA, 7-11.06.1997, p. 121.

25. Bobrowski K., Hug G.L., Marciniak B., Miller B., SchSneich Ch.Mechanism of one-electron oxidation of /3-, y-, and <5-hydroxyalkyl sulfides. Catalysis through intra-molecular proton transfer and sulfur-oxygen bond formation.


Journal of the American Chemical Society. 119,34,8000-8011 (1997).

26. Bobrowski K., Pogocki D., Hug G.L., Schftneich Ch.

OH-radical-induced oxidation of S-alkylglutathiones derivatives in aqueous solutions.20th Miller Conference on Radiation Chemistry. Programme and Abstracts. Bowness-on-Winder-mere, Cumbria, United Kingdom, 22-27.03.1997,1 p.

27. Bobrowski K., Pogocki D., Hug G.L., SchOneich Ch.Peptide bond participation in the *OH radical induced oxidation of S-alkylglutathiones.5th International Meeting on Pulse Investigations in Chemistry, Biology and Physics. PULS'97.Szczyrk, Poland, 13-19.09.1997, pp. S2-P1.

28. Bobrowski K., Schttneich Ch,Wewnatrzczasteczkowe przeniesienie protonu pomiedzy kwasem glutaminowym i metionin^ w pepty-dach oligoprolinowych (Intermolecular proton transfer between glutamic acid and methionine inoligoproline peptides).XL Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inzynierow i Technik6wPrzemyshi Chemicznego. Streszczenia. Gdansk, Poland, 22-26.09.1997, p. S-17, K3.

29. Bojarski J., Legocka I., Zimek Z.Adhesive properties of heat-melt glue modified by radiation.10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, 11-16.05.1997, p. 35.

30. Bojarski J., Strzelczak G., Zimek Z.Radiacyjna odpornos'C poliolefin i ich kompozyt6w. Cz.I. Polipropylen. (Radiation resistance of poly-propylene and its composites. Part I. Polypropylene).Polimery, 42,3,189-194 (1997).

31. Bojarski J., Zimek Z.

Polipropylen modyfikowany odporny radiacyjnie (Modified polypropylene radiation resistant).IV Wiosenna Szkola Sterylizacji Radiacyjnej Sprze.tu Medycznego, Przeszczep6w, Farmaceutyk6w iKosmetyk6w. Warszawa, Poland, 26-27.05.1997, pp. XVII/l-XVII/7.

32. Borkowski M., Lis S., Choppin G.R.

Extraction of NpO2- from NaCl and NaClO4 solutions at various ionic strength for calculation ofpitzer parameters.Sixth International Conference on the Chemistry and Migration Behaviour of Actinides and FissionProducts in the Geosphere. Migration'97. Abstracts. Sendai, Japan, 26-31.10.1997, pp. PA2-04.

33. Bouzyk E., Iwaneriko T., Jarocewicz N., Kruszewski M.. Sochanowicz B,, Szumiel I.Antioxidant defense system in differentially hydrogen peroxide sensitive L5178Y sublines.Free Radical Biology and Medicine, 22,4,697-704 (1997).

34. Bouzyk E., Kruszewski M.

Uszkodzenia DNA wywolane przez jony Cr(VI) w dw6ch podliniach mysiej bialaczki L5178Y r6z-ni^cych sie, aktywnoSci^ enzym6w antyoksydacyjnych (DNA damage caused by Cr(VI) ions in twoL5178Y mouse lymphoma sublines with various antioxidant enzyme activities).XXXIII Zjazd Polskiego Towarzystwa Biochemicznego. Streszczenia. Katowice, Poland, 9-12.09.1997,p. 95.

35. Buczkowski M., Wawszczak D., Starosta W.

Trekowe membrany filtracyjne oraz ich zastosowania biomedyczne (Particle track membranes andtheir biomedical application).IV Wiosenna Szkola Sterylizacji Radiacyjnej Sprze,tu Medycznego, Przeszczepow, Farmaceutyk6w iKosmetyk6w. Warszawa, Poland, 26-27.05.1997, pp. XVIII/l-XVIII/10.

36. BukowskiP.Badania por6wnawcze rdznych gatunkow we.gla (Comparative studies on various sorts of coal).Branzowy Magazyn Przemystowy. Energetyka Cieplna i Zawodowa, 21,3-30 (1997).

122 THE 1NCT PUBLICATIONS IN 1997

37. Charzynska M., LeSniewska J., Grqdzka I., Szumiel I.

Degradation of nuclear DNA during higher plant development - programmed cell death of anthertapetum.Plant Cytogenetics. Spring Symposium. Abstracts. Cieszyn, Poland, 19-22.05.1997, p. 67.

38. Chmieiewski A.G.

Electron beam exhaust gas treatment.Interregional Training Course on Developments in the Application of Electron Beams in Industryand Environmental Protection. Warszawa, Poland, 6-17.10.1997.


Praktyczne zastosowania techniki jadrowej w przemys'le (Practical applications of nuclear techniquein industry).Branzowy Magazyn Przemyslowy. Przemysl Chemiczny, 19,6 (1997).


Przemyslowe zastosowania wiazki elektronow (Industrial applications of electron beams).Sympozjum "Promieniowanie. Historia i Wspolczesno^". Lodz, Poland, 24-25.04.1997, pp. 75-92.

41. Chmieiewski A.G.Przemyslowe zastosowania wiazki elektron6w (Industrial applications of electron beams).IV Wiosenna Szkola Sterylizacji Radiacyjnej Sprzetu Medycznego, Przeszczepow, Farmaceutyk6w iKosmetyk6w. Warszawa, Poland, 26-27.05.1997, pp. XXII/l-XXII/17.


Recent development in electron beam flue gas treatment in Poland.10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, 11-16.05.1997, p. 62.


Solid waste treatment.Interregional Training Course on Developments in the Application of Electron Beams in Industryand Environmental Protection. Warszawa, Poland, 6-17.10.1997.

44. Chmieiewski A.G.Technological and economical aspects of electron beam application for simultaneous SO2 and NOX

removal.Osma Mie.dzynarodowa Konferencja "Elektryczny t u k t^czeniowy" oraz Sympozjum "Elektrotech-nologie Ochrony Srodowiska". Materialy Konferencyjne (Cze.sC" I.). Lodz, Poland, 3-6.09.1997, pp.332-334.

45. Chmieiewski A.G., Harasimowicz M.

Influence of gamma and electron irradiation on transport properties of nanofiltration and hyper-filtration membranes.Nukleonika, 42,4,857-862 (1997).

46. Chmieiewski A.G., Harasimowicz M., Zakrzewska-Trznadel G.

Purification of radioactive wastes by low temperature evaporation (membrane distillation).Separation Science and Technology, 32,1-4,709-720 (1997).

47. Chmieiewski A.G., Iller E.Alternatywna technologia jednoczesnego usuwania SO2 i NOx (Alternative technology of simulta-neous removal of SO2 and NOx).Budownictwo Technika Ekologia, 1,47-48 (1997).

48. Chmieiewski A.G., Iller E.Nowa technologia jednoczesnej eliminacji SO2 i NOx z gaz6w odiotowych (New simultaneous tech-nology of removal SO2 and NOx from flue gases).Environment 97. Ochrona Srodowiska w Duzych Miastach i Aglomeracjach Miejskich. tod2, Poland,17-18.06.1997, p. 1.


49. Chmielewski A.G., Mer E.Nowa technologia jednoczesnej eliminacji SO2 i NOx z gazów odlotowych (New simultaneous tech-nology of removal SO2 and NOx from flue gases).Konferencja Naukowo-Techniczna nt. "Ochrona Powietrza. Nowoczesne Technologie w Świetle Obo-wiązujących Norm". Poznań, Poland, 5-6.06.1997,10 p.

50. Chmielewski A.G.,IUer£.Technical and economical aspects of electron beam installations for treatment of flue gas from powerplant.International Symposium on Radiation Technology for Conservation of the Environment. ExtendedSynopsis. Zakopane, Poland, 8-12.09.1997.

51. Chmielewski A.G., Owczarczyk A., Romanowski M., Urbański P., Stcgowski Z., Nowak K., Tańczyk R.,Pachan M., Jabłoński R.Zastosowanie technik jądrowych w Polsce (Application of nuclear techniques in Poland).Perspektywy Wykorzystania Atomistyki w Polsce. Referaty sesji naukowej V Walnego Zjazdu Polskie-go Towarzystwa Nukleonicznego. Raport PTN 1/97. Warszawa, Poland, 7.12.1996, pp. 5-13.

52. Chmielewski A.G., Owczarczyk A., Romanowski M., Urbański P., Stcgowski Z., Nowak K., Tańczyk R.,Pachan M., Jabłoński R.Zastosowanie technik jądrowych w Polsce (Application of nuclear techniques in Poland).Postępy Techniki Jądrowej, 40,2,7-16 (1997).

53. Chmielewski A.G., Tymiński B., Dobrowoiski A., Sato S., Tokunaga O., Machi S.Influence of gas flow patterns on NOx removal efficiency.10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, 11-16.05.1997, p. 59.

54. Chmielewski A.G., Tymiński B., Dobrowoiski A., Tokunaga O., Machi S.Influence of dose distribution and flow pattern between irradiation stages on removal of NOx.International Symposium on Radiation Technology for Conservation of the Environment. ExtendedSynopsis. Zakopane, Poland, 8-12.09.1997.

55. Chmielewski A.G., Tymiński B., Iller E., Zimek Z., Licki J.New developments in electron beam applications for industrial off-gases purification.The Fourth International Conference on Advanced Oxidation Technologies for Water and Air Reme-diation. Abstracts. Orlando, Florida, USA, 23-26.09.1997, p. 47-48.

56. Chmielewski A.G., Tymiński B., Zakrzewska-Trznadel G., Tokunaga O., Machi S.Collection and application of by-product formed in EB flue gas treatment process.International Symposium on Radiation Technology for Conservation of the Environment. ExtendedSynopsis. Zakopane, Poland, 8-12.09.1997.

57. Chmielewski A.G., Urbański T.S., Migdał W.Separation technologies for metals recovery from industrial wastes.Hydrometallurgy, 45,333-344 (1997).

58. Chmielewski A.G., Zakrzewska-Trznadel G., Miljevic N.R., Hook van WA.Multistage process of deuterium and heavy oxygen enrichment by membrane distillation.Separation Science and Technology, 32,1-4,527-539 (1997).

59. Chmielewski A.G., Zimek Z., Bułka S., Licki J., Villanueva L., Ahumada L., Honkonen V., Nichipor H.Electron-beam treatment for high-sulfur gases, with and without ammonia injection.10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, 11-16.05.1997, p. 60.

60. Chmielewski A.G., Zimek Z., liter E., Tymiński B., Licki J.Intense electron beam application for flue gas treatment.1997 IEEE International Conference on Plasma Science. San Diego, California, USA, 19-22.05.1997,p. 292.

61. Chmielewski A.G., Zimek Z., Panta P., Bułka S., Licki J.Optimization of electron energy in electron beam flue gas treatment process.


10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, 11-16.05.1997, p. 61.

62. Chwastowska J., Skwara W., Sterlińska E., Dudek J., Pszonicki L.Oznaczanie i specjacja rtęci w wodach naturalnych (Determination and speciation of mercury in natu-ral waters).Materiały VI Poznańskiego Konwersatorium Analitycznego "Nowoczesne Metody Przygotowania Pró-bek i Oznaczania Śladowych Ilości Pierwiastków". Streszczenia. Poznań, Poland, 17-18.04.1997, p. 15.

63. Ciesielski B., Stuglik Z., Yakushev A.B.The effect of high let of the Fe ions on the shape and power saturation of EPR signal induced in ala-ninę.Scientific Report 1995-1996, JINR Dubna 1997, pp. 194-195.

64. Ciesielski B., Stuglik Z., Yakushev A.B.The effects of 108 MeV Fe-56 ions on free radical relaxation in polycrystalline L-«-alanine measuredby EPR spectroscopy.VI International School-Seminar "Heavy Ion Physics". Abstracts. Dubna, Russia, 22-27.09.1997, pp.265-266.

65. Cieśla K., Ferain E., Legras R., Vansant E.F., Grzebieniak K.Wpływ promieniowania ciężkich jonów na przekształcenia strukturalne folii poliestrowych (The in-fluence of heavy ions irradiation on the structural changes in polyester films).XL Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i TechnikówPrzemysłu Chemicznego. Streszczenia. Gdańsk, Poland, 22-26.09.1997, p. S12, Pil.

66. Cieśla K., Ferain £., Legras R., Vansant E.F., Trautmann Ch., Grzebieniak K.Application of DSC for the studies of heavy ion irradiation effects in polyester films.Calorimetry Experimental Thermodynamics and Thermal Analysis Conference. CETTA'97. Abs-tracts. Zakopane, Poland, 8-13.09.1997, p. 139.

67. Cieśla K., Roos Y., Vansant E.F., Ghiszewski W.Physico-chemical changes in gamma irradiated proteins studied by thermal analysis.Calorimetry Experimental Thermodynamics and Thermal Analysis Conference. CETTA'97. Abs-tracts. Zakopane, Poland, 8-13.09.1997, p. 38.

68. Cieśla K., Vansant E.F., Roos Y., Ghiszewski W.Badania, przy zastosowaniu metod analizy termicznej, wpływu promieniowania gamma na przebiegdenaturacji i rozkładu termicznego białek (The influence of gamma irradiation on denaturation andthermal decomposition processes in proteins studied by thermal analysis).XL Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i TechnikówPrzemysłu Chemicznego. Streszczenia. Gdańsk, Poland, 22-26.09.1997, p. S19, PI.

69. Cromer S., Hambright P., Grodkowski J., Neta P.Tetrabenzoporphyrins: metal incorporation and exchange kinetics, ligational equilibria and pulseradiolysis studies.Journal of Porphyrins and Phthalocyanines, 1,45-54 (1997).

70. Danko B., Dybczynski R.Determination of molybdenum and uranium in biological materials by radiochemical neutron activa-tion analysis.Journal of Radiochemical and Nuclear Chemistry, 216,1,51-57 (1997).

71. Deimas R., Loos-Neskovic C, Bartoś B., Bilewicz A., Hussonnois M., Ardisson G.Searching for cluster decay of 2 3 2Th: A chemical separation scheme for sodium-24 from thorium.Radiochimica Acta, 76,181-184 (1997).

72. DembińskiW.Rynek uranu oraz produkcji i przerobu paliw reaktorowych, 1995/1996 (The market of uranium andreactor fuel production and reprocessing, 1995/1996).Postępy Techniki Jądrowej, 40,1,7-10 (1997).


73. Beptula A., Lada W., Croce F., Appetecchi G.B., Ciancia A., Giorgi L., Brignocchi A., Bartolomeo Di A.Synthesis and preliminary electrochemical characterization of LixMn2CM±(5 (x=0.55-l.l) powdersobtained by the complex sol-gel process (CSGP).Proceedings of the Second International Symposium on New Materials for Fuel Cell and ModernBattery Systems II. Montreal, Quebec, Canada, 6-10.06.1997, pp. 732-744.

74. Deptuta A., Lada W., Olczak T., Goretta K.C., Bartolomeo Di A., Casadio S.Sol-gel process for preparation of YBa2Cu4Os from acidic acetates/ammonia/ascorbic acid systems.Materials Research Bulletin, 32,3,319-325 (1997).

75. DybczyriskiR.Reference materials and their significance for quality assurance in inorganic trace analysis.Ill International Symposium "Forum Chemiczne". Book of Abstracts. Warszawa, Poland, 14-16.04.1997,pp. 10-11.

76. DybczyriskiR.The significance of very accurate RNAA methods for quality assurance and certification of candidatereference materials.Proceedings of an International Symposium on Harmonization of Health Related EnvironmentalMeasurements Using Nuclear and Isotopic Techniques. Hyderabad, India, 4-7.11.1996, Vienna, Aus-tria, IAEA, 1997, pp. 199-211.

77. Dybczynski R., Kulisa K., Polkowska-Motrenko H., Samczyriski Z., Szopa Z., Wasek M.Neutron activation analysis as a tool for checking homogeneity of certified reference materials.Chemia Analityczna, 42,815-824 (1997).

78. Dybczynski R., Polkowska-Motrenko H., Samczynski Z., Szopa Z.Nowy polski material odniesienia: Lis"cie tytoniu typu Virginia (CTA-VTL-2) dla nieorganicznejanalizy sladowej i mikroanalizy (New Polish certified reference material: Virginia Tobacco Leaves(CTA-VTL-2) for inorganic trace analysis including microanalysis).Materiafy VI Poznanskiego Konwersatorium Analitycznego "Nowoczesne Metody Przygotowania Pr6-bek i Oznaczania Sladowych Ilos"ci Pierwiastk6w". Streszczenia. Poznan, Poland, 17-18.04.1997, p. 13.

79. Dybczynski R., Polkowska-Motrenko H., Samczynski Z., Szopa Z.Przygotowanie i atestacja nowego polskiego materiahi odniesienia liScie tytoniu typu Virginia(CTA-VTL-2) dla potrzeb nieorganicznej analizy sladowej i mikroanalizy (Preparation and certifi-cation of the new Polish reference material Virginia Tobacco Leaves (CTA-VTL-2) for inorganictrace analysis including microanalysis).XL Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inzynier6w i Technik6wPrzemyshi Chemicznego. Streszczenia. Gdansk, Poland, 22-26.09.1997, p. SI, K3.

80. Dziedzic-Gocfowska A., Stachowicz W.Sterilization of tissue allografts.In: Advances in Tissue Banking. Vol. 1. Ed. G.O. Philips. World Scientific, Singapore 1997, pp.261-321.

81. Dzwigalski Z., Roman K.Wyrzutnia elektronowa liniowego akceleratora elektron6w LAE10 (Electron gun of linear electronaccelerator LAE10).Technologia Elektronowa. VI Konferencja Naukowa. Tom 2. Referaty. Krynica, Poland, 6-9.05.1997,pp. 307-310.

82. Gniazdowska E.Hydration of oxaalkanes in aqueous solutions.International Conference of PhD Students. Section Proceeding. Natural Science. Miskolc, Hungary,11-17.08.1997, pp. 58-62.

83. Gniazdowska E., Narbutt J.Hydratacja oksalkan6w w roztworach wodnych (Hydration of oxaalkanes in aqueous solutions).XL Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inzynier6w i Technik6wPrzemyshi Chemicznego. Streszczenia. Gdansk, Poland, 22-26.09.1997, p. S5, K4.


84. Gorecki P., Kfdzia B., Migdai W., Owczarczyk B.Irradiation as an alternative environment friendly method for microbiological decontamination ofherbal raw materials.International Symposium on Radiation Technology for Conservation of the Environment. ExtendedSynopsis. Zakopane, Poland, 8-12.09.1997.

85. Goretta K.C., Xu Y., Cook R.E., Feng L.R., Deptula A., Lada W., Olczak T., Xu M., Balachandran U.Synthesis and properties of a Bi2Sr2CaCu2Ox-BaTiO3 composite powder.Superconductivity Science and Technology, 10,853-856 (1997).

86. G6ral A.B., Panta P.P., Maciak J., Pogorzelska J.The CNF ability of heavy electron.Bulletin of the Polish Academy of Sciences. Technical Sciences, 45,1,109-115 (1997).

87. Grigoriew H., Chmielewski A.G.X-ray study of the influence of water on the cellulose membrane structure.Journal of Materials Science Letters, 16,1945-1947 (1997).

88. Grodkowski J., Behar D., Neta P., Hambright P.Iron porphyrin-catalyzed of CO2. Photochemical and radiation chemical studies.Journal of Physical Chemistry, 101, 3,248-254 (1997).

89. Grodkowski J., Behar D., Neta P., Hambright P.Iron-porphyrin catalyzed reduction of CO2. Photochemical and radiation chemical studies.5th International Meeting on Pulse Investigations in Chemistry, Biology and Physics. PULS'97.Szczyrk, Poland, 13-19.09.1997, pp. S2-P5.

90. Grodkowski J., Behar D., Neta P., Hambright P.Iron-porphyrin catalyzed reduction of CO2. Photochemical and radiation chemical studies.XVIIIth International Conference on Photochemistry. Book of Abstracts. Warszawa, Poland,3-8.08.1997, p. IP30.

91. Honkonen V., Ruuskanen J., Aatamila M., Makelfi J., Lehtoma'ki J., Svarfvar B., Chmielewski A.G.,Zimek Z., Ostapczuk A.VOC removal by simultaneous electron beam and biofilter application.International Symposium on Radiation Technology for Conservation of the Environment. ExtendedSynopsis. Zakopane, Poland, 8-12.09.1997.

92. Hug G.L., Bobrowski K., Marciniak B.Photooxidation of methionine derivatives by the 4-carboxybenzophenone triplet state in aqueoussolution. Stabilization of sulfur-radical-cation centers.XVIIIth International Conference on Photochemistry. Book of Abstracts. Warszawa, Poland,3-8.08.1997, p. O3.2.

93. Iller E., Owczarczyk A., Palige J., Chmielewski A.G.Gas flow dynamics in flue gas irradiation vessel.10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, 11-16.05.1997, p. 108.

94. Jackowski Z., Chmielewski A.G., Zimek Z., Genuario R., Confuorto N.New advanced electron beam technology for flue gas treatment.10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, 11-16.05.1997, p. 109.

95. Jaworska A., Sochanowicz B.Bcl-2/Bax ratio and radiation sensitivity of two L5178Y cell lines crossensitive to ionizing radiationand H2O2.Radioprotection, 32, Cl-200 (1997).

96. Kaczmarek S.H., Pracka I., Lukasiewicz T., Warchoi S., Jabtoriski R., Boulon G., Moroz Z,, Stejpka K.Influence of ionizing radiation on SrLaGa3O7 single crystals doped with rare-earth elements.Biuletyn WAT, 46,12,133-148 (1997).


97. Kaczmarek S.H., Żendzian W., Łukasiewicz T., Stępka K., Moroz Z., Warchoł S.Sensybilizacja właściwości laserowych kryształu CTH:YAG promieniowaniem jonizującym (Sensitiza-tion of laser properties of crystal CTH:YAG by ionizing radiation).Materiały Elektroniczne, 25,3,23-34 (1997).

98. Kałuskul.Aktualne przepisy międzynarodowe dotyczące sterylizacji radiacyjnej (Actual international standardsconcerning radiation sterilization).IV Wiosenna Szkoła Sterylizacji Radiacyjnej Sprzętu Medycznego, Przeszczepów, Farmaceutyków iKosmetyków. Warszawa, Poland, 26-27.05.1997, pp. XII/l-XH/6.

99. Kałuskal.Wymagania dotyczące organizacji procesu sterylizacji radiacyjnej (Requirement for radiation steri-lization processing of medical products).IV Wiosenna Szkoła Sterylizacji Radiacyjnej Sprzętu Medycznego, Przeszczepów, Farmaceutyków iKosmetyków. Warszawa, Poland, 26-27.05.1997, pp. VIII/l-VIII/4.

100. Kieczkowska H.E., Pleschke J.M., Althaus F.R.Towards to protein family with poly(ADP-ribose)-binding sequence motifs.The 12th International Symposium on ADP-ribosylation Reactions. From Bacterial Pathogenesis toCancer. Abstracts. Cancun, Mexico, 10-14.05.1997, p. 68.

101. Kieczkowska H.E., Szumiel L, Althaus F.R.Low dose ionizing radiation effect on poly(ADP-ribose)-binding proteins.Radioprotection, 32, Cl-421 (1997).

102. Kowalak S.., Kraszona K., Stuglik Z.Application of alaninę supported on the molecular sieves for dosimetric devices.International Conference. Post-Congress Symposium EUROPACAT-3 "Zeolite Catalysis and Indus-trial Progress". Abstracts. Kraków, Poland, 7-11.09.1997, pp. 71-72.

103. Kowalska E., Urbański P.XRF full-spectrum calibration technique using artificial neural network.Nukleonika, 42,4,879-888 (1997).

104. Kraszewski M.L5178Y cell lines - a useful model for the study of transition metal ions involvement in cell physio-logy.Seminar on Interactions Between Iron Metabolism Reactive Oxygen Species and Nitric Oxide.Abstracts. Jastrzębiec, Poland, 6.11.1997.

105. Kraszewski M., Iwaneńko T., Wojewódzka M.Hydrogen peroxide-induced DNA damage in two L5178Y sublines.Conference on "Mechanisms of DNA Repair and Mutagenesis" on the 100th Anniversary of theDiscovery of Polonium and Radium. Abstracts. Warszawa, Poland, 8-11.10.1997, p. 69.

106. Kraszewski M., Kruszewska H., Inaba H., Jeggo P., Szumiel I.Homologous recombination in CHO cell lines defective in DNA damage processing.European Radiation Research'97. Programme and Abstracts. Oxford, England, 24-26.09.1997, p. 45.

107. Kraszewski M,, Kruszewska H., Jarocewicz N., Inaba H., Jeggo P., Szumiel I.Spontaneous homologous recombination in cho cell lines defective in DNA damage processing.Conference on "Mechanisms of DNA Repair and Mutagenesis" on the 100th Anniversary of theDiscovery of Polonium and Radium. Abstracts. Warszawa, Poland, 8-11.10.1997, p. 68.

108. Kraszewski M., Wojewódzka M., Iwaneńko T., Collins A.R.Application of the comet assay for monitoring DNA damage in workers professionally at risk ofexposure to chronic low doses of ionizing radiation.Workshop of the "Biomarkers in Monitoring of Occupational and Environmental Exposure toOrganic Genotoxic Substances. Abstracts. Ustroń, Poland, 23-24.10.1997, p. 50.


109. Kraszewski M., Wojewódzka M., Iwaneńko T., Collins A.R.Application of the comet assay for monitoring DNA damage in workers professionally at risk ofexposure to low doses of ionizing radiation.Workshop in Memory of Maria Skiodowska-Curie "Radioactivity: Risk and Hope". Book of Abstracts.Kraków, Poland, 6-7.10.1997.

110. Kulisa K., Dybczyński R., Polkowska-Motrenko H.Efekt przeładowania kolumny w chromatografii jonów. Porównanie rozdzielań aniono- i kationo-wymiennych (Effect of column overloading in ion chromatography. Comparison of anion and cationexchange separations).Materiały VI Poznańskiego Konwersatorium Analitycznego "Nowoczesne Metody Przygotowania Pró-bek i Oznaczania Śladowych Ilości Pierwiastków". Streszczenia. Poznań, Poland, 17-18.04.1997, p. 17.

111. Leciejewicz J., Ptasiewicz-Bąk H., Paluchowska B.Molecular ribbons composed of calcium atoms bridged by carboxylate oxygens in theX-ray structureof calcium complex with 3-aminopyrazine-2-carboxylic acid.Polish Journal of Chemistry, 71,1359-1364 (1997).

112. Leśniewska J., Grądzka I., Szumiel I., Charzyńska M.PCD - related DNA degradation in the nuclei of anther tapetum identified by the comet assay.22nd Conference on Embryology. Plants, Animals, Humans. Abstracts. Osieczany, Poland,14-17.05.1997, p. 59.

113. Lewandowska-Szumieł M., Zimek Z., Kudelska D., Mazur M.Ocena wpływu sterylizacji radiacyjnej na toksyczność wybranych materiałów implantacyjnych (Evalua-tion of the toxicity of radiosterilized implantable materials).Polimery, 42,3,195-199 (1997).

114. Licki J., Chmielewski A.G., Iller E., Zakrzewska-Trznadel G., Tokunaga O.Analytical methods and monitoring system for electron beam flue gas treatment process.10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, 11-16.05.1997, p. 146.

115. Lipiński P., Kraszewski M., Drapier J.-C, Retmańska H.Regulation of intracellular iron metabolism in differentially hydrogen peroxide (H2O2) sensitiveL5178Y sublines.Seminar of Interactions Between Iron Metabolism Reactive Oxygen Species and Nitric Oxide.Abstracts. Jastrzębiec, Poland, 6.11.1997.

116. Lis S., Borkowski M., But S.Badanie kompleksowania jonów lantanowców (III) w szerokim zakresie stężeń ligandów pseudo-halogenkowych (Investigation of complex formation of lanthanides (III) with pseudohalide ligands inwide range of concentrations).XL Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i TechnikówPrzemysłu Chemicznego. Streszczenia. Gdańsk, Poland, 22-26.09.1997, p. S7, P36.

117. Łukasiewicz A., Waliś L.Organie fibres impregnated with polymerized aminotriazole complexes with transition metals.Materials Letters, 30,249-251 (1997).

118. Łukasiewicz A., Waliś L., Grigoriew H., Kaszuwara W., Leonowicz M.New ferromagnetic materials containing free metal and metal carbide phases from aminotriazolecomplexes with transition metals.Materials Letters, 30,83-85 (1997).

119. Machaj B., Stuglik Z., Panta P., Kahiska I., Bryl-Sandelewska T., Strzałkowski J., Malicki W.Computerized PVC absorbance reader as the device for quick detection of dose distribution on, underand inside the electron irradiated objects.International Symposium on Radiation Technology for Conservation of the Environment. ExtendedSynopsis. Zakopane, Poland, 8-12.09.1997.

120. Malec-Czechowska K., Bryl-Sandelewska T.Radiacyjna higienizacja kosmetyków (Radiation hygienisation of cosmetics).


IV Wiosenna Szkola Sterylizacji Radiacyjnej Sprze.tu Medycznego, Przeszczep6w, Farmaceutyk6w iKosmetykow. Warszawa, Poland, 26-27.05.1997, pp. XIX/l-XIX/12.

121. Malec-Czechowska K., Dancewicz A.M., Szot Z.Screaning method for detection of irradiated cereal grains.Nukleonika, 42,4,847-856 (1997).

122. Malec-Czechowska K., Dancewicz A.M., Szot Z.Thermoluminescence, germination and DNA "comet" assay used for detection of irradiated food-stuffs.European Society for New Methods in Agricultural Research and International Union of Radio-ecology (IUR) Working Group Soil-to-Plant Transfer Annual Meeting. Book of Abstracts. Ghent,Belgium, 29.08-02.09.1997, p. 9.

123. MalickiW.,StugIikZ.Dozymetrowanie Srednich dawek wysokoenergetycznego promieniowania elektronowego przy pomo-cy kalorymetru magnezowego (Dosimetry of medium doses of high energy electrons irradiations by amagnesium calorimeter).XL Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inzynierow i Technik6wPrzemyshi Chemicznego. Streszczenia. Gdansk, Poland, 22-26.09.1997, p. S19, Kl.

124. Marciniak B., Bobrowski K., Hug G.L.Photoinduced electron transfer involving sulfur-containing organic compounds.XVIIIth International Conference on Photochemistry. Book of Abstracts. Warszawa, Poland,3-8.08.1997, p. IP56.

125. MichalikJ.Paramagnetic silver clusters in molecular sieves.Third European ESR Meeting "Modern Aspects of Structure and Dynamic Investigations of Para-magnetic Systems by EPR. Book of Abstracts. Leipzig, Germany, 25-28.08.1997, p. L15.

126. Michalik J., Sadto J., Kevan L., Jong-Sung Yu.Radiation-induced silver agglomeration in zeolite rho.11th International Zeolite Conference on "Discussions on Zeolite and Microporous Materials". Sup-plementary Materials. Seoul, Korea, 12-17.08.1996 (1997), pp. 401-402 (RP139).

127. MichalikJ., Sadto J., Kodaira T., Shimamura S,, Yamada H.ESR and optical studies on silver clusters in sodalites and zeolites rho.5th International Meeting on Pulse Investigations in Chemistry, Biology and Physics. PULS'97.Szczyrk, Poland, 13-19.09.1997, pp. S7-P3.

128. Michalik J., Sadto J., Pol van der A., Reijerse E.EPR and ESEEM studies on silver hydroxymethyl radicals in molecular sieves,Acta Chemica Scandinavica, 51,330-333 (1997).

129. Michalik J., Sadto J., Wqsowicz T.Paramagnetic silver clusters in molecular sieves.Proceedings of International Seventh Beijing Conference and Exhibition on Instrumental Analysis. E.Magnetic Resonance. Shanghai, China, 14-17.10.1997, pp. E137-E138.

130. Migdat W., Owczarczyk B., Kfdzia B., Holderna-Kedzia E., Segiet-Kujawa E.The efeect of ionizing radiation on microbiological decontamination of medical herbs and biologicallyactive compounds.10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, 11-16.05.1997, p. 164.

131. Mioduski T.Hydration and covalence of the Ln2+ and An2+ ions vs. alkaline earth ions as reflected in solubilityand cocrystallization of their sulfates.Comments Inorganic Chemistry, 19,4,231-244 (1997).

132. Mioduski T.The "regular" and "inverse" tetrad effect.


Comments Inorganic Chemistry, 19, 2,93-120 (1997).

133. Muntener C, Kleczkowska H.E., Auer B., Althaus F.R.Phenotypic alterations in 3T3-cells derived from transgenic PARP^'-mice.The 12th International Symposium on ADP-ribosylation Reactions. From Bacterial Pathogenesis toCancer. Abstracts. Cancun, Mexico, 10-14.05.1997, p. 17.

134. Narbutt J., Czerwiriski M.Hydrogen-bonded water in the second coordination sphere of the central metal ion in cheiate com-plexes. Theoretical (DFT) studies.Co-ordination Chemistry Discussion Group. Abstracts. Warwick, England, 7-8.07.1997. p. P35.

135. Narbutt J., Czerwinski M.Wiqzanie wodorowe wody w drugiej sferze koordynacyjnej chelat6w metali przejs"ciowych. Obliczeniametoda, DFT (Hydrogen bonding of water in the second coordination sphere of transition metalchelates. DFT calculations).XL, Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inzynier6w i Technik6wPrzemyslu Chemicznego. Streszczenia, Gdansk, Poland, 22-26.09.1997, p. S7, W6.

136. Narbutt J., Fuks L.Outer-sphere hydration - a factor differentiating tetrakis(acetylacetonato)actinides(IV) in liquid-li-quid partition systems.Radiochimica Acta, 78,27-31 (1997).

137. Narbutt J., Krejzler J., Dymecka D.Liczby koordynacyjne skandu, indu i talu (III) w kompleksach chelatowych (Coordination number ofscandium, indium and thallium (III) in cheiate complexes).XL Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inzynier6w i Technik6wPrzemyshi Chemicznego. Streszczenia. Gdansk, Poland, 22-26.09,1997, p. S7, K7.

138. Nichipor H., Radouk E., Chmielewski A,G., Zimek Z.Energy consumption of the SO2 removal from the humid air under electron beam and electric fieldinfluence.International Symposium on Radiation Technology for Conservation of the Environment. ExtendedSynopsis. Zakopane (near Cracow), Poland, 8-12.09.1997.

139. Nichipor H., Radouk E., Chmielewski A.G., Zimek Z.SO2 oxidation in humid air under influence of electron beam and electrical field pulses.10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, 11-16.05.1997, p. 183.

140. Ostrowski K., Dziedzic-Godawska A., Stachowicz W., Michalik J., Strzdczak G., Sadto J.Limites de la detection par spectroscopie EPR des doses cumulees de radiations ionisantes dans lescoquilles de mollusques.Journal de Chimie Physique et de Physico Chimie Biologique, 94,382-389 (1997).

141. Owczarczyk B., Migdal W., Zabielski J.Radiation hygienisation of food for the control of microbial quality in hazard critical control pointsystem.10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, 11-16.05.1997, p. 191.

142. Paluchowska B., Maurin J.K., Leciejewicz J.Direct and outer-sphere coordination of the magnesium ions in the crystal structures of complexeswith 2-furancarboxylic acid (I) and 3-furancarboxylic acid (II).Journal of Chemical Crystallography, 27,3,177-182 (1997).

143. Paluchowska B., Maurin J.K., Leciejewicz J.Hetero-ring oxygen coordination to strontium in strontium bis(2-furan-carboxylate).Acta Crystallographica, C53,287-289 (1997).


144. Paluchowska B., Maurin J.K., Leciejewicz J.The role of heteroring oxygen in the process of coordination of alkaline earth metal ions by 2- and3-furancarboxylic acids.Seventeenth European Crystallographic Meeting. Book of Abstracts. Lisboa, Portugal, 24-28.08.1997,p. 117.

145. Paluchowska B., Maurin J.K., Leciejewicz J.X-ray structural studies on 2- and 3-furancarboxylate complexes of some 3-d electron elements.Seminarium "Nieuporza,dkowane struktury krystaliczne" i XXXIX Konwersatorium Krystalograficz-ne. Wroclaw, Poland, 25-27.06.1996, p. 67.

146. Panta P.Obrobka radiacyjna materiatew - zasady opracowywania technologii radiacyjnej (Radiation pro-cessing of materials - principles and developments in radiation technology).IV Wiosenna Szkoia Sterylizacji Radiacyjnej Sprzetu Medycznego, Przeszczep6w, Farmaceutyk6w iKosmetyk6w. Warszawa, Poland, 26-27.05.1997, pp. XXII/l-XXII/8.

147. Panta P., Zagorski Z.P., Gtuszewski WJ.Thermal defects of water, graphite and polystyrene affecting calorimetric response.International Symposium on Radiation Technology for Conservation of the Environment. ExtendedSynopsis. Zakopane, Poland, 8-12.09.1997.

148. Panta P., Zimek Z., Gtuszewski W., Kowalewski R., Wojtynska E.Badania dozymetryczne wia,zki szybkich elektron6w akceleratorowych w procesach radiacyjnej mody-fikacji tworzyw sztucznych (Dosimetry of fast electron beams in radiation modification of syntheticpolymers).XL Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inzynierow i Technik6wPrzemyslu Chemicznego. Streszczenia. Gdansk, Poland, 22-26.09.1997, p. S12, K18.

149. Panta P., Zimek Z., Gtuszewski W., Kowalewski R., Wojtyriska E., Wnuk J.Effect of ionizing radiation on properties of acrylic pressure sensitive adhesives.International Symposium on Radiation Technology for Conservation of the Environment. ExtendedSynopsis. Zakopane, Poland, 8-12.09.1997.

150. Pariczyk E., Chajecki T., Walis" L., Bukowski A.Oznaczanie zanieczyszczen w krzemie o czystoSci p61przewodnikowej instrumental^ metoda, reak-torowej neutronowej analizy aktywacyjnej (Investigation of purity silicon wafers by instrumentalneutron activation analysis).Technologia Elektronowa. VI Konferencja Naukowa. Tom 1. Referaty. Krynica, Poland, 6-9.05.1997,pp. 278-282.

151. Fawlukojc* A., Bajdor K., Dobrowolski J.Cz., Leciejewicz J., Natkaniec I.The IINS spectroscopy of amino acids: L-isoleucine.Spectrochimica Acta. Part A, 53,927-931 (1997).

152. Petrukhin O.M., Shipulo E.V., Nagy V., Pazukhina Yu.E-, Narbutt J.Intermolecular interaction and partition constants of metal tris-acetylacetonates: A short theoreticalreview.Solvent Extraction and Ion Exchange, 15,5,757-776 (1997).

153. Piekoszewski J., Langner J., Walis" L., Werner Z.Intense plasma pulses: two modes of the use for surface processing purposes.Surface and Coatings Technology, 93,209-212 (1997).

154. Piekoszewski J., WaliS L., Langner J.Surface morphology of nitrogen-alloyed steels using high intensity pulsed plasma beams.Materials Letters, 32,49-53 (1997).

155. Pleschke J.M., KleczkowskaHE., MalangaM., SchmitzA., Vergeres G., AlthausF.K.Marcks, p53 and p21: new targets of poly(ADP-ribose)-binding.The 12th International Symposium on ADP-ribosylation Reactions. From Bacterial Pathogenesis toCancer. Abstracts. Cancun, Mexico, 10-14.05.1997, p. 69.


156. Pogocki D.Oddziaływanie promieniowania jonizującego z materią (Ionizing radiation interaction with matter).IV Wiosenna Szkoła Sterylizacji Radiacyjnej Sprzętu Medycznego, Przeszczepów, Farmaceutyków iKosmetyków. Warszawa, Poland, 26-27.05.1997, pp. I/1-I/12.

157. Pogocki D., Bobrowski K., Hug G., Schoneich Ch.Rodnikowe utlenianie S-alkilowych pochodnych glutationu (Radical oxidation of S-alkyl ghitathionederivatives).XL Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i TechnikówPrzemysłu Chemicznego. Streszczenia. Gdańsk, Poland, 22-26.09.1997, p. S17, P21.

158. Pogocki D., Ścięgosz A., Bobrowski K., Asmus K.-D.OH radical induced oxidation of conformationally constrained sulphur-containing amino acids.5th International Meeting on Pulse Investigations in Chemistry, Biology and Physics. PULS'97.Szczyrk, Poland, 13-19.09.1997, pp. S2-P7.

159. PrzybytniakG.Niektóre aspekty uszkodzeń DNA indukowanych promieniowaniem jonizującym (Some aspects ofDNA damages induced by ionizing radiation).XVII Szkoła Jesienna "Radon - występowanie i konsekwencje". Materiały konferencyjne. Zakopane,Poland, 22-26.09.1997, pp. 24-39.

160. Przybytniak G., Hiittermann J., Ambroż H., Wieland B.The influence of cysteamine on free radical formation in frozen aqueous containing dCMP.Nukleonika, 42,2,323-332 (1997).

161. Ptasiewicz-Bąk H,, Lcciejewicz J.The crystal structures of diaquobis(3-aminopyrazine-2-carboxylato-N,O)magnesium(II)monohydrateand 3-aminopyrazine-2-carboxylic acid.Polish Journal of Chemistry, 71,1350-1358 (1997).

162. Ptasiewicz-Bąk H., Leciejewicz J.A pyrazine-bridged chain structure of magnesium complex with pyrazine-2,3-dicarboxylic acid.Polish Journal of Chemistry, 71,493-500 (1997).

163. Ptasiewicz-Bąk H., Leciejewicz J.Two-dimensional molecular layers in the crystals of calcium complex with pyrazine-2,3-dicarboxylicacid.Polish Journal of Chemistry, 71,1603-1610 (1997).

164. Ptasiewicz-Bąk H., Tellgren R., Olovsson I., Koll A.Location of the proton in the very strong OHO hydrogen bonds in 2-(N,N-diethylamino-N-oxy-methyl)-4,6-dichlorophenol. A single crystal neutron diffraction study.Zeitschrift fiir Kristallographie, 212,126-129 (1997).

165. Rafalski A., Zagórski Z.P.Nadtlenki w napromieniowanym polipropylenie (Peroxides in irradiated polypropylene).Materiały XIII Konferencji Naukowej "Modyfikacja Polimerów". Kudowa Zdrój, Poland, 11-14,09.1997,p. 363.

166. Sadło J., Matthys P., Vanhaelewyn G., Callens F., Michalik J., Stachowicz W.EPR and ENDOR of CO^~ radicals in human tooth enamel heated at 400°C.V International Workshop "Electron Magnetic Resonance of Disordered Systems" and III Interna-tional Seminar "Applied EPR". Abstracts. Sofia-Bojana, Bulgaria, 9-17.06.1997, p. 38.

167. Samczyński Z., Dybczyński R.Niektóre zastosowania jonitów amfoterycznych do rozdzielania i oznaczania śladowych ilości jonównieorganicznych (Some examples of the use of amphoteric ion exchange resins for separation anddetermination of trace amounts of inorganic ions).XL Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i TechnikówPrzemysłu Chemicznego. Streszczenia. Gdańsk, Poland, 22-26.09.1997, p. SI, Kl l .


168. Samczyriski Z., Dybczyriski R.Some examples of the use of amphoteric ion-exchange resins for inorganic separations.Journal of Chromatography A, 789,157-167 (1997).

169. Samochocka K., Kruszewski M., Szumiel I.Interaction of some organic plantinum (II) complexes with L5178Y-R and L5178Y-S cells.Chemico-Biological Interactions, 105,145-155 (1997).

170. Shadley J.D., Wojcik A., Bonk K., Streffer C.Do low doses of ionizing radiation induce chromosomal repair activity? Screening human T ce.'lextracts microinjected into mouse embryos.Nukleonika, 42,3,629-640 (1997).

171. Siekierski S.Ionic radii: Effect of shell radius, cation charge and lone electron pair.Comments Inorganic Chemistry, 19,2,121-131 (1997).

172. Siekierski S.Struktura ukladu okresowego i wlasnos"ci transaktynowc6w (Structure of the Periodic Table and pro-perties of Transactinide Elements).XL Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inzynier6w i Technik6wPrzemysiu Chemicznego. Streszczenia. Gdansk, Poland, 22-26.09.1997, p. WP9.

173. StachowiczW.Aspects of detection the irradiated foods by EPR spectroscopy.V International Workshop "Electron Magnetic Resonance of Disordered Systems" and III Interna-tional Seminar "Applied EPR". Abstracts. Sofia-Bojana, Bulgaria, 8-17.06.1997, p. 39.

174. StachowiczW.Irradiation of spices and herbs.Interregional Training Course on Developments in the Application of Electron Beams in Industryand Environmental Protection. Warszawa, Poland, 6-17.10.1997.

175. StachowiczW.Metody sterylizacji medycznej (Methods of radiation sterilization).IV Wiosenna Szkoia Sterylizacji Radiacyjnej Sprze,tu Medycznego, Przeszczepo"w, Farmaceutyk6w iKosmetyk6w. Warszawa, Poland, 26-27.05.1997, pp. III/1-III/14.

176. Stachowicz W., Strzelczak G., Michalik J.EPR detection of foods preserved with ionizing radiation (gamma rays and 10 MeV electrons).10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, 11-16.05.1997, p. 222.

177. Strzelczak G., Bobrowski K.Badanie peptydoV metioninowych metoda. EPR (An investigation of methionine containing peptidesby ESR method).XL Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inzynier6w i Technik6wPrzemyshi Chemicznego. Streszczenia. Gdansk, Poland, 22-26.09.1997, p. S17, P27.

178. Strzelczak G., Bobrowski K., Holcman J.Reactions of the hydrated electron with oligopeptides.20th Miller Conference on Radiation Chemistry. Programme and Abstracts. Bowness-on-Winder-mere, Cumbria, United Kingdom, 22-27.03.1997,1 p.

179. Strzelczak-Burlihska G., Bobrowski K., Pogocki D.. Michalik J.ESR study of radiation induced radicals in polycrystalline methionine and its homopeptides.Nukleonika, 42,2,333-342 (1997).

180. StuglikZ.Kontrola procesu sterylizacji radiacyjnej w stacjach korzystaja_cych z akceleratorow elektron6w(Control of radiation sterilization process in sterilization facilities using electron accelerator).IV Wiosenna Szkoia Sterylizacji Radiacyjnej Sprzetu Medycznego, Przeszczep6w, Farmaceutyk6w iKosmetyk6w. Warszawa, Poland, 26-27.05.1997, pp. IX/l-IX/5.


181. StuglikZ.Wykorzystanie polimer6w w dozymetrii promieniowarl jonizuja_cych (Polymer applications in thedosimetry of ionizing radiation).Polimery, 42,3,156-161 (1997).

182. StuglikZ.,ApelP.Yu.An attempt of experimental determination of differential energy of ion pair formation in air, wair, for240 MeV Ca-40,300 MeV Co-59 and 220 MeV Fe-56 ions.VI International School-Seminar "Heavy Ion Physics". Abstracts. Dubna, Russia, 22-27.09.1997, p.267.

183. StuglikZ.,SadtoJ.A response of L-a-alanine and standard bone powder on 3.4 MeV/amu 59Co ion beams.Applied Radiation and Isotopes, 47,11/12,1219-1222 (1997).

184. Szot Z.Zmiany w DNA. Marker radiacyjnie utrwalonej zywnoSci (Changes in DNA. Marker of the food pre-served by radiation).Post^py Techniki Ja.drowej, 40,3,29-43 (1997).

185. Szumiel I., Kapiszewska M., Gnjdzka L, Sochanowicz B., Gasiska A., Jaworska A.Proto-oncogene expression, cell cycle arrests and apoptosis in X-irradiated L5178Y sublines.Workshop in Memory of Maria Sktodowska-Curie "Radioactivity: Risk and Hope". Book of Abstracts.Krak6w, Poland, 6-7.10.1997.

186. SzuroielI.,W6jcikA.Wpfyw promieniowania na organizmy zywe (Influence of radiation on live organisms).IV Wiosenna Szkola Sterylizacji Radiacyjnej Sprze,tu Medycznego, Przeszczep6w, Farmaceutykow iKosmetyk6w. Warszawa, Poland, 26-27.05.1997, pp. II/1-II/14.

187. Szytuta A., Baran S., Leciejewicz J., Penc B., Stusser N., Ding Y., Zygmunt A., Zukrowski J.Antiferromagnetic properties in RFe2Ge2 (R=Tb, Dy, Ho).Journal of Physics: Condensed Matter, 9,6781-6789 (1997).

188. Szytuta A., Kolenda M., Leciejewicz J., Stusser N.Non-collinear antiferromagnetic structure of hexagonal TbPtSn.Journal of Magnetism and Magnetic Materials, 164,377-380 (1997).

189. Trojanowicz M., Chudziak A., Bryi-Sandeiewska T.Radiolytic degradation of chlorophenols for their removal from polluted waters.International Symposium on Radiation Technology for Conservation of the Environment. ExtendedSynopsis. Zakopane, Poland, 8-12.09.1997.

190. Trojanowicz M., Chudziak A., Bryl-Sandelewska T.Radiolytic degradation of chlorophenols for their removal from polluted waters.4th Meeting on Nuclear Applications. Proceedings. Pocos de Caldas, Brazil, 18-22.08.1997, pp.293-300.

191. Trojanowicz M., Chudziak A., Bryl-Sandelewska T.Use of reversed-phase HPLC with solid-phase extraction for monitoring of radiolytic degradation ofchlorophenols for environmental protection.Journal of Radioanalytical and Nuclear Chemistry, 224,1-2,131-136 (1997).

192. Urbanski P., Kowalska E.Linear and non-linear multivariate calibration of some XRF instruments.Nukleonika, 42,3,719-726 (1997).

193. Vanhaelewyn G., Sadlo J., van Calenberg S., Mondelaers W., van Cteemput O., Callens F.Recent electron paramagnetic resonance and electron nuclear double resonance results related foodcontaining crystalline sugar.XXVIi Annual Meeting "European Society for New Methods in Agricultural Research". Book ofAbstracts. Ghent, Belgium, 29.08-2.09.1997, p. 2.


194. Villanueva L.Z., Ahumada L.S., Ellison W., Chmielewski A.G., Zimek Z., Butka S.Prospects of utilizing electron beam irradiation technology to augment control of SO2 and otheremmision from Chilean copper smelting plants.International Symposium on Radiation Technology for Conservation of the Environment. ExtendedSynopsis. Zakopane, Poland, 9-12.09.1997.

195. WaliS L.Technika radiacyjna w Instytucie Chemii i Techniki Ja.drowej (Radiation technique at the Institute ofNuclear Chemistry and Technology).Polimery, 42,3,139-140 (1997).

196. WalK L., Rowinska L., Nowicki A.Oczyszczanie indu, galu i antymonu w procesie stapiania z zuzlem syntetycznym (Purification ofindium, gallium and antimonium by remelting under synthetic slags).Technologia Elektronowa. VI Konferencja Naukowa. Tom 1. Referaty. Krynica, Poland, 6-9.05.1997,pp. 336-339.

197. Warchol S., Krynicki J., Rzewuski H., Groetzschel R.Damage buildup and amorphization in ion - implanted GaAsi-xPx-Nukleonika, 42,3,675-682 (1997).

198. Wisniowski P., Bobrowski K.'OH radical induced oxidation of thioamides: stability of the hydroxysulphuranyl radical.5th International Meeting on Pulse Investigations in Chemistry, Biology and Physics. PULS'97.Szczyrk, Poland, 13-19.09.1997, pp. S2-P11.

199. WiSniowski P., Bobrowski K.Wpfyw grup funkcyjnych na inicjowane radiacyjnie procesy rodnikowe w tioeterach (Influence ofneighbouring functional groups on initiated radiochemically radical processes in thioethers).XL Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inzynier6w i Technik6wPrzemyshi Chemicznego. Streszczenia. Gdansk, Poland, 22-26.09.1997, p. S17, P30.

200. Wojewodzka M., Kruszewski M., Iwanenko T., Collins A.R.Application of the comet assay for monitoring DNA damage in workers exposed to chronic low doseirradiation.Comet Workshop. Abstracts of Presentation. London, England, 8-10.05.1997, p. 1.

201. Wojew6dzka M., Kruszewski M., Iwanenko T., Collins A.R.Application of the comet assay for monitoring DNA damage in workers exposed to chronic low doseirradiation.Conference on "Mechanisms of DNA Repair and Mutagenesis" on the 100th Anniversary of theDiscovery of Polonium and Radium. Abstracts. Warszawa, Poland, 8-11.10.1997, p. 87.

202. Wojewodzka M., Kruszewski M., Szumiel I.DNA repair in adapted human lymphocytes.Radioprotection, 32, Cl-409-410 (1997).

203. Wojewddzka M., Kruszewski M., Szumiel I.Effect of signal transduction inhibition in adapted lymphocytes: micronuclei frequency and DNArepair.International Journal of Radiation Biology, 71,3,245-252 (1997).

204. Wojewddzka M., Zaim J., Schans van der G.P., Kruszewski M., Szumiel I.DNA repair in radioadapted human lymphocytes.7th International Conference on Environmental Mutagens. Abstracts. Toulouse, France, 7-12.09.1997, p.S57.

205. Wojtowicz A., Dziedzic-Goctawska A., Kaminski A., Stachowicz W., Wojtowicz K., Marks S.C. Jr.,Yamauchi M.Alterations of mineral crystallinity and collagen cross-linking of bones in osteopetrotic toothless(tl/tl) rats and their improvement after treatment with colony stimulating factor-1.Bone, 20,2,127-132 (1997).


206. Wojtyńska E., Bułhak Z., Szabłewska B.Badania nad poprawieniem odporności na sterylizację radiacyjną plastyfikowanego polichlorku winy-lu). (Studies on improving the resistance of plasticized PVC to sterilization radiation).Polimery, 42,3,200-206 (1997).

207. Wójcik A., Strefter C.Radiation-induced aberrations in human chromosomes 1 and 2 analyzed by whole chromosomepainting.Conference on "Mechanisms of DNA Repair and Mutagenesis" on the 100th Anniversary of theDiscovery of Polonium and Radium. Abstracts. Warszawa, Poland, 8-11.10.1997, p. 86.

208. Wójcik A., Szumieli.Dozymetria biologiczna w przypadkach awaryjnych (Biological dosimetry after radiation accidents).Bezpieczeństwo Jądrowe i Ochrona Radiologiczna, 30,1-2,56-59 (1997).

209. Zagórski Z.P.Bać się radonu? (Shall we be afraid of radon?).Wiedza i Życie, 8,56-59 (1997).

210. Zagórski Z.P.Metody sterylizacji polimerowych wyrobów medycznych (Methods of radiation sterilization of medicalproducts made of polimers).Zastosowanie Polimerów w Nowoczesnych Technikach Medycznych. Materiały Seminarium. Ustroń,Poland, 8-10.10.1997, pp. 163-172.

211. Zagórski Z.P.Radiation processing and market economy.10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, 11-16.05.1997, p. 252.

212. Zagórski Z.P.Radon.Wiadomości chemiczne, 51,9-10,593-614 (1997).

213. Zagórski Z.P.Radon - rzut oka na całość zagadnienia (Radon - survey of the whole problem).XVII Szkoła Jesienna PTBR "Radon - występowanie, konsekwencje". Materiały Konferencyjne. Zako-pane, Poland, 22-26.09.1997, p. 82-114.

214. Zagórski Z.P.Role of the matrix in the alanine-powder dosimetry.10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, 11-16.05.1997, p. 254.

215. Zagórski Z.P.Wybrane zagadnienia chemii radiacyjnej polimerów. (Selected topics in the radiation chemistry ofpolymers).Polimery, 42,3,141-147 (1997).

216. Zagórski Z.P.Znaczenie prac Marii Skłodowskiej-Curie dla chemii (The importance of Marie Skłodowska-Curiediscoveries for the development of chemistry).XVII Szkoła Jesienna PTBR "Radon - występowanie i konsekwencje". Materiały konferencyjne. Zako-pane, Poland, 22-26.09.1997, pp. 10-23.

217. Zagórstó Z.P., Przybytniak G.K.Optical properties of the radical anion derived from a-alanine by deamination.Nukleonika, 42,2,373-378 (1997).

218. Zagórski Z.P., Rafaiski A.Free radicals in irradiated unstabilized polypropylene, as seen by diffuse reflection absorp-tion-spectrophotometry.


10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, 11-16.05.1997, p. 253.

219. Zag6rski Z.P., Sehested K.Transients and stable radical from the deamination of a-alanine.5th International Meeting on Pulse Investigations in Chemistry, Biology and Physics. PULS'97.Szczyrk, Poland, 13-19.09.1997, pp. S7-P5.

220. ZimekZ.Akceleratory elektron6w. Nowe mozliwoSci i perspektywy zastosowan w chemii i technice radiacyjnej(Electron accelerators. New possibilities and perspectives of applications in chemistry and radiationtechnique).Poste.py Techniki Ja,drowej, 40,2,17-23 (1997).

221. ZimekZ.Akceleratory elektronbw dla potrzeb sterylizacji radiacyjnej (Electron accelerators for radiationsterilization).IV Wiosenna Szkola Sterylizacji Radiacyjnej Sprze.tu Medycznego, Przeszczep6w, Farmaceutyk6w iKosmetyk6w. Warszawa, Poland, 26-27.05.1997, pp. VI/l-VI/5.

222. ZimekZ.Akceleratory elektron6w w zastosowaniu do radiacyjnej modyfikacji polimer6w. (Electron accele-rators as applied to radiation-induced modification of polymers).Polimery, 42,3,148-155 (1997).

223. ZimekZ.Aspekty ekonomiczne sterylizacji radiacyjnej (Economic aspects of radiation sterilization).IV Wiosenna Szkola Sterylizacji Radiacyjnej Sprzetu Medycznego, Przeszczep6w, Farmaceutykow iKosmetyk6w. Warszawa, Poland, 26-27.05.1997, pp. X/l-X/6.

224. ZimekZ.Construction and operation of electron accelerators.Interregional Training Course on Developments in the Application of Electron Beams in Industryand Environmental Protection. Warszawa, Poland, 6-17.10.1997.

225. Zimek Z., Chmielewski A.G., Bulka S., Nichipor H.Flue gas treatment by simultaneous application of electron beam and microwave discharge.1997 IEEE International Conference on Plasma Science. San Diego, California, USA, 19-22.05.1997,p. 292.

226. Zimek Z., Chmielewski A.G., Bulka S., Sunaga H., Tokunaga O., Sato S.Dose distribution in longitudinal irradiation vessel for flue gas treatment.10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, 11-16.05.1997, p. 260.

227. Zimek Z., Chmielewski A.G., Bulka S., Tokunaga O., Sunaga H.Electrical energy utilization in electron beam irradiation process of SO2 and NOx removal from fluegases.10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, p. 259.

228. Zimek Z., Kahiska I.Economical aspects of radiation sterilization with electron beam.International Symposium on Radiation Technology for Conservation of the Environment. ExtendedSynopsis. Zakopane, Poland, 8-12.09.1997.

229. Zimek Z., Wozniak A., Panta P., Ghiszewski W.Low energy high intensity electron beam - X-ray conversion for radiation processing.10th International Meeting on Radiation Processing. Conference Program and Abstracts. Anaheim,California, USA, 11-16.05.1997, p. 261.


SUPPLEMENT LIST OF THE INCT PUBLICATIONS IN 1996

230. Harasiniowicz M., Chmielewski A.G.Application of ultrafiltration and complexation for the treatment of low-level radioactive effluents.International Workshop "Colloid Science in Membrane Engineering". Proceedings. Toulouse, France,13-15.05.1996.

231. Kleczkowska H.E., Szumiel I., Althaus F.R.Poly(ADP-ribose) metabolism and radiation sensitivity of two mouse lymphoma cell sublines.8th Lome Cancer Conference. Book of Abstracts. Lome, Victoria, Australia, 8-11.02.1996.

232. StuglikZ.,SadioJ.A response of L-a-iApplied Radiation Isotopes, 47,11/12,1219-1222 (1996).A response of L-a-alanine and standard bone powder on 3.4 MeV/amu 59Co ion beams.

THE INCT REPORTS IN 1997 139

THE INCT REPORTS IN 1997

1. Annual Report 1996.IChTJ, Warszawa 1997,156 p.

2. Panta P.P., Bulka S., Ghaszewski W.Dose distribution measurements in reaction vessel of pilot plant at EPS KAWE_CZYN.IChTJ, Warszawa 1997. Raporty IChTJ. Seria A nr 1/97,20 p.

3. Bilewicz A.Wpfyw efektu relatywistycznego na wiasnoSci chemiczne pierwiastka 104 (Influence of relativistic effecton chemical properties of element 104.IChTJ, Warszawa 1997. Raporty IChTJ. Seria A nr 2/97,64 p.

4. Dybczynski R., Polkowska-Motrenko H., Samczynski Z., Szopa Z.Preparation and certification of the Polish reference material VIRGINIA TOBACCO LEAVES(CTA-VTL-2) for inorganic trace analysis including microanalysis.IChTJ, Warszawa 1997. Raporty IChTJ. Seria A nr 3/97,76 p.

5. Radoszewski T.Metoda wzorcowania radiometru typ RGR-40 zr6dlem radu 226Ra (Calibration method of typeRGR-40 radiometer by means of radium 226Ra source).IChTJ, Warszawa 1997. Raporty IChTJ. Seria B nr 1/97,12 p.

6. Kulisa K., Dybczynski R., Polkowska-Motrenko H.Zbadanie przydatnoSci posiadanego zestawu do chromatografii jon6w do oznaczania kation6w metalialkalicznych i innych w wodach (A study on suitability of the ion chromatography equipment of Dionex2000i/SP for the determination of alkali metals and other inorganic cations in aqeous solutions).IChTJ, Warszawa 1997. Raporty IChTJ. Seria B nr 2/97,16 p.

7. Chwastowska J., Skwara W., Sterlinska E., Dudek J., Pszonicki L.Oznaczanie i specjacja rte.ci w wodach naturalnych w zakresie ste_zen ponizej 1 ng/ml (Determinationand speciation of mercury in natural waters in the concentration range below 1 ng/ml).IChTJ, Warszawa 1997. Raporty IChTJ. Seria B nr 3/97,14 p.

8. Zaim J., Kruszewski M., Gra.dzka I.Dzialanie bleomycyny na kom<5rki podlinii L5178Y (Bleomycin effect on L5178Y cells).IChTJ, Warszawa 1997. Raporty IChTJ. Seria B nr 4/97,28 p.

9. Machaj B., Strzaikowski J., Smolko K.Czytnik dawki folii dozymetrycznej (Dose reader of dosimetric foil).IChTJ, Warszawa 1997. Raporty IChTJ. Seria B nr 5/97,16 p.

10. Wasek M., Szopa Z., Dybczynski R.Rozpoznanie mozliwoSci zastosowania instrumentalnej wersji NAA do wielopierwiastkowej analizyduzych serii materiatew waznych z punktu widzenia ekologii i geologii (A study on the possiblity ofapplication of instrumental NAA for multielement large-scale analysis of materials important forecology and geology).IChTJ, Warszawa 1997. Raporty IChTJ. Seria B nr 6/97,20 p.

11. Dembinski W., Poniriski M., Fidler R.Studies on fractionation of ytterbium isotopes in Yb(IH)-acetate/Yb-amalgam system. Even-odd effect.IChTJ, Warszawa 1997. Raporty IChTJ. Seria B nr 7/97,22 p.

140 THE INCT REPORTS IN 1997

12. Mirowicz J., Machaj B.Sonda scyntylacyjna do zastosowań przemysłowych stabilizowana układem ARW (AGC controlledscintillation probe for industrial application).IChTJ, Warszawa 1997. Raporty IChTJ. Seria B nr 8/97,18 p.

13. Antoniak W.Programy w języku MATLAB do wygładzania widm promieniowania X (MATLAB programs forsmoothing X-ray spectra).IChTJ, Warszawa 1997. Raporty IChTJ. Seria B nr 9/97,22 p.

14. Urbański P., Kowalska E.Zastosowanie metody bootstrap do badania liniowych modeli regresyjnych (Application of thebootstrap method for assessment of linear regression models).IChTJ, Warszawa 1997. Raporty IChTJ. Seria B nr 10/97,26 p.

15. Malicki W., Bryl-Sandelewska T., Stuglik Z.Ocena czytnika CD-96 przeznaczonego do szybkiego mierzenia absorbancji taśmowych dozymetrówfoliowych i archiwizowania wyników pomiaru (Valuation of a CD-96 reader dedicated to quick read-outand archivisation of foil dosimeter absorbance).IChTJ, Warszawa 1997. Raporty IChTJ. Seria B nr 11/97,16 p.

16. Machaj B.Pomiar koncentracji radonu za pomocą komory Lucasa (Measurement of radon concentration in airemploying Lucas chamber).IChTJ, Warszawa 1997. Raporty IChTJ. Seria B nr 12/97,22 p.

17. Machaj B.Powtarzalność pomiarów za pomocą komory Lucasa (Repeatability of Lucas chamber measurements).IChTJ, Warszawa 1997. Raporty IChTJ. Seria B nr 13/97,22 p.

18. van der Schans G.P., Timmerman AJ., Wojewódzka M., Zaim J.Validation of an immunochemical assay for the detection of DNA damage as a tool for biologicaldosimetry of human exposure to ionising radiation.IChTJ, Warszawa 1997. Raporty IChTJ. Seria B nr 14/97,22 p.

NUKLEONIKA 141

NUKLEONIKATHE 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. (technicalphysics, nuclear physics); Prof. Zbigniew Jaworowski, Ph.D., D.Sc. (radiationprotection); 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 Urbanski, Ph.D., D.Sc. (measuring instruments,nucleonic control systems)

ADVISORY BOARD

Prof. Gregory R. Choppin (USA), Dr William A. Cramp (Great Britain), Prof. AndreiGagarinsky (Russia), Prof. Alexander van Hook (USA), Prof. Larry Kevan (USA),Prof. Evgeni A. Krasavin (JINR-Dubna), Prof. Samuel H. Levine (USA), Dr SueoMachi (Austria), Dr James D. Navratil (USA), Prof. Anthony H.W. Nias (GreatBritain), Dr Shoichi Sato (Japan), Prof. Robert H. Schuler (USA)

CONTENTS OF No. 1/97

1. Andrejczuk A., Zukowski E., Dobrzyfiski L., Neumann K.U., Ziebeck K.R.A.Compton profile studies of Cu2MnAl Heusler alloy.

2. Baranov V. V., Berestov A. V., Martsynkevich B.A., Rudak E.A., Talat A.S.Hyperfine splitting and behaviour of positronium spin polarization.

3. Bondarev I.V.Positronium self-localization in alkali halide crystals.

4. Bondarev I.V.Temperature dependence of positronium diffusivity in alkali halide crystals,

5. Borek J., Osoba W.Free volume in selected vinyl polymers.

6. Bororlski E., Jarlborg T. „.On electron-positron scattering in metal lattices.

7. Brunner S., Puff W., Logar B., Mascher P., Balogh A.G., Baumann M.Vacancy-type detects in electron and proton irradiated ZnO and ZnS.

8. Byakov V.M., Stepanov S.V.Formation of Ps and Mu and radiation chemistry of liquids. Temperature effects.

9. Chabik S., Kostrzewa M., Dobrzyfiski L., Redco K., Waliszewski J., Firszt F., Le,gowski S., MeczyfiskaH., Szatkowski J.Positron lifetime measurements in Zn(i-X)Mg(X)Se.

10. Chabik S., Rudzifiska W., Szuszkiewicz M., Szymaftski C.

Positron annihilation in solid and liquid Bi66.7Sn33.2 alloy.

142 NUKLEONIKA.

11. Chiba M., Hamatsu R., Hirose T., Matsumoto T., Yang J.Measurements of electron-positron annihilation at rest into four and five photons.

12. Chojcan J., Ciesielski K., Goworek T.Momentum distribution of e+-e' pairs annihilation freely and via pick-off in some organic solids.

13. Consolati G., Quasso F.Magnetic quenching experiments with spin polarized positrons.

14. Dobrzynski L., Holas A,Maximum entropy method in momentum density reconstruction.

15.DryzekJ.,DryzekE.The coincidence spectrometer of Doppler broadening of annihilation line.

16. Dryzek J.Remarks on positron annihilation characteristics in nonhomogeneous systems.

17. Dugdale S.B., Fretwell H.M., Alam M.A., West R.N., Shiotani N., Kontrym-Sznajd G.Fermiology through 2D-ACAR and Compton scattering a new approach.

18. Fretwell H.M., Duffy J.A., Clarke A.P., Dugdale S.B., Alam M.A., Evans R.Phase behaviour in confined geometry via positronium annihilation spectroscopy.

19. Grone R., Hascik J., Slugen V., Kuriplach J., Lipka R., Pietryzk P., Vitazek K.Five detector set-up for positron 1D-ACAR study of 60Co containing materials.

20. J&kli G., Baranowski A, Jerie K., Glinski J., Orzechowski K.Structure of aqueous solutions of tetrabutylammonium bromide investigated by positron annihilationand ultrasonic methods.

21. Kontrym-Sznajd G.Reconstruction techniques in positron annihilation.

22. Kontrym-Sznajd G.New approach to Compton profiles data analysis.

23. Kuriplach J., Dauwe C, Segers D., Sob M.Detection of Ti-rich precipitates in iron by means of positron annihilation spectroscopy.

24. Kuriplach J., Sob M., Dauwe C.Preferential positron annihilation in Fe-Al system.

25. Logar B., Puff W., Brunner S., Balogh A.G., Baumann H.Structural, thermal and radiation induced defects in Ni-Al.

26. Nancheva N., Feschiev N., Misheva M., Djurelov N., Kotlarowa T., Elenkov D.Defects in sputter-deposited titatnium films, studied by positron annihilation and X-ray diffraction.

27. Nicht E.M., Bauer G., Vostry P., Cieslar M., Blazek P.Electrical resistivity and positron lifetime studies of the Cu-Mn system.

28. Osoba W.A positron lifetime spectrometer with BaF2 scintillators.

29. Pajajc J., Pietrzak R., Szuszkiewicz M.Positron annihilation in deformed and hydrogenated Cu-50% Pd alloy.

30. Pietrzak R., Chabik S., Szatanik R.Investigation of positron annihilation and electrical resistivity in Ni-H system with copper "decoration".

31. Rubaszek A, Szotek Z., Temmerman W.M.Non-local electron-positron correlation effects in potassium.

32. Rybka C, Goworek T., Ciesielski K.Building-up the Ps component during polymerization.

NUKLEONIKA 143

33. Sob M., Turek L, Vitek V.Atomic configuration and electronic structure of extended defects from the point of view of positronannihilation: a grain boundary example.

34. Sormann H., Kontryn-Sznajd G.Sensitivity of electron-positron momentum densities to the positron wave function: theoretical andnumerical results.

35. Stachowiak H,, Borofiski E.Misunderstandings connected with the problem of electron positron interaction in metals.

36. Stachowiak H., Borofiski E., Banach G.Self-consistent calculation of electron density distribution in metals in HNC approximation.

37. Stachowiak H.Many-body theory of elctron-positron interaction in metallic lithium.

38. Stepanov S.V., Byakov V.M.Slowing down and track structure of positrons and mouns in ordinary and heavy water.

39. WiSniewski G., Karwasz G.P., Brusa R.S., Zecca A.Doppler-broadening studies of surface-modified conducting polyethylene.


1. Symons M.C.R.Radicals in DNA as seen by ESR spectroscopy.

2. Sevilla M.D., Becker D., Razskazovskii Y.Electron and hole transfer with DNA and its hydration layer.

3. Elger G., Mossier K, Tian O., Johnen E., Fuhs M., Kurreck H., MObius K.EPR studies of photoinduced electron transfer reactions in cyclohexylene linked chlorinquinones.

4. Gilbert B.C., Silvester S.EPR studies of the role of copper in bio-organic free radical reactions. Copper-catalysed oxidations ofthiols with peroxides, especially those involving glutathione.

5. Przybytniak G., Hiittermann J., Ambroz H., Weiland B.The influence of crysteamine on free radical formation in frozen aqueous matrices containing dCMP.

6. Strzelczak-Burlinska G., Bobrowski K., Pogocki D., Michalik J.ESR study of radiation induced radicals in polycrystalline methionine and its homopeptides Sx.

7. Dzierze,ga-Le.cznar A., Pilawa B., Stejpien K., Wilczok T.EPR studies of synthetic pheo- and mixed type-melanins.

8. Sagstuen E., Hole E.O., Haugedal S.R., Lund A., Eid O.I., Erickson R.EPR and ENDOR analysis of X-irradiated L-alanine and NaHC2CM • H2O. Simulation of microwavepower dependence of satellite lines.

9. Zagorski Z.P., Przybytniak G.K.Optical properties of the radical anion derived from a-alanine by deamination.

10. Komorowska M., Czyzewska H.The effect of near infrared radiation on erythrocyte membranes; EPR study.

11. Jezierski A., Lisowski J., Drozd J., Jerzykiewicz M., Bylinska E., Czechowski R, Witek B.EPR monitoring of plant degradation humification and coalification.

12. Gerson F.ESR of organic radical ions: a personal account.

13. Davies A.G.EPR spectroscopy and electron distribution.

144 NUKLEONIKA

14. Ulanski P., Bo the E., Hildenbrand K, von Sonntag C, Rosiak J.M.The influence of repulsive electrostatic forces on the lifetime of poly(acrylic acid) radicals in aqueoussolution.

15. Dzilifiski K., Szymanski T., Krzyminiewski R., Sinyakov G.N., Shulga AM.Effect of the resolution degree of EPR spectra on the accuracy of hyperfine structure parameters deter-mined for isotope substituted Zn-chlorin radicals.

16. Pilawa B., Wie,ckowski AB., Koztowski M., Wachowska H.Multicomponent structure of EPR spectra of bituminous coal modified in the potassium-liquid ammo-nia system.

17. Pilawa B., Wie,ckowski A.B,, Lewandowski M.EPR studies of thermal decomposition of coal samples.

18. Kumagai J., Yoshida H., Ichikawa T.Electronic structure of charge carriers in a polysilane quartum wire.

19. Jezierska J., Ozarowski A., Vuc'kovic' G.EPR studies on binuclear copper (II) complexes in solutions with N,N',N",N'"-tetrakis(2-pyridylme-thyl)-l,4,8,ll-tetraazacyclotetradecane.

20. Oliva C, Forni L., Vishniakov AV.Cu2+O' hole pairs and O" spin bags in La2-xMxCuO4 oxide mixtures.

21. Luan Z., Xu J., Kevan L.Cupric ion exchange into tubular aluminosilicate MCM-41 material with variable framework Si/Alratios.

22. Abidi N., Deroide B., Zanchetta J.V.Water complexes Mn2+ as a probe in the ESR study of silica phases obtaine by the sol-gel process.

23. Hrabafiski R., Kassiba AEPR of Mn2+ study of phase of transitions in K2Z11CI4.

24.LechJ.,Sle,zakAEPR of divalent manganese in non-Kramers hosts.

25. Slezak A, Lech J.EPR as a tool for studying slags and slag-like systems.

26. Paradowski M.L., Misiak L.E.EPR study of Gd3+ in Lao.9Ndo.1F3 single crystal.

27. Krupski M., Morawski P., Usachev AE.Influence of pressure and temperature on the EPR spectrum of Gd3+ ion in Cs2NaLaCl6 single crystal.

28. Yahiro H., Nagata M., Shiotani M., Lindgren M, Li H., Lund AMotional dynamics of NO2 adsorbed on cation-exchanged mordenites.

29. Callens F.J.Comparative EPR and ENDOR results on carbonate derived radicals in different host materials.

30. Jaworski M., Sienkiewicz A, Scholes C.P.Double-stacked dielectric ring resonator for EPR measurements of biological samples.

31.Wie.ckowskiA.B.Numerical methods in resonance line shape analysis.

32. Harryvan D., van Faassen E.Motional spin relaxation in photoexcited triplet states.

33. Hoffmann S.K., Goslar J., Hilczer W., Gramza M., Morawski P., Augustyniak M.A.Nuclear spin spectral diffusion and nuclear motion effects in the low temperature behaviour of theelectron spin phase memory time in magnetically diluted solid.

NUKLEONIKA 145


1. In memoriam - prof. Bill Cramp2. In memoriam - prof. Tadeusz Niewiadomski3. Shadley J.D., W6jcik A, Bonk K., Streffer C.

Do low doses of ionizing radiation induce chromosomal repair activity? Screening human T cellextracts microinjected into mouse embroys.

4. Bierlkiewicz M, Liniecki J., Biatobrzeski J., KapuSciriski J.OOrvt

Organ absorbed doses, effective dose and radiological risk related to application of Tc-IgG and"mTc-ECD complexes.

5. Kowalska M.Relative biological effectiveness of tritiated water to killing mouse C3H10T1/2 cells.

6. Grzybowska D.Concentration of Cs in marine fish from the southern Baltic sea in 1990-1995.

7. Warchol S.A, Krynicki J., Rzewuski H., Groetzschel R.Damage buildup and amorphization in ion - implanted GaAsi-xPx.

8. Domatiska G., Janczyszyn J., Taczanowski S.Consideration of the 232Th-233U cycle in optimization of selected blanket parameters of a fusion -fission hybrid system.

9. Szuta AAssessment of fission gas release from fuel rods of Qinshan nuclear power plant.

10. Janczyszyn J., Hussein M.O.Accelerator driven systems for energy generation nuclear waste transmutation and weapons plutoniumreduction.

11. Urbanski P., Kowalska E.Linear and non-linear multivariate calibration of some XRF instruments.

12. Schwabe J.AIC-144, automatic isochronous cyclotron main parameters, status.


1. Bystritsky V.M., Grebenyuk V.M., Parzhitski S.S., Penkov F.M., Sidorov V.T., Stolupin V.A., BulgakovT.L., Mesyats G.A., Sinebryukhov A.A., Sinebryukhov V.A, Chalkovsky S.A., Luchinsky A.V.,Ratakhin N.A, Sorokin S.A, Bystritskii V.M., Toor A, Filipowicz M., Gula A., tqcki E., Woiniak J.,GulaE.A new approach in the experimental studies of nuclear reactions at ultralow energies.

2. Ignatowicz S.Gamma irradiation as a quarantine treatment of apples infested with diapausing eggs of the Europeanred spider mite, Panonychus ulmi (Koch) (Acarina: Tetranychidae).

3. Ignatowicz S., Banasik-Sogala K.Reduced melanization after death in larvae of the khapra beetle, Trogoderma granarium, as a result ofthe irradiation treatment.

4.PihowiczW.,KrukK.Optimization procedure for main design parameters of containments of stationary PWR reactors.

5. Mattiolo Marchese S.R., Del Mastro N.L.Sensitivity fo cysters (Crassostrea brasiliana) to radiation.

6. Malec-Czechowska K., Dancewicz A.M., Szot Z.Screaning method for detection of irradiated cereal grains.

7. Chmielewski A.G., Harasimowicz M.Influence of gamma and electron irradiation on transport properties of nanofiltration and hyperfiltra-tion membranes.

146 NUKLEON1KA

8. Tutay A., Fuchs H., Homeyer H., Budzanowski A., Pausch G., Siwek A., Taymaz A.Calibration procedures for detectors of the multidetector-setup ARGUS.

9. Kowalska E., Urbański P.XRF full-spectrum calibration technique using artificial neutral network.

10. Waligórski M.P.R.On the present paradigm of radiation protection - a track structure perspective.

Information and subscription

INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGYNUKLEONIKA

Dorodna 16,00-981 Warszawa 91, P.O. Box 97, Polandphone: (+48-22) 811-06-56 or 811-30-21 int. 14-91; tlx 813027; fax: (+48-22) 811-15-32;

e-mail: [email protected]

THE INCT PATENTS AND PATENT APPLICATIONS IN 1997 147

THE INCT PATENTS AND PATENT APPLICATIONS IN 1997

PATENTS

1. Method for removal of sulphur dioxide from gases and for production of suphuric acid and anequipment for application of this method.AG. Chmielewski, T.S. Urbanski, B. Tyminski, E. Iller, A. Krylowicz, C. Wawrzyk, Z. Ratajewicz, J.UsidusPolish Patent 171927

2. Method for removal of sulphur dioxide from gases and for production of suphuric acid and anequipment for application of this method.A.G. Chmielewski, T.S. Urbanski, B. Tyminski, E. Iller, A. Krylowicz, C. Wawrzyk, Z. Ratajewicz, J.UsidusPolish Patent 171929

3. Dosimeter for estimation of picowave dose energy.Z.P. Zag6rskiPolish Patent 172237

4. Method for obtaining high-temperature superconductors.A. Deptula, W. Lada, T. Olczak, M.T. Lanagan, S.E. Dorris, K.C. Gorett, R.B. PoeppelPolish Patent 172618

5. Method and an equipment for removal of undesirable components from industrial flue gases.Z. Zimek, Z. Jackowski, AG. ChmielewskiPolish Patent 172964

6. Method and an equipment for removal of undesirable components from industrial flue gases.Z. Zimek, Z. Jackowski, AG. ChmielewskiPolish Patent 173176

7. Method for recovery of metals, particularly of the platinum metals, from used catalysts.A NowickiPolish Patent 173277

PATENT APPLICATIONS

1. Method and a device for mixing of gases reacting chemically.B. Tyminski, AG. ChmielewskiP. 318047

2. Filtration adapter.M. Buczkowski, W. Starosta, J. Kielkiewicz, W. RuminskiP. 324063

148 CONFERENCES ORGANIZED BY THE INCT IN 1997

CONFERENCES ORGANIZED BY THE INCT IN 1997

1. THE 8th COORDINTATION MEETING OF IAEA, JAERI AND INCT, 24-26MARCH 1997, TAKASAKI, JAPAN

• Outline of the pilot plant in EPS KAW^CZYNA.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Dose rate distribution in the reactorH. Sunaga (Takasaki Radiation Chemistry Research Establishment, Japan Atomic Energy ResearchInstitute, Takasaki, Japan)

• Effects of multi-stage irradiation and moisture in the gasH. Namba (Takasaki Radiation Chemistry Research Establishment, Japan Atomic Energy ResearchInstitute, Takasaki, Japan)

• Optimum method for by-products collectionO. Tokunaga (Takasaki Radiation Chemistry Research Establishment, Japan Atomic Energy ResearchInstitute, Takasaki, Japan)

• Control of the electron acceleratorZ. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Optimization of the processA.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Progress of IAEA model project in EPS POMORZANYS. Machi (International Atomic Energy Agency, Vienna, Austria)

• Demonstration project of EB process in BulgariaS. Machi (International Atomic Energy Agency, Vienna, Austria)

• Demonstration project of EB process in ChengduS. Aoki (Ebara Co., Tokyo, Japan)

• Summary and conclusion of the research cooperationS. Hashimoto (Takasaki Radiation Chemistry Research Establishment, Japan Atomic Energy ResearchInstitute, Takasaki, Japan)

2. RESEARCH CO-ORDINATING MEETING OF THE CO-ORDINATE RESEARCHPROGRAMME ON VALIDATION OF NUCLEAR TECHNIQUES FOR ANALYSESOF PRECIOUS AND RARE METALS IN MINERAL CONCENTRATES, 1-4 SEP-TEMBER, WARSZAWA, POLAND

• Validation of nuclear techniques for analysis of precious and rare metals in mineral concentrates.MINTEK/SABS candidate reference materials for heavy minerals from beach sandA. Faanhof (Atomic Energy Corporation of South Africa Ltd., Pretoria, South Africa)

• Application of neutron activation analysis and induced coupled plasma-atomic emission spectrometrymethods for REEs analysis in VietnamLe Ba Thuan, Vu Hoang Minh, Nguyen Van Sue, Thai Ba Cau (Institute for Technology of Radioactiveand Rare Elements, Hanoi, Vietnam)

• Determination of precious and rare metals in minerals concentrates and tailings, using ko based instru-mental neutron activation analysisB. Torres Chamorro (Peruvian Nuclear Energy Institute, Lima, Peru)

• Investigation on possibilities of using chelating ion exchange resin Chelex 100 for the separation ofplatinum, palladium and gold from other elements and from each otherZ. Samczynski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Application of nuclear analytical techniques in the characterization of copper concentratesN.T. Gras Rebolledo (Chilean Nuclear Energy Commission, Santiago, Chile)

CONFERENCES ORGANIZED BY THE INCT IN 1997 _ ?

• Neutron activation analysis in geoanalytical chemistry studies at the Dalhousie University Slowpoke-2Reactor FacilityA. Chatt, J. Holzbecher (Dalhousie University, Halifax, Canada)

• Optimization of instrumental neutron activation analysis for minor and trace element determinationand micro fire assay preconcentration of noble metals for analysis of rocks, minerals and products ofprocessing the mineral raw materialsG.M. Kolesov (Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy ofSciences, Moscow, Russia)

3. INTERNATIONAL SYMPOSIUM ON RADIATION TECHNOLOGY FOR CON-SERVATION OF THE ENVIRONMENT, 8-12 SEPTEMBER 1997, ZAKOPANE,POLAND

• Current issues in environmental protectionS. Wilczkowiak (Ministry of Environmental Protection, Natural Resources and Forestry, Poland)

Purification of Exhaust GasesChairman: N. Frank (USA), A.6. Chmielewski (Poland)

• Electron beam powerplant flue gas treatmentAG. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Collection and application of by-product formed in electron beam flue gas treatment processA.G. Chmielewski, B. Tyminski, G. Zakrzewska-Trznadel (Institute of Nuclear Chemistry and Tech-nology, Warszawa, Poland)

• Dose rate effects on the e-scrub process - experiments and theoryR.P. Genuario, B.M. Penetrante (Virginia Accelerators Corporation, USA)

• Decomposition of tetrachloroethylene by ionizing radiationT. Hakoda, K. Hirota, S. Hashimoto (Takasaki Radiation Chemistry Research Establishment, JapanAtomic Energy Research Institute, Takasaki, Japan)

• The decomposition of polychlorinated aromatic hydrocarbons in the offgas of a municipal wasteincinerator by electron beamH.-R. Paur (Forschungszentrum Karlsruhe GmbH, Germany)

• VOC removal by simultaneous electron beam and biofilter applicationV. Honkonen, J. Ruuskanen (University of Kuopio, Finland)

• Pre-feasibility study for an electron beam flue gas treatment demonstration plant to Eletropaulo'sPiratiningaD. de C.R. Poli (Brazilian Nuclear Energy Commission, Brazil)

• Development of a wet variant of electron beam gas treatmentO.L. Fainchtein, V.V. Piotrovsky, R.A. Salimov (ENERGOSTAL, Ukraine)

Radiation Chemistry and EnvironmentChairman: H.-R. Paur (Germany)

• Radiation chemistry and the environmentN. Getoff (Institut fur Theoretische Chemie und Strahlenchemie, Universita't Wien, Austria)

• Technical and economical aspects of electron beam installations for flue gas treatment from power plantAG. Chmielewski, E. Iller (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Influence of dose distribution and flow pattern between irradiation stages on removal of NO*AG. Chmielewski, A Dobrowolski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Energy consumption of the SO2 removal from humid air under electron beam and electric field influenceH. Nichipor, E. Radouk (Institute of Radiation, Physical and Chemical Problems, Academy of Sciences,Republic of Belarus)

• Prospects of utilizing electron beam irradiation technology to augment control of SO2 and otheremissions from Chilean copper smelting plantsL.Z. Villanueva, L.S. Alumanda (Chilean Nuclear Energy Commission, Chile)

ISO CONFERENCES ORGANIZED BY THE 1NCT IN 1997

Purification and Decontamination of WaterChairman: N. Getoff (Austria), T, Waite (USA)

• Creation and operation of full scale electron beam systems for treatment of water, wastewater andmedical wasteT. Waite (University of Miami, USA)

• Improvement on conventional parameters of actual industrial effluent by electron beam irradiationC.L. Duarte, M.H.O. Sampa (Brazilian Nuclear Energy Commission, Brazil)

• Effect of addition of heavy metal ion on decoloration and degradation of azo dye in aqueous solution bygamma irradiation combined with ozoneM.J. Lee, J.H. Jin (Korea Atomic Energy Research Institute, Ministry of Science and Technology,Korea)

• Treatment of coffee wastewater by gamma irradiationY. Aguilera, R. Consuegra, M. Rapado (Institute Superior de Ciencias y Tecnologia Nucleares, Havana,Cuba)

• Effect of gamma irradiation on some organic pollutants in waterAM. Dessouki, S. Abdel-Aal (National Center for Radiation Research and Technology, Cairo, Egypt)

• New environmental applications of radiation technologyA. Pikaev (Institute of Physical Chemistry, Russian Academy of Sciences, Moscow, Russia)

• Radiolytic degradation of chlorophenols for their removal from polluted watersM. Trojanowicz, A. Chudziak, T. Bryl-Sandelewska (Institute of Nuclear Chemistry and Technology,Warszawa, Poland)

• Radiation induced decomposition of chlorinated benzaldehydes in aqueous solutionM. BekbOlet, I. Balcioglu (Institute of Environmental Sciences, Bogazici University, Turkey), N. Getoff(Institut fiir Theoretische Chemie und Strahlenchemie, Universita't Wien, Austria)

• Hydroxyl radical induced dechlorination of pentachlorophenol in waterXingwang Fang, Yongke He (Department of Technical Physics, Peking University, China)

• Radiation induced decomposition of pentachlorophenol in waterYongke He, Jun Liu (Department of Technical Physics, Peking University, China)

Sewage Sludge TreatmentChairman: M.H.O. Sampa (Brazil)

• Sewage sludge irradiators-batch and continuous flowD.S. Lavale, S. Gangadharan (Board of Radiation and Isotope Technology, Project House, India)

• Recycling of sewage sludge: Nile Tilapia feeding with irradiated and dried sludge from beer industryW. Chuapoehuk, S. Piadang, W. Tinnungwattana (Office for Atomic Energy for Peace, Bangkok,Thailand)

• Agriculture reuse feasibility studies of sludges for the sewage sludge irradiation plant in ArgentinaC. Magnavacca, J.G. Graino (Comision National de Energia Atomica, Centro Atomico Ezeiza, BuenosAires, Argentina)

• Irradiation treatment of sewage sludge - history and prospectsBao Borong, Wu Minghong (Shanghai Applied Radiation Institute, Shanghai University, China)

• Gamma radiation disinfection of municipal waste for reusing as a carrier for inoculantN.M. Hung, D.D. Nhan (Institute for Nuclear Science and Technique, Vietnam)

• Research activities of Samsung Heavy Industries on the conservation of environmentB. Han, D.K. Kim (Samsung Heavy Industries Co., Korea), A. Pikaev (Institute of Physical Chemistry,Russian Academy of Sciences, Moscow, Russia)

Biomedical ApplicationsChairman: E.A. Hegazy (Egypt)

• Biomedical applicationsJ. Rosiak (Technical University of £6dz, Poland)

• Use of different type of electron beam radiation equipment for biotechnical materials processingO. Ferdes, R. Minea (MRT-National Agency for Atomic Energy, Bucharest, Romania)

CONFERENCES ORGANIZED BY THE INCT IN 1997 151

• Formation of free-standing sterilized edible-films from irradiated caseinatesD. Brault, G. D'Aprano, M. Lacroix (Instiut Armand-Frappier, Canada)

• Formation of sterilized edible-films based on caseinates effects of calcium and plasticizersE. Mezgheri, G. D'Asprano, M. Lacroix (Instiut Armand-Frappier, Canada)

• Irradiation as an alternative environment friendly method for microbiological decontamination ofherbal raw materialsP. G6recki, W. Migdal (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

Recycling and Treatment of Plastic and Solid WasteChairman: I, Silverman (USA)

• Recycling and treatment of plastic wasteT. Czvikowszky (Technical University of Budapest, Hungary)

• Development of radiation processes for better environmentAB. Majali, R.S. Deshpande (Bhabha Atomic Research Centre, India)

• The regeneration of polluted active carbon by radiation techniquesBao Borong, Wu Minghong (Shanghai Applied Radiation Institute, Shanghai University, China)

FacilitiesChairman: Z. Zimek (Poland)• Status of industial irradiation technology

N. Studer (Studer AG Werk Hard, Switzerland)• A new semi-mobile plant for radiation processing of waste

G. Liccione, A Tata (Italy)

• High repetition pulsed accelerator for electron beam technologyT. Ruskov (Institute of Nuclear Research and Nuclear Energy, Sofia, Bulgaria), G. V. Dolbilov (Russia)

• Economical aspects of radiation sterilization with electron beamZ. Zimek, I. Kahiska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Electron processing systems for environmental applicationsY. Hoshi, K. Mizusawa, M. Kashiwagi (Nissin High Voltage Co., Ltd., Japan)

Quality Assurance, Quality ControlChairman: Z. Zag6rski (Poland)

• Application of fluorimetry for dosimetry purposesA. Kovacs, L. Wojnarovits (Institute of Isotopes of Hungarian Academy of Sciences, Budapest,Hungary), W.L. McLaughlin (USA)

• Application of radioisotope tracer techniques in evaluation of irradiation vessel of flue gas treatmentsystemJ.-H. Jin, MJ. Lee (Korea Atomic Energy Research Institute, Ministry of Science and Technology, Korea)

• Computerized PVC absorbance reader as the device for quick detection of dose distribution on, underand inside electron irradiated objectB. Machaj, Z. Stuglik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Thermal defects of water, graphite and polystyrene affecting calorimetric responseP.P. Panta, Z.P. Zag6rski, W. Gluszewski (Institute of Nuclear Chemistry and Technology, Warszawa,Poland)

Transfer of Technology Through Technical Co-operation ProjectsChairman: A. Majali (India)

a Nuclear technology for sustinable developmentS. Machi (International Atomic Energy Agency, Vienna, Austria)

• Potential for radiation processing as a technique for the conservation of environment in GhanaCM. Gbedemah (Ghana Atomic Energy Commission, Ghana)

• An overview of environmental pollution status and waste treatment technology used in PakistanT. Javed, R.M. Qureshi (Pakistan Institute of Nuclear Science and Technology, Pakistan)

152 CONFERENCES ORGANIZED BY THE INCT IN 1997

o IRASM - a multipurpose irradiation facility in RomaniaC.C. Panta, I.V. Moise, E. Bratu (MRT - National Agency for Atomic Energy, Romania)

• Industrial gamma irradiation facility with a wet storage source in SyriaI. Othmar, A. Moussa (Syria)

• Electron beam processing programme, wastewater and sludge treatment in BrazilM.H.O. Sampa, P.R. Rela (Brazilian Nuclear Energy Commission, Brazil)

Curing, Crosslinking and GraftingChairman: T. Czvikowsky (Hungary)• Radiation technology application

J. Garnett (Department of Chemistry, University of Western Sydney Nepean, Australia)• Ionic membranes obtained by radiation grafting for the use in waste treatment

E. A Hegazy, H. Abd El-Rehim (National Center for Radiation Research and Technology, Cairo, Egypt)• Radiation graft copolymers of acrylamide onto polypropylene fiber as metal uptake for water soluble

G.T. Rekso, E. Ischan (Centre for the Application of Isotopes and Radiation, Indonesia)• Radiation response of Philippine natural rubber latex

A.M. Dela Rosa, L.V. Abad (Phillippine Nuclear Research Institute, Phillippines)• Effect of ionizing radiation on properties of acrylic pressure sensitive adhesives

P.P. Panta, Z. Zimek, W. Gluszewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)


COURSES ORGANIZED BY THE INCT IN 1997

1. IV WIOSENNA SZKOLA STERYLIZACJI RADIACYJNEJ SPRZEJTJ MEDYCZ-NEGO, PRZESZCZEP6W, FARMACEUTYK6W I KOSMETYK6W (TRAININGCOURSE ON RADIATION STERILIZATION OF MEDICAL PRODUCTS,IMPLANT MATERIALS, COSMETICS AND PHARMACEUTICALS), 26-27 MAY1997, WARSZAWA, POLAND

Organizing Committee: Prof. A.G. Chmielewski, Ph.D., D.Sc. (Chairman); Z. Zimek, Ph.D.; I. Kaiuska,M.Sc; W. Ghiszewski, M.Sc. (Secretary)

Lectures

• Przemyslowe zastosowanie wi^zki elektron6w (Industrial application of electron beam)A.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Oddziafywanie promieniowania jonizuj^cego z materia (Effects of the ionizing radiation on the matter)D. Pogocki (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Wpfyw promieniowania jonizujacego na organizmy zywe (Influence of the ionizing radiation on theviable species)I. Szumiel, A. Wojcik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Zagadnienia mikrobiologiczne sterylizacji radiacyjnej (Microbiological aspects of radiation steriliza-tion)E. Czerniawski (University of Lodz, Poland)

• Sterylizacja radiacyjna we Francji (Radiation sterilization in France)P. Icre (COFRAR S.A., France)

• Akceleratory elektron6w dla potrzeb sterylizacji radiacyjnej (Electron accelerators for radiation steri-lization needs)Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Sterylizacja w zr6dlach gamma (Radiation sterilization with gamma rays)W. Bogus (Technical University of Lodz, Poland)

• Wymagania dotyczace organizacji procesu sterylizacji radiacyjnej (Requirements concerning radiationsterilization process in the INCT)I. Kahiska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Kontrola procesu sterylizacji radiacyjnej (Radiation sterilization process control)Z. Stuglik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Aspekty ekonomiczne sterylizacji radiacyjnej (Economical aspects of radiation sterilization)Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Przepisy mie.dzynarodowe dotycz^ce sterylizacji radiacyjnej (The international regulations for radiationsterilization)K. Mehta (International Atomic Energy Agency, Vienna, Austria)

• Zasady dopuszczania wyrob6w sterylizowanych radiacyjnie do stosowania w medycynie (Requirementsconcerning the release of radiation sterilization products to be used in medicine)T. Achmatowicz (Institute for Drugs, Warszawa, Poland)

• Sterylizacja radiacyjna biostatycznych przeszczep6w tkankowych (Radiation sterilization of biostatictissue transplants)A Dziedzic-Gociawska (Medical Academy of Warsaw, Poland)

• Sztuczne materiafy implantacyjne (Artificial implant materials)M. Lewandowska-Szumiel (Medical Academy of Warsaw, Poland)

• Medyczne materiafy hydrozelowe (Medical hydrogel materials)J.M. Rosiak (Technical University of Lodz, Poland)

154 COURSES ORGANIZED BY THE INCT IN 1997

• Polipropylen odporny radiacyjnie (Polypropylene - radiation resistant)J. Bojarski, Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Trekowe membrany filtracyjne oraz ich zastosowanie biomedyczne (Track membrane and their applica-tion in medicine)M. Buczkowski, D. Wawszczak, W. Starosta (Institute of Nuclear Chemistry and Technology, Warsza-wa, Poland)

• Radiacyjna higienizacja kosmetyk6w (Radiation hygenization of cosmetics)K. Malec-Czechowska, T. Bryl-Sandelewska (Institute of Nuclear Chemistry and Technology, Warsza-wa, Poland)

• Sterylizacja radiacyjna na Swiecie w s\vietle X konferencji IMRP w USA (Radiation sterilization in theworld now, presented on the 10th International Meeting on Radiation Processing, USA, 1997)Z.P. Zag6rski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Metody zwalczania szkodliwych owad6w przy uzyciu radiacji na przykladzie zywiaka chlebowca (Stegob-ium paniceum L.) (Overcoming with noxious insects by applying irradiation described on the exampleof Stegobium paniceum L.)A. Krajewski (Agricultural University of Warsaw, Poland)

• Obr6bka radiacyjna materiatow - zasady opracowywania technologii radiacyjnych (Radiation processing- requirements for work up the radiation technology)P. Panta (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Metody sterylizaqi (Sterilization methods)W. Stachowicz (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

2. INTERREGIONAL TRAINING COURSE ON DEVELOPMENTS IN THE APPLI-CATION OF ELECTRON BEAMS IN INDUSTRY AND ENVIRONMENTAL PRO-TECTION, 6-17 OCTOBER 1997, WARSZAWA, POLAND

Technical Officer: S. Machi, Ph.D., Deputy Director General, IAEACourse Director: Prof. A.G. Chmielewski, Ph.D., D.Sc.Course Coordinators: K. Malec-Czechowska, M.Sc, I. Kahiska, M.Sc.

Lectures

• History of radiation chemistry of water and aqueous solutionsJ. Kroh (Technical University of L6di, Poland)

• Prospects of radiation technology application for industrial and environmental protectionS. Machi (International Atomic Energy Agency, Vienna, Austria)

• Construction and operation of electron acceleratorsZ. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Physical aspects of radiation processingM.R. Cleland (AECL Accelerators, USA)

• Economics of radiation processingM.R. Cleland (AECL Accelerators, USA)

• Crosslinking of plastics by means of ionizing radiationA, Zyball (BGS Beta-Gamma-Serive GmbH, Germany)

• Biochemical productsJ.M. Rosiak (Technical University of L6d£, Poland)

• Electron beam exhaust gas treatmentA.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Radiation processing of aqueous systemsP. Gehringer (Austrian Research Center Seibersdorf, Austria)

• Operating characteristics of low energy EB equipmentS.V. Nablo (Electron Processing Systems Inc., USA)

• Industrial application of low energy electron processorsS.V. Nablo (Electron Processing Systems Inc., USA)


• Sterilization of disable medical productsT. Sadat, C. Reinhard (Thomson - CSF, France)

• Sewage sludge solid waste treatmentA.G. Chmielewski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Overview of food irradiation 1997R. Molins (International Atomic Energy Agency, Vienna, Austria)

• Food irradiation - new developmentsR. Molins (International Atomic Energy Agency, Vienna, Austria)

• Radiation sterilization of meals for special usesR. Molins (International Atomic Energy Agency, Vienna, Austria)

• Food preservationT. Sadat (Thomson - CSF, France)

• Irradiation of spices and herbsW. Stachowicz (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

Demonstrations and experiments

Heat-shrinkable materials manufacturing (tubes and tapes)• Products and equipment characteristics. Process set up - extrusion, irradiation, expansion - introductory

lectureZ. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Facility demonstration. Accelerator LAE 13/9 and equipment for heat-shrinkable materials manu-facturingI. Kaluska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Experiments with heat-shrinkable materialsI. Kaluska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

Environmental EB-applications• Sludge hygenization, high SO2 flue gas treatment VOC removal - introductory lecture

Z. Zimek (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Pilot facility demonstrationS. Bulka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)Visit to laboratory and facilities in L6d£Sterilization of medical products

• Product and equipment characteristics. Process organization and control. Dosimetry and micro-biological test - introductory lectureI. Kaluska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Pilot and industrial facilities demonstrationI. Kaluska (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Dosimetry in electron beam radiation processing - introductory lectureZ. Stuglik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Dosimetry experimentsZ. Stuglik (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

Food irradiation• Product and equipment characteristics. Process organization and control. Dosimetry - introductory

lectureW. Migdal (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Pilot facility demonstrationB. Owczarczyk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Experiments - irradiation of spicesB. Owczarczyk (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Detection of irradiated foodW. Stachowicz, K. Malec-Czechowska (Institute of Nuclear Chemistry and Technology, Warszawa,Poland)

156 COURSES ORGANIZED BY THE 1NCT IN 1997

Flue gas treatment• EB pilot plant of flue gas purification from SO2 and NOX at the KAWE_CZYN Power Plant - intro-

ductory lectureE. Iller, B. Tyminski (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

• Analytical measurements and process control for EB flue gas treatment process - introductory lectureJ. Licki (Institute of Atomic Energy, Otwock-Swierk, Poland)

• Experiments - dosimetryS. Bulka (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)

3. POSTGRADUATTON COURSES. COURSE OF POLLUTION CONTROL IN NATU-RAL ENVIRONMENT, 15 NOVEMBER-15 DECEMBER 1997, UNIVERSITY OFSAO PAULO, BRAZIL

Course Director: D. de Castro Rubio Poll, Ph.D.Lecturers: Prof. A.G. ChmieiewsW, Ph.D., D.Sc; E. Iller, Ph.D.; J. PaJige, Ph.D.

Lectures• Emission of pollutants from industrial sources• Worldwide inventory of pollutants (SO2, NOx, VOC) emission• Environmental chemistry• Wet and dry depositions• Environment and human health degradation due to emission of pollutants• Emission limits and worldwide environmental protection policy• Primary technical methods of emission control• Conventional technologies for removal of SO2 and NOx• New advanced flue gas treatment technologies• Electron beam flue gases treatment• Solid waste generation, treatment and recycling• Incineration and off - gases treatment• Electron beam technologies for solid waste treatment and recycling• Industrial and municipal waste water• Waste water treatment• Radiotracer investigations in protection of water environment• Waste water electron beam treatment• Dams and environment

PhD THESES 157

PhD THESES

1. Maria Wojewódzka, M.Sc.Indukcja odpowiedzi adaptacyjnej w limfocytach ludzkich (Induction of the adaptive resonanse inhuman lymphocytes)supervisor: Prof. Irena Szumiel, Ph.D., D.Sc.University of Warsaw, Faculty of Biology, 28.04.1997

2. Grażyna Zakrzewska-Trznadel, M.Sc.Efekty izotopowe H/D i O16/O18 w procesie permeacji wody z przemianą fazową (H/D and O16/O18

(Isotope effect in the process of water permeation coupled with phase transition)supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology, 05.06.1997

3. Andrzej Pawlukojć, M.Sc.Badania właściwości dynamicznych molekuł aminokwasów alifatycznych metodą nieelastycznego nieko-herentnego rozpraszenia neutronów termicznych (Studies of dynamie properties of aliphatic amino-acide molecules using the method of nonelastic scattering of thermal neutrons)supervisor: Prof. Janusz Leciejewicz, Ph.D., D.Sc.Institute of Atomic Energy, 08.10.1997

4. Ryszard Wierzchnicki, M.Sc.Parametryzacja ruchu osadów dennych dla warunków wielorewowej strefy brzegowej na podstawieznacznikowych badań terenowych (Characteristics and parametrisation of bedload movement formultibar conditions of the coastal zone on the base of field study)supervisor: AssocProf. Zbigniew Pruszak, Ph.D., D.Sc.Polish Academy of Sciences, Institute of Hydroengineering, 12.12.1997

5. Grażyna Strzelczak, M.Sc.Badania metodą EPR inicjowanych radiacyjnie procesów rodnikowych w polikrystalicznych aminokwa-sach i peptydach zawierających siarkę (ESR study of radiation-induced radical process in polycrys-talline atnino acids and peptides containing sulphur)supervisor: AssocProf. Jacek Michalik, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology, 18.12.1997

DOCTOR OF CHEMISTRY DEGREE PROGRAMME

The Institute of Nuclear Chemistry and Technology offers the four years Ph.D. degree programme tograduates 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.

Besides of the employment for candidates accepted for the forementioned programme, the Instituteoffers an opportunity of application for supplemental doctorial scholarship.

During the programme each participant takes part in a 45 h course of lectures of fundamental physicalchemistry, 30 h specialization course and is obliged to give an annual seminar on a topic of his/herdissertation area. The final requirements for the Ph.D. programme graduates, consistent with the Ministryof 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.

158 PhD THESES

Applicants for the Ph.D. degree programme are accepted all around the year. Detailed information canbe obtained from Admission Secretary, Dr. Jadwiga Krejzler (phone: (+48-22) 811-27-35), or from theScientific Information Department of the Institute (phone: (+48-22) 811-25-78).

RESEARCH PROJECTS AND CONTRACTS 159

RESEARCH PROJECTS AND CONTRACTS

RESEARCH PROJECTS GRANTED BYTHE POLISH STATE COMMITTEE FOR SCIENTIFIC RESEARCH

IN 1997 AND IN PREVIOUS YEARS

1. Investigation of homogeneity of reference materials intended for microanalysis by means of neutronactivation analysis method.supervisor: Prof. Rajmund Dybczyfiski, Ph.D., D.Sc.

2. Concentration of radioactive wastes using the membrane distillation (MD) process.supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

3. Examination of activation of the nuclear transcription factor NF*B in two sublines of L5178Y cellsdamaged with X-rays or hydrogen peroxide.supervisor: Prof. Irena Szumiel, Ph.D., D.Sc.

4. Identification of irradiated food by use of single cell electrophoresis (comet assay),supervisor: Prof. Zbigniew Szot, Ph.D., D.Sc.

5. Investigations of new generation of particle track membranes and their applications.supervisor: AssocProf. Tadeusz Zbltowski, Ph.D., D.Sc.

6. The influence of the even-odd nucleus number and other factors on the isotope effect accompanyingthe extraction of the f-electron elements.supervisor: Wojciech Dembinski, Ph.D.

7. High coordination number of metal ions in chelate complexes.supervisor: AssocProf. Jerzy Narbutt, Ph.D., D.Sc.

8. EPR studies of radiation induced radical processes in polycrystaliine amino acids and peptides con-taining sulfur.supervisor: AssocProf. Jacek Michalik, Ph.D., D.Sc.

9. Optical spectra of free radicals in polypropylene at room temperature.supervisor: Prof. Zbigniew P. Zag6rski, Ph.D., D.Sc.

10. The inelastic incoherent neutron scattering investigation of hydrogen bonds vibrations in aliphaticamino acids.supervisor: Prof. Janusz Leciejewicz, Ph.D., D.Sc.

11. Polymer materials with adhesive properties modified by fast electron beams.supervisor: Przemyslaw Panta, Ph.D.

12. Polypropylene composites with thermoplastic elastomers modified by radiation processing.supervisor: AssocProf. Jacek Michalik, Ph.D., D.Sc.

13. Investigation of modifiers used for the determination of elements of the Groups V and VI by graphitefurnace atomic absorption spectrometry.supervisor: Prof. Leon Pszonicki, Ph.D., D.Sc.

14. Determination of a small and extremely small amounts of uranium in biological materials byradiochemical neutron activation analysis.supervisor: Prof. Rajmund Dybczynski, Ph.D., D.Sc.

15. Research on the influence of "protective enzymes" on cell resistance of two L5178Y sublines to hydro-gen peroxide.supervisor: Elzbieta Bouzyk, Ph.D.

16. Characteristics of action of camptothecin, inhibitor of topoisomerase I, in murine lymphoma cellsL5178Y.supervisor: Prof. Irena Szumiel, Ph.D., D.Sc.

17. Multivariate statistical methods for analysis in radiometric measurements.supervisor: Prof. Piotr Urbanski, Ph.D., D.Sc.

160 RESEARCH PROJECTS AND CONTRACTS

18. Separation analytical application of amphoteric ion exchange resin retardion 11A8.supervisor: Prof. Rajmund Dybczynski, Ph.D., D.Sc.

19. Influence of relativistic effect on chemical properties of the heaviest elements.supervisor: Aleksander Bilewicz, Ph.D.

20. Differential scanning calorimetry and X-ray diffraction studies of the physico-chemical transformationoccurring in the polyester films under influence of heavy ions irradiation.supervisor: Krystyna CieSla, Ph.D.

21. Application of a multi-counter neutron detector for fissionable isotopes identification and determi-nation of their spatial distribution in bulk samples.supervisor: AssocProf. Tadeusz Zoltowski, Ph.D., D.Sc.

22. Optimization of radiation removal process of SO2 and NOX from flue gases containing highconcentration of SO2. (supervision of IEA PhD fellow)supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

23. The transport and activation of the corrosion products in the nuclear reactor equipped withindependent multi-loop cooling, (supervision of IEA PhD fellow)supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

IMPLEMENTATION PROJECTS GRANTED BYTHE POLISH STATE COMMITTEE FOR SCIENTIFIC RESEARCH IN 1997

1. Thermo-melt glue polymer composites with adhesive properties for heat-shrinkable products.3T09B54496C/2871

2. Irradiation method for microbiological decontamination of herbal raw materials.5 PO6G 004 96 C/2870

3. Serenissima. Investigation and restauration of XV-XVIII century Venice paintings from NationalMuseum Collection in Warsaw. Elaboration of model of physical-chemical and restauration researchesof XV-XVIII century Venice paintings from National Museum Collection in Warsaw.1HO1E 001 96C/3009

GOVERNMENT STRATEGIC PROGRAM

The management of radioactive wastes and burnt nuclear fuel1. Elaboration and studies on novel engineered barriers preventing migration of most toxic radionuclides

from nuclear waste repositories.SPR-4-4bsupervisor: AssocProf. Jerzy Narbutt, Ph.D., D.Sc.

2. Concentration of liquid low- and medium-level radioactive wastes by membrane methods.SPR-4-1supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

IAEA RESEARCH CONTRACTS IN 1997

1. Complexation and distribution of ecologically important metals in heterogenous systems.POL/7377/RBprincipal investigator: AssocProf. Jerzy Narbutt, Ph.D., D.Sc.

2. Synthesis and studies of new selective absorbents for beryllium, strontium and radium radionuclides.POL/7216/RBprincipal investigator: Aleksander Bilewicz, Ph.D.

3. Preparation and certification of the new certified reference material VIRGINIA TOBACCO LEAVESand development of neutron activation analysis (NAA) methods for checking the homogeneity.7192/R2/RBprincipal investigator: Prof. Rajmund Dybczyfiski, Ph.D., D.Sc.

RESEARCH PROJECTS AND CONTRACTS 161

4. Materials for in-situ monitoring of light water reactor (LWR) water chemistry by optical methods.8426/RBprincipal investigator: Leon Fuks, Ph.D.

5. Thin layer alanine dosimeter with optical spectrophotometric evaluation.8533/RBprincipal investigator: Prof. Zbigniew P. Zag6rski, Ph.D., D.Sc.

IAEA TECHNICAL CONTRACTS IN 1997

1. Electron beam flue gas treatment.POL/8/013

2. Industrial scale demonstration plant for electron beam purification of flue gases.POL/8/014

3. 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.r electronics for gauge, soft-ware.IRA8/012/190C

EUROPEAN COMMISSION RESEARCH PROJECTS IN 1997

1. The comet assay: application in gentoxicity testing and as a screening method for assessing theexposure of human populations to genotoxins.CIPA-CT94-0129supervisor: Marcin Kruszewski, Ph.D.

2. Examination of homological recombination in mammalian cell mutants defective in DNA doublestrand break repair,ERB CIPD CT-930417supervisor: Prof. Irena Szumiel, Ph.D., D.Sc.

3. Establishment of an Eastern European Network of Laboratories for Identification of IrradiatedFoodstuffs.

a) ERB CIPA CT 940134-2supervisor: Waclaw Stachowicz, Ph.D.

b) ERB CIPA CT 940134-3supervisor: Wojciech Migdal, Ph.D.

4. Development of heavy duty reactor window for industrial scale removal of NOX and SO2 from flue gasby electron beam treatment.IC15-CT97-0711supervisor: Prof. Jerzy Piekoszewski, Ph.D., D.Sc.

5. Accreditation for high dose measurement.EU INCO Copernicus Project ICI5-CT96-0824supervisor: Zofia Stuglik, Ph.D.

OTHER FOREIGN CONTRACTS IN 1997

1. Preparation of cathodic materials precursors for fabrication of rechargeable Li batteries (Limanganates, LiCoCh, LiNio.5Coo.5O2) by sol-gel process.2526-ERG/TEAContract with ENEA, Italyprincipal investigator: Andrzej Deptula, Ph.D.

2. Validation of an immunochemical assay for the detection of DNA damage as a tool for biologicaldosimetry of human exposure to ionizing radiation.Contract with TNO Prins Maurits, Laboratory, Rijswijk, Hollandprincipal investigator: Marcin Kruszewski, Ph.D.

162 RESEARCH PROJECTS AND CONTRACTS

3. Rental contract for flue gas treatment pilot plant.KEPRI-P-97008Contract with the Korean Electric Power Corporationprincipal investigator: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

4. Training and collaboration on eb flue gas treatment laboratory installation design.a) Contract with Tenaga National Research and Development SDN BHD, Kajang, Malaysia

principal investigator: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

b) Contract with Malaysian Institute for Nuclear Technology Research (MINT), Kajang, Malaysiaprincipal investigator: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.


LIST OF VISITORS TO THE INCT IN 1997

1.

2.

3.

4.

5.

6.

7.

8.

9.

10.

11.

12.

13.

14.

15.

16.

17.

18.

19.

20.

21.

22.

23.

24.

25.

26.

27.

28.

29.

30.

NameA.M.A. AbdallahA. Abedinzadeh

I. Al-GanadE. AllorentA. BelousovV. Bierozkin

M.B.C. BulajicA. Collins

E. Cortes Toro

R. DelmasM. Demski

M.H. De OliveraSampaT. DrobinaM. DusinskaW. EllisonAL. FainchteinH. Falkenbery

R. FiedlerN. FrankK. Fuji

A. Gabelova

R. GenuarioO. Giiven

P. HansenM. HarkOnenS. Hashimoto

H. Hashizume

Hasni Hasan

V. Honkonen

Y. Hoshi

InstitutionUniversity of MansouraAtomic Energy Organization of Iran, Nuclear Re-search CenterMineral Resources Geological Survey Corp.Ecole de Mines de NantesInstitute of Electrophysical ApparatusInstitute of Crystallography, Russian Academy ofSciencesEcole de Mines de NantesRowett Research Institute

Chilean Nuclear Energy Commission, Departmentof Nuclear ApplicationCEA/CNR, Laboratoire Pierre SueScientific Production Complex of Linear Accelera-tors and Cyclotrons, NPK Luts NIIEFAIPEN Instituto de Pesquisas Energeticos e Nuc-learesJoint Institute for Nuclear Research, DubnaInstitute of Prevetive and Clinical MedicineEllison ConsultantsENERGOSTALWorld Bank

Safeguard Analytical LaboratoryInternational Business ConsultantsNational Institute for Research in Inorganic Ma-terialsCancer Research Institute, Slovak Academy ofSciencesVirginia Accelarators CorporationResearch and Isotopes Division, IAEA

Ris$ National LaboratoryVirginia Accelarators CorporationTakasaki Radiation Chemistry Research Establish-mentNational Institute for Research in Inorganic Ma-terialsMalaysian Institute for Nuclear Technology Re-searchUniversity of Kuopio, Department of Applied Phy-sicsNissin High Voltage Co., Ltd.

CountryEgyptIran

YemenFranceRussiaRussia

FranceGreatBritainChile

FranceRussia

Brazil

RussiaSlovakiaUSA

UkraineUSA

AustriaUSA

Japan

Slovakia

USA

UnitedNations

DenmarkUSA

Japan

Japan

Malaysia

Finland

Japan

Periodone weektwo weeks

short visitthree monthsone weektwo weeks

three monthsshort visit

short visit

two weeks

one week

short visit

short visitshort visitshort visitshort visitshort visit

short visitfour weeksone week

short visit

two short visitsshort visit

short visittwo short visitsshort visit

one week

three weeks

short visit

short visit

164 LIST OF VISITORS TO THE INCT IN 1997

31.

32.

33.

34.

35.

36.

37.

38.

39.

40.

41.

42.

43.

44.

45.

46.

47.

48.

49.

50.

51.

52.

53.

54.

55.

56.

57.

58.

59.

60.

61.

62.

63.

64.

Ch. Houce-LevinR. HouvilainenG.L. Hug

P. IcreH. InabaJoong Kuk ChunF. JorgensenT.J. Kemp

Kihun Joh

Kyung-Ryong JangA. Lund

S. Machi

K. Mehta

M. Mekawy

Mohd Said Jousef

M. MostafaviG.S. MurthyH. Nichipor

H. Norkojouri

A. Pikajev

B.M. RzyskiM.V. SagaidakL. Salnikov

J. SatyanarayanaR.F. Schader Fruh

A. Shahrokhi

D. Slamenova

R. Stetina

T. TanakaA.J. TimmermanS. Timochin

O. Tokunaga

G. van der SchansJ.E. Vargas

Institute CurieUniversity of HelsinkiRadiation Laboratory University of Notre Dame

CORFRAR S.A.National Institute of Radiological SciencesSamsung Heavy Industries Co.Ristf National LaboratoryUniversity of Warwick, Department of Chemistry

Samsung Heavy Industries Co.

Samsung Heavy Industries Co.Linkoping University, Department of Physics andMeasurement TechnologyInternational Atomic Energy Agency

International Atomic Energy Agency

National Center for Radiation Research andTechnologyMalaysian Institute for Nuclear Technology Re-searchUniversitc de ParisSchool of Chemistry, Andhra UniversityInstitute of Radiation Physical and Chemical Prob-lems, Academy of Sciences of BelarusAtomic Energy Organization of Iran, Nuclear Re-search Center

Institute for Physical Chemistry, Russian Academyof SciencesIPEN-CHEN/SPENERGOSTALInstitute of Radiation Physical and Chemical Prob-lems, Academy of Sciences of BelarusSchool of Chemistry, Andhra UniversityChilean Nuclear Energy Commission, Departmentof Nuclear ApplicationsAtomic Energy Organization of Iran, Nuclear Re-search Center

Cancer Research Institute, Slovak Academy ofSciencesInstitute of Experimental Medicine, Czech Aca-demy of SciencesChubu Electric Power Co., NagoyaPrins Maurits Laboratory, TNOJoint Institute for Nuclear Research, DubnaTakasaki Radiation Chemistry Research Establish-ment

Prins Maurits Laboratory, TNOUniversity of South Carolina

FranceFinland

USA

FranceJapanKoreaDenmarkGreatBritainKorea

Korea

Sweden

UnitedNationsUnitedNationsEgypt

Malaysia

FranceIndiaBelarus

Iran

Russia

BrazilUkraineBelarus

IndiaChile

Iran

Slovakia

CzechRepublicJapanHollandRussiaJapan

HollandUSA

one weekshort visitone week

short visitshort visitone monthshort visitone week

one month;short visitone month

short visit

short visit

short visit

two months

three weeks

two weekstwo weeksfour weeks

two months

short visit

two weekstwo weeksshort visit

eight monthsone week

one month

short visit

short visit

short visittwo short visitsshort visitone week

short visitshort visit


65.

66.67.68.69.

70.71.

H. Vera Ruiz

L.M. VillanuevaU. WaldschlagerJ. WishartH. Yamada

Yong Jun ChoA. Zomosa

Research and Isotopes Division, IAEA

Chilean Nuclear Energy CommissionInstitute of Environmental TechnologiesBrookhaven National LaboratoryNational Institute for Research in Inorganic Ma-terialsSamsung Heavy Industries Co.University of Santiago

UnitedNationsChileGermanyUSAJapan

KoreaChile

short visit

short visitshort visittwo short visitsone week

one monthshort visit

166 THE INCT SEMINARS IN 1997

THE INCT SEMINARS IN 1997

1. Prof. G.S. Murphy (Andhra University, India)Nuclear programme of India with special reference to waste management.

2. Assoc. Prof. A. Sereno (University of Porto, Portugal)Use of thermal methods to characterize physical state of foods.

3. Dr H. Inaba (National Institute of Radiological Sciences, Chiba, Japan)X-ray and daunorubicin-induced apoptosis in murine lymphoma cell lines L5178Y and 3SB.

4. Prof. K. Zakrzewski, Assoc. Prof. J. Sablinski (Institute of Haematology and Blood Transfusion,Warszawa, Poland), Dr Z. We.grzynowicz (Institute of Haematology and Blood Transfusion, Warszawa,Poland)Profesor Edward Kowalski - hematolog i radiobiolog - wspomnienie w 30. rocznice. s"mierci pierwszegokierownika Zakiadu Radiobiologii i Ochrony Zdrowia (In commemoration of Professor EdwardKowalski - haematologist and radiobiologist - first Head of the Department of Radiobiology andHealth Protection, in the 30-ieth anniversary of his death).

5. Dr J. Navratil (Rust Federal Services of Idaho, USA)Overview of activities at the Idaho National Engineering Laboratory.

6. Dr R. Fiedler (International Atomic Energy Agency, Vienna, Austria)The total evaporation measurements method in mass spectrometry.

7. Prof. J.E. Vargas (University of South Carolina, USA)An example of the application of artificial intelligence to an industrial problem.

8. Dr J.F. Wishart (Brookhaven National Laboratory, Upton, USA)The new photocathode electron gun accelerator at Brookhaven. Long-distance electron transfer inproteins and peptides.

9. Prof. Ch. Hou6e-Levin (Universite Paris Sud, Orsay, France)One-electron reduction of disulfide bonds in proteins as a probe of the micro-environmental influenceon protein reactivity.

10. Prof. A.M. Abdallah (Mansoura University, Egypt)Some analytical concepts with industrial applications.

U.S. Timokhin, M.Sc. (Joint Institute of Nuclear Research, Dubna, Russia)Thermochromatographic studies of chemistry of elements 102-106.

12. Dr T. Drobina (Joint Institute of Nuclear Research, Dubna, Russia)A sensitive method for determination of plutonium in the environment.

13. Prof. T.J. Kemp (University of Warwick, Great Britain)Application of electrospray and MALDI in determining degradation mechanisms of polymers.

A COMPUTER NETWORK (LAN) IN THE INCT 167

A COMPUTER NETWORK (LAN) IN THE INCT

A computer network in the Institute of Nuclear Chemisty and Technology is based - inphysical layer - on the technology 10 Base-T. This is a multistar type of network. Eachbuilding in the area of the Institute is connected by fiber optic cables to the net hub and iswired with an UTP cable, category 5, in a star configuration. The network transfers datawith a speed of 10 MB/s.

Most of the hosts attached to this LAN network are the PC computers. At presentabout 80 PC computers is connected to LAN. Almost all the PC computers are equippedwith cards made by 3Com (Etherlink III - 3C509). Only a few PC have cards of otherproducers. There are many network applications installed on the PC computers, includingFTP programs, working under DOS (FTP, Telnet) and Windows applications (e.g. WWWbrowser).

Packets are routes outside the Institute by a CISCO router (model 2514). The computernetwork uses the communication protocol TCP/IP and is connected to a wide area networkInternet node, located in Warszawa. Our LAN is connected with the Internet by dedicatedline, leased from TP S.A. using two Motorola modems (model 3266).

We have one server (running under the UNIX operating system) connected to LAN:Challenge S produced by Silicon Graphics with the configuration: 32 MB of RAM, 2.5 GBof disk memory, CD reader, cartridge tape drive DAT and one Ethernet controller. Thechallenge is a mail server and also a name resolver (a host runs DNS software - DomainName Service - which translates names of computers into IP addresses).

INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGYDorodna 16, 03-195 Warszawa, PolandPhone: (+48)-(22) 11-06-56Fax: (+48)-(22) 11-15-32Telex: 813027 ichtj piE-mail: [email protected]

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