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ANNUAL REPORT
2011
INSTITUTE
OF NUCLEAR CHEMISTRY
AND TECHNOLOGY
EDITORS
Prof. Jacek Michalik, Ph.D., D.Sc.
Wiktor Smułek, Ph.D.
Ewa Godlewska-Para, M.Sc.
PRINTING
Sylwester Wojtas
© Copyright by the Institute of Nuclear Chemistry and Technology, Warszawa 2012
All rights reserved
CONTENTS
GENERAL INFORMATION
7
MANAGEMENT OF THE INSTITUTE
9
MANAGING STAFF OF THE INSTITUTE
9
HEADS OF THE INCT DEPARTMENTS
9
SCIENTIFIC COUNCIL (2008-2011)
9
11
ORGANIZATION SCHEME
13
SCIENTIFIC STAFF
14
PROFESSORS
14
SENIOR SCIENTISTS (Ph.D.)
14
CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY
17
–
2
OXIDIZING RADICALS AND THEIR REACTIVITY IN IONIC LIQUIDS BASED ON NTf ANION
J. Grodkowski, R. Kocia, J. Mirkowski, M. Nyga, A. Sulich, T. Szreder
19
FREE RADICAL REACTIONS OF NICOTINE
K. Kosno, M. Celuch, J. Mirkowski, I. Janik, D. Pogocki
20
PRELIMINARY STUDIES ON RADIATION DEGRADATION OF AQUEOUS SOLUTION OF LINURON
M. Celuch, A. Bojanowska-Czajka, K. Kulisa, J. Kisała, K. Kosno, D. Pogocki
23
REACTIVITY OF C-CENTRED RADICALS STABILIZED IN ZSM-5 ZEOLITE
M. Sterniczuk, J. Sadło, G. Strzelczak, J. Michalik
25
MULTIFREQUENCY EPR STUDY ON γ-IRRADIATED BONE SUBSTITUTING BIOMATERIALS
J. Sadło, G. Strzelczak, M. Lewandowska-Szumieł, M. Sterniczuk, J. Michalik
26
SURFACE MODIFICATION OF POLY(ESTERURETHANE) BY RADIATION-INDUCED GRAFTING
OF N-ISOPROPYLACRYLAMIDE
M. Walo, G. Przybytniak, M. Barsbay, P.A. Kavaklı, O. Guven
28
RADIATION-INDUCED REDUCTION OF CARBON DIOXIDE AS POSSIBLE EXPLANATION
OF ABIOTIC FORMATION OF METHANE
E.M. Kornacka, Z.P. Zagórski
30
STUDIES OF PHYSICOCHEMICAL PROPERTIES OF GELS BASED ON IRRADIATED WHEAT
STARCH
K. Cieśla, W. Głuszewski
31
CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY
37
ION EXCHANGE EVIDENCE FOR CHEMICAL ISOTOPE EFFECTS OF GALLIUM AND INDIUM
IN AQUEOUS HCl SOLUTIONS
I. Herdzik-Koniecko, S. Siekierski, J. Narbutt
39
NEW METHOD FOR DISSOLUTION OF THORIUM OXIDE
K. Łyczko, M. Łyczko, I. Herdzik-Koniecko, B. Zielińska
41
44
LABELLING OF DOTATATE WITH CYCLOTRON PRODUCED Sc
S. Krajewski, I. Cydzik, K. Abbas, A. Bulgheroni, A. Bilewicz, A. Majkowska-Pilip, F. Simonell
42
99m
Tc-LABELLED VASOPRESSIN ANALOGUE d(CH2)5[D-Tyr(Et2),Ile4,Eda9]AVP AS A POTENTIAL
RADIOPHARMACEUTICAL FOR SMALL-CELL LUNG CANCER (SCLC) IMAGING
E. Gniazdowska, P. Koźmiński, K. Bańkowski
43
THE CONCEPT OF A HYBRID SYSTEM FOR TREATMENT OF LIQUID LOW- AND MEDIUM-LEVEL
RADIOACTIVE WASTE
G. Zakrzewska-Trznadel, A. Miśkiewicz, A. Jaworska-Sobczak, M. Harasimowicz
45
STUDIES ON THE LEACHING OF URANIUM FROM LOWER TRIASSIC PERIBALTIC SANDSTONES
G. Zakrzewska-Trznadel, K. Kiegiel, K. Frąckiewicz, D. Gajda, E. Chajduk, I. Bartosiewicz, J. Chwastowska,
S. Wołkowicz, J.B. Miecznik, R. Strzelecki
47
SYNTHESIS OF URANIUM DIOXIDE MICROSPHERES BY WATER AND NITRATE EXTRACTION
FROM URANYL-ASCORBATE SOLS
M. Brykała, A. Deptuła, W. Łada, T. Olczak, D. Wawszczak, T. Smoliński
48
SYNTHESIS OF PEROVSKITE BY COMPLEX SOL-GEL PROCESS FOR NUCLEAR WASTE
IMMOBILIZATION
T. Smoliński, A. Deptuła, T. Olczak, W. Łada, D. Wawszczak, M. Brykała, F. Zaza, A.G. Chmielewski
51
CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY
55
OPTIMIZATION OF A FINGER-PRICK BLOOD COLLECTION METHOD FOR THE γ-H2AX ASSAY:
POTENTIAL APPLICATION IN POPULATION TRIAGE
M. Wojewódzka, A. Lankoff, M. Kruszewski
57
CLONOGENIC ABILITY DOES NOT CORRESPOND TO DNA DAMAGE INDUCED IN HUMAN
CELLS TREATED IN VITRO WITH SILVER AND TITANIUM DIOXIDE NANOPARTICLES
I. Grądzka, T. Bartłomiejczyk, T. Iwaneńko, M. Wojewódzka, A. Lankoff, M. Dusinska, G. Brunborg, I. Szumiel,
M. Kruszewski
58
COMPARISON OF FREQUENCIES OF DICENTRIC CHROMOSOMES AND HISTONE γ-H2AX FOCI
IN HUMAN LYMPHOCYTES X-IRRADIATED AT 4, 20 AND 37oC
A. Lankoff, S. Sommer, I. Buraczewska, T. Bartłomiejczyk, T. Iwaneńko, H. Lisowska, A. Węgierek-Ciuk, I. Szumiel,
I. Wewiór, A. Banasik-Nowak
59
THE EFFECT OF CONJUGATED LINOLEIC ACID (CLA) SUPPLEMENTATION ON LIPID RAFT
PROPERTIES AND RADIOSENSITIVITY OF HUMAN COLON CANCER HT-29 CELLS
I. Grądzka, B. Sochanowicz, K. Brzóska, G. Wójciuk, Ch. Degen, G. Jahreis, I. Szumiel
60
LABORATORY OF NUCLEAR ANALYTICAL METHODS
63
RADIOLYTIC DECOMPOSITION OF DICLOFENAC – ANALYTICAL, TOXICOLOGICAL AND PULSE
RADIOLYSIS STUDIES
A. Bojanowska-Czajka, G. Kciuk, M. Gumiela, G. Nałęcz-Jawecki, K. Bobrowski, M. Trojanowicz
64
ELABORATION OF OPTIMAL CONDITIONS OF GEOLOGICAL MATERIALS ANALYSIS
FOR URANIUM DETERMINATION
I. Bartosiewicz, E. Chajduk, M. Pyszynska, J. Chwastowska, H. Polkowska-Motrenko
68
LABORATORY OF MATERIAL RESEARCH
71
STRUCTURAL STUDIES IN Li(I) ION COORDINATION CHEMISTRY
W. Starosta, J. Leciejewicz
73
NANOPORES WITH CONTROLLED PROFILES IN TRACK-ETCHED MEMBRANES
B. Sartowska, O. Orelovitch, A. Presz, I. Blonskaya, P. Apel
77
IMPROVEMENT OF TRIBOLOGICAL PROPERTIES OF STAINLESS STEEL BY ALLOYING
ITS SURFACE LAYER WITH RARE EARTH ELEMENTS USING HIGH INTENSITY PULSED PLASMA
BEAMS
B. Sartowska, J. Piekoszewski, L. Waliś, J. Senatorski, M. Barlak, W. Starosta, C. Pochrybniak, I. Pokorska
79
INAA AS A SOURCE OF INFORMATION FOR THE PROVENANCE OF ALABASTER SCULPTURES
T. Śliwa, E. Pańczyk
80
POLLUTION CONTROL TECHNOLOGIES LABORATORY
85
MODELLING STUDY OF NOx REMOVAL IN FLUE GAS IN THE PRESENCE OF C2H6
UNDER ELECTRON BEAM IRRADIATION
Y. Sun, V. Morgunov, A.G. Chmielewski
86
EMISSION PROCESSES IN THE BALTIC SEA REGION – PLASMA TECHNOLOGIES
IN ENVIRONMENTAL PROTECTION (PlasTEP)
S. Witman, A. Pawelec, A.G. Chmielewski
87
STABLE ISOTOPE LABORATORY
89
STABLE ISOTOPES METHODS FOR JUICE AUTHENTICITY CONTROL
R. Wierzchnicki
91
STABLE ISOTOPE RATIO ANALYSIS TO CHARACTERIZE CHOSEN SAMPLES OF POLISH HONEY
K. Malec-Czechowska, R. Wierzchnicki
92
LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES
A STUDY OF FILMS: CTA, B3 AND PVC AS POTENTIAL DOSIMETERS FOR DOSIMETRY
AT LOW TEMPERATURES
A. Korzeniowska-Sobczuk, K. Doner, M. Karlińska
95
96
LABORATORY FOR DETECTION OF IRRADIATED FOOD
99
INCT PARTICIPATES IN THE INTERCOMPARATIVE EXERCISE FOR QUALITY ASSURANCE
ON TL, PSL AND EPR IRRADIATED FOOD DETECTION METHODS
W. Stachowicz, M. Sadowska, G. Liśkiewicz, G.P. Guzik
100
EFFECTIVENESS OF DIFFERENT PROCEDURES OF MINERAL ISOLATION FROM IRRADIATED
SPICES SUITABLE FOR THERMOLUMINESCENCE DETECTION METHOD
M. Sadowska, W. Stachowicz
102
LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS
107
THE RADIOMETRIC PROBES FOR INDUSTRIAL MEASURING SYSTEMS
A. Jakowiuk, E. Kowalska, J. Pieńkos, P. Filipiak, Ł. Modzelewski, J. Palige, J. Kraś
108
MOBILE DOSIMETRIC GATE
A. Jakowiuk, E. Kowalska, J. Pieńkos, P. Filipiak, Ł. Modzelewski
109
PUBLICATIONS IN 2011
113
ARTICLES
113
BOOKS
119
CHAPTERS IN BOOKS
119
THE INCT PUBLICATIONS
121
CONFERENCE PROCEEDINGS
121
CONFERENCE ABSTRACTS
124
SUPPLEMENT LIST OF THE PUBLICATIONS IN 2010
137
NUKLEONIKA
139
INTERVIEWS IN 2011
143
THE INCT PATENTS AND PATENT APPLICATIONS IN 2011
144
PATENTS
144
PATENT APPLICATIONS
144
CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2011
146
Ph.D./D.Sc. THESES IN 2011
148
Ph.D. THESES
148
D.Sc. THESES
148
EDUCATION
149
Ph.D. PROGRAMME IN CHEMISTRY
149
TRAINING OF STUDENTS
149
RESEARCH PROJECTS AND CONTRACTS
RESEARCH PROJECTS GRANTED BY THE NATIONAL SCIENCE CENTRE
IN 2011
151
151
DEVELOPMENT PROJECTS GRANTED BY THE NATIONAL CENTRE
FOR RESEARCH AND DEVELOPMENT IN 2011
151
INTERNATIONAL PROJECTS CO-FUNDED BY THE MINISTRY OF SCIENCE
AND HIGHER EDUCATION IN 2011
152
STRATEGIC PROJECT “NEW TECHNOLOGIES SUPPORTING DEVELOPMENT
OF SAFE NUCLEAR ENERGY”
153
STRATEGIC PROJECT “ADVANCED TECHNOLOGIES FOR GAINING ENERGY”
153
IAEA RESEARCH CONTRACTS IN 2011
153
IAEA TECHNICAL AND REGIONAL CONTRACTS IN 2011
154
PROJECTS WITHIN THE FRAME OF EUROPEAN UNION FRAME
PROGRAMMES IN 2011
154
EUROPEAN REGIONAL DEVELOPMENT FUND: BALTIC SEA REGION
PROGRAMME
154
INTERNATIONAL RESEARCH PROGRAMMES IN 2011
154
STRUCTURAL FUND: OPERATIONAL PROGRAMME INNOVATIVE ECONOMY
155
LIST OF VISITORS TO THE INCT IN 2011
156
THE INCT SEMINARS IN 2011
158
LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2011
159
LECTURES
159
SEMINARS
163
AWARDS IN 2011
164
INDEX OF THE AUTHORS
166
GENERAL INFORMATION
7
GENERAL INFORMATION
Poland decided to start a national nuclear energy programme 55 years ago and the Institute of Nuclear Research (IBJ) was established. Research in nuclear and analytical chemistry, nuclear chemical engineering and technology (including fuel cycle), radiochemistry
and radiation chemistry, and radiobiology were carried out mainly in the Chemistry Division, located in Warsaw Żerań, which became the interdisciplinary Institute of Nuclear
Chemistry and Technology (INCT) in 1983.
The INCT is Poland’s most advanced institution in the fields of radiochemistry, radiation chemistry, nuclear chemical engineering and technology, application of nuclear
methods in material engineering and process engineering, radioanalytical techniques, design and production of instruments based on nuclear techniques, environmental research,
cellular radiobiology, etc. The results of work at the INCT have been implemented in various branches of the national economy, particularly in industry, medicine, environmental
protection and agriculture. Basic research is focused on: radiochemistry, chemistry of isotopes, physical chemistry of separation processes, cellular radiobiology, and radiation
chemistry, particularly that based on pulse radiolysis method. With its nine electron accelerators in operation and with staff experienced in the field of electron beam application,
the Institute is one of the most advanced centres of science and technology in this domain.
The Institute has four pilot plants equipped in six electron accelerators: for radiation sterilization of medical devices and transplantation grafts; for radiation modification of polymers; for removal of SO2 and NOx from flue gases; for food hygiene. The electron beam
flue gas treatment in EPS Pomorzany with the accelerators power over 1 MW is a biggest
radiation processing facility ever built.
The Institute trains many of IAEA’s Fellows and plays a leading role in agency regional
projects. Because of its achievements, the INCT has been nominated the IAEA’s Collaborating Centre in Radiation Technology and Industrial Dosimetry (www-naweb.iaea.org/
na/collaborating-centres.html).
The INCT has started implementing several projects in the programme “Innovative
Economy” POIG, granted on the basis of high evaluation of the Institute’s achievements:
• Centre of Radiochemistry and Nuclear Chemistry – meeting the needs of nuclear power
and nuclear medicine;
• Analysis of thorium usage effects in a power nuclear reactor (coordinated by the Institute of Atomic Energy);
• Analysis of the possibilities of uranium extraction from indigenous resources (in cooperation with the Polish Geological Institute – NRI);
• New generation of intelligent radiometric tools with wireless data transmission;
• Development of a multi-parametric triage approach for an assessment of radiation exposure in a large-scale radiological emergency;
• New generation of electrical wires modified by radiation.
The INCT is a leading institute in Poland regarding the implementation of nuclear
energy related EU projects. Its expertise and infrastructure was the basis for participation
in EURATOM and FP7 grants:
• ACSEPT: Actinide Recycling by Separation and Transmutation;
• ADVANCE: Ageing Diagnostics and Prognostics of Low-voltage I&C Cables;
• IPPA: Implementing Public Participation Approaches in Radioactive Wastes Disposal;
• MULTIBIODOSE: Multidisciplinary Biodosimetric Tools to Manage High Scale Radiological Casualties;
• NEWLANCER: New MS Linking for an Advanced Cohesion in Euratom Research.
The mission of the INCT is the implementation of nuclear energy for social development, health and environmental protection.
The Institute represents the Polish Government in Euroatom Fuel Supply Agency,
in Fuel Supply Working Group of Global Nuclear Energy Partnership and in Radioactive
8
GENERAL INFORMATION
Waste Management Committee of the Nuclear Energy Agency (Organisation for Economic
Co-operation and Development).
The Institute is listed in the cathegory I of scientific institutions based on the evaluation of the Ministry of Science and Higher Education.
The INCT Scientific Council has rights to grant D.Sc. and Ph.D. degrees in the field
of chemistry. The Institute carries out third level studies (doctorate) in the field of nuclear
and radiation chemistry and in 2011 one D.Sc. and four Ph.D. theses were defended.
In 2011, the INCT scientists published 67 papers in scientific journals registered in
the Philadelphia list, among them 39 papers in journals with an impact factor (IF) higher
than 1.0. Five scientific books and 17 chapters in the books were written by the INCT research workers.
The INCT had actively participated in the numerous events associated with the International Year of Chemistry (IYC 2011) and the 100th Anniversary of Maria Skłodowska-Curie Nobel prize in chemistry. We took part, among others, in exhibition in Brussels
“Maria Skłodowska-Curie in science, yesterday and today”, in education project “Following Maria Skłodowska-Curie – questioning”, in main IYC 2011 event – scientific picnic in
the Institute of Physical Chemistry and in the lectures and exhibitions in Adam Mickiewicz
University in Poznań under the name “Life and work of Maria Skłodowska-Curie – women
in science”.
Annual awards of the INCT Director-General for the best publications in 2011 were
granted:
• first degree award to Krzysztof Bobrowski for the chapter “Chemistry of sulfur-centered
radicals” in the book “Recent trends in radiation chemistry”;
• second degree award to Andrzej Pawlukojć for five publications on the structure and
dynamics of charge transfer (CT) complexes published in international journals with
high IF;
• third degree award to Janusz Leciejewicz and Wojciech Starosta for five publications on
the properties of new complexes of uranium, lead, zinc and lithium with a pyridazine-carboxylic ligand published in “Acta Crystallographica”.
The research teams in the INCT were involved in organization of 11 scientific meetings:
• Polish National Group Meeting in the frame of IPPA FP7 EU Project (5 April 2011,
Warszawa, Poland);
• Seminar on the Exchange of Information on Nuclear Safety and Radiological Protection with participation of government delegations of Austria and Poland (25-26 May
2011, Warszawa, Poland);
• Polish National Group Meeting in the frame of IPPA FP7 EU Project (1 July 2011,
Warszawa, Poland);
• PlasTEP Summer School and Training Course in Warsaw/Szczecin (25 July-5 August
2011, Warszawa/Szczecin, Poland);
• Workshop “Current trends in radiation chemistry research” (26 August 2011, Warszawa,
Poland);
• International Conference on Development and Applications of Nuclear Technologies
NUTECH-2011 (11-14 September 2011, Kraków, Poland);
• Polish Reference Group Meeting in the frame of IPPA FP7 EU Project (20 September
2011, Warszawa, Poland);
• XI Training Course on Radiation Sterilization and Hygenization (20-21 October 2011,
Warszawa, Poland);
• Coordination Meeting on Radiation Engineered Nanostructures – Supporting Radiation Synthesis and the Characterization of Nanomaterials for Health Care, Environmental Protection and Clean Energy Applications, RER/8/014 (16-18 November 2011,
Warszawa, Poland);
• 1st Workshop in the frame of IPPA FP7 EU Project (24 November 2011, Warszawa,
Poland);
• IX Conference “For the city and environment – problems of waste disposal” (28 November 2011, Warszawa, Poland).
The INCT also is editor of the scientific journal “Nukleonika” (www.nukleonika.pl).
9
MANAGING STAFF OF THE INSTITUTE
Director
Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.
Deputy Director for Research and Development
Prof. Jacek Michalik, Ph.D., D.Sc.
Deputy Director of Finances
Wojciech Maciąg, M.Sc.
Deputy Director of Maintenance and Marketing
Roman Janusz, M.Sc.
Accountant General
Maria Małkiewicz, M.Sc.
HEADS OF THE INCT DEPARTMENTS
• Centre for Radiation Research and Technology
Zbigniew Zimek, Ph.D.
• Centre for Radiochemistry and Nuclear
Chemistry
Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc.
• Centre for Radiobiology and Biological
Dosimetry
Prof. Marcin Kruszewski, Ph.D., D.Sc.
• Laboratory of Nuclear Control Systems
and Methods
Jacek Palige, Ph.D.
• Laboratory of Material Research
Wojciech Starosta, Ph.D.
• Laboratory of Nuclear Analytical Methods
Halina Polkowska-Motrenko, Ph.D., D.Sc,
professor in INCT
• Stable Isotope Laboratory
Ryszard Wierzchnicki, Ph.D.
• Pollution Control Technologies Laboratory
Andrzej Pawelec, Ph.D.
• Laboratory for Detection of Irradiated Food
Wacław Stachowicz, Ph.D.
• Laboratory for Measurements of Technological
Doses
Anna Korzeniowska-Sobczuk, M.Sc.
1. Prof. Grzegorz Bartosz, Ph.D., D.Sc.
University of Łódź
4. Prof. Stanisław Chibowski, Ph.D., D.Sc.
Maria Curie-Skłodowska University
2. Prof. Aleksander Bilewicz, Ph.D., D.Sc.
Institute of Nuclear Chemistry and Technology
5. Prof. Rajmund Dybczyński, Ph.D., D.Sc.
3. Prof. Krzysztof Bobrowski, Ph.D., D.Sc.
(Vice-chairman)
6. Prof. Zbigniew Florjańczyk, Ph.D., D.Sc.
(Chairman)
Warsaw University of Technology
10
7. Prof. Zbigniew Galus, Ph.D., D.Sc.
University of Warsaw
8. Prof. Henryk Górecki, Ph.D., D.Sc.
Wrocław University of Technology
9. Prof. Leon Gradoń, Ph.D., D.Sc.
10. Jan Grodkowski, Ph.D., D.Sc., professor
in INCT
11. Edward Iller, Ph.D., D.Sc., professor in NCBJ
National Centre for Nuclear Research
12. Tomasz Jackowski, M.Sc.
Ministry of Economy
13. Iwona Kałuska, M.Sc.
14. Prof. Marcin Kruszewski, Ph.D., D.Sc.
(Vice-chairman)
15. Prof. Marek Wojciech Lankosz, Ph.D., D.Sc.
AGH University of Science and Technology
16. Prof. Janusz Lipkowski, Ph.D., D.Sc.
Institute of Physical Chemistry, Polish Academy
of Sciences
17. Zygmunt Łuczyński, Ph.D.
Institute of Electronic Materials Technology
18. Prof. Andrzej Marcinek, Ph.D., D.Sc.
Technical University of Łódź
19. Prof. Bronisław Marciniak, Ph.D., D.Sc.
Adam Mickiewicz University
20. Wojciech Migdał, Ph.D., D.Sc., professor
in INCT
24. Halina Polkowska-Motrenko, Ph.D. D.Sc.,
professor in INCT
25. Grażyna Przybytniak, Ph.D., D.Sc., professor
in INCT
26. Prof. Leon Pszonicki, Ph.D., D.Sc.
27. Jarosław Sadło, Ph.D.
28. Ryszard Siemion, M.Sc.
PKN ORLEN
29. Prof. Irena Szumiel, Ph.D., D.Sc.
30. Prof. Marek Trojanowicz, Ph.D., D.Sc.
31. Hanna Ewa Trojanowska, M.Sc.
Undersecretary of State in the Ministry
of Economy
32. Andrzej Tyrała, M.Sc.
Warszawskie Zakłady Farmaceutyczne POLFA S.A.
33. Piotr Urbański, Ph.D., D.Sc., professor
in INCT
(Vice-chairman)
34. Lech Waliś, Ph.D.
35. Maria Wojewódzka, Ph.D.
36. Prof. Zbigniew Zagórski, Ph.D., D.Sc.
37. Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc.,
21. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc.
(Vice-chairman)
22. Jan Paweł Pieńkos, Eng.
38. Zbigniew Zimek, Ph.D.
professor in INCT
23. Dariusz Pogocki, Ph.D., D.Sc., professor
in INCT
HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (2008-2011)
1.
Prof. Antoni Dancewicz, Ph.D., D.Sc.
2.
Prof. Sławomir Siekierski, Ph.D.
11
1. Prof. Grzegorz Bartosz, Ph.D., D.Sc.
University of Łódź
2. Prof. Aleksander Bilewicz, Ph.D., D.Sc.
3. Prof. Krzysztof Bobrowski, Ph.D., D.Sc.
(Vice-chairman)
4. Marcin Brykała, M.Sc.
5. Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.
6. Andrzej Chwas, M.Sc.
Ministry of Economy
7. Jadwiga Chwastowska, Ph.D., D.Sc., professor
in INCT
8. Krystyna Cieśla, Ph.D., D.Sc., professor
in INCT
9. Jakub Dudek, Ph.D.
10. Prof. Rajmund Dybczyński, Ph.D., D.Sc.
11. Prof. Zbigniew Florjańczyk, Ph.D., D.Sc.
(Chairman)
12. Prof. Zbigniew Galus, Ph.D., D.Sc.
13. Prof. Henryk Górecki, Ph.D., D.Sc.
Wrocław University of Technology
19. Anna Lankoff, Ph.D., D.Sc., professor
in INCT
20. Prof. Marek Wojciech Lankosz, Ph.D., D.Sc.
AGH University of Science and Technology
21. Prof. Janusz Lipkowski, Ph.D., D.Sc.
Institute of Physical Chemistry, Polish Academy
of Sciences
22. Zygmunt Łuczyński, Ph.D.
Institute of Electronic Materials Technology
23. Prof. Jacek Michalik, Ph.D., D.Sc.
24. Wojciech Migdał, Ph.D., D.Sc., professor
in INCT
25. Prof. Jarosław Mizera, Ph.D., D.Sc.
26. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc.
27. Andrzej Pawlukojć, Ph.D., D.Sc., professor
in INCT
28. Dariusz Pogocki, Ph.D., D.Sc., professor
in INCT
29. Halina Polkowska-Motrenko, Ph.D., D.Sc.,
professor in INCT
30. Grażyna Przybytniak, Ph.D., D.Sc., professor
in INCT
14. Prof. Leon Gradoń, Ph.D., D.Sc.
31. Prof. Janusz Rosiak, Ph.D., D.Sc.
Technical University of Łódź
15. Jan Grodkowski, Ph.D., D.Sc., professor
32. Lech Waliś, Ph.D.
in INCT
16. Edward Iller, Ph.D., D.Sc., professor in NCBJ
National Centre for Nuclear Research
17. Adrian Jakowiuk, M.Sc.
18. Prof. Marcin Kruszewski, Ph.D., D.Sc.
(Vice-chairman)
33. Maria Wojewódzka, Ph.D.
34. Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc.,
professor in INCT
(Vice-chairman)
35. Zbigniew Zimek, Ph.D.
12
HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (2011-2015)
1. Prof. Sławomir Siekierski, Ph.D.
2. Prof. Irena Szumiel, Ph.D., D.Sc.
3. Prof. Zbigniew Paweł Zagórski, Ph.D., D.Sc.
13
ORGANIZATION SCHEME
Scientific
Council
DIRECTOR
Accountant
General
Deputy Director
of Finances
Deputy Director
of Maintenance and Marketing
Deputy Director
for Research and Development
Laboratory of Nuclear
Analytical Methods
Centre for Radiation Research
and Technology
Stable Isotope Laboratory
Centre for Radiobiology
and Biological Dosimetry
Pollution Control Technologies
Laboratory
Laboratory for Detection
of Irradiated Food
Centre for Radiochemistry
and Nuclear Chemistry
Laboratory for Measurements
of Technological Doses
Laboratory of Material
Research
Laboratory of Nuclear Control
Systems and Methods
14
SCIENTIFIC STAFF
SCIENTIFIC STAFF
PROFESSORS
1. Bilewicz Aleksander
radiochemistry, inorganic chemistry
13. Migdał Wojciech, professor in INCT
chemistry, science of commodies
2. Bobrowski Krzysztof
radiation chemistry, photochemistry, biophysics
14. Ostyk-Narbutt Jerzy
radiochemistry, coordination chemistry
3. Chmielewski Andrzej G.
chemical and process engineering, nuclear chemical engineering, isotope chemistry
15. Pawlukojć Andrzej, professor in INCT
chemistry
4. Chwastowska Jadwiga, professor in INCT
analytical chemistry
5. Cieśla Krystyna, professor in INCT
physical chemistry
16. Pogocki Dariusz, professor in INCT
radiation chemistry, pulse radiolysis
17. Polkowska-Motrenko Halina, professor
in INCT
6. Dybczyński Rajmund
18. Przybytniak Grażyna, professor in INCT
radiation chemistry
7. Grigoriew Helena, professor in INCT
solid state physics, diffraction research of non-crystalline matter
19. Siekierski Sławomir
physical chemistry, inorganic chemistry
8. Grodkowski Jan, professor in INCT
radiation chemistry
9. Kruszewski Marcin
radiobiology
10. Lankoff Anna, professor in INCT
biology
11. Leciejewicz Janusz Tadeusz
crystallography, solid state physics, material
science
20. Szumiel Irena
cellular radiobiology
21. Trojanowicz Marek
22. Zagórski Zbigniew
physical chemistry, radiation chemistry, electrochemistry
23. Zakrzewska-Trznadel Grażyna, professor
in INCT
process and chemical engineering
12. Michalik Jacek
radiation chemistry, surface chemistry, radical
chemistry
SENIOR SCIENTISTS (Ph.D.)
1. Barlak Marek
chemistry
5. Buczkowski Marek
physics
2. Bartłomiejczyk Teresa
biology
6. Chajduk Ewelina
chemistry
3. Bojanowska-Czajka Anna
chemistry
7. Danilczuk Marek
chemistry
4. Brzóska Kamil
biochemistry
8. Deptuła Andrzej
chemistry
SCIENTIFIC STAFF
9. Dobrowolski Andrzej
chemistry
15
31. Ostapczuk Anna
chemistry
10. Dudek Jakub
chemistry
32. Ozimiński Wojciech
chemistry
11. Frąckiewicz Kinga
chemistry
33. Palige Jacek
metallurgy
12. Fuks Leon
chemistry
34. Pawelec Andrzej
chemical engineering
13. Głuszewski Wojciech
chemistry
35. Pruszyński Marek
chemistry
14. Gniazdowska Ewa
chemistry
36. Ptaszek Sylwia
15. Grądzka Iwona
biology
37. Rafalski Andrzej
radiation chemistry
16. Harasimowicz Marian
technical nuclear physics, theory of elementary
particles
38. Roubinek Otton
chemistry
17. Herdzik-Koniecko Irena
chemistry
18. Kciuk Gabriel
chemistry
19. Kiegiel Katarzyna
chemistry
20. Kierzek Joachim
physics
21. Kornacka Ewa
chemistry
22. Kunicki-Goldfinger Jerzy
conservator/restorer of art
23. Lewandowska-Siwkiewicz Hanna
chemistry
24. Łyczko Krzysztof
chemistry
25. Łyczko Monika
chemistry
26. Machaj Bronisław
radiometry
27. Majkowska-Pilip Agnieszka
chemistry
28. Męczyńska-Wielgosz Sylwia
chemistry
29. Mirkowski Jacek
nuclear and medical electronics
30. Nowicki Andrzej
organic chemistry and technology, high-temperature technology
39. Sadło Jarosław
chemistry
40. Samczyński Zbigniew
41. Sartowska Bożena
material engineering
42. Skwara Witold
43. Sochanowicz Barbara
biology
44. Sommer Sylwester
radiobiology, cytogenetics
45. Stachowicz Wacław
radiation chemistry, EPR spectroscopy
46. Starosta Wojciech
chemistry
47. Strzelczak Grażyna
radiation chemistry
48. Sun Yongxia
chemistry
49. Szreder Tomasz
chemistry
50. Turek Janusz
chemistry
51. Waliś Lech
material science, material engineering
52. Warchoł Stanisław
solid state physics
53. Wierzchnicki Ryszard
16
SCIENTIFIC STAFF
54. Wiśniowski Paweł
radiation chemistry, photochemistry, biophysics
57. Zielińska Barbara
chemistry
55. Wojewódzka Maria
radiobiology
58. Zimek Zbigniew
electronics, accelerator techniques, radiation
processing
56. Wójciuk Karolina
chemistry
CENTRE
FOR RADIATION RESEARCH
AND TECHNOLOGY
Electron beams (EB) offered by the Centre for Radiation Research and Technology located at
the Institute of Nuclear Chemistry and Technology (INCT) are dedicated to basic research,
R&D and radiation technology applications.
The Centre, in collaboration with the universities from Poland and abroad, apply EB technology for fundamental research on the electron beam-induced chemistry and transformation
of materials. Research in the field of radiation chemistry includes studies on the mechanism
and kinetics of radiation-induced processes in liquid and solid phases by the pulse radiolysis
method. The pulse radiolysis experimental set-up allows direct time-resolved observation of
short-lived intermediates (typically within the nanosecond to millisecond time domain), is
complemented by steady-state radiolysis, stop-flow absorption spectrofluorimetry and product analysis using chromatographic methods. Studies on radiation-induced intermediates are
dedicated to energy and charge transfer processes and radical reactions in model compounds
of biological relevance aromatic thioethers, peptides and proteins, as well as observation of
atoms, clusters, radicals by electron paramagnetic resonance (EPR) and electron nuclear
double resonance (ENDOR), also focused on research problems in nanophase chemistry and
radiation-induced cross-linking of selected and/or modified polymers and copolymers.
This research has a wide range of potential applications, including creating more environmentally friendly and sustainable packaging, improving product safety, and modifying material
properties. Electron accelerators provide streams of electrons to initiate chemical reactions or
break of chemical bonds more efficiently than the existing thermal and chemical approaches,
helping to reduce energy consumption and decrease the cost of the process. The Centre may
offer currently four electron accelerators for study of the effects of accelerated electrons on a
wide range of chemical compounds with a focus on electron beam-induced polymerization,
polymer modification and controlled degradation of macromolecules. EB technology has a
great potential to promote innovation, including new ways to save energy and reduce the use
of hazardous substances as well as to enable more eco-friendly manufacturing processes.
Advanced EB technology offered by the Centre provides a unique platform with the application for: sterilization medical devices, pharmaceutical materials, food products shelf life
extension, polymer advanced materials, air pollution removal technology and others. EB accelerators replace frequently thermal and chemical processes for cleaner, more efficient,
lower-cost manufacturing. EB accelerators sterilize products and packaging, improve the performance of plastics and other materials, and eliminate pollution for industries such as pharmaceutical, medical devices, food, and plastics.
The Centre offers EB in the energy range from 0.5 to 10 MeV with an average beam power
up to 20 kW and three laboratory-size gamma sources with Co-60. Research activity are supported by such unique laboratory equipment as:
• nanosecond pulse radiolysis and laser photolysis set-ups,
• EPR paramagnetic spectroscopy for solid material investigation,
• pilot installation for polymer modification,
• laboratory experimental stand for removal of pollutants from gas phase,
• laboratory of polymer and non-material characterization,
• microbiological laboratory,
• dosimetric laboratory,
• pilot facility for radiation sterilization and food product processing.
The unique technical basis makes it possible to organize a wide internal and international
cooperation in the field of radiation chemistry and radiation processing including programmes
supported by the European Union and the International Atomic Energy Agency (IAEA). It
should be noticed that currently there is no other suitable European experimental basis for
study radiation chemistry, physics and radiation processing in a full range of electron energy
and beam power.
Since 2010, at the INCT on the basis of the Centre for Radiation Research and Technology,
an IAEA Collaborating Centre for Radiation Processing and Industrial Dosimetry is functioning. That is the best example of capability and great potential of concentrated equipment,
methods and staff working towards application of innovative radiation technology.
19
OXIDIZING RADICALS AND THEIR REACTIVITY IN IONIC LIQUIDS
BASED ON NTf2– ANION
Jan Grodkowski, Rafał Kocia, Jacek Mirkowski, Małgorzata Nyga, Agnieszka Sulich,
Tomasz Szreder
Ionic liquids (ILs) belong to quickly expanding
field of science. Their properties: negligible vapour
pressure, non-flammability, thermal and chemical
resistance, high conductivity, possibility to be reused and others make them a very attractive alternative to classical solvents [1-4]. Additionally, the
properties of ILs can be controlled to a large extent by variation of both cation or anion [5, 6].
The aim of the study is to understand radical-ion
reactions in selected ILs. We focused on kinetics
and spectral characteristic of oxidizing species
N6●– in these solvents. The N6●– radical belongs to
pseudohalide radicals family and is known as intermediate in radiation chemistry. This radical is a
strong one-electron oxidant and can be used in
studies of electron transfer reactions. Since reactions in water are very fast and individuals are very
short-lived, the spectral and kinetic characterization of species participating in reaction (1) in aqueous solutions were investigated before [7, 8]. Equilibrium constant values (K) for reaction (1) was
determined to be equal to 0.33 [9] and 200 [10] in
water and acetonitrile, respectively.
Due to high viscosity of ILs radiation-induced
reactions are slowed down in such media. Thus,
one can expect different behaviour of certain species. For instance, the participation of presolvated
electron vary with viscosity of medium. In very viscose solvents presolvated electrons are more likely
to react before their solvation and thus influence
radiation yield of radicals species [11].
N3− + N3● ' N6●−
(1)
In the present paper the mechanism of the
azide radical anion dimmer N6●– formation (1) was
studied in three different ILs: methyltributylammonium N,N-bis(trifluoromethylosulphonyl)imide
(MeBu3NTf2), 1-hexyl-3-methylimidazolium N,N-bis(trifluoromethylosulphonyl)imide (hmimNTf2)
and triethylammonium N,N-bis(trifluoromethylosulphonyl)imide (Et3NHNTf2), (Fig.1). All of ILs
base on the same anion N,N-bis(trifluoromethylosulphonyl)imide which was used to obtain low
melting point of solvents.
The most useful technique to study the chemistry of short-life free radicals is pulse radiolysis.
In our research we used 10 ns pulses of 10 MeV
electrons from a LINAC linear electron accelerator (LAE 10) with spectrophotometric detection.
Energy from the incident electron beam radiation
was absorbed in ILs generating a range of ILs excited states (IL*), electrons and ionized species.
The electron deficiency species often called “holes”
[12] react with azide anion forming azide radical N3●
according to reaction (2). Then, the azide radicals
react as mentioned above via reaction (1) forming
N6●–.
IL⊕”hole” + N3– → N3● + IL
(2)
Spectrum of the N3–/MeBu3NNTf2 system, recorded by means of pulse radiolysis, is shown in Fig.2.
Basing on the literature data [7, 8] the band with
distinct absorption maxima at 700 nm was assigned to N6●–. Observed increase of absorption of
A
B
C
D
Fig.2. Pulse radiolysis of N2O-saturated solution of tetrabutylammonium azide (0.06 M) in MeBu3NNTf2: (■) 1 μs,
(●) 5 μs, (▲) 10 μs, (▼) 40 μs after the pulse; 20 Gy.
this band with N3− concentration confirmed our
assignment. The calculation of equilibrium constants was carried out basing on the equation:
1
1
1
1
=
+
×
G G 0 G 0K [N 3− ]
Fig.1. Methyltributylammonium cation (a), triethylammonium cation – Et3NH+ (b), 1-hexyl-3-methylimidazolium cation – hmim+ (c), N,N-bis(trifluoromethylosulphonyl)imide
anion (d).
(3)
where: G0 – the radiolytic yield at 700 nm at infinitely high N3− concentrations, G – the radiolytic
yield at given N3− concentrations, K = [N6–●]/[N3●]
[N3–] – the equilibrium constant.
20
A plot of 1/G vs. 1/[N3–] is a straight line. From
the slope of this line, K value can be extracted.
Obtained K values in MeBu3NTf2 and hmimNTf2
were determined to be equal to 7 ± 2 and 6 ± 1,
respectively. In protic ionic liquids (Et3NHNTf2) we
did not observe formation of N6●– which is probably
due to the reaction of N3● with the amine resulting
from the radiolysis of ionic liquid, or from contamination from the synthesis of IL (Et3NHNTf2).
From the obtained data, it can be observed that
the K value does not dramatically change in the
case when methyltributylammonium bis[(trifluoromethyl)sulphonyl]imide (MeBu3NNTf2) is satured
with water (0.15% mass percent of water). The
equilibrium constant K in this case was determined
to be equal to 7.
Concluding, the low K value can be interpreted
in terms of the relatively little difference in free
energy of formation of the N6●– radical as compared to the sum of free energy formation of N3–
and N3● species and may reflect the difficulty in
forming stable bonding in N6●– species. Stability of
N6●– radical in ionic liquids is much higher as compared to aqueous solutions.
References
[1].
Aparicio S., Atilhan M., Karadas F.: Ind. Eng. Chem.
Res., 49, 9580-9595 (2010).
[2]. Endres F., El Abedin S.Z.: Phys. Chem. Chem. Phys.,
8, 2101-2116 (2006).
[3]. Plechkova N.V., Seddon K.R.: Chem. Soc. Rev., 37,
123-150 (2008).
[4]. Wasserscheid P., Keim W.: Angew. Chem. Int. Ed.,
39, 3772-3789 (2000).
[5]. Earle M.J., Seddon K.R.: Pure Appl. Chem., 72,
1391-1398 (2000).
[6]. Welton T.: Chem. Rev., 99, 2071-2083 (1999).
[7]. Alfassi Z.B., Prutz W.A., Schuler R.H.: J. Phys. Chem.,
90, 1198-1203 (1986).
[8]. Hayon E., Simic M.: J. Am. Chem. Soc., 92, 7486-7487
(1970).
[9]. Butler J., Land E.J., Swallow A.J., Prytz W.: Radiat.
Phys. Chem., 23, 265 (1984).
[10]. Workentin M.S., Wagner B.D., Negri F., Zgierski M.,
Lusztyk J., Siebrand W., Wayner D.D.M.: Phys.
Chem., 99, 94-101 (1995).
[11]. Wishart J.W., Lall-Ramnarine S.I., Raju R., Scumpia
A., Bellevue S., Ragbir R., Engel R.: Radiat. Phys.
Chem., 72, 99-104 (2005).
[12]. Wishart J.F.: J. Phys. Chem. Lett., 1, 3225-3231 (2010).
FREE RADICAL REACTIONS OF NICOTINE
Katarzyna Kosno1/, Monika Celuch1/, Jacek Mirkowski1/, Ireneusz Janik2/, Dariusz Pogocki1,3/
1/
2/
Institute of Nuclear Chemistry and Technology, Warszawa, Poland
Notre Dame Radiation Laboratory, University of Notre Dame, USA
3/
Faculty of Biology and Agriculture, University of Rzeszów, Poland
Nicotine (3-(1-methyl-2-pyrrolidinyl)pyridine), a
natural alkaloid of main responsibility for tobacco
smoking addiction, has some medical applications.
Besides its common usage in nicotine replacement
accompanied by an extensive oxidative stress, where
nervous tissue is exposed to the presence of oxygen
radicals beyond a threshold for proper antioxidant
neutralization [2-4], and therapeutic usage of nic-
Fig.1. Acid-base properties of nicotine in aqueous solution at 25oC [6].
therapy, is applied in neurodegenerative diseases
diagnosis, and for alleviation of some symptoms
and ailments accompanying these diseases [1].
Nicotine can have a potential protective effect on
nerve cells. Neurodegenerative diseases are usually
otine can be related to its free radical scavenging
capacity.
Nicotine molecule is made of two rings – aromatic pyridine and aliphatic pyrrolidine. In physiological pH of blood 7.4, ca. 76% (37oC) of nicotine
Fig.2. Alternative pathways of ●OH radical reaction with nicotine.
21
0.1 μs
2 μs
60 μs
155 μs
Fig.3. Transient absorption spectra obtained by ●OH-attack on nicotine recorded 0.1 μs (○), 2 μs (●), 60 μs (■) and 155 μs
(▲) after the pulse in the N2O-saturated 1 mM nicotine solution, at pH 10. Inset: kinetic traces recorded at λ = 330 and
460 nm, respectively.
is protonated at pyrrolidine nitrogen [5] (Fig.1).
This protonation can influence its reactivity in
radical reactions.
Free radical reactions of nicotine in aqueous
solution can be initiated by water radiolysis [7, 8].
Nicotine radical reactions were studied for the
first time with pulse radiolysis technique by Wang
et al. in 2003 [9]. These authors suggested that nicotine reacts with hydrated electron, hydrogen atom
and hydroxyl radical producing anion radical and
neutral radicals, respectively. However, their kinetics data (rate constants) are not consistent with
the results previously obtained by Getoff’s group
for nicotine molecular components, i.e. pyridine
and pyrrolidine [10, 11].
Combining reaction mechanisms proposed for
model compounds, three alternative pathways of
nicotine reaction with hydroxyl radical (Fig.2) can
be taken into account. However, basing on thermodynamics calculation, the most stable product of
these reactions are the radicals located at 2’-carbon
atom as 2’-carbon-hydrogen bond has the lowest
BDE (bond dissociation energy) due to 2’-radical
stabilization by the interactions with π electrons of
pyridine ring and the nonbonding electron pair of
the nitrogen atom. Importantly, protonation elim-
inates coupling with a lone pair and the data from
DFT calculations indicating an increase of BDE
for C2’−H bond.
We have studied the reaction of nicotine and
its model compounds with ●OH radicals with a ns
pulse-radiolysis technique applying UV-Vis time-resolved detection systems. Pulse radiolysis experiments at the Institute of Nuclear Chemistry
and Technology (INCT) were performed with a
LAE 10 linear accelerator with typical pulse lengths
of 4-10 ns [12]. Absorbed dose per pulse was ca.
20 Gy.
Pulse radiolysis experiments at the Notre Dame
Radiation Laboratory were performed with a Titan
Beta Model TBS-8/16-1 electron linear accelerator, which provided 4-5 ns pulses of 8 MeV electrons [13]. Absorbed doses per pulse were in the
range 4-12 Gy.
Reactions with ●OH radicals were studied in
aqueous solution saturated with N2O, which scavenges hydrated electrons and nearly doubles the
amount of ●OH radicals [14]. In the reaction of
●
OH radicals with nicotine we obtained transient
products absorbing with the maxima at 330 and
460 nm (Fig.3). The build-up kinetics at these two
maxima are essentially the same, so they probably
Table. Rate constants k [dm3mol–1s–1] for the reaction of ●OH radicals with nicotine and its model compounds.
Reagent
Nicotine
IChTJ, NDRL
OH
Wang et al. [9]
IChTJ
Pyrrolidine
Getoff et al. [11]
Getoff et al. [10]
3.2 × 10 (pH = 1, 4.5 × 10 (pH = 7, 1.4 × 10 (pH = 3, 1.0 × 10 (pH = 2.0-4.5, 9.6 × 109 (pH = 2)
λmax = 330 nm)
λmax = 460 nm)
λmax = 320 nm)
λmax = 315 nm)
1.45 × 1010 (pH = 8)
9
9
2.7 × 10 (pH = 5.6,
5.3 × 10 (pH = 10, 3.0 × 109 (pH = 10,
5.7 × 109 (pH = 6.2,
λmax = 330 nm)
λmax = 320 nm)
λmax = 322 nm)
λ = 222.5 nm)
8
●
Pyridine
3.8 × 109 (pH = 7.4,
λmax = 330 nm)
6.2 × 109 (pH = 10,
λmax = 330 nm)
8
8
8
max
2.1 × 1010 (pH = 13.2,
λmax = 230 nm)
22
0.1 μs
1.5 μs
20.0 μs
45.5 μs
137.6 μs
Fig.4. Transient absorption spectra obtained by ●OH-attack on pyridine recorded 0.1 μs (■), 1.5 μs (●), 20 μs (□), 45.5 μs
(▲) and 137.6 μs (○) after the pulse in the N2O-saturated 1 mM pyridine solution, at pH 10. Inset: kinetic traces recorded
at λ = 320 nm.
Fig.5. Reaction scheme of N3●-induced nicotine 1e-oxidation.
0.03 μs
5.6 μs
36 μs
102 μs
155 μs
Fig.6. Transient absorption spectra obtained by N3●-attack on nicotine recorded 0.03 μs (■), 5.6 μs (○), 36 μs (●), 102 μs
(□) and 155 μs (▲) after the pulse in the N2O-saturated 1 mM nicotine solution containing 10 mM NaN3, at pH 10. Inset:
kinetic traces recorded at λ = 330 and 460 nm, respectively.
come from the same product. The second-order
rate constants, k(OH+Nic), determined at 330 nm are
collected in Table. It can be noticed that the rate
constant at pH 7.4 is almost one order of magnitude higher than that obtained by Wang et al.
However, our values are very close to those previously measured for pyridine [10, 11], suggesting a
close similarity of the reactions pathways.
In order to examine this similarity, we conduct
analogous experiments for pyridine obtaining
(similarly to the results of Getoff et al. [10, 11])
transient absorption spectra with one distinct maximum at 320 nm and a broad absorption band in
the visible range (Fig.4). (The calculated rate constants, presented in Table, are also very close.)
We conducted similar experiments for aqueous solutions of pyrrolidine, but in this case we did
not observe short-lived transient species absorbing in the examined 280-600 nm wavelength range.
Earlier work of Getoff et al. shows that transient
products of ●OH radicals reaction with pyrrolidine
are characterized by a single absorption maximum
at about 230 nm [10].
In order to examine 1e-oxidation pathway of
nicotine reaction we studied it using the reaction
of nicotine with azide radical (N3●), which reacts
mainly via electron transfer. It is a weak oxidant
not abstracting hydrogen atoms nor forming adducts to π-electron systems. In such process nicotine radical cations are generated (Fig.5).
The pulse-radiolysis experiments were conducted here in N2O-saturated 1 mM nicotine aqueous
solution containing 10 mM NaN3. The transient
absorption spectra with two pronounced maxima
at 330 and 460 nm, were obtained (Fig.6).
23
Our results support the assumption that ●OH
radicals can react with nicotine following three
different pathways: (i) addition to pyridine ring,
(ii) direct hydrogen abstraction from pyrrolidine
ring, and (iii) one-electron oxidation of nitrogen
at pyrrolidine ring.
References
[1].
[2].
[3].
[4].
[5].
[6].
[7].
[8].
[9].
[10].
[11].
[12].
[13].
[14].
Pogocki D., Ruman T., Danilczuk M., Danilczuk M.,
Celuch M., Wałajtys-Rode E.: Eur. J. Pharm., 563,
18-39 (2007).
Halliwell B., Gutteridge J.M.: Free radicals in biology
and medicine. Oxford University Press, Oxford 1999.
Andersen J.K.: Nat. Med., 10, Suppl. S18-S25 (2004).
Winyard P.G., Blake D.R., Evans C.H.: Free radicals
and inflammation. Birkhäuser Verlag, Basel 2000.
Nielsen H.M., Rassing M.R.: Eur. J. Pharm Sci., 16,
151-157 (2002).
CRC Handbook of Chemistry and Physics. CRC
Press, 2004.
Baldacchino G., Hickel B.: Water radiolysis under extreme conditions. Application to the nuclear industry.
In: Radiation chemistry. EDP Sciences, France 2008,
pp. 53-54.
Buxton G.V.: An overview of the radiation chemistry
of liquids. In: Radiation chemistry. EDP Sciences,
France 2008, pp. 3-10.
Li W.Z., Wang S.L., Wang M., Sun X.Y., Ni Y.M.:
Spectrosc. Spect. Anal., 23, 3, 481-484 (2002).
Getoff N., Schwörer F.: Int. J. Radiat. Phys. Chem.,
7, 1, 47-49 (1975).
Getoff N., Solar S., Sehested K., Holcman J.: Radiat.
Phys. Chem., 41, 6, 825-834 (1993).
Bobrowski K.: Nukleonika, 50, 3, 67-76 (2005).
Hug G.L., Wang Y., Schöneich Ch., Jiang P.-Y., Fessenden R.W.: Radiat. Phys. Chem., 54, 559-566 (1999).
Janata E., Schuler R.H.: J. Phys. Chem., 86, 11,
2078-2084 (1982).
PRELIMINARY STUDIES ON RADIATION DEGRADATION
OF AQUEOUS SOLUTION OF LINURON
Monika Celuch1/, Anna Bojanowska-Czajka1/, Krzysztof Kulisa1/, Joanna Kisała2/,
Katarzyna Kosno1/, Dariusz Pogocki1,2/
1/
2/
Faculty of Biology and Agriculture, University of Rzeszów, Poland
Phenylurea herbicides were introduced in the
1950s, and since that time their use has become significant. Linuron (N-(3,4-dichlorophenyl)-N’-metoxy-N’-methylurea) is one of the most commonly
used phenylurea herbicides. It has been broadly
used to control weeds by inhibiting photosynthesis.
Linuron (Fig.1) has been reported to inhibit the
Fig.1. Chemical structure of linuron.
activity of 5-α-reductase, reduce testosterone production. Its naturally decayed intermediates (i.e.
chloroaniline) have been suspected as endocrine
disruptors.
Linuron is widely used in pre- and postemergence for treatment of both crop and non-crop
cultures. This herbicide is moderately persistent
in soils, with a field half-life 30 to 70 days, and are
slightly to moderately soluble in water (81 mg/dm3
at 25oC). Since linuron can give rise to important
residues in soil and in water and simultaneously it
is resistant to the standard oxidants such as chlorine and permanganate, there is a strong need for
finding new methods and/or developing known
ones for effective degradation of linuron. For decomposition of pesticides, some microbiological
and advanced oxidation processes (AOPs) are used,
e.g. O3/UV, O3/H2O2, electro- or photo-Fenton and
others. Some of them were successfully used also
for linuron degradation [1-13].
Mechanisms of pesticides degradation are very
complex and depend on many environmental fac-
24
tors as pH changes, presence of metal ions, etc.
Detailed understanding of pesticides decomposition is very important as some by-products can be
much more toxic than the parent compound. Detailed describing of mentioned reactions should
allow to predict degradation pathway of some
molecule and designed structure and in such a
way to decrease toxicity of by-products.
Ionizing radiation has been applied to the decomposition of different groups of compounds
[14, 15]. This seems to be a very effective way of
its degradation, especially in the case of particularly oxidation-resistant compounds.
In our work linuron (technical grade) was obtained from Zakłady Chemiczne Organika-Sarzyna
S.A. (Poland) and the other chemicals were purchased from Sigma-Aldrich with highest analytical
grade and, apart from linuron, all were used without further purification. Linuron was recrystallized
from DMSO (dimethyl sulphoxide) befor use. For
pH adjustment, solutions of 70% perchloric acid
(HClO4) and 50% sodium hydroxide (NaOH) were
used. All experiments were carried out at room
temperature. Experiments were performed using
a solution of linuron concentration equal to 0.0641
g/dm3 and pH 10. Specially constructed glass tubes
were used during saturation of samples with N2O,
and following the irradiation in a Co-60 source
(dose rate – 7.6 kGy/h). In analytical determination of linuron and products of its decomposition
some chromatographic techniques were used:
HPLC (high-performance liquid chromatography)
technique with spectrophotometric detection (at
254 nm) and ion-chromatography (HPIC – high-performance ion chromatography) with conductometric detection. HPLC analyses were carried
out just after irradiation and 9 days after irradiation. Results obtained for the samples measured
just after irradiation show about a 20% decrease
of linuron concentration for the absorbed dose of
1 kGy (Fig.2).
were observed and pH of the stored solution decreased from 10 to 7. HPIC analysis shows substantial amount of acetates and formates (Fig.3).
Fig.3. Concentration of anionic products of linuron degradation formed as post-radiation effect.
The results of our preliminary studies are very
interesting and important from both basic and
environmental research. Degradation processes
should be examined to detailed described mechanism of linuron decomposition. Due to the fact
that very often by-products are more toxic than
the parent compound, as many as possible intermediates products should be identified. Also the
influence of some environmental factors (pH,
metal ions, inorganic anions, etc.) on the degradation process should be examined.
References
[1].
[2].
[3].
[4].
[5].
[6].
[7].
[8].
[9].
[10].
[11].
[12].
Fig.2. Yield of radiation-induced degradation of linuron.
[13].
Degradation process is relatively slow and no
significant amount of degradation products were
observed. During analysis of samples stored 9 days
at a temperature of about 6oC, some new peaks
[14].
[15].
Farre M.J., Domenech X., Peral J.: Water Res., 40,
13, 2533-2540 (2006).
Farre M.J., Domenech X., Peral J.: J. Hazard. Mater.,
147, 1-2, 167-174 (2007).
Gatidou G., Iatrou E.: Environ. Sci. Pollut. Res., 18,
6, 949-957 (2011).
Katsumata H., Kaneco S., Suzuki T., Ohta K., Yobiko
Y.: Chem. Eng. J., 108, 3, 269-276 (2005).
Katsumata H., Kobayashi T., Kaneco S., Suzuki T.,
Ohta K.: Chem. Eng. J., 166, 2, 468-473 (2011).
Rao Y.F., Chu W.: Chemosphere, 74, 11, 1444-1449
(2009).
Rao Y.F., Chu W.: J. Hazard. Mater., 180, 1-3, 514-523
(2010).
Zouaghi R., Zertal A., David B., Guittonneau S.:
Rev. Sci. Eau, 20, 2, 163-172 (2007).
Ghalwa N.A., Hamada M.,. Shawish H.M.A, Shubair
O.: Electrochemical degradation of linuron in aqueous solution using Pb/PbO2 and C/PbO2 electrodes.
Arabian J. Chem. (2011), in press.
Faure V., Boule P.: Pestic. Sci., 51, 4, 413-418 (1997).
Sung M., Huang C.P.: J. Hazard. Mater., 141, 1,
140-147 (2007).
Bourgin M., Violleau F., Debrauwer L., Albet J.: J.
Hazard. Mater., 190, 1-3, 60-68 (2011).
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Sci. Total Environ., 291, 1-3, 33-44 (2002).
Liu S.Y., Chen Y.P., Yu H.Q., Zhang S.J.: Chemosphere, 59, 13-19 (2005).
Drzewicz P., Trojanowicz M., Zona R., Solar S.,
Geringer P.: Radiat. Phys. Chem., 69, 281-287 (2004).
25
REACTIVITY OF C-CENTRED RADICALS STABILIZED
IN ZSM-5 ZEOLITE
Marcin Sterniczuk, Jarosław Sadło, Grażyna Strzelczak, Jacek Michalik
Radicals play an important role in catalysis. Their
structure and properties are difficult to study because of their extremely high reactivity. Matrix
isolation technique in halocarbon and noble gas
matrices and trapping in zeolites are the methods
of choice for studying electronic structure and geometry of radical ions in solids [1-3]. In this paper
we present a study on the reactivity of carbon
paramagnetic centres generated radiolytically in
H-ZSM-5 zeolites. We generate free radicals by
γ-irradiation at liquid nitrogen temperature of
zeolites exposed earlier to carbon monoxide and
follow their reactions by electron paramagnetic
resonance (EPR) spectroscopy gradually increasing temperature. Based on EPR measurements,
we measure their ractivity and postulate the sites
of their stabilization owing to quantum mechanics
computation.
The H-ZSM-5 zeolite samples placed in spectrosil tubes were degassed and next dehydrated at
300oC on vacuum line under the pressure of 10–5
Torr. Carbon monoxides, 12CO and 13CO were adsorbed at room temperature under the pressure
range 5-100 Torr. Then the EPR tubings were
sealed and irradiated at 77 K in a 60Co γ-source
with a dose of 6 kGy. The EPR spectra were recorded with an X-band Bruker ESP 300E spectrometer equipped with a transfer nitrogen dewar.
The temperature of the sample during EPR measurments was controlled by a Bruker variable temperature unit in the range 100-380 K.
The EPR spectrum of γ-irradiated H-ZSM-5/
13
CO recorded at 300 K consists of two doublets:
anisotropic doublet A with gx = 2.0005, gy = 2.0010,
gz = 1.9995, Ax = 30.2 mT, Ay = 27.4 mT, Az = 26.0
mT and isotropic doublet B – giso = 2.0002, Aiso =
21.4 mT. We assigned signal A to two paramagnetic centre which are characterized by the same
EPR parameters: the first one – 13CO+● radical
cation interacting with lattice oxygen between Si
and Al atoms and the second one – 13CO+● radical
Fig.1. Temperature dependence of H-ZSM-5/13CO spectra.
cation interacting with lattice oxygen between two
silica atoms. Instead, signal B we assigned to 13CO
interacting with oxygen bonded to one only Si
atom. The stability of A and B doublets depends
on sample dehydration temperature, however always signal B is more stable than signal A. In a
sample dehydrated above 300oC doublet A disappears completely at 350 K, while signal B is still
detected at 370 K (Fig.1). In hydrated samples
both signals are much less stable; signal A decays
at 160 K and B – at 200 K. When H-ZSM-5/13CO
zeolite is exposed at 77 K just after irradiation to
5 Torr of oxygen, the doublets A and B disappear
completely and a singlet with axial anisotropy:
C(gII)
C(g┴)
Fig.2. Temperature dependence of H-ZSM-5/13CO+O2. The
arrow shows the next measuring steps.
g┴ = 2.0065, gll = 2.0470 and additional structure
in the central part is recorded (Fig.2). During
thermal annealing above 200 K, signals A and B
start appearing, reaching the highest intensity
around 300 K. However, when the temperature of
EPR measurments decreases again to 100 K, the
doublets disappear. The process is reversible and
Fig.3. Distribution of unpaired electron spin density on
paramagnetic centre A.
26
the 13CO+● doublets are recorded only above 200
K. A similar effect was observed by Vedrine et al.
[4] in zeolite H-Y exposed to 13CO and was explained by coadsorption of O2 molecule on the CO+●
tropic singlet of peroxy radical. In the H-Y zeolite,
Vedrine observed only one CO+● centre (centre
A). Our results prove that all the observed CO+●
centres in H-ZSM-5 zeolites are able to coadsorb
oxygen forming peroxy radicals. To better understand the reactivity between the carbon-centred
radicals and molecular oxygen we applied the DFT
method. Computation clearly shows how the unpaired electron density is distributed on paramagnetic centre before (Fig.3) and after coadsorption
of oxygen (Fig.4). Unpaired electron density before oxygen adsorption was localized principally
on the carbon atom. After O2 coadsorption, we are
observing a change of electron spin density distribution, the unpaired electron being localized almost only on the oxygen atoms.
References
Fig.4. Distribution of unpaired electron spin density on
coadsorbed complex with oxygen.
centre. This leads to the transfer of unpaired electron from carbon to the oxygen nucleus which is
manifested in the EPR spectrum as axially aniso-
[1]. Knight L.B., Jr., Steadman J.: J. Chem. Phys., 77, 1750
(1982).
[2]. Garcia H., Roth H.D.: Chem. Rev., 102, 3947 (2002).
[3]. Knight L.B., Jr., Gregory B.W., Cobranchi S.T., Williams F., Qin X.: J. Am. Chem. Soc., 110, 327 (1988).
[4]. Vedrine J.C., Massardier J., Abou-Kais A.: Can. J.
Chem., 54, 1678 (1976).
MULTIFREQUENCY EPR STUDY ON γ-IRRADIATED BONE
SUBSTITUTING BIOMATERIALS
Jarosław Sadło, Grażyna Strzelczak, Małgorzata Lewandowska-Szumieł1/, Marcin Sterniczuk,
Jacek Michalik
1/
Department of Histology and Embryology, Medical University of Warsaw, Poland
For years, orthopaedic surgeons have been using
many synthetic materials (metals, plastics, polymers, ceramics, etc.) to replace human tissues in
order to restore their lost functions. The biomaterial market is expanding rapidly, parallel to the
growing demands for bone graft substitute materials. The substitutes should promote the formation of new natural bone, while the external material should be degraded. Therefore, a great
variety of specially synthesized calcium phosphate
materials to be used as bone graft substitute materials is proposed [1].
Hydroxyapatite (HA) Ca10(PO4)6(OH)2 is the
major mineral phase in natural bone and teeth, so
synthetic HA is widely used in medicine and dentistry because of its biocompatibility and bioactivity properties. Producers of bone graft substitute
materials often describe their products as chemically and mineralogically identical to the inorganic
part of bone [2].
In bone which has been exposed to ionizing
radiation several radicals are induced, which can
be detected by electron paramagnetic resonance
(EPR) spectroscopy.
In the present study we apply X- and Q-band
EPR spectroscopy to identify paramagnetic centres
which are responsible for EPR signals that are
stable at room temperature in γ-irradiated bone
substituting biomaterials based on hydroxyapatite
[3-5].
Two types of synthetic bone substituting materials – NanoBone® (Artoss GmbH) and HA
Biocer (CHEMA), a synthetic chemically pure hydroxyapatite powder purchased from Sigma-Aldrich
Co. and powdered defatted human compact bone
samples in natural form, obtained from the National
Centre of Tissue and Cell Banking (Warszawa,
Poland) were used in this study.
All samples were irradiated at room temperature, with a dose of 5 kGy in a 60Co gamma source
“Issledovatel”.
The EPR measurements at X- (9.5 GHz) and
Q-band (34 GHz) were carried out at room temperature just after the gamma irradiation, one day
and five days later, in order to make sure that all
signals derived from the unstable radicals decayed.
The most stable and intense EPR signal in
both natural bone and synthetic HA is an anisotropic singlet of an orthorhombic symmetry, with
the following spectroscopic parameters of the g
tensor: gx = 2.0030, gy = 1.9973, gz = 2.0017 and
peak-to-peak width ΔHpp = 0.85 mT (Fig.1). EPR
spectrum of synthetic HA recorded in X-band
(Fig.1a) represents CO2– radical anion. The spectrum recorded in Q-band (Fig.1b) is much better
resolved giving evidence that is consists of two
27
assure that the hydroxyapatite used in their product is almost the same as in autologous bone.
However, the EPR study of irradiated compact
bone and the synthetic graft materials suggests
that their microscopic structures are different.
NanoBone®
Fig.1. EPR spectra of synthetic hydroxyapatite powder
sample γ-irradiated at room temperature: (a) recorded in
X-band 1 day after irradiation, (b) recorded in Q-band 1 day
after irradiation.
separate signals: CO2– orthorhombic and isotropic
CO2– with g factor gav = 2.0006 [3, 5-7].
The EPR signals of the irradiated synthetic
bone grafts substitute NanoBone® and HA Biocer
detected in the X-band looks like a broad singlet
with two inflection points. The Q-band spectrum
is much better resolved showing clearly the signal
anisotropy with the orthorombic g factor of gx =
2.0041, gy = 2.0036, gz = 2.0018, characteristic of
the CO33– anion radical.
After 5 days of storage, the EPR spectrum was
changed in a similar way for both NanoBone®
and HA Biocer samples, showing a weak high-field component (gll = 1.997) of the CO2– signal
(Fig.2).
The EPR results prove clearly that the long-lasting radiation effects associated with carbon-centered radicals in commercial bone substitutes
are different than those in biological hydroxyapatites. It might be related to the different locations
of the CO32– anions and/or the CO2 molecules in
both types of materials. HA Biocer and NanoBone® are commercial synthetic bone substituting or reconstructing materials based on hydroxyapatite. Producers of both the graft materials
Fig.2. EPR spectra of NanoBone® powder sample γ-irradiated at room temperature: (a) recorded in X-band 1 day
after irradiation, (b) recorded in X-band after 5 days storage, (c) recorded in Q-band 1 day after irradiation.
The results presented prove that EPR spectroscopy is a useful tool for studying subtle structural changes in bone substitute materials.
References
[1]. Dorozhkin S.V.: Biomaterials, 31, 1465-1485 (2010).
[2]. Leventouri Th.: Biomaterials, 27, 3339-3342 (2006).
[3]. Strzelczak G., Sadło J., Michalik J.: Nukleonika, 54,
247-250 (2009).
[4]. Fattibene P., Callens F.: Appl. Radiat. Isot., 68, 2033
(2010).
[5]. Callens F., Vanhaelewyn G., Matthys P., Boesman E.:
Appl. Magn. Reson., 14, 235-254 (1998).
[6]. Strzelczak G., Sadlo J., Danilczuk M., Stachowicz W.,
Callens F., Vanhaelewyn G., Goovearts E., Michalik J.:
Spectrochim. Acta Part A, 67, 1206-1209 (2007).
[7]. Ikeya M.: New application of electron spin resonance:
dating, dosimetry and microscopy. Eds. M.R. Zimmerman, N. Whitehead. World Scientific, Singapore 1993.
28
SURFACE MODIFICATION OF POLY(ESTERURETHANE)
BY RADIATION-INDUCED GRAFTING OF N-ISOPROPYLACRYLAMIDE
Marta Walo, Grażyna Przybytniak, Murat Barsbay1/, Pınar Akkas Kavaklı1/, Olgun Guven1/
1/
Department of Chemistry, Hacettepe University, Ankara, Turkey
It is generally known that the required properties
of biomaterials are biocompatibility, sterilizability,
adequate mechanical and thermal properties as
well as specific surface characteristic [1]. Among
the polymeric biomaterials, polyurethanes (PUR)
have attracted a great interest due to their unique
chemical and physical properties. Biomedical polyurethanes are widely used in medicine for production of scaffolds in tissue engineering and for
manufacturing medical devices, such as vascular
grafts, artificial hearts, wound dressings, blood tubing, catheters and mammary implants [2]. Polyurethanes are microphase-separated polymers containing hard and soft segments arranged alternately.
Thanks to the possibility to model their properties
by selecting various types and molecular weights
of the oligodiol, the chemical structure and symmetry of diisocyanate, the hard/soft segment weight
ratio, the synthesis method, PUR can be used for
specific clinical applications. However, it is difficult to synthesize polyurethanes with appropriate
bulk and surface properties simultaneously. It is
well known that the surface properties of materials
in contact with biological systems play a key role
in determining the outcome of biological material
interactions [3]. Therefore, selected functional
groups must be introduced to surfaces in order to
change their properties. There is a multitude of
surface modification methods including chemical
treatment, immobilizing biological molecules, radiation grafting of hydrophilic monomers and gas
plasma treatment [4]. Among these methods, radiation-induced graft polymerization is a well-known
technique for modifying the chemical and physical
properties of polymeric materials without altering
their inherent properties.
The aim of the reported researches was to
modify the surface of polyurethane by radiation-induced grafting to improve its hydrophilicity. The
samples used for grafting were synthesized by a
two-step polycondensation without any catalyst,
solvent and additives. PUR was constructed from
soft segments of oligo(ethylene-buthylene adipate)
diol end-capped with molecular mass of 2000 Da
and hard segments of isophorone diisocyanate and
1,4-butanediol. The weight ratio between hard
and soft segment was 40:60. In this study the mutual radiation grafting of N-isopropylacrylamide
(NIPAAm) onto polyurethanes films was performed. At the first stage of investigations, several important factors determining the final effect of graft
polymerization were tested, namely: monomer concentration, homopolymer suppressor concentration
and dose. Then, non-grafted and grafted polyurethanes with different grafting yield (GY) of 22, 59
and 77% were characterized using the following
methods: ATR-FTIR spectroscopy, thermogravimetric analysis (TGA), gel permeation chroma-
tography (GPC), contact angle measurements (CA)
and X-ray photoelectron spectroscopy (XPS).
Chemical structures of non-grafted PUR and
PNIPAAm (poly(N-isopropylacrylamide)) grafted
Fig.1. ATR-FTIR spectra of PUR (A) and PUR-g-NIPAAm
(B), GY = 22%.
PUR were investigated by FTIR spectroscopy
(Fig.1). Analysing the carbonyl region of PUR
and PUR-g-NIPAAm a new C=O stretching band
at about 1656 cm–1 characteristic of PNIPAAm
structure appeared.
For neat PUR two steps decomposition, it is
revealed in the TGA curves (Fig.2). The first low
temperature stage of thermal degradation is associated with scission of the urethane linkages in
hard segments combined with the emission of
carbon dioxide. The second one corresponds to
the soft segment chain cleavages. After NIPAAm
grafting, the changes on TGA thermogram were
observed as a newly formed peak at around 400oC
attributed to the degradation of PNIPAAm.
On the basis of GPC results, it was found that
the grafting of NIPAAm onto polyurethane surface causes a shift of the chromatograms to higher
molecular weight regions. A new peak appearing
in the GPC traces is attributed to the grafted
Fig.2. DTG thermograms of PUR and PUR-g-NIPAAm.
29
dominant participation of C-O and C-C/C-H
groups in the PUR surface. Carbonyl groups of
the ester units also contribute significantly to the
surface structure (25%), contrary to the peak at
288.6 eV attributed to N(H)-C(O)-O whose participation does not exceed 4%. For PUR-g-NIPAAm
with GY = 22%, C-O-C(O) and C-N groups conTable 1. Deconvolution of C1s XPS spectra.
Sample
Peak
Centre [eV]
Ratio [%]
A
288.6
3.9
B
287.0
25.0
C
285.1
15.3
D
284.0
55.8
A
287.9
30.1
B
286.8
23.2
C
285.2
25.2
D
284.2
21.5
PUR
Fig.3. GPC chromatograms of PUR and PUR-g-NIPAAm
in THF (tertrahydrofuran).
PNIPAAm chains, and the intensity of this peak
increases with increasing grafting yield. These results clearly proved formation of the covalent
bonds between the PNIPAAm chains and the polyurethane surface (Fig.3).
PUR-g-NIPAAm
stitute 25% of the C1s bands, whereas before
grafting their contribution was about 10% smaller.
Additionally, for the grafted surface summary input of N(H)-C(O)-O and N-C-C(O) enhances significantly as compared to the untreated PUR
(Table 1).
Surface hydrophilicity of the PUR film was enhanced by grafting of NIPAAm (Table 2). It was
observed that the contact angle measured vs. water
diminished to about 67 deg for the sample grafted
to GY = 77%.
Table 2. Contact angle measurements vs. water at 23oC.
Sample
PUR
PUR-g-NIPAAm
GY [%]
0
22
59
77
CA [deg]
87.0
71.0
69.0
67.0
The obtained results suggest that the radiation-induced grafting seems to be a promising method
to improve the biocompatibility of polymers for
biomedical applications. By introducing specific
functional groups to the trunk polymer, surface
properties changed significantly. Contact angle,
which is an important macroscopic parameter characterizing surface wettability, decreases from 87
to 67 deg confirming increasing hydrophicility of
polyurethane surface.
References
Fig.4. XPS spectra of C1s for PUR and PUR-g-NIPAAm,
GY = 22%.
XPS results confirmed NIPPAm grafting onto
polyurethane surface (Fig.4). High-resolution C1s
region comprising four distinct peaks indicates
[1]. Chen K., Kuo J., Chen C.: Biomaterials, 21, 161-171
(2000).
[2]. Gorna K., Gogolewski S.: Polym. Degrad. Stabil., 79,
465-474 (2003).
[3]. Gold J.: Eur. Cell. Mater., 10, Suppl. 1 (2005).
[4]. Alves P., Coelho J.F.J., Haack J., Rota A., Bruinink A.,
Gil M.H.: Eur. Polym. J., 45, 1412-1419 (2009).
30
RADIATION-INDUCED REDUCTION OF CARBON DIOXIDE
AS POSSIBLE EXPLANATION OF ABIOTIC FORMATION OF METHANE
Ewa Maria Kornacka, Zbigniew Paweł Zagórski
The presence of methane (CH4) and carbon dioxide (CO2) in the solar system, in particular, on
the planet Mars is explained by different hypotheses, especially by biotic formation in the last-mentioned case. The explanation providing formation of methane as the by-product of life processes is doubtful in the light of few arguments for
existence of the present and of any time ago, of
life on Mars.
In view of justified considerations of ionizing
radiation on the surface of Mars, present and actual and consequences of the phenomenon [1, 2],
we propose the formation of methane from carbon dioxide in the presence of water by chemical
reactions induced by ionizing radiation, abundant
on the surface of Mars, due to its weak protection
by a thin atmosphere, very different from the thick
atmosphere around the Earth.
Raw materials for the set of chemical reactions, induced by ionizing radiation coming from
the outer space are minerals incorporating water,
surrounded by atmosphere rich in carbon dioxide
and Martian ice consisting of water and carbon
dioxide mixed ice, covering parts of the surface of
Mars, under constant thawing and freezing in cold
regions of Mars. The road map of methane formation is complicated and involves several steps,
through intermediates.
In checking these possibilities, we have started
from two materials, resembling those which may
be present on Mars. First, it was montmorillonite
as a model compound of Martian regolith, containing bound and added water (cf. [3]) and the second was CO2/H2O ice obtained by freezing from a
gaseous mixture. Both materials were gamma-irradiated in ampoules filled with carbon dioxide,
and the gas phase was analysed by gas chromatography on a column in an argon stream. Products
were identified as hydrogen formed directly from
both forms of water, as it is the common case described in [4, 5] and as methane.
Both materials were also investigated in separate experiments after irradiation, by EPR (electron paramagnetic resonance) spectroscopy for
identification of intermediates leading to the formation of methane.
Gas chromatographic results will be published
later.
A mixture of CO2/H2O was obtained by flowing
of carbon dioxide saturated with aqueous vapour
into liquid nitrogen. Resulting solid phase was irradiated to a dose of 20 kGy at 77 K (Fig.1). EPR
spectra were measured with a Bruker X-band
ESR-300 spectrometer at 77 K using a microwave
power of 10 mW. Samples were annealed by warming to required temperatures, as measured by a
thermocouple placed in the middle of the samples,
then re-cooled down to 77 K and spectra were recorded [6]. Double integration of the experimental
spectra and the signals were recorded.
Fig.1. EPR spectra of irradiated mixing media CO2/H2O.
Most atmospheric carbon dioxide on Earth has
been changed biologically into CaCO3 during the
last 600 million years. Solid carbon dioxide is present in nature on several planets, also on the surface of Mars.
Figure 2 shows the EPR spectra of solid carbon
dioxide irradiated by γ-rays at 77 K and measured
also at 77 K after annealing to indicated temperatures. It turned out that in the sample a contaminant of water coming from the moisture was found
and three peaks belonging to ●OH radicals – gzz =
2.055, gxx = 2.029, gyy = 1.995 – were observed at
120 K. The character of the recorded spectra suggests interaction between the radicals present in
atmosphere. Peroxy radicals such as HO2, CH3O
and NO2 were measured in free troposphere and
a atmosphere boundary layer [7]. The radicals are
not stable because they quickly disappeared and
at 120 K their amount is ca. 50%, but at 150 K
they convert to such a different radical which
shows a spectrum in the form of singlet.
Fig.2. EPR spectra of irradiated solid carbon dioxide.
Three spectra were identified corresponding
to the radicals: hydroxyl radical, carbon dioxide
radical, superoxide radical. At least one unidentified species was found whose extreme lines are
indicated by the arrows in Fig.3.
Fig.3. Isolated EPR spectra of selected radicals.
Methane formed is a stable compound remaining in the atmosphere, or bound in situ as a clathrate if sufficient amount of water is available.
There are assumptions, that methane aqueous
clathrates exist on Mars.
Answering the question of quantities of methane which can be formed in the proposed way, one
has to know the flux of ionizing radiation on the
surface of Mars. Astonishingly, in spite of several
kinds of measurements of the surface of Mars, the
exposure to ionizing radiation, important in view
of possible human exploration, has not been measured (or not published to avoid objections to human exploration missions, or even panic). A paper,
which was kept for one year in the editors processing [8], does not mention the dose on the surface of the space ship; another paper [9] mentioning the sterilization of the surface of Mars does
not give the dose of radiation, etc. There are some
clues, as considering the radiation flux on the surface of Mars, because it must be similar to the flux
on the surface of any object in the outer space in
the solar system. Recalculation of data in Ref. [10]
suggests that an average dose of 0.1 Gy per day
may be liberally assumed. All calculations are estimates in orders of magnitudes only.
The discussed intensity of ionizing radiation
reaching Mars is difficult to estimate, because of
highly non-homogeneous character of radiations,
by both quality measured by LET and distribution
in time. As the flux of galactic cosmic rays may be
considered stable, more intensive radiation is
reaching Mars during periodical Sun activity. In
particular, that radiation is considered specially
dangerous for the crew in space. A warning is announced to hide behind the cargo of the space
ship, after electromagnetic, faster radiation than
31
protons, is signalled as approaching. A mixed character of ionizing radiation leaves open the question of the depth-dose distribution, which is deep
in the case of low LET fractions. One should note
that it is anyway deeper than in the case of
UV+VIS radiation which also can contribute to
methane formation, but its action is limited to a
thin surface of Mars.
Presented hypothesis cannot be a complete and
final one, because there are many paths involved
in reaching final stable products of radiolysis. Only
the primary products, as observed by EPR, are of
a zero order considering kinetics and, therefore,
are independent of the temperature of irradiated
material. However, secondary products of chemical changes of the primaries can be temperature
dependent.
Another problem is the total balance of radiation, in particular the question of the excess of
oxygen, resulting from the conversion of carbon
dioxide to methane. One explanation is the assumed formation of hydrogen peroxide, suggested by
Houtkooper [11], and listed among other compounds of Mars by Irwin and Schulze-Makuch [12].
Another one is the decomposition of one of primaries observed by EPR into molecular oxygen,
disappearing in the gaseous sink, surrounding irradiated clays or mixed ice.
This investigation is supported by European
COST action CM0703 and by the Ministry of
Science and Higher Education grant.
References
[1].
[2].
Zagórski Z.P.: Nukleonika, 50, Suppl. 2, 59-63 (2005).
Zagórski Z.P.: Role of radiation chemistry in the
origin of life, early evolution and in transportation
through cosmic space. Chapter 5. In: Astrobiology:
emergence, search and detection of life. Ed. V.A. Basiuk. American Scientific Publishers, 2010, 57 p.
[3]. Ehlmann B.L. et al.: Nature, 479, 53-60 (2011).
[4]. Zagórski Z.P.: Indian J. Rad. Res., 3, 89-93 (2006).
[5]. Zagórski Z.P.: Origins Life Evol. Biospheres, 36, 3,
244-246 (2006).
[6]. Kornacka E.M., Ambroż H.B., Przybytniak G.K.:
Radiat. Phys. Chem., 70, 677-686 (2004).
[7]. Mihelcic D., Voltz-Thomas A., Patz H.W., Kley D.: J.
Atm. Chem., 11, 271-297 (1990)
[8]. Pálfalvi J.K.: Radiat. Meas., 44, 724-728 (2009).
[9]. Dartnell L.R.: Astrobiology, 11, 551-582 (2011).
[10]. Semkova J. et al.: Adv. Space Res., 49, 471-478
(2012).
[11]. Houtkooper J.M., Schulze-Makuch D.: Int. J. Astrobiol., 6, 147-152 (2007).
[12]. Irwin L.N., Schulze-Makuch D.: Cosmic biology.
Springer, New York 2011.
STUDIES OF PHYSICOCHEMICAL PROPERTIES OF GELS
BASED ON IRRADIATED WHEAT STARCH
Krystyna Cieśla, Wojciech Głuszewski
Starches derived from various plants are an abundant and cheap raw material with a high potential
for application in various food, pharmaceutical
and technical industries [1]. Gelling properties of
starch, viscosity and stability of gels appear to be
the crucial factors that affect its possible application. This concerns the application of modified
starches as the functional additives in food prod-
32
ucts (gelling, firming or bulking agents, thickeners
and emulsifiers) or as a component of plastics and
packaging (films and coatings), including active
packaging and variety of delivering systems (paper,
textile, chemical, food and pharmaceutical industries). This occurs because the film forming ability
depends on the properties of the starch gel.
Although potato starch is in Poland largely
used for this purposes, the possibility of application of other starches seems to be also beneficial.
Wheat starch appears as an alternative due to the
content of naturally occurring lipids that make it
possible to modify the functional properties of
starch additives or to obtain products with reduced
hydrophilicity as compared to the starch not containing hydrophobic additives. The gels prepared
basing on wheat starch reveal a lower viscosity as
compared to the gels prepared basing on the potato starch. This might be beneficial for some applications requiring a high content of the solid
matter accompanied by low or medium viscosity
(i.e. textile or paper coatings).
Starch degradation accompanied by oxidation
are desirable processes that enable to obtain products forming gels with reduced viscosity in relation
to those formed by the native starch. Several chemical and enzymatic methods are involved in modification of starch properties leading to obtain on
an industrial scale appropriate products that can
serve for the production of gels with the required
viscoelastic properties. Research concerning the
development of methods of starch modification
and testing the new products containing such
hydrocolloids are being conducted [2]. Ionizing
radiation seems to be a perspective alternative
method enabling to reduce the use of toxic and
strong chemicals, in relation to chemical methods,
to reduce the costs in relation to the enzymatic
methods, and easily steering of the process by the
way of irradiation parameters. Such methods appear to be perspective also for starch modification,
(independently of the present restriction concerning foodstuffs) in regard to the occurring degradation and oxidation processes leading to a significant
decrease in swelling power and viscosity of gels
[1, 3, 4]. Accordingly, some trials were done last
years for re-investigation of the radiation processes
in starches in relation to their possible practical
implementation [5].
Our results dealing with gelatinization behaviour of the irradiated starches have shown a decrease in the swelling power induced by irradiation accompanied by an increase in the content of
water soluble fraction [4]. It was also found that
gamma irradiation performed for the wheat starch
lead to the improvement of the functional properties of the films prepared basing on this starch
[6]. Wheat starch films have appeared, moreover,
more elastic as compared to the potato starch films,
although their tensile strength was smaller [6].
Accordingly, the present studies dealt with the
influence of irradiation performed for wheat starch
on the viscoelastic properties and stability of the
formed gels. These properties were related to the
gelling behaviour of the starch and to the structure of the gels.
The solid wheat starch of Sigma production
(S-5127) was irradiated with Co-60 gamma radiation in air at ambient temperature in a gamma cell
“Issledovatel” placed in the Centre for Radiation
Research and Technology, Institute of Nuclear
Chemistry and Technology (INCT). The doses of
5, 10, 20 and 30 kGy were applied with a dose rate
of 0.36 Gys–1.
Gelling behaviour of the starch was examined
using a procedure described in [4]). This concerns
determination of the volume of the gel formed
after heating of 3 ml aliquots of 20% starch suspensions at selected temperatures (50, 60, 75, 90,
120oC) during 40 min, and centrifuged. Then, the
apparent amylose content was evaluated basing a
blue value method. A Beckman DU-68 spectrometer was applied for the collection of VIS spectroscopy data.
For examination of the viscoelastic properties
[7], 20 wt% gels were prepared. Gelatinization was
carried out on an oil bath maintained at 140oC (1 h
at a temperature in the range from 70 to 140oC
and 30 min at 140oC). The gels were cooled down
to 25oC and submitted to examination using a
Brookfield viscometer DVII+Pro connected to a
thermostat. Three experimental procedures were
applied:
• Procedure I: Dependence of the shear stress,
torque and viscosity on the applied shear rate
(rotation speed) were determined for the gel
sample (non-irradiated) maintained at the required temperature. The selected temperatures
were: 25, 35, 50, 75, 90 and 95oC. The measurements were carried out during increase and decrease of the shear rate. These experiments were
done during increase of temperature followed
by decrease of temperature.
• Procedure II: Examination of the gels were
carried out at the selected shear rate during dynamic heating with an average rate of 3.5 oC/min
followed by cooling with an average rate of 1.4
o
C/min. The value of shear rate equal to 20.9 s–1
was selected basing on the results arising from
experiment I. The measurements were performed at 25oC and after increasing/decreasing temperature with a step of 5 till 95oC.
• Procedure III: Examination of the gels were
carried out at the selected shear rate during
prolonged storage at ambient temperature. The
minimum value of shear rate 1.1 s–1 (5 RPM)
was selected for this purpose.
For SEM observation gels containing 12.5% of
dry matter were prepared on the way of heating
the starch suspensions for 35 min in glass tubes
placed in a heating chamber stabilized at 100oC.
With the purpose of attaining freezing, a drop of
hot gel was flowed out or made a smear on the
frozen metal surface. SEM studies were conducted
at depressed temperature (-15oC) at low vacuum
using a Quanta 200 Microscope (FEI) installed in
the Analytical Centre, Warsaw University of Life
Sciences (SGGW).
33
the process increases due to the more advanced
gelatinization (Fig.2).
Figure 3 present the example of dependence of
the shear stress on the shear rate recorded during
the increasing or decreasing temperature for the
gel prepared using the non-irradiated starch. The
curves show hysteresis with the values recorded
on the increasing shear rate in most of the cases
higher than the values recorded on the decreasing
shear rate. As can be expected, decrease in the
shear stress (and in viscosity) was observed as related to the increase of temperature. However,
higher values of shear stress and viscosity were recorded at a temperature of 95oC than at 90oC. At
the same shear rate, all the values of shear stress
Fig.1. Dose dependence of the volume of gel formed at
120oC after heating of 3 ml of starch suspension.
Decrease in swelling power (Fig.1) accompanied
by an increase in the apparent amylose and leaching of the grains during gelatinization (shown by
the increasing absorbance of the polyiodine com-
Fig.4. The dependence of the shear stress on temperature,
determined (at the shear strain equal to 17.6 s–1) on the
basis of the data obtained during heating (data in Fig.3)
and during cooling (data not shown) in the frame of experiment I for the gel formed using the non-irradiated
starch.
Fig.2. Dose dependence of the maximum absorbance of the
polyiodine complexes formed by the small molecular fraction of the irradiated native potato starched after heating
at the selected temperatures.
plex; Fig.2) are related to the decrease in the molecular mass of starch after irradiation. The increasing amount of the gel formed and the higher absorbances are detected when the temperature of
A
were higher during cooling as compared to the
values recorded during heating. The dependence
of the shear stress on temperature, determined on
the basis of the data obtained in the frame of experiment I shows the significant increase of this
parameter during cooling below 35oC (Fig.4). On
the contrary, experiment II (dynamic heating and
cooling) carried out for the residue obtained after
experiment I indicated only small differences of
B
Fig.3. The dependence of the shear stress on shear rate recorded during the increasing temperature for the gel prepared
using the non-irradiated starch: A – 25, 30, 50 and 70oC; B – 90 and 95oC.
34
A
Although the considerably higher values of shear
stress were observed during heating of the non-irradiated samples in all the temperature range, the
values recorded during cooling at a temperature
lower than 80oC became comparable for both
samples.
The hysteresis in the shear rate – shear stress
curves was observed also in the case of the gels
obtained basing on the starch irradiated using a 10
kGy dose.
A
B
B
Fig.5. The dependence of the shear stress on the temperature determined at the shear strain equal to 20.9 s–1 during
dynamic heating and cooling (experiment II) for the gel
formed using the non-irradiated starch (A) and the starch
irradiated using a 10 kGy dose (B).
the gel shear stress during cooling. Moreover, decrease of this parameter was observed contrary to
the increase determined basing data from experiment I. The curve representing dependence of
shear stress on the temperature during heating
was similar to that shown in Fig.5, with the difference that the increase in shear stress starts already
at a temperature higher than 75oC.
Therefore, experiment of the II type was carried
out for both the gels obtained basing on the non-irradated starch and the starch irradiated using a
dose of 10 kGy. The gels obtained basing on the
irradiated starch were characterized by the lower
stress (and consequently viscosity) as compared to
the gels obtained basing on the non-irradiated
starch (Fig.5). In the cases of both samples, the
increase in the shear stress was observed during
heating at a temperature higher than 85oC. Moreover, the increase in shear stress was recorded also
during heating in the range of the intermediate
temperature above 35-50oC. The fluent decrease
in shear stress was observed during cooling in the
case of both samples. However, this decrease was
more evident in the case of the irradiated starch.
Fig.6. The changes of the shear stress of the gels (formerly
processed) during storage at 25oC at the shear strain equal
to 1.1 s–1: (A) non-irradiated starch, (B) starch irradiated
using a 10 kGy dose.
The gels with the same “history” prepared basing on the non-irradiated starch and the starch irradiated using a 10 kGy dose both have revealed
after the dynamic cooling a relatively low viscosity
(12.4 and 5.6 cP). However, the viscosity considerably increased already after 10 min of storage at
room temperature.
It appears that the stability of the parameters
of the cold gels of both types, irradiated and non-irradiated, might be different. Therefore, the experiment of the III type was performed after a
heating-cooling cycle (Fig.6). It can be stated that
the stress in the non-irradiated gels decreases gradually during storage with a minimally slow stirring,
while the stress in the gels irradiated using 10 kGy
dose, after the fast preliminary decrease, stabilizes
at a relatively constant level.
Table. The shear stress values at a shear rate of 12.1 s–1 and the average values of dynamic viscosity determined for the
20% gels of wheat starch at a temperature of 25oC: directly after preparation (measurement I) and after subsequent 13 h
(measurement II).
Dose [kGy]
Shear stress calculated at shear rate of 12.1 s–1
–1
–1
The average dynamic viscosity
I [D cm ]
II [D cm ]
II/I
I [P]
II [P]
II/I
0
10 746
10 937
1.02
986 ± 126
1 050 ± 118
1.06
10
5 756
66 233
1.17
370 ± 29
405 ± 36
1.36
20
3 019
5 643
1.87
181 ± 17
362 ± 29
2.00
Consequently, the studies of the gels stability
were continued under static conditions. The measurements were done according to an experimental procedure (I) at a temperature of 25oC directly
after preparation and after the subsequent 13 h
for the gels prepared using the non-irradiated
starch and two irradiated starches (10 and 20 kGy).
The viscoelastic properties of the gels containing
the non-irradiated starch have revealed no essential differences after 13 h storage as compared
to the fresh gels and only negligible differences
could be detected in the case of the starch irradiated using a 10 kGy dose. On the contrary, the
gels obtained basing on the starch irradiated using
a 20 kGy dose were characterized after storage by
the double value of the preliminary viscosity and
shear stress (Table).
A
35
ones. Beside to viscoelastic properties, the stability of these properties of both the type gels depends strongly on their history and the procedures
applied during examination. Therefore, when the
gels were slowly stirred at room temperature (after
additional heating-cooling treatment), a stability
of the gels formed using the irradiated starch (10
kGy) was higher than the stability of the non-irradiated specimens. On the contrary, the stability of
the freshly prepared gels left without stirring was
the lower, the higher was irradiation dose. Moreover, the gradual increment in gel strength occurs
contrary to the stirred gels. The differences in the
gels properties were related to the differences in
their structure. Dependence of viscoelastic properties of the gels on their thermal history is probably connected with the increasing amount of the
B
Fig.7. Examples of SEM images of the wheat starch gels: (A) non-irradiated, (B) irradiated with a 30 kGy dose (magnification – 1000x).
The SEM images of the non-irradiated gels indicate generally a honey-comb structure (Fig.7A),
similarly as in the case of the potato starch gels
[8]. However, a considerable distribution of the
honey-comb cages were observed. After irradiation, lengthening of the cages accompanied with
the reduction in thickness of the transverse walls
can be noticed (Fig.7B), leading to the gel orientation. The effect is similar to that observed in the
case of potato starch, finally resulting in the increased gel homogeneity. The observed changes
might be attributed to the radiation-induced weakening of the internal forces in gels, indicated by
their smaller strength (as shown by the lower values
of viscoelastic parameters).
In summary, it can be stated that although irradiation induces lowering of the strength of the
starch gels, the relatively fast dynamic cooling
might result in the similar viscoelastic properties
in both the cases: the gels formed using the non-irradiated starch and those formed using the irradiated starch (10 kGy). Slow cooling, as well as
even short storage at room temperature induces,
however, a high increase in the gel strength and
this increase is much higher in the case of the non-irradiated species as compared to the irradiated
apparent amylose leached from the grains during
the prolonged thermal treatment. The participation of these formerly leached short molecular
products (larger in the case of the irradiated
starch) in further formation of crosslinkages in
the gel might have an additional impact on the
faster strengthening during storage of the gels
formed using the non-irradiated starch.
References
[1]. Cieśla K.: Przekształcenia struktury nadcząsteczkowej
w polimerach naturalnych inicjowane promieniowaniem jonizującym (Transformation of supramolecular
structure initialised in natural polymers by gamma irradiation). Institute of Nuclear Chemistry and Technology, Warszawa 2009, 223 p. (in Polish).
[2]. Tomasik P.: Przemysł Spożywczy, 54 (4), 16-18 (2000),
in Polish.
[3]. Raffi J., Agnel J.P., Thiery C.J., Fréjaville C.M., Saint-Lèbe L.J.: Agric. Food Chem., 29, 127-132 (1981).
[4]. Cieśla K., Eliasson A.-C.: Acta Alimentaria, 36 (1),
111-126 (2007).
[5]. Chung H.-J., Lee S.-Y., Kim J.-H., Lee J.-W., Buyn
M.-W., Lim S.-T.: J. Cereal Sci., 52, 53-58 (2010).
[6]. Cieśla K., Nowicki A., Buczkowski M.: Nukleonika,
55, 2, 233-242 (2010).
[7]. Cieśla K. et al.: Wpływ promieniowania gamma na
właściwości skrobi: oddziaływania z wodą i z lipidami,
36
folie skrobiowo-lipidowe (Influence of gamma irradiation on the starch properties: starch interaction
with water and lipids, starch-lipid films). Projekt badawczy 2 P6T 026 27 Sprawozdanie merytoryczne 2007
(in Polish).
[8]. Cieśla K., Sartowska B., Królak E., Głuszewski W.:
Gamma irradiation influence on structure of potato
starch gels studied by SEM. In: Annual Report 2006.
Institute of Nuclear Chemistry and Technology, Warszawa 2007, pp. 49-52.
CENTRE FOR RADIOCHEMISTRY
AND NUCLEAR CHEMISTRY
Chemical issues of nuclear power and radiopharmaceutical chemistry – the top two domains
of contemporary applied radio- and nuclear chemistry over the world – remained the subject
of the research activity of the Centre for Radiochemistry and Nuclear Chemistry in 2011. The
main research projects from the Centre were financed from the European Commission (FP7
Euratom, Fission), from the Operational Programme Innovative Economy (PO IG), as well as
from the National Science Centre (NCN) and the National Centre for Research and
Development (NCBiR).
In line with the governmental plans to develop nuclear power programme in Poland, the
main efforts of the Centre were focused on the chemical issues of nuclear power. The research
teams of three Centre laboratories (Laboratory of Radiochemical Separation Methods, Laboratory of Membrane Processes and Technologies, and Laboratory of Sol-Gel Technology)
continued their studies on radioactive waste managing, and on special nuclear materials. As
a partner in the European Collaborative Project “Actinide recycling by separation and transmutation” (ACSEPT), we carried out studies on solvent extractive separation of americium
from highly radioactive nuclear waste by using new selective poly-N-heterocyclic ligands, followed by theoretical investigations of potential reasons of their selectivity, as well as studies on
sol-gel producing uranium dioxide matrices for nuclear transmutation of the separated americium (MOX fuels). Further work on new types of MOX nuclear fuels based on uranium oxides
and carbides is the subject of a new Collaborative Project “Advanced fuels for generation IV
reactors: reprocessing and dissolution” (ASGARD), that starts in 2012 with participation of
our Sol-Gel team.
Realization of two other European FP7 projects started in 2011. These are: (i) Collaborative
Project “Implementing public participation approaches in radioactive waste disposal” (IPPA),
aimed at creation of the arena for exchange of opinions and public acceptation of the problems of radioactive waste disposal, and (ii) “New MS linking for an advanced cohesion in
Euratom research” (NEWLANCER), aimed at the increase of participation of Polish teams
in the coming research Euratom programmes.
On the national scale, the Centre coordinated the research project devoted to the possibilities of producing uranium from indigenous resources, and completed participation in the
research project on the use of thorium based fuels in nuclear power reactors, both financed
from PO IG. We evaluated Polish uranium resources and adapted efficient methods for extracting uranium from these materials.
Within the new NCBiR strategic project “Supporting technologies for the development of
safe nuclear power” that started in 2011, the Centre coordinates the workpackage entitled
“The development of supporting technologies for the management of spent nuclear fuel and
radioactive waste”. Within another NCBiR project, a small membrane plant has been designed for managing liquid low-radioactive waste. Within own, Institute statutory research,
novel methods were studied for separation of metal ions, based on combination of membrane
processes with adsorption (biosorbents), and complex formation with ultrafiltration, considered the basis for further technologies of radioactive waste management. Sol-gel methods have
also been elaborated for obtaining novel materials (silica glasses, SYNROC matrices) making
it possible to encapsulate and immobilize nuclear waste.
Radiopharmaceutical chemistry research, conducted mainly in the Laboratories of Radiopharmaceuticals Synthesis and Studies, and of Radiochemical Separation Methods, were focused on obtaining novel potential radiopharmaceuticals, both diagnostic and therapeutic, by
either labelling novel biological vectors (peptides) with well-known radionuclides (99mTc,
188
Re), or labelling of the known vectors with unusual radionuclides therapeutic 123Ra and
PET 44Sc, including labelling with the use of functionalized nanozeolites. A number of novel
99m
Tc-labelled bioconjugates were synthesised and tested as potential receptor-imaging radiopharmaceuticals. A sol-gel method has been elaborated for producing yttrium oxide microspheres as precursors of potential radiopharmaceuticals for anticancer therapy. Apart from
the Institute statutory research, the research in this field were funded from eight NCN and
NCBiR projects, some of them under international cooperation.
The international and national scientific cooperation of the Centre in both main fields of
its activity, and the participation of the Centre researchers in international organizations and
associations, described in the previous issues of INCT Annual Reports (2009 and 2010), were
successfully continued and developed. Two young researchers continue their post-doc contracts at Duke University (NC, USA) and the Institute of Transuranium Elements JRC,
Karlsruhe (Germany). One member of the Centre staff defended her PhD thesis. Five medals
or other prizes have been awarded to the staff of the Laboratory of Sol-Gel Technology at
three international trade shows and exhibitions for their three inventions of new materials.
Two PhD students employed at the Centre have been granted with special half-year fellowships funded by the Government of Mazovia Province, and one got a European fellowship for
a 3-month research stay at the Forschungszentrum Jülich (Germany).
On the occasion of the International Year of Chemistry and the International Year of
Maria Skłodowska-Curie, numerous staff members of the Centre were very active in organizing performances that popularized nuclear chemistry and its role in developing nuclear power
and nuclear medicine, i.e. scientific exhibitions and demonstrations for the public, in particular
pupils and students, as well as in presenting invited lectures related to scientific conferences
and seminars both in Poland and abroad.
The research activity of the Centre staff was complemented by their participation in the
realization of the big PO IG project “Centre for Radiochemistry and Nuclear Chemistry –
meeting the needs of nuclear power and nuclear medicine”, directed towards modernization
of the research infrastructure of the Centre (laboratories and research equipment), funded
from the structural funds of EU and of the Government of Poland.
39
ION EXCHANGE EVIDENCE FOR CHEMICAL ISOTOPE EFFECTS
OF GALLIUM AND INDIUM IN AQUEOUS HCl SOLUTIONS
Irena Herdzik-Koniecko, Sławomir Siekierski, Jerzy Narbutt
Ion exchange chromatography was applied to study
the chemical isotope effects of gallium and indium
in ligand exchange reactions in aqueous HCl solutions. Cation and anion exchange resins, strongly
acidic Dowex 50W-X8 and strongly basic Dowex
1-X8, were used as solid phases separating isotopically enriched chemical forms of the metals.
In order to enhance the isotope separation by increasing the path through the beds of ion exchangers, the merry-go-round elution method was
used, where the band leaving a standard, 1 m long
chromatographic column was introduced back on
the top of the column after each cycle. The number
of cycles varied from 5 to 9, except for Ga on anion
exchanger where – due to a large broadening of
the band – it was equal to only two. Isotope ratios,
It has been found that on the cation exchanger
the light isotope 69Ga was enriched at the front
part of the elution band and the heavy isotope
71
Ga at the end part (Fig.1), whereas the light 113In
isotope was enriched at the end part and the heavy
isotope 115In at the front part (Fig.2). The isotope
separation factor ε was equal to 3.3 × 10–5 for Ga
and 2.0 × 10–4 for In [1]. The picture was found to
be reversed in the case of the anion exchange,
where the heavy gallium isotope was enriched at
the front part and the heavy indium isotope at the
Fig.3. Elution curve and isotope ratio, Ri (▲), of gallium in
the anion exchanger/2.5 M HCl system after 2 cycles. Ro
denotes the gallium isotope ratio in the feed solution.
Fig.1. Elution curve and isotope ratio, Ri (▲), of gallium in
the cation exchanger/2.5 M HCl system after 7 cycles. Ro
denotes the gallium isotope ratio in the feed solution.
Ri, the ratios of the mass of the light isotope to
that of the heavy isotope (69Ga/71Ga and 113In/115In)
were determined in selected fractions, i, of the effluent by means of the inductively coupled plasma
mass spectrometer (ICP-MS, Elan 6100, Perkin El-
end part of the band (Figs.3 and 4), with ε equal
to ~10–3 and 1.7 × 10–4, respectively [2]. Moreover,
the chromatographic band of gallium, eluted from
the anion exchanger column was extremely broad
and asymmetric (Fig.3).
Our analysis shows that the opposite isotope
effects for the two elements, the neighbours in
group 13 of the periodic table, can be explained in
terms of the significant difference in their coordination chemistries, which is a manifestation of the
so-called secondary periodicity observed in numerous properties of group 13 elements [3]. In fact,
stability constants of chloride complexes, low for
[Ga(H2O)5Cl]2+ and high for [In(H2O)5Cl]2+, dif-
Fig.2. Elution curve and isotope ratio, Ri (▲), of indium in
the cation exchanger/0.5 M HCl system after 9 cycles. Ro
denotes the indium isotope ratio in the feed solution.
mer Sciex). In the feed solution the isotope ratios,
Ro, were equal to 1.50677 for gallium and 0.04482
for indium.
Fig.4. Elution curve and isotope ratio, Ri (▲), of indium in
the anion exchanger/1 M HCl system after 5 cycles. Ro denotes the indium isotope ratio in the feed solution.
40
fer by about three orders of magnitude [4]. Gallium
and indium also differ in the coordination number
and in the structure of their highest chloride complexes: tetrahedral for gallium and octahedral for
indium. Analysis of the numerical values of the stability constants of the Ga and In chlorides leads to
the conclusion that the Ga3+–OH2 bond is slightly
stronger than the Ga3+–Cl– bond, whereas for the
indium complexes the bond strength is reversed
and the difference of bonds energies is much greater. Therefore, the energy of the Ga3+–OH2 bond
in hexahydrate [Ga(H2O)6]3+ (which because of its
+3 charge prevails in the resin phase) is greater
than the average energy of the Ga–ligand bonds
in the [Ga(H2O)5Cl]2+ complex (which prevails in
the 2.5 M HCl solution [4]). The above assumption
permits to expect, in accordance with the Bigeleisen-Mayer theory [5], the enrichment of the heavy
71
Ga isotope in the resin phase, i.e. at the end part
of the band, in agreement with the experiment
(Fig.1). Small difference in the bond energies, the
fact that only one Cl– anion is replaced by the H2O
molecule upon [Ga(H2O)6]3+ adsorption, and practically no change in the coordination geometry,
from [Ga(H2O)5Cl]2+ to [Ga(H2O)6]3+ species point
to the small value of the isotope separation coefficient for Ga (ε = 3.3 × 10–5).
On the contrary, much weaker the In3+–OH2
than the In3+–Cl– bond permits to expect the enrichment of the heavy 115In isotope in the aqueous
phase, i.e. at the front part of the band eluted by
0.5 M HCl; opposite to gallium but also in agreement with the experiment (Fig.2). The isotope separation factor for indium, ε = 2.0 × 10–4, one order
of magnitude greater than that for gallium, points
to much greater difference in the energy between
the In3+–Cl– and In3+–OH2 bonds than the respective difference for gallium, which is consistent with
the reported stability constants [4]. The other factor contributing to the higher ε value for indium
than for gallium is the greater change in the coordination sphere of the former, accompanying adsorption process. Because the indium complexes
predominating in 0.5 M HCl are [In(H2O)4Cl2]+
and [In(H2O)3Cl3], hence two or even three Cl–
ions have to be replaced by H2O molecules upon
[In(H2O)6]3+ adsorption, whereas in the case of
gallium, only one Cl– ion is replaced by H2O molecule (see above).
The end boundary of the gallium elution band,
somewhat more broadened than the front boundary (Fig.1), implies slightly slower substitution of
H2O by Cl–, that accompanies [Ga(H2O)6]3+ adsorption, than substitution of Cl– by H2O, that accompanies [Ga(H2O)5Cl]2+ desorption. On the
contrary, the indium elution band shows a sharp
end and broadened front boundary (Fig.2), which
suggests faster substitution of H2O by Cl– (desorption) than the reverse substitution.
The picture observed in the case of anion exchange systems is fully consistent with that observed for cation exchanger, but with the opposite
directions of the isotope effects. The anionic
[GaCl4]– complex is probably the only form adsorbed on the anion exchange resin, and the energy
of the Ga3+–Cl– bond is somewhat smaller than
the average energy of the Ga–ligand bonds in the
[Ga(H2O)5Cl]2+ complex which predominates in
the aqueous phase [4]. Therefore, according to
the theory, the light isotope ought to be enriched
in the resin and at the end part of the elution
band. Really, Fig.3 shows that the light isotope
69
Ga is enriched at the diffuse end part and the
heavy isotope 71Ga at the less diffuse front part of
the band. The very large width of the elution band
(only two cycles of the merry-go-round method
could be performed) points to particularly slow
changes between tetrahedral and octahedral species: [GaCl4]– ↔ [Ga(H2O)4Cl2]+; that accompany
the sorption/desorption processes of gallium on the
anion exchanger, as confirmed by kinetic studies
[6]. The asymmetric shape of the band (very long
tail) seems to be due to particularly slow change
from tetrahedral to octahedral coordination upon
desorption. The great change of the coordination
is probably the main reason of the high value of ε,
equal to about 10–3, though the asymmetry of the
band makes this value only approximate.
Contrary to gallium, the merry-go-round method consisting of 5 cycles was successfully applied
for indium on the anion exchanger, for which the
band profile at 1 M HCl shows a sharp front and
slightly broadened end boundary (Fig.4). Owing
to the charge, the main species in the resin is
[InCl6]3– with admixture of the lower charged
[In(H2O)Cl5]2–, while the more hydrated complexes with weaker In–ligand bonds predominate
in the aqueous phase (see above). Therefore, according to the theory and contrary to gallium, the
heavy isotope ought to be enriched in the resin
and at the end part of the elution band. Indeed,
the experiment shows that 115In is enriched at the
end part of the band, whereas 113In is enriched at
the narrow front part (Fig.4). The band is broader
than those eluted from the cation exchanger, but
sharper than that for gallium. This picture can be
attributed to the quite different composition of
indium complexes predominating in both phases,
but to the same octahedral coordination of the
species. The ε value, equal to 1.7 × 10–4, a little bit
lower than that for indium in the cation exchange
system, reflects some smaller number of exchanged
ligands, accompanying sorption/desorption in the
present system, at the same difference in the energy
between the In-ligand bonds. The broadened end
boundary of the band means that the conversion
of [InCl6]3– into the eluted, partly hydrated forms,
is slightly slower than the reverse process.
It is interesting to notice that the observed enrichment of the front part of the elution band of
indium in the light isotope and the end part in the
heavy isotope in the anion exchanger/Cl– system
shows the same pattern as that of gallium in the
anion exchanger/NCS– system [7]. The reason is
that both metals form rather strong complexes, of
similar strength, in the respective solutions – indium with Cl– ions [4] whereas gallium with NCS–
ions [8].
In conclusion, we state that the opposite directions and various magnitudes of the chemical iso-
tope effects for gallium and indium, observed in
separation systems consisting of ion exchange resins and aqueous HCl solutions, can be explained,
in accordance with the Bigeleisen-Mayer theory,
in terms of the differences in coordination chemistry of chloride complexes of these two elements.
These differences appear in the composition and
coordination geometry of the separated complexes,
as well as in the strength of the M3+–OH2 and
M3+–Cl– bonds. In particular, the processes of gallium sorption/desorption in the system anion exchanger/HCl are accompanied by the mutual conversion of tetrahedral and octahedral gallium
chlorides. This great difference between the two
forms results in the high value of isotope separation factor, but the slow kinetics of these processes
makes the elution band of gallium very broad and
asymmetric.
The different pattern of isotope enrichment for
gallium and indium, the neighbouring elements in
group 13, is an example of the secondary periodicity present in numerous chemical properties of
these elements.
41
References
[1]. Dembiński W., Herdzik I., Skwara W., Bulska E., Wysocka A.I.: Nukleonika., 51, 217-220 (2006).
[2]. Herdzik I., Dembiński W., Skwara W., Bulska E., Wysocka A.: Gallium and indium isotope effects in the
Dowex 1-X8/HCl system. In: INCT Annual Report
2006. Institute of Nuclear Chemistry and Technology,
Warszawa 2007, pp. 81-82.
[3]. Siekierski S., Burgess J.: Concise chemistry of the elements. Horwood Publishing, Chichester 2002, pp. 90-91.
[4]. Wood S.A., Samson I.M.: Ore Geol. Rev.., 28, 57-102
(2006).
[5]. Bigeleisen J., Mayer M.: J. Chem. Phys., 15, 261-267
(1947).
[6]. Herdzik I., Narbutt J.: Kinetics of ion exchange of gallium and indium ions in the system aqueous HCl solution/anion exchange resin (Dowex 1-X8). In: INCT
Annual Report 2008. Institute of Nuclear Chemistry
and Technology, Warszawa 2009, pp. 86-88.
[7]. Machlan L.A., Gramlich J.W.: Anal. Chem., 60, 37-39
(1988).
[8]. Das R.C., Dash A.C., Mishra J.P.: J. Inorg. Nucl. Chem.,
30, 2417-2423 (1968).
NEW METHOD FOR DISSOLUTION OF THORIUM OXIDE
Krzysztof Łyczko, Monika Łyczko, Irena Herdzik-Koniecko, Barbara Zielińska
Recently, the interest revived in the thorium-uranium fuel cycle, in which – as a result of irradiation
by neutrons – thorium-232 (a fertile material) is
converted into uranium-233 (a fissile material).
For nuclear power reactors that use thorium oxide,
it is necessary to develop a method of thorium recovering from spent fuel. However, the problem
of dissolving ThO2 becomes the goal not only for
the nuclear issues, but also for the processing of
ores containing thorium oxide.
It is known that thorium oxide is chemically an
inert compound. In aqueous solution it dissolves
in concentrated nitric acid only in the presence of
small amounts of fluoride ions. The most common
method of dissolving of ThO2 is to treat it with the
so-called THOREX solution, containing 13 M
HNO3, 0.02-0.05 M HF and 0.1 M Al(NO3)3 [1]. In
this system, hydrofluoric acid becomes a catalyst
of the reaction, and aluminium nitrate protects
against the corrosive action of HF, preventing the
precipitation of thorium fluoride as well. Another
way of obtaining thorium compounds easily soluble in aqueous solutions is sintering thorium
oxide with ammonium sulphate at temperatures
of 250, 365 or 450oC, which gives (NH4)4Th(SO4)4,
(NH4)2Th(SO4)3, or Th(SO4)2, respectively [2].
Hydrated Th4+ ions exist in aqueous solutions only
at low pH. For concentrated thorium solutions,
the hydrolysis is considerable even at pH 1. Therefore, when dissolving ThO2 and other thorium
compounds in aqueous media very low pH value
should be maintained.
We have found another simple route for conversion of thorium oxide into a soluble form during its heating in the concentrated aqueous solution of trifluoromethanesulphonic (triflic) acid
under reflux condition [3]. As a result of this reaction, we obtain an easily soluble in aqueous
media a thorium trifluoromethanesulphonate (triflate) salt. With the appropriate concentration of
acid this dissolution process can be shortened to
several or tens of minutes. It turned out that adding a small amount of water to the concentrated
triflic acid significantly accelerates the dissolution
process. The synthesis of thorium triflate in the
reaction of triflic acid with thorium nitrate [4] or
with thorium hydroxide [5] was described earlier.
The method presented herein has many advantages. It is achieved in a very simple system
without necessity of adding to the solution other
inconvenient compounds such as hydrofluoric acid
and aluminium nitrate. Furthermore, in a small
volume of solution, a large amount of ThO2 can
be dissolved. The approach described may be important in the processing of nuclear fuel based on
thorium oxide and in processing of ores containing ThO2. It can become a competitive method
compared to that currently used, applying a mixture of mineral acids HNO3 and HF.
This work was financed by the Operational
Programme Innovative Economy and supported
by the European Regional Development Fund
(project POIG 01.03.01-00-076/08-00 “Analysis of
thorium use in nuclear power plant”).
References
[1]. Takeuchi T., Hanson C.K., Wadsworth M.E.: J. Inorg.
Nucl. Chem., 33, 1089-1098 (1971).
[2]. Chaudhury S., Keskar M., Patil A.V., Mudher K.D.S.,
Venugopal V.: Radiochem. Acta, 94, 357-361 (2006).
[3]. Łyczko K., Łyczko M., Herdzik I., Zielińska B.: Method
of dissolution of thorium oxide. Polish Patent Applica-
42
tion No. P-390844 (2010); European Patent Application No. 11460009.1-2111 (2011).
[4]. Bouby M., Billard I., MacCordick J.: J. Alloys Comp.,
271-273, 206-210 (1998).
[5]. Walker M.: Process for the preparation of aryl ketones
generating reduced amounts of toxic byproducts. US
Patent No. 6362375 (2002).
LABELLING OF DOTATATE WITH CYCLOTRON PRODUCED 44Sc
Seweryn Krajewski, Izabela Cydzik1/, Kamel Abbas1/, Antonio Bulgheroni1/,
Aleksander Bilewicz, Agnieszka Majkowska-Pilip, Federica Simonell1/
1/
European Commission Joint Research Centre, Institute for Health and Consumer Protection, Ispra,
Italy
177
Lu- and 90Y-DOTATATEs have been introduced by the European Association of Nuclear
Medicine into the Investigational Medicinal Products List, since both radiopharmaceuticals are highly promising agents for peptide receptor radionuclide therapy. They are used in treatment of inoperable and metastasized neuroendocrine tumours,
which overexpress somatostatin receptors [1, 2].
68
Ga-DOTATATE is used to visualize such tumours
and plan targeted radionuclide therapy. However,
it demonstrates a number of pharmacokinetic drawbacks, which could be avoided by using the longer-lived 44Sc (τ1/2 = 3.92 h) as a prospective radionuclide for PET (positron emission tomography)
imaging. 44Sc has better nuclear properties than
68
Ga and, contrary to Ga3+, forms complexes of
structure similar to those of Y3+ and Lu3+ [3].
Scandium-44 can be obtained from a 44Ti/44Sc
generator, but the cost of 44Ti production is very
high [4]. Alternatively, it can be produced in small
medical cyclotrons by the 44Ca(p,n)44Sc nuclear
reaction. The aim of our study was to optimize the
parameters for 44CaCO3 irradiation, in order to
maximize the production of 44Sc with minimal impurities of 44mSc and to develop a simple procedure of 44Sc separation from the calcium target
for labelling the DOTATATE.
Highly enriched 44CaCO3 (Isoflex, Russia) was
used as a target material. Irradiations were performed using the Scanditronix MC 40 cyclotron of
the European Commission Joint Research Centre
(Ispra, Italy). In order to optimize the yield of 44Sc
formed in the 44Ca(p,n)44Sc reaction, 44CaCO3 targets of 2 mg in the form of dry powder were irradiated by protons in the energy range from 5.5 to 23
MeV. The activity of the samples was measured
by high resolution γ-ray spectrometry.
For labelling experiments, 5-10 mg of the
44
CaCO3 were irradiated for approximately 1 h by
a proton beam of 9 MeV on the target and applying the proton current of 5-15 μA. Afterwards, the
target material was dissolved in 1 ml of 0.1 M HCl
and diluted with 1 ml of water. Then, the solution
was passed through a commercially available column (d = 0.8 cm, h = 4.0 cm) filled with chelating
ion exchange resin Chelex 100. After adsorption
of 44Sc, the column was washed with 30 ml of 0.01
M HCl and the effluent containing enriched 44Ca
was collected for target recovery. The scandium
radionuclides were eluted with 1 M HCl in 0.5 ml
fractions.
44
Sc-DOTATATE radiobioconjugate was synthesized using 10, 25 and 38 nmol of the peptide in
sodium acetate buffer of pH = 6. The solution
was heated for 30 min at 95oC. Product formation
and reaction yield were estimated by instant thin-layer chromatography. The 0.1 M citric buffer
was used as the eluent. Free 44Sc moved with the
front boundary of the solution whereas the labelled bioconjugate stayed at the starting point. The
10 cm ITLC strip was cut in the middle and each
part was measured with a γ-spectrometer.
The volume of the collected effluent was decreased to less than 1 ml in a drier heated at 140oC.
Next, 200 μl of concentrated ammonia was added
to the solution, which was then heated at 170oC to
decompose NH4Cl and to obtain pure 44Ca(OH)2.
The recovered target was irradiated for 1 h with a
proton beam of 9 MeV and a current of 10 μA.
Next, the separation and labelling procedures were
Table 1. Activity of 44Sc and 44mSc as a function of the proton energy on the target. The optimum proton beam energy is
marked in bold.
44
Sc [kBq]
44m
Sc [kBq]
44m
Proton energy [MeV]
Proton energy on target [MeV]
Sc [%]
19.0
5.57
25.8
0.02
0.081
19.5
7.28
4 240
0.94
0.022
20.0
7.88
4 350
2.6
0.060
20.5
8.89
27 000
43
0.159
21.0
9.83
31 000
57.8
0.186
21.5
10.7
9 370
23
0.245
23.0
13.2
13 600
76
0.559
26.0
17.5
4 600
40
0.869
repeated, but instead of sodium acetate buffer,
the ammonia acetate buffer was used.
The analysis of the results obtained from optimization studies shows that in the proton energy
range of 9-10 MeV on the target, the amount of
44
Sc reaches a maximum (Table 1) with a minimum
production of 44mSc impurity that is estimated to
(0.16%). The 44Sc activity obtained after irradiation of a 5 mg target was around 40 MBq for 1 h
irradiation and a 10 μA proton current. The activity can be easily increased by prolonging the irradiation time, using higher beam current and amount
of the target material.
Fig. Elution curve of 44Sc with 1 M HCl from column filled
with Chelex 100 resin.
The separation on the Chelex 100 resin is very
efficient. More than 60% of 44Sc activity was eluted with 1 M HCl in three initial 0.5 ml fractions
(Fig.). The content of Ca2+ in 44Sc was less than 1
ppm, which was measured with ICP-MS (inductively coupled plasma mass spectroscopy).
We obtained a high yield of labelling DOTATATE with 44Sc. The labelling yield exceeded 98%
for all amounts of the bioconjugate (Table 2),
which shows that very pure and n.c.a. 44Sc was obtained. When the yield of reaction is not high
enough, the labelled peptide can be purified on a
Sep-Pak® C-18 column.
43
Table 2. Labelling yield as a function of the amount of
DOTATATE used in the reaction.
Amount of peptide [nmol]
Yield of labelling [%]
31
98.2
25
99.5
10
98.3
First experiments on the recovery of the calcium target showed that up to 50% of 44Ca could be
recovered. The work was performed on small
amounts of the target (5 mg), which could strongly
influence the final efficiency. This issue requires
further studies. The recovered 44Ca target was irradiated again, 44Sc was separated from the target
on the Chelex 100 column and 25 nmol of DOTATATE was labelled with a yield of 99.5%.
Irradiations of 44Ca provide an opportunity to
produce GBq activity levels of 44Sc. The proposed
separation process of 44Sc from the calcium target
is simple and fast. The obtained 44Sc can be used,
instead of 68Ga, in PET imaging and in planning
peptide receptor radionuclide therapy with 177Luand 90Y-DOTATATEs. 44CaCO3 is expensive, but
the production cost of 44Sc-DOTATATE can be
reduced by target recovery.
References
[1]. Kwekkeboom D.J., Teunissen J.J., Bakker W.H., Kooij
P.P., de Herder W.W., Feelders R.A., van Eijck C.H.,
Esser J.-P., Kam B.L., Krenning E.P.: J. Clin. Oncol.,
23, 2754-2762 (2005).
[2]. Kunikowska J., Królicki L., Hubalewska-Dydejczyk A.,
Mikołajczak R., Sowa-Staszczak A., Pawlak D.: Eur. J.
Nucl. Med. Mol. Imag., 38, 1788-1797 (2011).
[3]. Majkowska-Pilip A., Bilewicz A.: J. Inorg. Biochem.,
105, 313-320 (2011).
[4]. Zhernosekov K., Bunka M., Hohn A., Schibli R., Türler
A.: J. Labelled Compd. Radiopharm., 54, S239 (2011).
99m
Tc-LABELLED VASOPRESSIN ANALOGUE
d(CH2)5[D-Tyr(Et2),Ile4,Eda9]AVP
AS A POTENTIAL RADIOPHARMACEUTICAL
FOR SMALL-CELL LUNG CANCER (SCLC) IMAGING
Ewa Gniazdowska, Przemysław Koźmiński, Krzysztof Bańkowski1/
1/
Pharmaceutical Research Institute, Warszawa, Poland
The aim of the work was to synthesize and investigate the conjugate of the d(CH2)5[D-Tyr(Et2),Ile4,
Eda9]AVP (AVP(an)) peptide, the analogue of
vasopressin, with a mixed-ligands “4+1” technetium(III) complex.
Vasopressin (arginine vasopressin, (Arg8)-Vasopressin, AVP) is a cyclic peptide (disulphide bond
between Cys1 and Cys6) containing nine amino
acid residue (Cys1-Tyr2-Phe3-Gln4-Asn5-Cys6-Pro7-Arg8-Gly9). AVP is a peptide hormone found in
most mammals, including humans. AVP regulates
body retention of water, being released when the
body is dehydrated (antiduretic action of AVP,
mediated via V2 type receptors). In addition to its
predominantly antidiuretic and blood pressure activities, vasopressin demonstrates a variety of
neurological effects on central nervous system
(CNS). It is involved, via different receptor subtypes, in higher brain functions, including cognitive abilities and emotionality. In the recent years,
interest increased in the role of vasopressin in its
participation in such diseases as schizophrenia
and autism [1]. The half-live of the vasopressin
peptide in vivo is about 15-20 min [2]. The overexpression of vasopressin receptor V2 has been
found on small-cell lung cancer (SCLC) [3-5].
Physicochemical properties of the 99mTc-labelled
vasopressin peptide were already studied [6].
44
The AVP analogue, AVP(an), is one of the
several effective antagonists (Fig.1A) of the antidiuretic (V2-receptor) responses to arginine vasopressin [7].
The “4+1” mixed-ligand technetium complex
consists of central metal ion Tc(III) coordinated
by a tetradentate tripodal chelator tris(2-mercaptoethyl)-amine, NS3, and a monodentate isocyanide
ligand previously coupled with the selected biomolecule (Fig.1B). The identity of the 99mTc-laA
O
N
H
N
O
O
N
H
O
H
N
H
N
N
H
O
O
O
B
O
H
N
NH2
N
H
R
N
S
O
N
N
N
O
S
thesized according to the procedures described in
Refs. [6, 8-11].
MS of CN-AVP(an), (m/z): calcd – 1231.61, found
– 616.1 [M+H]+, 1254.3 [M+Na]+.
MS of Re(NS3)(CN-(AVP(an)), (m/z): calcd –
1612.1, found – 806.8 [M+H]+, 1634.5 [M+Na]+.
The 99mTc-labelled AVP(an) conjugate was
formed in two-step synthesis, via the 99mTc-EDTA
intermediate complex [6, 8, 9, 11], with a final
yield of 95%.
M
S
N
9
O
Re
Fig.1. (A) d(CH2)5[D-Tyr(Et ),Ile ,Eda ]AVP, (AVP(an)); (B)
99m
belled AVP(an) was corroborated by investigation of an analogous rhenium compound.
The analogue AVP(an), was a gift from Prof.
Maurice Manning from the University of Toledo
(Ohio, USA).
The compounds: tetradentate NS3 ligand
(tris(2-mercaptoethyl)-amine; 2,2’,2’’-nitrilotriethanethiol, R=H), aliphatic linker CN-BFCA
(BFCA – bifunctional coupling agent) – monodentate isocyanide ligand (isocyanobutyric succinimidyl ester), CN-AVP(an) – the isocyanide linker
CN-BFCA coupled with AVP(an) and the “cold
rhenium precursor” Re(NS3)(PMe2Ph) were syn-
The HPLC chromatograms of the compounds
Re(NS3)(CN-AVP(an)), RT = 15.9 min, and
99m
Tc(NS3)(CN-AVP(an)), RT = 16.3, min are
shown in Fig.2.
The log P value of -0.44 ± 0.03 for the 99mTc-labelled AVP(an) was found (the value may be corrected by introduction a hydrophilic group, R, at
the periphery of the NS3 ligand).
The conjugate 99mTc(NS3)(CN-AVP(an)) exhibits high stability. Figure 3 shows the percentage
of intact conjugate in the challenge experiments
with an excess (10 mM) of histidine or cysteine
during incubation of the isolated conjugate at
37oC. After 24 h of incubation, the obtained HPLC
chromatograms have shown the existence of one
radioactive species in the solution, of the retention time characteristic of the complex studied.
The HPLC chromatograms obtained after incubation of 99mTc(NS3)(CN-AVP(an)) conjugate
in human or rat serum are shown in Fig.4. The
conjugate studied is also very stable in human and
rat serum, on the contrary to the 99mTc-labelled
arginine vasopressin peptide. The biomolecule
AVP(an), the antagonist of the V2 vasopressin receptor, does not undergo enzymatic biodegradation in vivo, even in rat serum.
99m
Tc(NS3)(CN-AVP(an))
labeling mixture, g detection
100
Tc(NS 3)(CN-AVP(an))
99m
Tc(NS3)(CN-AVP(an))
purified, g detection
0
5
10
15
20
25
75
50
99m
Re(NS3)(CN-AVP(an))
UV-Vis detection, 220 nm
0
Tc-labelled peptides using the “4+1” approach.
30
min
Fig.2. The HPLC chromatograms of the 99mTc/Re complexes prepared in this study (analytical Phenomenex column – Jupiter Proteo, 4 μm, 90 Å, 250 × 4.6 mm; under
condition: solvent A – water with 0.1% TFA (v/v), solvent
B – acetonitrile with 0.1% TFA (v/v); gradient elution –
0-20 min 20 to 80% solvent B, 10 min 80% solvent B;
1 ml/min, γ-detection).
% of intact
4
peptide
N
M=99mTc,
S
2
C
S
in 10 mM histidine solution
25
in 10 mM cysteine solution
0
0
4
8
12
16
20
24
time of incubation [h]
Fig.3. Histidine and cysteine challenge experiments: the
percentage of intact 99mTc(NS3)(CN-AVP(an)) complex remaining after various incubation times at 37oC.
B
cpm
cpm
A
45
after 15 min of incubation
0
0
0
5
10
15
20
0
25
5
10
15
20
25
min
min
Fig.4. HPLC chromatograms of 99mTc(NS3)(CN-AVP(an)) conjugate after incubation at 37oC in human (A) and rat (B)
serum (analyses carried out under the conditions described above).
In conclusion, one can say that the novel
conjugate of the vasopressin peptide analogue
d(CH2)5[D-Tyr(Et2),Ile4,Eda9]AVP with the “4+1”
mixed-ligands technetium(III) complex can be
considered promising diagnostic radiopharmaceutical for patients suffering from small-cell lung
cancer.
References
[1].
[2].
[3].
[4].
[5].
Frank E., Landgraf R.: Best Pract. Res. Clin. Anaesthesiol., 22, 265-273 (2008).
Guyton A.C., Hall J.E.: Text book of medical physiology. 10th ed. Saunders W.B., Philadelphia, PA 2000.
Pequeux C., Breton C., Hendrick J.-C., Martens
M.-T.H., Winkler R., Legros J.-J.: Cancer Res., 62,
4623-4629 (2002).
North W.G., Fay M.J., Longo K.A., Jiniin Du: Cancer
Res., 58. 1866-1871 (1998).
Pequeux C., Keegan B.P., Hagelstein M.-T., Geenen
V., Legros J.-J., North W.G.: Endocr. Relat. Cancer,
11, 871-885 (2004).
Gniazdowska E., Kozminski P., Bankowski K., Pietzsch
H.-J.: Vasopressin peptide (AVP) labelled with a “4+1”
mixed-ligand technetium complex. In: INCT Annual
Report 2008. Institute of Nuclear Chemistry and
Technology, Warszawa 2009, pp. 77-81.
[7]. Manning M., Przybylski J., Grzonka Z., Nawrocka
E., Lammek B., Misicka A., Ling Ling Cheng: J.
Med. Chem., 35, 3895-3904 (1992) and references
cited therein.
[8]. Seifert S., Kuenstler J.-U., Schiller E., Pietzsch H.-J.,
Pawelke B., Bergmann R., Spies H.: Bioconjugate
Chem., 15, 856-863 (2004).
[9]. Kunstler J.-U., Seidel G., Bergmann R., Gniazdowska E., Walther M., Schiller E., Decristoforo C.,
Stephan H., Haubner R., Steinbach J., Pietzsch H.-J.:
J. Med. Chem., 45, 3645-3655 (2010).
[10]. Spies H., Glaser M., Pietzsch H.-J., Hahn F.E., Luegger
T.: Inorg. Chim. Acta, 240, 465-478 (1995).
[11]. Kuenstler J.-U., Veerenda B., Figueroa S.D., Sieckman
G.L., Rold T.L., Hoffman T.J., Smith C.J., Pietzsch
H.-J.: Bioconjugate Chem., 18, 1651-1661 (2007).
[6].
THE CONCEPT OF A HYBRID SYSTEM FOR TREATMENT
OF LIQUID LOW- AND MEDIUM-LEVEL RADIOACTIVE WASTE
Grażyna Zakrzewska-Trznadel, Agnieszka Miśkiewicz, Agnieszka Jaworska-Sobczak,
Marian Harasimowicz
Radioactive wastes in Poland arise from research
reactors and from various applications of radioisotopes in industry, medicine and science. The waste
from around the country is collected, processed
and prepared for disposal at the Radioactive Waste
Management Plant at Świerk (Poland). At present,
only the institutional radioactive waste is treated
and conditioned there, however, the development
of the Programme of Polish Nuclear Energy will
imply necessary activities concerning the future
strategy of radioactive waste management.
The first step in the processing of low- and
medium-level liquid radioactive waste is a reduc-
tion in the volume of liquid containing small concentrations of radionuclides. Various methods for
concentrating radioactive waste have been studied
and developed at the Institute of Nuclear Chemistry and Technology (INCT), including membrane
processes. Reverse osmosis (RO) has been implemented at the Radioactive Waste Management
Plant. Other methods such as ultrafiltration (UF),
membrane distillation (MD) and adsorption processes were studied within the scope of national
and international projects. The current work presents the results of development studies performed at the INCT, aiming at implementation of
46
these methods at nuclear centres that produce
liquid wastes, as well as on the plans devoted to
longer term issues of low-level waste treatment
from the future nuclear power industry in Poland.
Implementation of liquid-radioactive-waste
management is difficult and requires effective
methods, including separation processes of high
selectivity. To obtain the desired effects, several
consecutive steps of treatment using various separation methods should be performed. More frequently, the use of hybrid systems which combine
two or more processes is considered to treat the
waste material. These systems, enabling higher decontamination factors, can also be considered as
selective methods for various types of metal ions,
allowing their recovery. Hybrid arrangements are
effective and flexible; they are useful in solving
complex technical problems encountered in the
economy and environmental protection.
The concept of small hybrid systems for lowand medium-level liquid radioactive waste treatment based on membrane processes was developed in the scope of the project No. R05-05806/2009
financed from the National Centre for Research
and Development (NCBiR). A variety of methods
– such as microfiltration (MF), chemical precipitation, ultrafiltration, seeded ultrafiltration (SUF),
nanofiltration (NF) and reverse osmosis, as a main
unit of processing – were tested at the INCT with
institutional radioactive wastes collected from the
Radioactive Waste Management Plant. As a final
step in the decontamination, the use of hydrophobic microfiltration membranes was proposed
as part of the membrane distillation unit to complete the entire scheme. The output streams from
the plant are: clean water that can be discharged
to the communal sewage system, and the concentrate of radioactive compounds, ready for immobilization – the last stage of waste conditioning.
The hybrid system for the treatment of liquid
low- and medium-level radioactive waste originated from nuclear applications (institutional waste)
was composed of four stages: pretreatment, basic
stage, final polishing and concentration stage
(Fig.). Radioactive aqueous waste enters the pretreatment stage where it is prepared before the
basic stage of processing, which is composed of
RO or UF membrane modules. In the pretreatment stage, all suspended matter is removed by
depth filters. The organic compounds and oxidizing agents like chlorine are retained by sintered or
granulated activated carbon filters. A large pro-
portion of the radioactivity load can be removed
in the precipitation process with ferric hydroxide
or ferrocyanides. Pretreated waste can be cleaned
with UF or RO membranes, depending on the
Fig. The scheme of the system for radioactive waste treatment.
waste composition. UF is generally applied for
colloidal solutions; however real waste containing
small cations like Co2+ or Cs+ can be treated in the
UF process enhanced by complexing agents (soluble polymers, cheap biopolymers), or dispersed
sorbents like activated carbon (SUF). After the
basic stage of processing, the final polishing of
permeate takes place in an MD module or in
standard ion exchange columns. The effluent from
this stage is relatively pure water (below clearance
limits: 10 Bq/L) that can be discharged to the sewage system or used as process water, e.g. for cleaning the membrane modules or other components
of the plant. Further concentration of retentate
from the membrane basic system occurs in the
concentration stage composed alternatively of
high-pressure desalination RO elements or of an
additional MD module.
Such a system is very flexible and universal.
The module design makes it possible developing
the capacity according to specific conditions and
actual needs, and an easy up-scaling. It is possible
to redesign some components if the composition
of the waste is stable enough and the rest of apparatuses guarantee the target goals: a clear effluent from the plant and a concentrate appropriate
for cementation and disposal. The whole installation can be a very useful tool for testing different
options of treatment depending on the waste composition.
The research has been supported by the National Centre for Research and Development
(NCBiR) – research grant No. R05-05806/2009.
47
STUDIES ON THE LEACHING OF URANIUM
FROM LOWER TRIASSIC PERIBALTIC SANDSTONES
Grażyna Zakrzewska-Trznadel, Katarzyna Kiegiel, Kinga Frąckiewicz, Dorota Gajda,
Ewelina Chajduk, Iwona Bartosiewicz, Jadwiga Chwastowska, Stanisław Wołkowicz1/,
Jerzy B. Miecznik1/, Ryszard Strzelecki1/
1/
Polish Geological Institute – National Research Institute, Warszawa, Poland
Nuclear power is one of the branches of power industry which, despite a temporary slowdown caused
by an accident in Fukushima, will be fast developing (reported by Cap Gemini). The alternative to
nuclear power for Europe is its dependence on
gas import from Russia [1].
The inevitable development of nuclear power
implicates the interest in evaluation of domestic
resources and possibilities of uranium exploitation [2] for production of nuclear fuel for Polish
reactors. The project entitled “Analysis of the
possibility of uranium supply from domestic resources”, developed by the Institute of Nuclear
Chemistry and Technology (INCT) and Polish
Geological Institute, makes an effort to evaluate
the possibility of uranium production from indigenous resources.The main objectives of the project are:
• to assess the possibility of exploitation of uranium resources in Poland,
• to work out methods for uranium extraction
from the ores and production of the yellow cake
– U3O8.
According to the assessments done by the Polish
Geological Institute, apart from the well-known
resources in Sudetes exploited in 1948-1973, there
are other deposits of uranium on the territory of
Poland: in the Lower Ordovician Dictyonema
shale of Podlasie Depression (North-East Poland)
with the metal concentration of 75-250 ppm, and
the most prospective uranium mineralization –
the Lower and Middle Triassic rocks of the central
parts of Peribaltic Syneclise [3]. The ore material
originating from these two resources was selected
for laboratory studies carried out in the scope of
the present project. The analysis of uranium con-
centration in sand stones from Peribaltic Syneclise shows a big diversity of uranium concentration
in the vertical profile: from 4.8 to 1316 ppm. In the
ores, uranium usually was accompanied by other
valuable metals, e.g. V, Mo, Th, La, Cu or Co, that
can be recovered in technological process to improve the economy of the whole venture. The
exemplary results of chemical analysis of Peribaltic sandstones are presented in Table.
The first stage of uranium extraction from the
sandstones is leaching by acidic or alkaline solutions. It is well established that many factors such
as temperature, pressure, leaching mode (acidic or
alkaline), and the concentration of reagent exert a
significant effect on the efficiency of extraction of
uranium and other metals from uranium ores. The
influence of all these factors on the leaching efficiency was examined. Prior to the leaching, the
samples of the ores were crushed and ground. The
experiments were performed in a round bottom
glass flask equipped with a reflux condenser and a
magnetic stirrer (Star FishTM, Multi-experiment
work station) at a temperature of 80oC under ambient pressure. The samples of grain size in the
range of 0÷0.2 mm were tested. The oxidizing
agent (MnO2 or 30% H2O2) was added to oxidize
all uranium to U(VI). The post-leaching solution
was separated from the leached ore by filtering
and successive washing with distilled water. A
sample of the solution was drawn for ICP-MS
analysis [4] to estimate the leaching efficiency.
The experiments performed with 10% H2SO4
lixiviant at 80oC showed the efficiency of uranium
extraction on the level of 63÷80%. The results are
shown in Fig.1. Very interesting results were obtained when alkaline lixiviants (5% Na2CO3/5%
Table.The content of selected metals in uranium ore samples.
Sample
notation
Deposit
notation
21/10/138
21/10/140
Sandstones
U
[ppm]
Th
[ppm]
Cu
[ppm]
Co
[ppm]
La
[ppm]
V
[ppm]
Yb
[ppm]
Ni
[ppm]
Fe
[ppm]
Ptaszków IG-1
1 120
4.0
42
127
14
142
0.8
21
8 080
Ptaszków IG-1
1 316
5.1
28
81
47
625
1.7
41
12 680
21/10/141
Ptaszków IG-1
1 144
14
47
117
51
717
2.5
52
21 590
21/10/142
Ptaszków IG-1
670
4.8
32
57
29
770
1.6
26
8 500
21/10/148
Ptaszków IG-1
526
10
46
71
43
232
2.3
36
28 270
21/10/149
Ptaszków IG-1
159
3.3
20
7.4
18
370
0.7
18
8 400
21/10/160
Krynica Morska
565
4.3
59
96
14
371
2.0
45
16 000
21/10/161
Krynica Morska
355
4.1
78
65
2 100
25
158
2.1
3 280
21/10/166
Krynica Morska
260
5.3
33
35
33
230
2.9
29
7 500
21/10/169
Krynica Morska
457
7.8
65
97
33
83
5.3
53
20 780
48
80
21/10/160
60
40
20
0
U
Th
La
V
Yb
Cu
21/10/138
100
21/10/142
% leaching efficiency
100
21/10/142
80
21/10/160
60
40
20
0
U
Th
La
V
Yb
Cu
metal
metal
Fig.1. Efficiency of acid leaching (10% H2SO4) of sandstones from Peribaltic Syneclise.
Fig.3. Efficiency of alkaline leaching (8% NaOH/18%
Na2CO3) of sandstones from Peribaltic Syneclise.
NaHCO3 and 8% NaOH/18% Na2CO3) were used
as leaching solution (Figs.2 and 3). These experiments show that the alkaline leaching is more selective than acidic leaching. In the post-leaching
solutions only uranium, vanadium, and copper
were detected.
of reagents, leaching mode, temperature, and particle size of ground ores. The effect of these factors was tested as well.
It is expected that the present project will provide the data answering the question whether indigenous resources can be considered as a potential reserve of uranium for Polish nuclear reactors
in the future.
The studies were supported by PO IG
01.01.02-14-094-09-00 research grant “Analysis of
the possibility of uranium supply from domestic
resources”.
100
21/10/138
80
21/10/142
21/10/160
60
40
References
20
0
U
Th
La
V
Yb
Cu
metal
Fig.2. Efficiency of alkaline leaching (5% Na2CO3/5%
NaHCO3) of sandstones from Peribaltic Syneclise.
When 5% Na2CO3/5% NaHCO3 was used as the
leaching solution, the yield of recovery of uranium
was low (20÷52%) (Fig.2). However, the leaching
with 8% NaOH/18% Na2CO3 was very satisfactory.
The almost complete extraction of uranium was
observed in that case (Fig.3).
The efficiency of uranium leaching also depends on other factors such as the concentration
[1]. Ciepiela D.: Energetykę jądrową na świecie czeka świetlana przyszłość (Nuclear power in the world waiting
for a bright future). http://www.elektrownia-jadrowa.
pl/energetyke-jadrowa-na-swiecie-czeka-swietlana-przyszlosc-html (2011), in Polish.
[2]. International status and prospects of nuclear power,
2010 edition. International Atomic Energy Agency,
Vienna 2011. http://www.iaea.org/books.
[3]. Miecznik J.B., Strzelecki R., Wołkowicz S.: Prz. Geol.,
59, 10, 688-697 (2011), in Polish.
[4]. Chajduk E., Kalbarczyk P., Dudek J., Polkowska-Motrenko H.: Isotope ratio measurements for uranium by
quadrupole-based inductively coupled plasma mass
spectrometry. In: INCT Annual Report 2010. Institute
of Nuclear Chemistry and Technology, Warszawa 2011,
pp. 77-78.
SYNTHESIS OF URANIUM DIOXIDE MICROSPHERES
BY WATER AND NITRATE EXTRACTION
FROM URANYL-ASCORBATE SOLS
Marcin Brykała, Andrzej Deptuła, Wiesława Łada, Tadeusz Olczak, Danuta Wawszczak,
Tomasz Smoliński
A new method for the synthesis of uranium dioxide
microspheres has been developed. It is a variant
of our patented complex sol-gel process (CSGP)
which has been used to synthesize high-quality
powders of a wide variety of complex oxides and
oxide compounds. In the new method, uranyl nitrate-ascorbate sols (alkalized by aqueous ammonia) were emulsified in 2-ethylhexanol-1 containing SPAN 80. Drops of emulsion were gelled by
extraction of water by solvent. The technique exhibited two serious disadvantages: long gelation
time and destruction of the microspheres during
thermal treatment owing to highly reactive components in the gels (ascorbic acid – ASC, NH4+,
NO3–). We, therefore, modified the gelation step by
simultaneously extracting water and nitrates using
Primene JMT (commercial name of aliphatic
amines, principally C18H37N2). We observed more
than one order of magnitude decrease in gelation
time, and the microspheres remained intact during heating, even when using relatively high (10
o
C/min) heating rates. The final thermal treat-
ment step was reduction at 1100oC in a gas mixture atmosphere containing hydrogen. Because of
the presence of ascorbic acid in the gels, the sinterability of the spherical powders was higher than that
of routinely synthesized uranium dioxide powder.
Uranium dioxide is the principal compound
used as nuclear fuel, either in the natural form or
enriched in 235U. For the present generation of
nuclear reactors, uranium dioxide powder is synthesized by various routes (e.g. thermal decomposition and reduction of U(VI) to U(IV) of simple
uranium substrates, such as uranium trioxides,
ammonium poliuranates or uranyl nitrate). If enriched UF6 is used, then the defluorinating step is
necessary, followed by further processing to UO2.
Finally, UO2 powders are pressed to pellets and
after sintering loaded into fuel rods.
Nuclear fuels of spherical shape are proposed
for IV generations of power nuclear reactors (e.g.
high temperature gas cooled reactors). The main
Fig.1. Flow chart of preparation of uranium dioxide in the
form of microspheres (< 100 μm) by CSGP and IChTJ
processes.
49
and the most popular method for fabrication of
uranium-containing spherical particles is the sol-gel process. It is a chemical method which mainly
involves the gelation of droplets of sol to the desired fuel material into gel microsphere. Afterwards, the gels are washed, dried and thermally
treated to obtain high density microspheres [1, 2].
At the Institute of Nuclear Chemistry and
Technology (INCT), a new method of synthesis of
uranium dioxides has been elaborated, by a new
variant of the sol-gel method – complex sol-gel
process (CSGP) [3, 4]. The main modification step
is the formation of uranyl-nitrate-ascorbate sols
from components alkalized by aqueous ammonia.
By applying of IChTJ process [5], final products
are obtained in the shape of medium-sized spherical particles with a diameter below 100 μm [6].
According to our best knowledge, CSGP has
never been applied for the preparation of uranium
dioxide [7]. It is important to recognize that the
sols and gels are not in thermodynamic equilibrium,
and their properties depend critically on the preparation conditions. Consequently, the effects of
changes in the conditions were difficult to predict,
and studies were conducted for the development
of the best parameters requested for these complexes. The following reagents were used: uranyl
nitrate (Chemapol Praha), ascorbic acid pharmaceutical grade (Takeda Europe GmBH), 2-ethylhexanol-1 (Acros Organics, 99%), SPAN-80 (Fluka),
and Primene JMT (Fluka). Gels and products were
characterized by the following methods: thermogravimetric analysis (TG) and differential thermal
analysis (DTA) with a Hungarian MON Derivatograph, scanning electron microscope (SEM)
observation with a Zeiss DSM 942 and Jeol
JSM64-90LV.
The CSGP and IChTJ processes applied to the
synthesis of spherical particles of uranium dioxide
consist of following steps which are shown in
Fig.1.
The first step of the method consists in the formation of complex solution – uranyl-nitrate-ascorbate sol (mole ratio U/ASC = 1) by addition of a
very strong complexing agent – ascorbic acid – this
is the salient feature of CSGP process. Afterwards,
partial hydrolysis by addition of ammonia solution
to a certain pH value before precipitation (approx.
pH ~ 4) is carried out. The results of potentiometric titration with ammonium hydroxide, of
various ascorbate-uranyl sols (0.001 M) obtained
Fig.2. Potentiometric titration of 0.001 M UO2(NO3)2 with
ammonia (0.1 M); MR – mole ratio.
50
from uranyl nitrate, are shown in Fig.2. In the
sample without ascorbic acid, we can observe a
small plateau in the pH region of ~6 (mole ratio
NH4OH/U = 3), connected with polymerization
of uranyl ion to polynuclear ions, followed by a
definite increase in pH (inflection point at approx.
mole ratio = 3.5), representing formation of ammonium polyuranates in the solution. These effects
are considerably disappearing with an increase in
ASC concentration, which confirms strong complexing ability of this reagent. Evidently, a value
of inflection points is proportionally higher with
an increase in the mole ratio ASC/U.
The next step, which influences obtaining of
the desired shape of final product, is the gelation
of complex sol. The sols can be gelled: into irregular agglomerates by evaporation of water; to
spherical particles, like kernels (Ø > 200 μm) by
internal gelation; and to medium sized spherical
particles (Ø < 100 μm) by modified external gelation – IChTJ process (Fig.1). The products, after
this part of method, are shown in Fig.3.
Fig.3. SEM of spherical particles of ascorbate-uranyl gel.
The final step of the combination of CSGP and
IChTJ processes is a non-destructive thermal
treatment with reduction U(VI) to U(IV). The
uranyl-nitrate-ascorbate gels were annealed according to the temperatures indicated by the results of thermal analysis – TG, DTA (Fig.4).
The first weight loss of all obtained gels, at
temperatures of 100-300oC, is connected to evaporation of molecular water and splitting the hy-
Fig.4. Thermal analysis (TG, DTA) of ascorbate-uranyl
gels.
droxide groups, but it is also connected to the decomposition of U-ASC-NO3-NH4OH gel when
one of the components – ammonium nitrate – decomposes with explosion. This means that thermal
treatment requests special procedures to avoid explosions. The simplest way was the application of
low heating rate (1-2 oC/min) to a temperature of
250oC, when the decomposition of ammonium nitrate occurs. Unfortunately, despite this procedure,
the spherical particles are chipped (Fig.5A).
Consequently, a new method of gelation sols
to spherical particles has been elaborated. This
procedure consists of the following steps: 1 M
uranyl-nitrate-ascorbate sols (alkalized with aqueous ammonia) were emulsified in 2-ethylhexanol-1
(2EH) containing SPAN 80. The gelation step was
modified by simultaneously extracting of water by
2EH and nitrates using Primene JMT. The volume
of used Primene JMT is 2% of the 2EH volume.
We observed that the microspheres remained intact during heating, even when using relatively
high (10 oC/min) heating rates (Fig.5B). These
positive results are the effect of lower concentration of nitrates in U-ASC-NO3-NH4OH, and consequently much less content of potentially explosive ammonium nitrate.
Fig.5. SEM of triuranium octoxide in the shape of spherical particles obtained by: A – IChTJ process, B – double extraction process.
For both curves, the next weight loss, with broad
exothermic effect at 400-600oC, is connected with
the combustion of ASC and the products of its decomposition. After that, the weight is stable and
represents the formation of triuranium octoxide
(U3O8).
The obtained triuranium octoxide was then reduced to uranium dioxide in the 5% hydrogen and
95% nitrogen atmosphere at a temperature of
900oC.
In conclusion, a new technique of gelation of
uranyl sols obtained from uranyl nitrate has been
elaborated. This modification (simultaneous extraction of water and nitrate anions) eliminates
the serious disadvantage – the destruction of microspheres during thermal treatment, which is
connected with violent decomposition of ammonium nitrates formed in time of alkalization of
uranyl-nitrate-ascorbate sol by ammonium hydroxide. After that, even relatively high heating
rates (10 oC/min) can be used.
It is necessary to underline that the preparation of uranyl gels from uranyl nitrate by extraction of nitrates without addition of ascorbic acid is
not possible.
The work has been carried out within the Collaborative Project ACSEPT (Actinide Recycling
by Separation and Transmutation), contract No.
FP7-CP-2007-211267.
51
References
[1]. Sood D.D.: J. Sol-Gel Sci. Technol., 59, 404 (2011).
[2]. Vaidya V.N.: J. Sol-Gel Sci. Technol., 46, 369 (2008).
[3]. Deptuła A., Brykała M., Łada W., Wawszczak D., Olczak T., Chmielewski A.G.: Method for obtaining uranium dioxide in the form of spherical and irregular
grains. Polish Patent Aplication No. P-389385 (2009);
UE Patent No. 101884385-1218 (2010); Russian Federation Patent Application No. 2010 136670; Republic
of Belarus Patent Application No. 2010 1305; Ukrainian Patent Application No. 2010 10756.
[4]. Deptuła A., Brykała M., Łada W., Olczak T., Wawszczak D., Modolo G., Daniels H., Chmielewski A.G.:
Synthesis of uranium dioxides by complex sol-gel processes (CSGP). In: Proceedings of the 3rd International Conference on Uranium, 40th Annual Hydrometallurgy Meeting, Saskatoon, Saskatchewan, Canada.
Vol.II. 2010, pp. 145-154.
[5]. Deptuła A., Hahn H., Rebandel J., Drozda W., Kalinowski B.: Sposób wytwarzania sferycznych ziaren
tlenków metali (Method for preparing spherical grains
of metal oxides). Polish Patent No. 83484, (1977).
[6]. Deptuła A., Brykała M., Łada W., Olczak T., Sartowska B., Chmielewski A.G.: Fusion Eng. Des., 84, 681
(2009).
[7]. Deptuła A., Łada W., Olczak T., Lanagan M.T., Dorris
S.E., Goretta K.C., Poeppel R.B.: Sposób wytwarzania
nadprzewodników wysokotemperaturowych (Method
for preparing of high temperature superconductors).
Polish Patent No. 172618 (1997).
SYNTHESIS OF PEROVSKITE BY COMPLEX SOL-GEL PROCESS
FOR NUCLEAR WASTE IMMOBILIZATION
Tomasz Smoliński, Andrzej Deptuła, Tadeusz Olczak, Wiesława Łada, Danuta Wawszczak,
Marcin Brykała, Fabio Zaza1/, Andrzej G. Chmielewski
1/
Italian National Agency for New Technologies, Energy and Environment (ENEA), CR Casaccia,
Rome, Italy
Synroc is a kind of “synthetic rock” which has
been invented by Ringwood in 1978 [1, 2]. It has
been regarded as the second generation of high
level waste (HLW) immobilization forms in the
world. Because of higher leaching resistance and
better durability, it can be a better solution for immobilizing nuclear waste [3, 4]. Basically, Synroc
materials are a ceramic made from several natural
minerals which incorporate nearly all of the elements present in high level radioactive waste into
their crystal structures [4]. This advanced ceramics
comprises geochemically stable natural titanate
minerals which occur naturally in the earth’s crust
[5-7]. Crystal structures of these materials allow to
incorporate almost all of the elements present in
high level radioactive waste. Synroc can take many
forms which depend on the type and form of waste
[5-7]. Synroc C consist of the following materials:
perovskite (CaTiO3), zirconolite (CaZrTi2O7) and
hollandite (BaAl2Ti6O16). Long-lived actinides
such as plutonium are immobilized in perovskite
and zirconolite. Perovskite immobilizes also strontium and barium. In hollandite is immobilized
caesium, potassium, rubidium and barium. The
most common method of production of Synroc is
its synthesis in solid-state reaction. Radioactive
waste elements are added into the obtained matrixes. After that, the material is pressed and sintered. An alternative solution for synthesis of the
various Synroc materials seems to be the sol-gel
method. This method allows for the direct incorporation of radioactive elements into the mineral
structure during its formation [3]. The homogeneous distribution of the components reduces the
Fig.1. Flow chart for preparation of Sr-doped perovskite.
52
sintering temperature and increases the product
resistance to leaching of radioactive elements.
In this work, our patented complex sol-gel
process (CSGP) [8, 9] was used to synthesize the
perovskite capable of incorporating significant
amounts of high level nuclear waste. The goal of
this work was limited to incorporating strontium
into titania ceramic, and studing the course of reaction and characterizing the final product.
The flow-chart of the preparation of Sr-doped
(mole 10%) titanate gels is shown in Fig.1. Commercial TiCl4 was introduced via pumping into
dechlorination step [8, 9]. During the dechlorination step, we observed decomposition and vigorous evolution of gas, due to oxidation of the ASC
by the nitrates. The resulting sols were nearly
transparent, pale yellow in colour, and stable. This
sol was used to produce perovskite of various
composition.
Thermal treatments were conducted in air.
Gels and final powders were characterized by
thermogravimetric analysis (TGA) and differential
thermal analysis (DTA). All the resulting products
were analysed by X-ray diffraction (XRD) as well.
Fig.2. Thermal analysis of gel powders dried at 105oC: (1) CaTiO3, (2) CaTiO3 + ASC, (3) CaTiO3 + 10% Sr, (4) CaTiO3
+ 10% Sr + ASC.
concentrated HCl. The titanium concentration
was ca. 4 mol/L. The main preparation step consisted of chloride elimination [8] by distillation
with nitric acid, addition of hydroxides of Ca and
Sr (mole 10%), evaporation of water and hydrochloric acid from sols to dry substance, grinding,
and thermal treatment to titanates of Ca and Sr.
There were synthesized four samples: CaTiO3
(P1), CaTiO3 + ASC (P2), CaTiO3 + 10% Sr (P3),
CaTiO3 + 10% Sr + ASC (P4).
To prevent precipitation we added ascorbic
acid (ASC) to samples P2 and P4 before the
The thermal decomposition of gels dried under
vacuum at 80oC is illustrated in Fig.2. For all four
gels, the loss of mass, Δm, became significant
above 120oC. TGA traces revealed systematic escape of volatile substance without clearly defined
thermal effects. Distinct exothermic effects have
been observed above 500oC, which was connected
to the formation of crystalline phase of perovskite.
In the samples prepared with ASC addition (P2,
P4) this temperature was lower.
The samples P1 and P2 treated at 450oC were
essentially amorphous. The samples containing
Fig.3. XRD patterns of titania gels cacined for 2 h at various temperatures.
53
Table. The samples analysed by XRD.
Samples
T [oC]
Chemical nature
Structure order/
disorder
Lattice systems
Size [nm]
P1
1200
CaTiO3
crystalline
orthorhombic
27.7
P2
1200
CaTiO3 (with ASC)
crystalline
orthorhombic
21.8
P3
1200
Sr0.1Ca0.9TiO3
crystalline
orthorhombic
22.4
P4
1200
Sr0.1Ca0.9TiO3 (with ASC)
crystalline
orthorhombic
22.4
P1
700
CaTiO3
crystalline
orthorhombic
27.6
P2
700
CaTiO3 (with ASC)
crystalline
orthorhombic
25.9
P3
700
Sr0.1Ca0.9TiO3
crystalline
orthorhombic
20.7
P4
700
crystalline
orthorhombic
23.0
P1
450
CaTiO3
amorphous
-
-
P2
450
CaTiO3 (with ASC)
amorphous
-
-
P3
450
Sr0.1Ca0.9TiO3
amorphous
-
-
P4
450
amorphous
-
-
strontium, small bands (presumably of non-reacted substrates) are observed. The samples calcined
at 700oC were fully crystalline and had a perfect
orthorhombic structure (Fig.3). This temperature
is significantly lower than that reported when
solid state reaction had been used [2]. The average crystallite sizes of our samples is between 20
to 28 nm (Table). Crystalline structure of synthesized perovskites is shown in Fig.4.
The Synroc materials – perovskite CaTiO3 also
Sr0.1Ca0.9TiO3, were synthesized directly by using
Fig.4. Crystalline structure: (1) Ca or Sr, (2) Ti, (3) O.
the complex sol-gel process. The gels prepared
from stable, transparent titanium-nitrate sols with
ASC addition, formed crystalline titanate phases
at lower temperatures than did gels without this
additive. The added strontium is homogeneously
distributed in the crystalline structures. The very
small crystallite size (20-28 nm) allows us to assume
that powders will be easy tractable by pressing and
sintering.
The complex sol-gel process for synthesizing of
Synroc material seems to be advantageous in comparison to conventional methods. Consequently,
we are going to synthesize other Synroc materials
containing various HLW (e.g. Cs, Co, and U or actinide surrogates e.g. Nd). We expect their increased
resistance to radionuclide leaching and improved
durability.
References
[1]. Ringwood A.E., Kesson S.E., Ware N.G., Hibberson
W., Major A.: Nature, 278, 219-223 (1979).
[2]. Ringwood A.E.: Am. Sci., 70, 2, 201-207 (1982).
[3]. Ringwood A.E., Oversby V.M., Kesson S.E., Sinclair
W., Ware N., Hibberson W., Major A.: Nucl. Chem.
Waste Manage., 2, 4, 287-305 (1981).
[4]. Ringwood A.E., Kessom S.E., Ware N.G., Hibberson
W.O., Major A.: Geochem. J., 13, 141-165 (1979).
[5]. Ojovan M.I., Lee W.E.: An introduction to nuclear
waste immobilization. Vol.1. Elsevier, London 2005,
316 p.
[6]. Woignier T., Reynes J., Phalippou J., Dussossoy J.L.: J.
Sol-Gel Sci. Technol., 19, 833-837 (2000).
[7]. Clarke D.R.: Ann. Rev. Mater. Sci., 13, 191-218 (1983).
[8]. Deptula A., Lada W., Olczak T., Lanagan M.T., Dorris
S.E., Goretta K.C., Poeppel R.B.: Sposób wytwarzania
nadprzewodników wysokotemperaturowych (Method
for preparing high-temperature superconductors). Polish
Patent No. 172618 (1997).
[9]. Deptuła A., Olczak T., Łada W., Sartowska B., Chmielewski A.G., Casadio S., Alvani C., Croce F., Goretta
K.C., Di Bartolomeo A.: Fabrication of spherical and
irregularly shaped powders of Li and Ba titanates from
titanium tetrachloride by inorganic sol-gel process. In:
Advances in Science and Technology 30, 10th International Ceramic Congress – Part A. Techna Srl, 2003,
pp. 441-452.
CENTRE FOR RADIOBIOLOGY
AND BIOLOGICAL DOSIMETRY
The Centre continued and completed the projects that were carried out in 2010. Studies carried
out in 2011 concentrated on two main topics: validation, adaptation and implementation of
various biodosimetric methods and biological effects of nanoparticles.
The biodosimetric methods can be divided into two categories: the first category is for radiation dose estimation in a multiparametric triage test for nuclear and radiological mass-casualty
incidents (supported by the European Union Structural Funds and Ministry of Regional Development, Poland, project No. POIG.01.03.01-14-054/09). The second category of methods is
that of cytogenetic methods and the work has been carried out in a close international cooperation in the frame of the European Union MULTIBIODOSE (241536 FP7-SECURITY
SEC-2009-4.3-02 Bio-dosimetric tools to manage radiological casualties) programme. It comprises, among others, validation of automating the scoring and implementation of telescoring
of the standard biodosimetric cytogenetic methods (dicentric assay, micronucleus test) as well
as optimization and validation of the γ-H2AX assay as a rapid triage device for a mass casualty scenario. The participation involves cooperation with other European laboratories, exchange of samples and microscopic preparations in order to unify the procedures and training.
Our contributions to the POIG.01.03.01-14-054/09 and MULTIBIODOSE programmes were
presented at the 1st International Nuclear Energy Congress (Warszawa), the 19th Nuclear
Medical Defence Conference (Monachium) and the XIV International Congress of Radiation Research (Warszawa).
As both programmes are targeted at testing large groups of potential victims, time is an
important factor and the speed of analysis counts more than accuracy. Hence the necessity to
establish automated, high-throughput, cytogenetic biodosimetry methods to process a large
number of samples for conducting the assays using peripheral blood from exposed individuals
according to internationally accepted protocols
(i.e. within days following radiation exposures).
The Centre is being prepared to participate in
triage tests with the use of various methodological approaches. An automated metaphase
finder and micronucleus finder is presently used
for validation of the biodosimetric methods.
The nanoparticle project is carried out in
the frame of the Polish Norwegian Research
Fund (PNRF-122-AI-1/07) in cooperation with
several laboratories (Norwegian Institute of Air Image analysis system METAFER 4, Metasystems with a
Research, Norwegian Institute of Public Health, Zeiss fluorescent microscope at the Centre for Radiobiology
National Institute of Public Health – National and Biological Dosimetry.
Institute of Hygiene, Warsaw University of Life
Sciences). During 2011, we studied the effects of DNA damage induced by treatment with
uncoated silver nanoparticles (Ag NP) 20 nm or 200 nm particles and titanium dioxide nanoparticles (TiO2 NP) 21 nm in three human cell lines: hepatocellular liver carcinoma HepG2,
colorectal adenocarcinoma HT29 and lung carcinoma A549. It was also presented at the
Annual Meeting of the Polish Biochemical Society in Kraków.
In cooperation with the Jena University, in the frame of the Ministry of Science and Higher
Education grant DPN/N23/NIEMCY/2009, we continued the study of the role of conjugated
linoleic acids (CLA) in the cellular response to X-rays. We have previously found that the
X-irradiated colon cancer HT-29 cells become markedly radiosensitized in result of culture in
a CLA complemented medium and this is accompanied by an impaired repair of DNA double
strand breaks. These data were further completed by determination of the formation and decay of the γ-H2AX “repair foci”, examination of the extent of chromosome fragmentation with
the use of the premature chromosome condensation (PCC) method and recently, by analysis of
lipid raft properties. These results were presented at the Annual Meeting of the Polish Biochemical Society and at the XIV International Congress of Radiation Research (Warszawa).
Three PhD theses were defended in 2011 by the Centre’s PhD students. During 2011, 12
papers were published and 26 posters and lectures presented at meetings in Poland or abroad,
and also at the 14th International Congress of Radiation Research that took place in Warszawa (28th August-1st September). The congress was organized by the Polish Radiation Research Society under the auspices of the Polish Presidency of the European Union Council.
Anna Lankoff and Marcin Kruszewski worked in the Organizing Committee, Irena Szumiel
– in the Scientific Committee. Most of the younger members of the Centre also participated
as volunteers in various organizational tasks during the sessions and symposia.
57
OPTIMIZATION OF A FINGER-PRICK BLOOD COLLECTION METHOD
FOR THE γ-H2AX ASSAY: POTENTIAL APPLICATION
IN POPULATION TRIAGE
Maria Wojewódzka, Anna Lankoff, Marcin Kruszewski
Accurate methods for measuring the biological effects of radiation are critical for estimating the
health risk from radiation exposure. Foci of γ-H2AX
which form in response to radiation-induced DNA
double strand breaks and can be quantified by immunofluorescence microscopy or flow cytometry
have been considered for application in population
triage [1-3]. However, application of this method
as a triage tool in large-scale radiological accidents
demands immediate blood collection and high
throughput sample processing and analysis. Since
the γ-H2AX foci scoring assay seems to be the
most sensitive to ionizing radiation, the aim of our
study was to optimize a finger-prick blood collection method for the automated γ-H2AX assay in
relation to various blood storage conditions.
Peripheral whole blood was collected from five
healthy volunteers. For each donor, blood samples
were irradiated with 250 kV X-rays (0, 0.2, 0.4, 0.6,
0.8, 1, 1.5, 2, 3, 4 Gy). After irradiation, one set of
samples was incubated at 37oC for 30 min. Three
other sets of samples were incubated at 0 and 37oC
for 24 h, followed by 30 min incubation at 37oC.
Blood samples (50 μl) were mixed with 900 μl of
medium and loaded into eppendorf tubes containing 100 μl of Histopaque 1077. The samples were
spun two times at 2000 g for 3 min. The cells were
spotted onto slides with a cytospin at 490 g for 10
min, fixed in paraformaldehyde for 30 min and
permeabilized/blocked in KCMT buffer (120 mM
KCl, 20 mM NaCl, 10 mM Triton, 1 mM EDTA)
containing 2% BSA and 10% low fat milk for 1 h at
temperature. Slides were mounted with DAPI Vectashield and analysed with an automated image
acquisition and analysis system Metafer (Metasystems, Germany).
Our results revealed that the number of γ-H2AX
foci was linearly related to the radiation dose. The
number of radiation-induced γ-H2AX foci obtained for samples incubated at 37oC for 30 min was
comparable to that for samples incubated at 0oC
for 24 h followed by 30 min incubation at 37oC
(Figs.1 and 2). This result points to the possibility
of sample storage in situations when very high
Fig.2. Dose response curve for radiation-induced γ-H2AX
foci in human peripheral blood lymphocytes incubated at
0oC for 24 h followed by 30 min incubation at 37oC.
numbers of samples have to be analysed in the
frame of a triage procedure. The number of radiation-induced γ-H2AX foci obtained for samples
incubated at 37oC for 24 h decreased significantly,
irrespective of the radiation dose (not shown). Also,
we observed that the inter-individual variation in
the number of spontaneous γ-H2AX foci (2-7 per
cell) was related to various blood storage conditions. To conclude, our finger-prick blood collection method for the γ-H2AX assay allows to obtain reproducible and quantitative results using
small aliquots of blood and appears to have a potential use for rapid population triage in case of a
large-scale radiological event.
References
Fig.1. Dose response curve for radiation-induced γ-H2AX
foci in human peripheral blood lymphocytes incubated at
37oC for 30 min.
room temperature. The cells were incubated with
monoclonal γ-H2AX antibody for 1 h, washed in
PBS and incubated with FITC-conjugated goat
anti-mouse secondary antibody for 45 min at room
[1]. Rothkam K., Horn S.: Ann. Ist. Super. Sanita, 45,
265-271 (2009).
[2]. Horn S., Barnard S., Rothkamm K.: PLoS ONE, 6,
e25113 (2011).
[3]. Roch-Lefevre S., Mandina T., Voisin P., Gaëtan G.,
Mesa J.E., Valente M., Bonnesoeur P., García O., Voisin
P., Roy L.: Radiat. Res., 174, 185-194 (2010).
58
CLONOGENIC ABILITY DOES NOT CORRESPOND TO DNA DAMAGE
INDUCED IN HUMAN CELLS TREATED IN VITRO
WITH SILVER AND TITANIUM DIOXIDE NANOPARTICLES
Iwona Grądzka, Teresa Bartłomiejczyk, Teresa Iwaneńko, Maria Wojewódzka, Anna Lankoff,
Maria Dusinska1/, Gunnar Brunborg2/, Irena Szumiel, Marcin Kruszewski
1/
2/
Norwegian Institute of Air Research, Oslo, Norway
Norwegian Institute of Public Health, Oslo, Norway
Due to their antibacterial properties, silver nanoparticles (Ag NP) have been integrated into hundreds of consumer products. They have also found
numerous technical and medical applications. It is
generally agreed that the oxidative stress is the
main cause of the Ag NP-induced effects at the
cellular level, such as genotoxicity and mutagenicity, disturbed mitochondrial respiration, impaired
proliferation and apoptotic death. These effects
may be the potential cause of toxicity of Ag NP
and are sufficient to raise concern for the human
health and the environment [1]. Although Ag NP
and TiO2 NP (titanium dioxide nanoparticles) belong to the NP most often studied, the mechanisms
of their biological effects are still not fully understood. Moreover, there are numerous discrepancies
in the reports on the extent of DNA damage induced by Ag NP in various mammalian cells in in
vitro studies [2]. Some of these discrepancies may
be due to the different properties of Ag NP preparations, such as their size, since they are prepared
according to different protocols, uncoated or coated with polymers such as polyvinylpyrrolidone,
polyethylenimine or starch. Additionally, different
treatment protocols involve preliminary NP dispersion, e.g. in either a BSA (bovine serum albumin)
or an FCS (foetal calf serum) containing medium.
Finally, cell type may affect the resulting extent of
genotoxic damage. There are relatively few data
on NP genotoxicity and no attempt has been made
to directly relate DNA damage to clonogenicity
loss.
Therefore, we undertook studies of the effects
of DNA damage induced by treatment with uncoated Ag NP 20 nm or 200 nm particles and TiO2
NP 21 nm in three human cell lines: hepatocellular liver carcinoma HepG2, colorectal adenocarcinoma HT29 and lung carcinoma A549. The end-points examined were DNA breakage estimated
by the comet assay and oxidative base damage
recognized by formamido-pyrimidine glycosylase
(FPG) and estimated with the FPG + comet assay,
frequencies of histone γ-H2AX foci and micronuclei, apoptosis and clonogenic survival. Each cell
line had a different pattern of DNA breakage and
base damage vs. NP concentration and time of treatment.
Figure illustrates the sensitivity difference to
applied NP treatment between the resistant A549
cells and the sensitive HepG2 cells. However, after
24 h treatment, these differences became smaller.
Titania NP were the least damaging in all cell lines.
Interestingly, there were no increases in the frequencies of histone γ-H2AX foci and micronuclei
A
B
Fig. DNA damage (single stand breaks, SSB, and base
damage recognized by FPG in cells treated with Ag NP or
Ag 200 nm particles and TiO2 NP for 2 h at concentrations
indicated: A – A549 cells, B – HepG2 cells; asterisks mark
the statistically significant difference from control (Student’s
t-test).
as compared to those in the untreated cells. This
means that the DNA damage types do not include
double strand breaks (DSB). The reported experiments provided no data that would directly correlate DNA damage induced by Ag NP or TiO2 NP
to early apoptosis or loss of clonogenic ability.
References
[1]. AshaRani P.V., Hande M.P., Valiyaveettil S.: BMC
Cell Biol., 10, 65 (2009).
[2]. Karlsson H.L.: Anal. Bioanal. Chem., 398, 651-666
(2010).
59
COMPARISON OF FREQUENCIES OF DICENTRIC CHROMOSOMES
AND HISTONE γ-H2AX FOCI
IN HUMAN LYMPHOCYTES X-IRRADIATED AT 4, 20 AND 37OC
Anna Lankoff, Sylwester Sommer, Iwona Buraczewska, Teresa Bartłomiejczyk,
Teresa Iwaneńko, Halina Lisowska1/, Aneta Węgierek-Ciuk1/, Irena Szumiel, Iwona Wewiór,
Anna Banasik-Nowak1/
1/
Department of Radiobiology and Immunology, Jan Kochanowski University, Kielce, Poland
In the frame of experiments aimed at validation,
adaptation and implementation of various biodosimetric methods we carried out a comparison of
frequencies of dicentric chromosomes and histone
γ+H2AX foci in human lymphocytes X-irradiated
at 4, 20 and 37oC. The effect of temperature at
which human lymphocytes are X-irradiated on dicentric chromosome frequency was first described
by Bajerska and Liniecki [1] and recently further
examined [2]. As it may affect the cytogenetic
evaluation of ionizing radiation dose, the temperature effect is both of practical and basic science
interest.
The experiments were carried out on blood
taken three times from four healthy male donors.
Mononuclear cells were isolated from the peripheral blood samples, suspended in the RPMI 1640
medium supplemented with foetal calf serum, antibiotics, L-glutamine and phytohaemagglutinin at
three temperatures mentioned above. After 30 min
incubation at the three temperatures, all samples
were irradiated with 0, 0.5, 1, 1.5, 2, 2.5 and 3 Gy
of γ 60Co (Siemens Theratron Elite 80) at a dose
rate of 1.1 Gy/min. Standard procedures were applied for the chromosomal microscopic preparations [3] and cell samples for the flow cytometric
determination of histone γ-H2AX foci [4].
Figure shows the three dose-effect curves for
dicentric chromosomes in peripheral blood lymphocytes γ-irradiated at three different tempera-
Fig. Dose-effect curves for dicentric chromosomes irradiated at three different temperatures, as indicated; each point
represents mean value with standard deviation indicated.
Asterisks mark statistically significant differences between
irradiation temperatures 4 and 37oC at doses 2, 2.5 and 3 Gy
(p < 0.05).
tures; each point represents mean value from 12
results (4 donors x 3 replicates). The dose-effect
curves were described by the following linear-quadratic equations (D – dose):
4oC: y = 0.002 + 0.024 · D + 0.024 · D2
20oC: y = 0.008 + 0.028 · D + 0.027 · D2
37oC: y = 0.008 + 0.025 · D + 0.038 · D2
Looking for the significance of differences between
aberration frequencies after irradiation at various
temperatures, we analysed the variance values at
experimental points for the respective doses (not
shown). No differences were found between temperatures 4 and 20oC, as well as 20 and 37oC. Statistically significant differences between irradiation temperatures 4 and 37oC were found at doses
2, 2.5 and 3 Gy (Fig.). Also, aberration distribution for each dose and irradiation temperature
was analysed to see whether it deviates from the
normal Poisson distribution. To this end, dispersion indices (variance-to-mean ratios) were calculated and used to calculate the u function, i.e. normalized dispersion index [5]. Their values (not
shown) are between the -1.96 to +1.96 limits, indicating no deviation from the Poisson distribution.
Further, the flow cytometric determination of
γ-H2AX foci was carried out at 1 and 24 h after
irradiation at the respective temperatures. The
dose-effect curves obtained were described by the
following linear equations:
4oC: y = 9.052 + 9.789 · D
20oC: y = 7.857 + 5.925 · D
37oC: y = 6.926 + 5.702 · D
Variance analysis showed no differences in the
total histone γ-H2AX fluorescence at 1 h after irradiation between the same doses and temperatures of exposure to γ rays, in contrast with the
data for dicentric chromosomes. The total histone
γ-H2AX fluorescence at 24 h after irradiation was
lower from that at 1 h independently of the exposure temperature. Fluorescence decrease (FD) was
calculated as
FD = (F1 – F24) · 100/F1
where F1 – fluorescence measured at 1 h post irradiation [%], F24 – fluorescence measured at 24 h
post irradiation [%]. FD was about 90%, i.e. close
to the control values, notwithstanding the dose
(F = 0.949, p = 0.458) or temperature at which irradiation was carried out (F = 1.612, p = 0.121).
On the one hand, the presented results point
to a lack of effect of the exposure temperature on
the initial double strand break level, as measured by
the γ-H2AX foci fluorescence. On the other hand,
the altered, temperature-dependent frequency of
dicentric chromosomes may be taken as indication
that the exposure temperature affects the fidelity
of double strand break rejoining.
References
[1]. Bajerska A., Liniecki J.: Int. J. Radiat. Biol., 16, 483-493
(1969).
60
[2]. Brzozowska K., Johannes C., Obe G., Hentschel R.,
Morand J., Moss R., Wittig A., Sauerwein W., Liniecki
J., Szumiel I.,Wojcik A.: Int. J. Radiat. Biol., 85, 891-899
(2009).
[3]. Sommer S., Buraczewska I., Wojewodzka M., Boużyk
E., Szumiel I., Wojcik A.: Int. J. Radiat. Biol., 81, 741-749
(2005).
[4]. Jucha A., Węgierek-Ciuk A., Koza Z., Lisowska H.,
Wójcik A., Wojewódzka M., Lankoff A.: Mutat. Res.,
696, 16-20 (2010).
[5]. Radhakrishna C.R., Chakravarti I.M.: Biometrics, 12,
264-282 (1956).
THE EFFECT
OF CONJUGATED LINOLEIC ACID (CLA) SUPPLEMENTATION
ON LIPID RAFT PROPERTIES AND RADIOSENSITIVITY
OF HUMAN COLON CANCER HT-29 CELLS
Iwona Grądzka, Barbara Sochanowicz, Kamil Brzóska, Grzegorz Wójciuk, Christian Degen1/,
Gerhard Jahreis1/, Irena Szumiel
1/
Institute of Nutrition, Friedrich Schiller University of Jena, Germany
Ionizing radiation-generated reactive oxygen species activate epidermal growth factor receptor
(EGFR) in the plasma membrane. Instead of being degraded upon internalization (as it takes place
after the ligand binding), thus activated EGFR
migrates to the nucleus in vesicles formed of caveolin-enriched lipid rafts. Translocation of the receptor is required for activation of DNA-dependent protein kinase (DNA-PK) – the key enzyme
of the non-homologous end joining (NHEJ), the
leic acid (c9,t11-CLA) which is the main isomer in
a mixture of CLA, derivatives of linoleic acid (LA,
C18:2, cis-9, cis-12), with two double bonds separated from each other by one single bond. CLA
are natural components of diary products and meat
of ruminants. C9,t11-CLA sensitizes human colon
cancer HT-29 cells to X-radiation (dose modification factor, D0 control/ D0 CLA = 1.55). The increase in radiosensitivity is not due to changes in
cell cycle progression or a decrease in DNA repair-
Fig.1. Distribution of EGFR and cav-1 among cellular membrane fractions. HT-29 cells were cultured without or with
70 μM c9,t11-CLA for 22 h, then irradiated with a dose of 5 Gy. Fifteen minutes after irradiation, membrane vesicles
were prepared according to a detergent-free method [1] and fractionated by flotation through OptiPrep gradients. 100 μl
aliquots of each fraction were subjected to Western blot analysis. A representative experiment of the three performed is
shown. Abbreviations for the experimental groups are in the text.
major double strand DNA break (DSB) repair
system in mammals. We examined the radiosensitizing properties of 9cis,11trans-conjugated lino-
-related gene expression (not shown), but is associated with a transcription-independent decrease in
DNA-PK activity that results in transient accumu-
lation of DSB during repair. The latter, however,
is not followed by a significant increase in chromosomal aberration frequencies (not shown).
Here, we report that c9,t11-CLA influences the
distribution of EGFR, cav-1 (caveolin-1) and cholesterol in cellular membrane fractions. Fractions
of cellular membranes from HT-29 cells, obtained
with the use of a detergent-free method [1], were
analysed in terms of the content of EGFR, cav-1
and cholesterol. Localization of EGFR and cav-1
in the membrane fractions, visualized by Western
blotting, is shown in Fig.1, while Fig.2 presents the
graphs of distribution of both proteins and cholesterol, normalized to protein content. Generally, in
preparations from c9,t11-CLA supplemented cells
(CLA, X+CLA) the distributions of all the three
membrane components were shifted towards lighter
(top) fractions compared to the distributions in the
corresponding control preparations (C, X). This
appears reasonable, as the CLA isomer incorporated into cellular lipids, increasing the overall
content of unsaturated fatty acids (not shown),
which must affect the density of the membrane
vesicles. Previously, it was established, that in the
density gradient preparations from mammalian
cells the EGFR-enriched fractions designated the
position of lipid rafts [1]. In this position, covered
by fractions 8-14 in our experiments (Fig.2), a co-occurrence of EGFR and cav-1 was observed in
control (C) but not in c9,t11-CLA supplemented
(CLA) cells. X-irradiation (X) did not essentially
change the relative distribution of the proteins, but
again, in X-irradiated and CLA-supplemented cells
(X+CLA), cav-1 was displaced from the EGFR-enriched region. Interestingly, the distributions of
cav-1 and cholesterol in the preparations from
non-supplemented cells (C, X) did not correlate
with one-another, whereas they nearly overlapped
in the preparations from c9,t11-CLA supplemented cells (CLA, X+CLA).
In conclusion, CLA supplementation of cell
culture medium for 24 h changes the pattern of
cholesterol and EGFR distribution in the lipid
rafts of HT-29 cells. This is accompanied by a decreased nuclear translocation of EGFR (not shown).
As reported by Dittmann et al. [2, 3], the EGFR
import to the nuclei is indispensable for the in-
61
Fig.2. Distribution of EGFR, cav-1 and cholesterol in fractions of cell membranes. The charts are based on the data
presented in Fig.1: the Western blots were scanned and
quantified using ImageJ software; the values were normalized to total protein content of each fraction and presented
as a percentage of all fractions. In addition, cholesterol
content in each fraction was measured and the distribution
of cholesterol/protein ratio was added to the charts. The
data for EGFR, cav-1 and cholesterol are from the same
experiment – a representative of three experiments performed.
crease in DNA-PK activity in response to ionizing
radiation, thus influencing the cellular radiation
sensitivity.
References
[1]. Macdonald J.L., Pike L.J.: J. Lipid Res., 46, 1061-1067
(2005).
[2]. Dittmann K., Mayer C., Fehrenbacher B., Schaller M.,
Raju U., Milas L., Chen D.J., Kehlbach R., Rodemann
H.P.: J. Biol. Chem., 280, 31182-31189 (2005).
[3]. Dittmann K., Mayer C., Fehrenbacher B., Schaller
M., Kehlbach R., Rodemann H.P.: FEBS Lett., 584,
3878-3884 (2010).
LABORATORY OF NUCLEAR
ANALYTICAL METHODS
The Laboratory of Nuclear Analytical Methods was created on the basis of the former
Department of Analytical Chemistry in 2009. The research programme of the Laboratory has
been focused on the development of nuclear and nuclear-related analytical methods for the
application in a nuclear chemical engineering, radiobiological and environmental problems
associated with the use of nuclear power (as well as other specific fields of high technology).
New procedures of chemical analysis for various types of materials are also being developed.
The main areas of activity of the Laboratory include inorganic trace analysis as well as analytical and radiochemical separation methods. The Laboratory cooperates with the centres
and laboratories of the INCT and provides analytical services for them as well as for outside
institutions. The Laboratory has been also involved in the preparation and certification of new
certified reference materials (CRMs) for inorganic trace analysis and is a provider of proficiency testing schemes on radionuclides and trace elements determination in food and environmental samples.
The main analytical techniques employed in the Laboratory comprise: neutron activation
analysis with the use of a nuclear reactor (instrumental and radiochemical modes), inductively
coupled plasma mass spectrometry (together with laser ablation and HPLC), atomic absorption spectrometry, HPLC including ion chromatography, as well as gamma-ray spectrometry
and alpha- and beta-counting. In 2011, the research projects carried out in the Laboratory
were concerned with:
• chemical aspects of nuclear power,
• radiopharmaceuticals and health protection,
• nuclear and related analytical techniques for environment protection.
In 2011, the Laboratory participated together with the Centre of Radiochemistry and
Nuclear Chemistry in two Operational Programme Innovative Economy (PO IG) projects.
The project on the use of thorium-based fuels in nuclear power reactors was coordinated by
the Institute of Atomic Energy POLATOM. The second project on the possibilities of producing uranium from indigenous resources, and to the safety of nuclear power, including radiation protection of humans and environment was coordinated by the INCT and the Polish
Geological Institute – National Research Institute was the partner.
In 2011, the Laboratory has started participation in the strategic research project from the
National Centre for Research and Development (NCBiR), Poland No. SP/J/3/143045/11 on
bioleaching of uranium mine waste heaps. The project is coordinated by the Faculty of Biology,
University of Warsaw.
Laboratory of Nuclear Analytical Methods is a provider of proficiency tests. Two main proficiency testing schemes are conducted: (i) on the determination of man-made radionuclides
and (ii) trace elements in waters, food and environmental samples. In 2011, proficiency test on
the determination of Am-241, H-3, Pu-239 and Ra-226 in water, food and environmental
samples was conducted on the request of the National Atomic Energy Agency, Poland for
laboratories forming radiation monitoring network in Poland. Proficiency testing scheme
PLANTS 11: Determination of As, Cd, Cr, Cu, Hg, Pb, Se and Zn in dry edible mushroom
powder was provided for laboratories analysing food and environmental samples. All proficiency tests are provided following requirements of ISO/IEC 17043:2010 and IUPAC International Harmonized Protocol (2006).
64
RADIOLYTIC DECOMPOSITION OF DICLOFENAC – ANALYTICAL,
TOXICOLOGICAL AND PULSE RADIOLYSIS STUDIES
Anna Bojanowska-Czajka, Gabriel Kciuk, Magdalena Gumiela1/, Grzegorz Nałęcz-Jawecki2/,
Krzysztof Bobrowski, Marek Trojanowicz
1/
2/
Department of Chemistry, University of Warsaw, Poland
Department of Environmental Health Sciences, Medical University of Warsaw, Poland
With commonly observed in recent decades an increase of the use of human and veterinary pharmaceuticals one can observe also an increase of
the presence of their residues in the environment.
This fact together with a finding of synthetic pharmaceuticals in finished drinking water causes an
increasing concern about potential environmental
and health harmful effects. The most commonly
accepted form of toxicity associated with environmental pharmaceutical residues is endocrine disruption, which means the disruption of chemical
signalling mechanisms controlling cellular development.
First reports about detecting pharmaceuticals
in environmental samples were published in the
early 1970s [1], and in 1965 it was observed for the
fist time that residues of steroid hormones are not
completely decomposed by wastewater treatment
[2]. Since then a fast increase of interest in different aspects of the presence of pharmaceutical residues in environmental waters is observed. Number
of papers published annually was about 500 in
2000, while it reached a level of about 3000 in 2010
[3]. In a recent decade this problem was a subject
of several published books, e.g. [4], and numerous
valuable review articles in scientific journals, e.g.
[3, 5].
Pharmaceuticals are a very large and diverse
group of chemicals consisting of both human and
veterinary medicinial compounds. It is assumed
that it consists of about 4500 species, including
pharmaceuticals which are in various stages of investigation. Research studies concerning their presence in the environment and their removal from
waters and wastes published so far, deal with about
160 human and veterinary pharmaceuticals and
about 30 by-products [5]. The main groups of pharmaceuticals, which are detected in the aqueous environment include anti-inflammatory drugs (analgestics), steroids and related hormones, antibiotics,
β-blockers and lipid regulators. Some of them are
consumed annually even in tens or hundreds of
tons. For instance, non-steroidal anti-inflammatory
drug paracetamol – 622 t in Germany in 2001, ibuprofen – 345 t in Germany in 2001, diclofenac
(DCF) – 86 t in Germany in 2001, and naproxen –
35 t in England in 2001 [6].
As the main source of wide presence of pharmaceuticals in the environment is considered municipal water discharge, of which many residual drugs
are not removed by current wastewater processes.
Another contributing sources are industries, farms
and hospitals, although as it was demonstrated recently by studies carried out in Norway, the point
sources discharges from hospitals typically make a
small contribution to the overall pharmaceutical
load in comparison to municipal sources [7]. Many
pharmaceuticals are excreted mainly as metabolites and hence their presence in the aquatic environment. A significant element of these environmental processes is also indirect potable water
reuse. Wastewater treatment plant discharge is directed to surface waters, and in some cases effluent dominated surface waters are used for drinking treatment facilities.
Besides increasing consumption of pharmaceuticals, a significant factor contributing to their presence in the environment is the limited efficiency
of their decomposition in wastewater treatment
plants, and in drinking water treatment plants. This
concerns such methods as UV irradiation, oxidation
with free chlorine, or even ozonation [8]. Concentration of some pharmaceuticals detected in effluents (antibiotics, non-steroidal anti-inflammatory
drugs or steroid hormones) may reach even fractions of mg/L [9]. This is then reflected by concentrations of pharmaceuticals and their metabolites
in worldwide tap water, which are found in some
cases in the level exceeding 1 μg/L (iodinated
X-ray contrast medium diatrizoate, analgesics
AMIDOPH, ibuprofen) [10]. Hence, strong attention is focused in recent years on the development of radical methods of decomposition, described as advances oxidation processes. Especially
efficient process is radiolytic decomposition by
the use of ionizing radiation (gamma or beam of
accelerated electrons), where, as a result of water
radiolysis taking place during irradiation of aqueous solutions, radicals of oxidative and reductive
properties are formed. These processes were already examined for satisfactory decomposition of
β-blockers [11], and antibiotics nitroimidazoles [12].
Very recently, when the present studies were in
progress, the first paper was published on radiolytic decomposition of diclofenac [13], which as a
widely used analgesic and a non-steroidal anti-inflammatory drug, is a subject of wide studies in
terms of its occurrence in waters and its removal
in wastewater treatment [14].
Frequent occurrence of pharmaceuticals in the
aquatic environment, and also in finished drinking
water, is a source of concern about their impact
on public health, although commonly encountered
opinion in the literature is that our current knowledge what is the effect of human exposure to low-dose mixture of pharmaceuticals is none. One can
find opinions about no appreciable risk to human
at detected concentrations of pharmaceutical residues [15], but due to consuming contaminated
drinking water over a lifetime, chronic toxic effects cannot be excluded because of lack of chronic
ecotoxicity data [16]. This creates both demand for
100
80
60
-
40
50 ppm NO3
2-
50 ppm CO3
2100 ppm CO3
50 ppm humic acid
20
0
0
1
2
3
Dose, kGy
4
5
60
40
20
0
1
2
3
4
5
Dose, kGy
Fig.1. Effect of dose on yield of radiolytic decomposition
of diclofenac in 50 mg/L aqueous solutions gamma-irradiated in different conditions: (■) aerated solution, (●) solution saturated with N2O, (▲) solution of pH 7.0, containing 0.52 mM tert-butanol and saturated with argon.
aqueous solution requires a dose of 4.0 kGy, in the
process carried out with scavenging of solvated
electron by saturation of irradiated solution with
N2O, the required dose drops down to 1 kGy. The
deaeration of irradiated solution by saturation with
argon and irradiation in the presence of tert-butanol decreases the yield of DCF irradiation only in
the range of doses from 0.5 to 3 kGy, whereas above
3 kGy has no effect. Such studies were not reported in recently published work [13], and they evidently show the predomination of oxidative decomposition of DCF by gamma irradiation.
The presence of such ●OH radical scavengers
as nitrate, carbonate or humic acid at 50 mg/L
level does not affect decomposition of DCF at an
initial level of 50 mg/L (Fig.2), which is in good
agreement with reported data [13]. It was ob-
B
100
80
0
Chloride concentration, ppm
Yield of decomposition %
A
dative and reductive conditions due to different
reactivity of different radicals. This was shown recently, e.g. for the decomposition of pesticide carbendazim [17]. As it is shown in Fig.1, while the
decomposition of DCF in 50 mg/L DCF in aerated
wide monitoring of presence of pharmaceuticals
in waters and wastes, and search for more efficient
and cost-effective methods of their removal.
In the coarse of this study aqueous solutions of
DCF were gamma-irradiated using a 60Co source
Gamma Chamber with a dose-rate of 8.0 kGy/h.
Using chromatographic methods several factors
affecting efficiency of radiolytic decomposition of
DCF and formation of products of radiolysis were
examined. The reversed-phase HPLC determinations of DCF were carried out using a Shimadzu
chromatograph with a diode array UV/Vis detector, a Luna ODS2, a 5 μm 250 × 4.6 mm analytical
column and a guard column from Phenomenex
(Torrance, CA, USA). The following conditions
were employed for determination of DCF: isocratic elution with eluent consisted of 50 mM
phosphate buffer of pH 7.0, methanol and acetonirile (58:21:21 v/v), flow-rate – 1.0 mL/min,
sample injection volume 20 – μL. The determinations were carried out without additional preconcentration, and limit of detection for DCF was
evaluated as 0.13 mg/L. The ion-chromatographic
determinations of chloride were performed using
a chromatograph Dionex model 2000i/sp, equipped with an ASRS I electrochemical anion self-regenerating suppressor, a conductivity detector,
an AG9HC guard column, and an AS9HC analytical anion exchange column from Dionex. Mobile
phase of the system was sodium carbonate and
sodium bicarbonate with a flow rate of 1 mL/min.
Studies in this stage of the project included experimental determination of the yield of radiolytic
decomposition of DCF in various conditions of
irradiation where different products of water radiolysis predominate. They also included effect of
the presence of selected scavengers of radicals
commonly occurring in natural waters, and also effect of matrices of different natural waters on the
efficiency of radiolytic decomposition. In numerous reported investigations of radiolytic decomposition of different organic pollutants it was shown
that the yield of decomposition is different in oxi-
65
15
14
13
12
11
10
9
8
7
6
5
4
3
2
1
0
2-
50 ppm NO3
250 ppm CO3
2100 ppm CO3
50 ppm humic acid)
0
1
2
3
4
5
Dose, kGy
Fig.2. Effect of the presence of selected scavengers of radicals on (A) yield of decomposition of diclofenac in aerated
aqueous solutions at initial concentration 50 mg/L, and (B) release of chloride during irradiation at different doses.
66
A
diolytic decomposition of organic pollutants was
reported also earlier, e.g. in radiolysis of pesticide
atrazine [18]. Humic acid as effective scavenger of
hydroxyl radicals may favour reaction of solvated
electron, which in the case of some transient products formed during radiolysis of DCF may lead to
more effective release of chloride.
The effectiveness of DCF decomposition carried out in complex matrix of river water is illustrated by chromatograms shown in Fig.3A. Irradiation of river water spiked with 50 mg/L DCF
with a 0.2 kGy dose leads to a 24% decrease of
DCF concentration. In the same figure it is shown
a chromatogram recorded for a Vistula river water
sample without irradiation, which indicates the
presence of 0.29 mg/L DCF. As it is shown in
Fig.3B, the yield of irradiation is similar for distilled and river waters, but evidently larger in tap
water, and these data require further investigations.
The goal of this work was also investigation of
the radiation-induced degradation pathway. The
knowledge regarding kinetic parameters of reactions of parathion with radical species (e–aq and
●
OH) will be useful in ascertaining the degradation reaction pathways. The radiolysis of water
and aqueous solution is based on the ionization of
water molecules, because in dilute solution, when
concentration ≤ 0.1 mol dm–3 the ionized molecules
are essentially those of the solvent:
H2O => ●OH + ●H + e–aq + H3O+ + H2O2
In this stage of the project the reaction between
diclofenac and hydroxyl radical (●OH), was studied
by the puls radiolysis method. A comparison between the obtained data and the data concerning
radical reactions of dichloro-derivatives aromatics
compounds available in the literature will give additional information about the nature of occurring
B
100
80
60
40
20
50 ppm DCF in distiled water
50 ppm DCF in tap water
50 ppm DCF in river water
0
0
1
2
3
4
5
Dose, kGy
Fig.3. Effect of different water matrices on yield of radiolytic decomposition of diclofenac with initial concentration
50 mg/L: A – HPLC chromatograms recorded for Vistula
river water spiked with 50 mg/L DCF and irradiated with
0.2 kGy dose (a), and for non-spiked Vistula river water
prior to the irradiation (b); B – yield of radiolytic decomposition of DCF in aerated solutions of 50 mg/L in distilled
water (■), tap water (●), and Vistula river water (▲).
served, however, only in this study that in the presence of 50 mg/L of humic acid in irradiated solution a much more effectively inorganic chloride
are released from transient products of DCF irradiation in comparison to other examined conditions of irradiation (Fig.2B). A favourable effect
of the presence of humic acid on the yield of ra-
3.24
k obs × 106 [s-1]
G × ε [dm3 J–1 cm–1] × 103
12
2.43
k = 1.24 × 1010 mol-1s-1dm3
10
8
6
4
2
1.62
0
0.0
0.2
0.4
0.6
0.8
concentration [mM]
[mM]
concentration
1.0
a
A
b
B
c
C
d
0.81
D
0.00
325
390
455
520
585
Wavelength [nm]
Fig.4. Absorption spectra recorded in pulse radiolysis system for 0.1 mM aqueous solution of diclofenac of pH 7.0 saturated with N2O at different time delays: (a) 0.12 ms, (b) 0.8 ms, (c) 16 ms and (d) 500 ms. Inset shows the Stern-Volmer
plot of the absorption growth at 370 nm.
radical reactions. The reaction of ●OH radical
with diclofenac water solution (at pH 5.6) was
carried out in solution saturated with N2O – a
well-known electron scavenger.
The main absorption spectrum constitutes of
three bands seen on the spectra recorded during
oxidation of DCF by ●OH radical. The first – most
intensive absorption band, is located at λmax = 370
nm, it grows up within < 0.8 μs time domain (Fig.4,
curve b), with rate k = (1.30 ± 0.06) × 107 s–1, and
decay with rate k = (6.4 ± 0.5) × 104 s–1. The second absorption band is located at a shorter wavelength, and also is built up within microsecond
time domain (Fig.4, curve b). The location of the
second band is changing with time, it starts at λmax
= 335 nm (Fig.4, curve a), after 0.8 μs is moved to
λmax = 325 nm (Fig.4, curve b), and after 6 μs is
seen as a shoulder of absorption band located at a
wavelength below λ = 320 nm (start of measurement). This observation clearly indicates that at
this region more than one species is responsible
for absorption, and therefore its interpretation is
ambiguous.
The absorption spectra recorded 0.8 μs after
electron pulse comprises additional shoulder-shape
absorption (Fig.4, curve b), and with elapsed time
it reveals absorption band located at λmax = 430
nm (Fig.4, curve c and d). The absorption recorded after the end of OH-radical reaction with DCF
(Fig.4, curve b) can be attributed to the primary
product(s) of oxidation diclofenac by ●OH radicals. Probably it is an adduct(s) of ●OH to aromatic rings of DCF (Fig.5).
The overall rate constant of the ●OH radical reaction with DCF deducted from the Stern-Volmer
plot of absorption build-up at λmax = 370 nm is
equal to k = 1.24 ± 0.02 × 1010 dm3 mol–1 s–1 (inset
10
irradiated solutions. This allows the determination
of authentic environmental impact of applied processes with the use of different test organisms. It
was not reposted so far for radiolytic decomposiO
Cl
O
Cl
Microtox
Cl
NH
+ HO
5
4
HO
Cl
Fig.5. Formation of diclofenac adduct(s).
tion of DCF. In this study three different tests
were employed, which are widely used in environmental toxicity studies. Microtox is based on the
use of the bioluminescent marine bacterium Vibrio
fisheri as the test organism, Spirotox is a test undertaken with a very large ciliated protozoan Spirostomum ambiguum, while Thamnotoxkit is a bioassay using larvae of the freshwater anostracen
crustacean Thamnocephalus platyurus hatched from
cysts. The toxicity studies were conducted for 50
mg/L DCF solutions irradiated in aerated solution
with doses up to 5 kGy. With all employed tests a
certain increase of toxicity was observed for the
applied doses in the range 0.5-0.8 kGy, where as it
was shown above about 50-60% of DCF is decomposed (Fig.6). This indicates a larger toxicity of
formed transient products from the decomposed
DCF. At a 3.5 kGy dose, where complete decomposition of DCF was observed (Fig.1), a 33% de-
B
C
Spirotox
Thamnotoxkit
6
4
3
2
2
1
1
0
8
5
3
1
2
3
4
5
4
2
0
0
OH
NH
TU 50
6
TU 50
7
6
O
Cl
Cl
8
7
OH
OH
10
9
8
OH
NH
10
A
9
TU 50
67
0
0
1
Dose, kGy
2
3
4
Dose, kGy
5
0
1
2
3
4
5
Dose, kGy
Fig.6. Toxicity changes observed with different toxicity tests at different applied doses for irradiation of 50 mg/L aerated
solution of diclofenac: A – Microtox, B – Spirotox, C – Thamnotoxkit.
in Fig.4). In a longer time scale the decay of absorptions band λmax = 370 nm is observed, which is
associated with the decay or transformations of
primary products. The absorption of transient
products of DCF oxidation recorded 0.5 ms after
electron pulse (Fig.4, curve d) reveals absorption
at λmax = 430 nm and a shoulder at shorter wavelengths.
A very important supplement to analytical investigation of the efficiency of radiolytic decomposition of organic pollutants for environmental
protection is the monitoring of toxicity changes of
crease of Microtox toxicity was observed, while
practically no changes of toxicity with two other
employed tests was found in comparison to initial
values prior to irradiation. This means a very low
toxicity of DCF for the organisms employed in
those two tests, and also a differentiated environmental impact of DCF residual in waters and
wastes.
References
[1].
Tabak H.H., Brunch R.L.: Devel. Ind. Microbiol., 11,
367-376 (1970).
68
[2].
[12]. Sanchez-Polo M., Lopez-Penalver J., Prados-Joya G.,
Ferro-Garcia M.A., Rivera-Ytrilla J.: Water Res., 43,
4028-4036 (2009).
[13]. Liu Q., Luo X., Zheng Z., Zheng B., Zhang J., Zhao
Y., Yang X., Wang L.: Environ. Sci. Pollut. Res., 18,
1243-1252 (2011).
[14]. Zhang Y., Geissen S.-U., Gal C.: Chemosphere, 73,
1151-1161 (2008).
[15]. Schulman L.J., Sargent E.V., Numann B.D., Faria E.C.,
Dolan D.G., Wargo J.P.: Hum. Ecol. Risk Assess., 8,
657-687 (2002).
[16]. Carlsson C., Johansson A.K., Alvan G., Bewrgman
K., Kuhler T.: Sci. Total Environ., 364, 67-87 (2006).
[17]. Bojanowska-Czajka A., Nichipor H., Drzewicz P.,
Szostek B., Gałęzowska A., Męczyńska S., Kruszewski M., Zimek Z., Nałęcz-Jawecki G., Trojanowicz M.:
J. Radioanal. Nucl. Chem., 289, 303-314 (2011).
[18]. Basfar A.A., Mohammed K.A., Al-Abduly A.J., Al-Shahrani A.A.: Ecotox. Environ. Safe., 72, 948-953 (2009).
Stumm-Zollinger E., Fair G.M.: J. Water Pollut.
Control Fed., 37, 1506-1510 (1965).
[3]. Fatta-Kassinos D., Meric S., Nikolaou A.: Anal. Bioanal. Chem., 399, 251-275 (2011).
[4]. Kümmerer K.: Pharmaceuticals in the environment:
sources, fate, effects and risks. Springer-Verlag 2008.
[5]. Mompelat S., Le Bot B., Thomas O.: Environ. Int.,
35, 803-814 (2009).
[6]. Fent K., Weston A.A., Caminada D.: Aquat. Toxicol.,
76, 122-159 (2006).
[7]. Langford K.H., Thomas K.V.: Environ. Int., 35, 766-770
(2009).
[8]. Snyder S.A.: Ozone Sci. Technol., 30, 65-69 (2008).
[9]. Ikehata K., Naghashkhar N.J., El-Din M.G.: Ozone
Sci. Eng., 28, 353-414 (2006).
[10]. Jones O.A., Lester J.N., Voulvoulis N.: Trends Biotechnol., 23, 163-167 (2005).
[11]. Song W., Cooper W.J., Mezyk S.P., Greaves J., Peake
B.M.: Environ. Sci. Technol., 42, 1256-1261 (2008).
ELABORATION OF OPTIMAL CONDITIONS
OF GEOLOGICAL MATERIALS ANALYSIS
FOR URANIUM DETERMINATION
Iwona Bartosiewicz, Ewelina Chajduk, Marta Pyszynska, Jadwiga Chwastowska,
Halina Polkowska-Motrenko
The plans of building a nuclear power plant in
Poland resulted from the fact that it is the most effective way to cover the growing demand for electricity. Because of this the problem of perspective
domestic uranium deposits has become very actual.
The purpose of our work was the elaboration
of optimal conditions of analysis of geological materials for uranium content. Dictyonema shales
and sandstones were chosen for the analysis. These
materials are known as uranium-bearing [1, 2]
and differ significantly in composition. Inductively
coupled plasma mass spectrometry was used for
the analysis [3-5].
The methods of digestion are essential for the
analysis of geological materials. Two methods of
digestion were taken into consideration: alkali fusion [6] and mineralization in a microwave digestion system with using suitable mineral acids [3, 7].
In the case of high content of organic substances,
especially in shales (20-30%), a stage of preliminary roasting before fusion is necessary (4.5 h at
550oC) when alkali fusion is applied. This stage prolongs the time of analysis. When the acid mineralization method is applied, hydrofluoric acid has
to be added to the digestion mixture to remove
silicon present in the sample. However, some elements like Al, Fe, alkaline earths and rare earth
elements form low soluble fluorides and such elements as U, Th, lanthanides form stable fluoride
complexes, what can cause losses of the determined elements. In order to avoid these effects,
boric acid is usually added to complex remaining
HF and to enable dissolution of the precipitated
fluorides [8-10]. In this work, the influence of different methods of digestion of geological samples
on the results of the determination of elements
was studied. The following methods of digestion
were examined:
a) fusion with Na2O2 [11] in zirconium crucibles;
b) mineralization in a closed microwave digestion
system (Anton Paar Multiwave 3000) of 250 mg
sample in a mixture of HNO3 + HF;
Table 1. Results of ICP-MS determination of U, Th, La, Yb in dictyonema shales using different digestion methods.
Fusion
Sample Element
with Na2O2
1
2
Mineralization
Evaporation
with H3BO3
Removing of F– in microwave digestion system
12 mL
4% H3BO3
0.5 g
H3BO3
1g
H3BO3
U
41
8
35
41
26
43
Th
12
0.14
7.3
15
7
11
La
40
0.28
29
43
18
43
Yb
4.0
0.21
3.5
3.7
2.5
3.3
U
100
40
83
103
80
100
Th
13
1.8
11
16
11
13
La
41
0.8
25
48
28
43
Yb
4.0
0.9
3.5
4.2
3.1
3.4
c) mineralization as described in point b) followed by removing of fluoride ions by evaporation
with H3BO3 solution on a hot plate;
d) mineralization as described in point b) followed by removing of fluoride ions applying two-step procedure with solid H3BO3 or 4% H3BO3
solution added in the second step.
The obtained results of the inductively coupled
plasma mass spectrometry (ICP-MS) analysis of
two different samples of dictyonema shales are
shown in Table 1.
The obtained results show that the use of two-step process (mineralization + removing fluorides
in a microwave digestion system using 4% H3BO3)
ensures complete recovery of elements which form
stable fluoride complexes. It reduces significantly
also the analysis time and can be recognized as an
optimal mineralization procedure.
Sandstones contain as a rule high content of silica
and not so high of organic substances. In that case
the digestion by fusion is preferred. The following
trace elements were determined: U, Th, Cu, Co,
Mn, Zn, La, V, Yb, Mo, Ni and Sb by the ICP-MS
method.
Elaborated procedures of analysis
Geological materials are heterogeneous, therefore much affords were made to get a representative sample. The analysed samples was homogenized by milling in an agate ball mill (dictyonema
shales) and in tungsten carbide ring mill (sandstones) to obtain the grain size less than 0.2 mm.
Then, the obtained fraction was carefully mixed.
Analysis of dictyonema shales
0.25 g of a sample was weighed directly to a digestion vessel, a mixture of 6 mL of HNO3 + 2 mL
of HF was added and the vessels were capped. The
digestion programme for geological materials was
applied. Then, the vessels were left for cooling and
opened. Twelve mL of 4% H3BO3 solution was
added and the second step of digestion was completed (50 bar, 220oC, 45 min). The obtained solution was transferred into a 50 mL PFA volumetric
flask and submitted to analysis by the ICP-MS
method.
Analysis of sandstones
0.5 g of a sample was weighed to zirconium
crucibles, 2 g of Na2O2 was added and carefully
mixed. The fusion process was carried out in an
oven at a temperature of 550oC during 1 h. The
alloy was dissolved in water, then HNO3 concd.
was added to attain 5 M, and the mixture was heated at a temperature of about 80oC to obtain clear
solution. The obtained solution was transferred to
a 250 mL volumetric flask and adjusted with water
to 250 mL.
Blanks were prepared in the same way as the
samples. After suitable dilution, the samples were
analysed by the ICP-MS method.
Conditions of determination by ICP-MS
The instrument used was ELAN DRC II
(Perkin Elmer) with a crossflow nebulizer with a
Scott double-pass spray chamber and Ni cones.
Optimization of experimental parameters of an
ICP-MS spectrometer was performed with respect
to the maximal ion intensity of chosen elements
69
Table 2. Working parameters for ICP-MS analysis.
RF power: 1000 W
Plasma gas: 13.0 L min–1
Auxiliary gas: 1.2 L min–1
Mass spectrometer
ELAN DRC II
Nebulizer gas: 0.92 L min–1
Lens voltage: 6.75 V
Detector mode: dual
Cones: Ni
Working mode: standard
(daily performance solutions of concentration of 1
ng mL–1 – Perkin Elmer). The optimal conditions
of analysis by the ICP-MS method (Table 2) were
established by checking the effect of the following
parameters: RF power, nebulizer gas flow and lens
voltage.
After sample decomposition, the obtained solutions were diluted with 0.7% HNO3 and In was
added as an internal standard prior to the analysis.
The following nuclides: 238U, 232Th, 63Cu, 59Co,
55
Mn, 66Zn, 139La, 51V, 174Yb, 98Mo, 60Ni, 121Sb and
57
Fe were selected since they are free from interference and are sufficiently abundant for quantitative measurement by ICP-MS.
Expanded uncertainty – U (k = 2) was evaluated
as 5-15%.
The elaborated methods were applied to the
analysis of 50 samples of dictyonema shales and
50 samples of sandstones. The examples of results
of analysis are presented in Table 3.
The uranium content range was from 41 to 215
ppm and 5 to 1316 ppm for shales and for sandstones, respectively. Beside uranium, V, Ni, Cu,
Mo, Mn were also determined, as they can be important for technology. From the obtained data, a
big diversity of uranium as well as other elements
Table 3. Results of analysis of some geological material
samples [mg kg–1].
Dictyonema shales
Element
Sandstone
Sample code
3
8
141
160
U
41
142
1144
565
Th
12
15
14
4.3
Cu
244
208
47
59
Co
13
20
117
96
Mn
94
50
890
640
Zn
240
4830
999
45
La
40
45
51
14
V
1730
1650
717
371
Yb
4.0
3.7
2.5
2.0
Mo
68
270
<5
<5
Ni
247
287
52
45
Sb
7.0
18
0.3
0.2
70
concentration is observed. Bigger diversity is observed in the case of sandstones samples.
References
[1].
[2].
[3].
[4].
[5].
Bareja E.: Kwart. Geol., 21, 4, 705-714 (1977), in
Polish.
Bareja E.: Kwart. Geol., 28, 2, 353-366 (1984) , in
Polish.
Krachler M., Mohl C., Emons H., Cozzi G., Barbante
C., Cescon P., Shotyk W.: J. Anal. At. Spectrom., 17,
844-855 (2002).
Balcerzak M.: Anal. Sci., 18, 737-750 (2002).
Celo V., Dabek-Zlotorzynska E., Mathieu D., Okonkaia I.: Open Chem. Biomed. Meth. J., 3, 143-152
(2010).
[6].
Galindo C., Mougin L., Nourreddine A.: Appl. Radiat.
Isot., 65, 9-16, (2007).
[7]. Chen M., Ma L.Q.: Soil Sci. Soc. Am. J., 65, 491-499
(2001).
[8]. Krachler M., Mohlb C., Emons H., Shotyk W.: Spectrochim. Acta Part B, 57, 1277-1289 (2002).
[9]. Swami K., Judd C.D., Orsini J.,· Yang K.X., Husain L.:
Fresenius J. Anal. Chem., 369, 63-70 (2001).
[10]. Ivanova Ju., Djingova R., Korhammer S., Markert B.:
Talanta, 54, 567-574 (2001).
[11]. Choy C.C., Korfiatis G.P., Meng X.: J. Hazard. Mater.,
136, 53-60 (2006).
LABORATORY
OF MATERIAL RESEARCH
Activities of the Laboratory are concentrated on:
• studies of coordination polymers built of s block metals and azine carboxylate ligands,
• synthesis of nanoscale porous metal organic framework materials (nanoMOFs) using particle track membranes as template,
• synthesis of functional materials – silver modified cotton and cellulose fibers using radiation beam techniques,
• modification of surface layer of engineering materials by implantation of lanthanide elements and nitrogen atoms using high intensity plasma pulses,
• characterization of art objects.
The design and construction of coordination polymers have been studied intensively in
recent years, as evidenced by the very rapid growth of publications. Particularly, the porous
coordination polymers or the so-called metal organic framework materials (MOFs) are of
great interest due to their potential applications for gas storage, gas separation, catalysis, sensors, etc. Despite of many achievements in the field, new rational and effective methods for
assembling coordination polymers with specific or desired structure are still awaited. Our interests are focused on light s block metals coordination polymers with carboxylic ligands with
carboxylic and/or nitrogen functionality. In the last year the crystal structures of seven new
lithium coordination polymers with azine dicarboxylic acids have been solved and published.
For many potential MOF applications, it is essential to obtain them on the nanometer length
scale (nanoMOFs). Nanoscopic dimensions are essential for many applications, particularly,
for biomedical applications, like drug carriers and diagnostic agents. They also find applications in the field of catalysis, to obtain materials with better kinetic properties due to higher
ratio of surface to bulk atoms, and for surface sensors development by integrating nanoscale
materials on the surface. For the synthesis of nanoMOFs, we have applied the so-called template synthesis method using particle track membranes. The possibility of HKUST-1 MOF
nanocrystals synthesis in the pores of track-etched membranes has been demonstrated. The
results were presented at the NUTECH 2011 conference and the paper concerning the results should appear in the conference materials in “Nukleonika”.
The production of the track-etched membranes is well-known in membrane science and described in the literature. However, the increasing interest of polymer track-etched membranes
with nano-channels still exists and is related to development and creation of nanoporous materials with unique properties. New achievements concerning membranes with diode-like
pores and membranes with highly asymmetrical nanopores have been obtained in the course
of the last years in the Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear
Research (Dubna, Russia). Their structural properties have been documented in the course
of joint research work of the Flerov Laboratory of Nuclear Reactions and the Laboratory of
Material Research.
In the cooperation with the National Nuclear Research Centre at Świerk (Poland) studies
on the modification of surface properties of AISI 316L stainless steel with REE (Ce+La) using high intensity pulsed plasma beams (HIPPB) have been carried out. The results of this
work show that improvement by alloying AISI 316L stainless steel with REE (Ce+La) leads
to the formation of a remelted and enriched with active elements near surface layer, and that
the obtained modified surface layers show marked improvement of tribological properties as
compared to initial material.
The research on radiation enhanced synthesis of silver nanoparticles on a number of polymeric matrices like cellulose and cotton fibres as well as powdered silica contained materials
have been continued. The silver ions deposited from a solution of silver salts were reduced
using accelerator electron beam. The materials obtained have been characterized using scanning electron microscope with back-scattered electrons detector (SEM-BSE), energy dispersive
X-ray (EDX), X-ray diffraction (XRD), electron paramagnetic resonance spectroscopy (EPR).
Their thermal properties have been determined using differential scanning calorimetry (DSC)
and thermogravimetric analysis (TGA) methods and their antibacterial and antifungal properties have been determined as well. The results were presented recently at the 27th Miller
Conference on Radiation Chemistry, International Meeting on Radiation Processing (IMRP
2011), 12th Tihany Symposium on Radiation Chemistry, International Conference on Development and Applications of Nuclear Technologies NUTECH 2011.
Nuclear analytical techniques have been applied in the Laboratory for many years for
examination, characterization and analysis of cultural heritage artefacts or art objects and
their component materials. The unique properties of this technique like high sensitivity, reproducibility, non-destructive and non-invasive character are crucial for an enhencement of
our knowledge concerning their elaboration, their evolution and degradation during time.
They provide a basis for their restoration and conservation. Recently, studies on the basic attributes and limitations of INAA technique for the analysis of alabaster sculptures has been
completed in the Laboratory.
73
STRUCTURAL STUDIES IN Li(I) ION COORDINATION CHEMISTRY
Wojciech Starosta, Janusz Leciejewicz
An analysis of the crystal structures of Li(I) ion
complexes with diazine carboxylate ligands determined up to now in the course of the present project
reveals a number of interesting features which are
briefly summarized below:
• Li(I) ions show an evident preference to adopt
distorted trigonal bipyramidal coordination geometry with coordination number five. Among
17 symmetry independent Li(I) ions, which were
observed in the crystal structures of 11 complexes
[1-11], 12 ions show this coordination mode, 4
ions distorted tetrahedral environment with coordination number four. In only one complex
[2] octahedral coordination with six coordinated atoms has been observed.
• Apart from one structure [5], the others show
more or less complicated polymeric molecular
patterns, irrespectively whether the ligand is
mono- or multicarboxylate.
• In three complexes [1, 6, 7] centrosymmetric
moieties have been found as building blocks of
the structures.
• Water molecules are active in 11 structures as
coordinating and bridging agents. Only in two
structures [9, 10] solvation water molecules have
been also detected. The structure of one complex [7] does not contain water molecules, but
besides the N,O bonding groups, nitrate groups
act as coordinating and bridging.
• In all compounds systems of hydrogen bonds
are responsible for the stability of their structures. Short hydrogen bonds linking protonated
and deprotonated carboxylic groups of the same
ligand molecule are observed in the structures
of three compounds [3, 4, 9].
In two more complexes short bonds with the hydrogen atom located at an inversion centre are
observed. They act as bridging to form catenated [2] and layered [11] molecular patterns.
Part 06. Poly[aqua(μ3-(pyridazine-4-carboxylato-κ2O:O:O’)lithium] [6]
The structural unit of the title compound is a
centrosymmetric dimer composed of two Li(I)
bridged by a bidentate carboxylate O1 atom, each
the carboxylate group and the pyridazine ring is
43.4(2)o. The pyridazine ring is almost planar with
r.m.s. of 0.0148(2) Å. Both ligand’s heterocyclic N
atoms remain coordination inactive. The Li(I) ion
is coordinated by the bridging carboxylato O1 and
O1(ii) atoms, a bridging carboxylato O2(i) donated
by the adjacent dimer and the aqua O3 atom resulting in a distorted tetrahedral coordination.
Carboxylato O2 atoms bridge the dimers into molecular layers which are approximately parallel to
the crystal bc plane. The structure of a layer can be
visualized as composed of corrugated loops with
four equal sides and the dimers at their apices.
Hydrophobic parts of pairs of pyridazine rings are
directed inside the loop with closest distance of
4.91(1) Å between ring centres while heterocyclic
N atoms are directed outside and participate in a
network of hydrogen bonds. The latter consist of
coordinated water molecules acting as donors and
Fig.2. The packing of layers composed of dimeric units
viewed along the c axis.
the pyridazine N atoms in an adjacent layer as acceptors. They form centrosymmetric rings which
give rise to a three-dimensional structure (Fig.2).
Part 07. Poly[(μ2-nitrato-κ2O;O’)(μ2-pyrimidinum-2-carboxylato-κ2O;O’)lithium] [7]
The structure of the title compound contains
Li(I) ions, each coordinated by two ligand carboxylato and two nitrato O atoms at the apices of a
distorted trigonal bipyramid. Its base is composed
Fig.1. A dimeric structural unit of the title compound with
atom labelling scheme and 50% probability displacement
ellipsoids. Symmetry code: (ii) -x, -y+1, -z.
donated by one of two symmetry related ligands
(Fig.1). The ligand carboxylate group C7/O1/O2
makes with the O1/Li1/O1(ii) Li(iii) plane a dihedral
angle of 10.9(1)o, while the dihedral angle between
Fig.3. A fragment of the structure with atom labelling
scheme. Non-hydrogen atoms are shown as 50% displacement ellipsoids. Symmetry code: (ii) -x+1, -y+1, -z+1; (iii)
-x+3/2, y+1/2, z.
74
of coplanar carboxylato O1, nitrato O11 and O12(ii)
atoms (Fig.3). The Li1 ion is shifted by 0.0548(2)
Å above this plane. The carboxylato O2(iii) is at the
apex of the pyramid. Li-O bond distances fall in
the range from 1.967(3) to 2.019(3) Å, commonly
observed in the structures of Li(I) complexes with
1 and 0.0069(1) Å for ring 3; carboxylate groups
C17/O11/O12 and C37/O31/O32 make with relevant rings dihedral angles of 11.2(1)o and 11.0(1)o,
respectively. The nitrate anion is planar (r.m.s.
Fig.5. A dimeric structural unit with atom labelling scheme
and 50% probability displacement ellipsoids. Symmetry
code: (i) -x+2, -y, -z+2; (ii) x, y+1, z; (iii) x, y+1, z.
Fig.4. Packing of molecular layers viewed along the a axis.
carboxylate ligands. The Li1-N1 bond distance of
2.467(3) Å as too long was not allowed in coordination of the Li1 ion. The pyrimidine ring is planar
with r.m.s. of 0.0074(1) Å. A hydrogen atom attached to the hetero-ring N2 atom, clearly visible
on the Fourier map, maintains the charge balance.
It links the N2 atom with the carboxylate O(i) atom
via a hydrogen bond of 2.5762(17) Å. Bond distances and bond angles within the pyrimidine ring
do not differ from those reported earlier in the
structures of other metal complexes with the title
ligand. The C7/O1/O2 carboxylate group makes
with ring a dihedral angle of 14.81(2)o. Two Li(I)
ions, one coordinated by the carboxylato O1 atom,
the other by the second carboxylato O2 atom of
the same ligand form molecular ribbons composed
of dimeric units (Fig.4). The latter bridged by nitrato O11 and O12(ii) atoms give rise to molecular
layers.
Part 08. Poly(di-μ2-aqua-μ2-(-5-methylpyrazine-2-carboxylato)-(5-methylpyrazine-2-carboxylato)-μ3-nitrato-trilithium] [8]
The asymmetric unit of the title compound contains three Li(I) ions, two 5-methylpyrazine-2-carboxylate anions, two water molecules and a nitrate
anion (Fig.5). The coordination environment of
the Li1 ion is composed of N11, O11(i), O1, O4
and O11 atoms. The latter three form a base of a
distorted trigonal bipyramid, N11, O11(i) atoms are
at its apices. Li1 ion is 0.0097(2) Å out of the basal
plane. The Li2 ion is coordinated by water O4, O5,
carboxylate O12(i) and nitrate O2(iii) atoms which
form a distorted tetrahedral coordination environment. The same distorted tetrahedral coordination geometry shows the Li3 ion sorrouded by
N31, O31, O1 and O5 atoms. Both methylpyrazine
rings are planar with r.m.s. of 0.0074(1) Å for ring
0.0002(1) Å). Its O1 atom acts as bidentate and
bridges Li1 and Li3 ions, while the O2 atom
chelates the Li2 ion. Nitrato O3 atom is coordination inactive. Li1 and Li1(i) ions bridged by bidentate carboxylate O11 and O11(i) form a core of a
centrosymmetric cluster composed of Li1 and Li3
ions bridged by bidentate nitrato O1 atom, Li1
and Li2 bridged by the aqua O4 atom, Li2 and Li3
bridged by the aqua O5 atom. The clusters bridged
via nitrato O1 and O2 atoms, form molecular columns along the crystal [010] direction (Fig.6) which
are held together by a network of hydrogen bonds
in which aqua O4 and O5 molecules are as donors
and carboxylate O31 and O32 atoms as acceptors.
π-π type interactions between methylpyrazine rings
belonging to adjacent columns are also observed
as indicated by the distances between the centroids
of slightly shifted each to the other hetero-rings
which amount to 3.694(3) and 3.796 Å.
Fig.6. The alignment of the polyhedra columns in the unit
cell.
Part 09. catena-Poly[[[aqualithium]-μ3-carboxy-pyrazine-2-carboxylato-κ4O 2,N 1:O 3,N 4]
monohydrate] [9]
The asymmetric cell of the title compound contains two symmetry independent Li(I) ions, two
ligand molecules, two coordinated and two solvation water molecules (Fig.7). Li(I) ions and the
ligands form two parallel molecular chains propagating in the crystal b direction (Fig.8). In each,
the Li ion shows a distorted trigonal bipyramidal
75
carboxylate groups C27/O21/O22 and C28/O23/O24
with the pyrazine ring 2 amount to 15.4(2)o and
4.3(1)o, respectively. Solvation and coordinated
water molecules participate in a network of hydrogen bonds which bridges the ribbons. They act
as donors, the carboxylato O atoms as acceptors.
Part 10. catena-Poly[[μ2-aqua-diaquabis(μ2-pyradizine-3,6-dicarboxylato) tetralithium]
monohydrate] [10]
The title compound is a polymeric complex with
four symmetry independent Li ions in the asymmetric cell. Two of them show distorted trigonal
bipyramidal geometry, the two other exhibit distorted tetrahedral coordination environment. The
asymmetric cell contains also two symmetry independent pyridazine-3,6-dicarboxylate ligand molecules (PY1 and PY2), three coordinated water
molecules and a solvation water molecule (Fig.9).
Fig.7. Two structural units of the title compound with atom
labelling scheme and 50% probability displacement ellipsoids. Symmetry code: (iii) -x+1, y-1/2, -z; (iv) -x, y+1/2,
-z+3/2.
coordination mode. The Li1 ion is 0.017(1) Å out
of the basal plane composed of carboxylato O11,
O14(i) and aqua O15 atoms; hetero N11 and N12(i)
atoms are at axial positions. The equatorial plane
in the case of the Li2 ion consists of carboxylate
O21, O24(ii) and water O25 atoms; hetero N21 and
N22(ii) form the apices. The Li2 ion is 0.012(1) Å
out of the basal plane. The observed Li-O and Li-N
bond distances are characteristic of Li(I) complexes
with diazine carboxylate ligands. Each ligand uses
both its N,O chelating sites to bridge Li(I) ions.
The second carboxylato O atoms do not participate
in coordination but remain protonated to maintain the charge balance. In both ligands these protons are active in short intra-molecular hydrogen
bonds of 2.393(3) Å and 2.416(3) Å. Bond lengths
and bond angles within both pyrazine rings do not
differ from those reported in the structures of two
modifications of the parent acid. Pyrazine rings are
planar with r.m.s. of 0.0040(2) Å and 0.0094(2) Å,
for ligand 1 and 2, respectively. The carboxylate
groups C17/O11/O12 and C8/O13/O14 make with
the pyrazine ring 1 dihedral angles of 4.8(1)o and
3.8(1)o, respectively. Dihedral angles made by the
Fig.8. Packing diagram of the structure viewed along the b
axis.
Fig.9. The structural unit of the title compound with atom
labelling scheme and 50% probability displacement ellipsoids. Symmetry code: (i) -x+2, -y, -z+2; (ii) -x+2, -y+1,
-z+2; (iii) -x+2, -y, -z+3; (iv) -x+2, -y+1, -z+1.
The equatorial plane of Li1 coordination polyhedron is composed of O11, N21, O24(iii) atoms;
the Li1 ion is 0.0285(2) Å out of the plane, O21
and N11 atoms are at axial positions. Li2 ion is
shifted by 0.0186(2) Å from the basal plane composed of O12(i), O23, N12 atoms; O13 and N22
atoms make the apices. Li3 ion is coordinated by
O21, O22(iv), O31, O42(i) atoms at the apices of a
distorted tetrahedron while the coordination tetrahedron of the Li4 ion is composed of O13(ii),
O14, O41, O42 atoms. Both pyridazine rings are
planar with r.m.s. of 0.0154(2) Å and 0.0123(2) Å
for the ring PY1 and PY2, respectively. Carboxylate C17/O11/O12 and C18/O13/O14 groups make
with the hetero-ring PY1 dihedral angles of 14.3(1)o
and 22.2(2)o, respectively. Dihedral angles formed with the hetero-ring 2 by carboxylate groups
C27/O21/O22 and C28/O23/O24 amount to 3.8(1)o
and 17.2(2)o, respectively. The Li1 and Li2 ions
bridged by hetero-ring N atoms donated by both
76
ligands along the Li1-N11-N12-Li2-N22-N21-Li1
pathway form a dimeric moiety. The C27/O21/O22
and C27(iv)/O21(iv)/O22(iv) groups acting as biden-
zine-2,6-dicarboxylate ligand molecule and a coordinated water molecule (Fig.11). The coordination environment of the Li1 ion is composed of
five atoms: ligand carboxylate O1, O1(i), heteroring N1, aqua O3 and O3(iii) atoms. Coplanar Li1,
N1, O3 and O3(iii) form the base of a distorted
trigonal bipyramid, with O1 and O1(i) atoms at its
apices. The observed Li-O and Li-N bond distances
are typical for Li(I) complexes with diazine carboxylate ligands. The aqua O3 atom bridges Li1
with Li1(ii) ion to form molecular ribbons which
propagate in the crystal c direction (Fig.12). The
Fig.10. Packing diagram of the structure viewed along the
b axis.
tate bridge the Li3 and Li3(iv) ions to form a loop
which joins a dimer with an adjacent from one side
via O21 and O21(iv) atoms since the latter are also
bonded to the Li1 and Li1(iv) ions, respectively. A
similar loop bridges the dimers from the other
side as the bidentate O13 atom links the Li2 and
Li4(ii) ions. A molecular ribbon propagating along
the crystal c direction can be visualized The ribbons
bridged by carboxylate and coordinated water O
atoms form molecular layers which are parallel to
the crystal bc plane and stacked along the a direction (Fig.10). The bridging of ribbons proceeds via
carboxylato O12 and O24 atoms: O12 atom is coordinated to the Li2(i) atom in an adjacent ribbon
while the Li2 ion – by the O12(i) atom from the
same ribbon. The O24 atom is chelated to the Li1(iii)
ion in the other adjacent ribbon, while the O24(iii)
atom is coordinated to the Li1 ion. In addition,
pairs of ribbons are bridged by coordinated aqua
O42 atoms via Li4-O42-Li3(i) and Li3-O42(i)-Li4(i)
links. An extended system of hydrogen bonds in
which coordinated water molecules are donors and
carboxylato O atoms in adjacent layers act as acceptors, maintains the stability of the structure.
Two intra-molecular hydrogen bonds are also observed.
Part 11. catena-Poly[[(6-carboxypyrazine-2-carboxylato)lithium]-μ-aqua] [11]
The asymmetric unit of the title compound
consists of a Li(I) ion, a singly deprotonated pyra-
Fig.12. The alignment of the ribbons viewed along the a
axis.
carboxylato O1 atom remains protonated and
mantains the charge balance. This proton, located
at an inversion centre, forms a short centrosymmetric O1-H1… O1(iv) hydrogen bond of 2.455(3)
Å which links adjacent ribbons to form molecular
layers. The pyrazine ring is planar with r.m.s of
0.0024(1) Å. The C7/O1/O2 and C7(i)/O1(i)/O2(i)
carboxylic groups make with it dihedral angles of
3.0(1)o. Bond distances and bond angles within the
ligand molecule do not differ from those reported
in the structure of pyrazine-2,6-dicarboxylic acid
dihydrate. The layers are held together by weak
hydrogen bonds in which the coordinated water
molecules act as donors and carboxylate O atoms
and hetero-ring N atoms from adjacent layers are
as acceptors.
References
[1].
[2].
Fig.11. The asymmetric unit of the title compound with atom
labelling scheme and 50% probability displacement ellipsoids. Symmetry code: (i) x, -y+3/2, z; (ii) x+1, y, z; (iii) x-1,
y, z; (iv) -x+1, -y+1, -z; (v) -x+1, y-1/2, -z; (vi) x, -y+1/2, z;
(vii) x-1, y+1/2, -z; (viii) -x+2, -y+1, -z.
[3].
[4].
Starosta W., Leciejewicz
m744-m745 (2010).
m1362-m1363 (2010).
m1561-m1562 (2010).
m50-m51 (2011).
J.: Acta Crystallogr., E66,
[5].
m202 (2011).
m425 (2011).
m818 (2011).
m1000-m1001 (2011).
[6].
[7].
[8].
77
[9].
Starosta W., Leciejewicz J.: Acta Crystallogr., E67,
m1133 (2011).
[10]. Starosta W., Leciejewicz J.: Acta Crystallogr., E67,
m1455-m1456 (2011).
[11]. Starosta W., Leciejewicz J.: Acta Crystallogr., E67,
m1708-m1709 (2011).
NANOPORES WITH CONTROLLED PROFILES
IN TRACK-ETCHED MEMBRANES
Bożena Sartowska, Oleg Orelovitch1/, Adam Presz2/, Irina Blonskaya1/, Pavel Apel1/
1/
Flerov Laboratory of Nuclear Reactions, Joint Institute for Nuclear Research, Dubna, Russia
2/
Institute of High Pressure Physics, Polish Academy of Sciences, Warszawa, Poland
The production of track-etched membranes is
well-known in membrane science and described in
the literature [1-4]. Latent ion tracks are the result
of the passage of swift ions through solid matter
which can be etched selectively in many materials.
As a result the conical, cylindrical or other shape
channels can be obtained. The increasing interest
of polymer track-etched membranes with nano-channels is connected with the development and
creation of nanoporous materials with unique
properties. The main directions of the research
work include:
(i) development of membranes with diode-like
pores, highly asymmetrical nanopores for molecular sensors; highly asymmetrical nanopores for atom beam optics, etc. [3, 5];
(ii) development of high-performance asymmetrical track membranes [3];
(iii) study of propagation of X-rays and acoustic
waves through track-etched membranes as
model porous medium [6];
(iv) development of nano-capillary bodies for modelling the transport of molecules and ions in
constrained volumes [5].
It has been found that conical nanopores are
cation selective and possess diode-like voltage-current characteristics [1, 7]. It has been also shown
that the shape of the pore tip determines the
transport properties of the asymmetric narrow
channels [8, 9].
Asymmetric pores have been produced by the
surfactant-controlled etching of heavy ion tracks
in a polymer foil. The formation of nanopores
with different tip shapes is based on the interplay
between the chemical attack by alkali ions and the
protection effect of the surfactant. These two
components of the etching solution diffuse into
the pore at different rates, which results in the formation of a channel with a narrow neck at the surface. Varying the etchant component concentrations makes it possible to control the degree of
tapering. The scheme of the etching process is presented in Fig.1.
Polyethylene terephthalate (PET) film 12-μm
thick (Hostaphan RNK, Mitsubishi Polyester Films)
was irradiated with accelerated heavy ions: 170-MeV
Xe-ion beam with the ion fluence in the range of
5 x 104 to 1 x 108 cm–2 from an IC-100 accelerator
at the Flerov Laboratory of Nuclear Reactions,
Joint Institute for Nuclear Research (Dubna,
Russia). In the next step of asymmetric membrane
Fig.1. Scheme of track etching in an ion-irradiated polymer
film in the presence of nano-sized surfactant molecules.
production one surface of the irradiated foil was
exposed to UV radiation from a source. After UV
exposure, the samples were etched during different times with sodium hydroxide solutions to which
0.05% (w/w) Dowfax 2A1 (Dow Chemicals) was
added at a constant temperature of 60oC. Alkaline
solutions with NaOH concentrations of 4 M, 5 M,
6 M were used to produce membranes with gradually increased tapering of the pore tips. The etched
samples were examined using an LEO 1530 (Zeiss,
Germany) field-emission scanning electron microscope (FESEM). Small pore density and pore diameters (tip region) were estimated by observing
the membrane surface. The pore profiles were determined via imaging of fractures of the samples.
The FESEM images of pores with highly tapered tips with the “bullet-like” shape produced
by etching at three different alkali concentrations
are shown in Fig.2. It can be clearly seen that use
of the lower alkali concentrations provides a less
pronounced bullet-like tip.
78
A
B
C
Fig.2. FESEM images of typical pore tip in membranes obtained by etching in surfactant-doped alkaline solutions: A – 4 M
NaOH, 7 min; B – 5 M NaOH, 6.5 min; C – 6 M NaOH, 5 min.
Pore radius a(x), nm
From the images of membrane fractures, one
can extract quantitative information on the pore
profile. The data measured for several single
channels were averaged to obtain a profile typical
of used etching conditions. Experimentally obtained tip profiles of the observed membranes are
200
(c)
150
(b)
100
(a)
50
0
0
1000
2000
3000
Depth x, nm
Fig.3. Experimentally obtained tip profiles for pores obtained by etching in surfactant-doped alkaline solutions:
(a) 4 M NaOH, 7 min; (b) 5 M NaOH, 6.5 min; (c) 6 M
NaOH, 5 min.
presented in Fig.3. The pore profile a(x) was fitted
using an exponential function suggested by Ramirez [9]:
a(x) = aR – (aR – aL) exp [-(x/d)n (d/h)n]
where: aR – pore diameter at the foil side exposed
to UV irradiation; aL – pore diameter at the foil
side not exposed to UV irradiation; d – pore length
(thickness of used polymer foil); n and h – parameters of the pore profile (here: n = 1). Profiles
shown in Fig.3 were calculated using this equation. The fitting curves (lines) and obtained experimental data (points) are presented in the diagram.
In conclusion: Surfactant controlled etching
method presented in this work allows us to control
the shape of track-etched pores in polymeric
membrane and the use of the described controlled
etching method can give pore channels unique
properties with potential practical applications,
for example: ultrafiltration and microfiltration
processes, cation selectivity, mimicking the properties of biological ion channels, nanocapillary
bodies for modelling molecule transport in constrained volumes.
This work has been partially supported by the
cooperation programme of the Polish scientific
institutes with the Joint Institute for Nuclear
Research in 2010 according the subject number
04-5-1076-2009/2011.
This work has been partially supported by the
Polish Ministry of Science and Higher Education
under the project with a decision 766/W-ZIBJ
DUBNA/2010/0.
References
[1]. Apel P.Yu., Korchev Yu.E., Siwy Z., Spohr R., Yoshida
M.: Nucl. Instrum. Meth. Phys. Res. B, 184, 337-346
(2001).
[2]. Apel P.Yu., Blonskaya I.V., Dmitriev S.N., Orelovitch
O.L., Presz A., Sartowska B.A.: Nanotechnology, 18,
305302-305308 (2007).
[3]. Apel P.Yu. et al.: Radiat. Meas., 43 (1), 552-555 (2008).
[4]. Apel P.Yu., Blonskaya I.V., Orelovitch O.L., Dmitriev
S.N.: Nucl. Instrum. Meth. Phys. Res. B, 267, 1023-1027
(2009).
[5]. Gillespie D., Boda D., He Y., Apel P., Siwy Z.S.:
Biophys. J., 95, 609-619 (2008).
[6]. Gomez Alvarez-Arenas T.E., Apel P.Yu., Orelovitch
O.L., Munoz M.: Radiat. Meas., 44, 1114-1118 (2009).
[7]. Siwy Z. et al.: Surf. Sci., 532-535, 1061-1066 (2003).
[8]. Cervera J., Schiedt B., Neumann R., Mafe S., Ramirez
P.: J. Chem. Phys., 124, 104706 (2006).
[9]. Ramirez P., Apel P.Yu., Cervera J., Mafe S.: Nanotechnology, 19, 315707 (2008).
79
IMPROVEMENT OF TRIBOLOGICAL PROPERTIES
OF STAINLESS STEEL BY ALLOYING ITS SURFACE LAYER
WITH RARE EARTH ELEMENTS
USING HIGH INTENSITY PULSED PLASMA BEAMS
Bożena Sartowska1/, Jerzy Piekoszewski1,2/, Lech Waliś1/, Jan Senatorski3/, Marek Barlak1,2/,
Wojciech Starosta1/, Cezary Pochrybniak2/, Irena Pokorska3/
1/
2/
The Andrzej Sołtan Institute for Nuclear Studies, Otwock-Świerk, Poland
3/
Institute of Precision Mechanics, Warszawa, Poland
Austenitic stainless steels are used in numerous
industrial applications, due to their very good corrosion resistance in different environments. This
is connected with an adherent and self-healing
passive film on the surface and thus received growing attention in nuclear and petrochemical industries, pulp and paper chemical, food and chemical
processing and biomedical industries. However,
poor tribological and mechanical properties of
austenitic stainless steels in terms of abrasion resistance limited their applications in engineering
fields.
Improvement of the wear resistance of austenitic stainless steels without loss of corrosion resistance can be achieved using different surface
treatment, for example: re-solidification techniques
or enrichment of the surface layer with reactive
elements. High oxygen affinity elements such as
Y, Ce, La, Er and other rare earth elements (REE)
added to steels in small amounts can improve their
resistance for electrochemical corrosion [1], high
temperature oxidation [1, 2] and wear [3, 4]. REE
can be alloyed during the steel making process or
can be added to the surface region of materials
using different surface modification techniques
such as: ion implantation [1, 2, 4, 5], sol-gel coating
[5], metal organic chemical vapour deposition [6].
Austenitic stainless steel AISI 316L was used as
the substrate for investigations. As a REE source,
the mischmetal with a composition: Ce – 65.3 wt%
and La – 34.0 wt% was used. REE were incorporated into one surface of steel samples using high
intensity pulsed plasma beams – HIPPB (106-108
W/cm2). The plasma pulses were generated in a
rod plasma injector (RPI) described in details
elsewhere [7]. The plasma pulses are formed at a
low pressure, high-current discharge between two
concentric sets of electrodes. Two modes of RPI
operation are possible: (i) pulse implantation doping (PID) – when plasma contains practically exclusively ions of the working gas and (ii) deposition by pulsed erosion (DPE) – when the beam
contains also ions/atoms eroded from ends of the
electrodes. The pulse energy was high enough for
melting the surface layer of material. The melt duration lasts in the μs range and the rapid solidification takes place. The cooling rate was estimated
in the range of 107-108 Ks–1. Heating and cooling
processes were of non-equilibrium type. The thickness of melting layer is about 1.5 μm.
Samples were irradiated with 3 pulses with an
energy of density 2.0 J/cm2, in DPE mode with ti-
tanium rods coated with mischmetal tips as electrodes and nitrogen as the working gas. The samples
were characterized by: scanning electron microscopy (SEM) with DSM 942 (Zeiss, Germany) for
initial and modified surface morphology observations, grazing angle X-ray diffraction (GXRD,
ω = 5o) with CuKα radiation with a diffractometer
D8 Advanced (Bruker, Germany) for material
structure determination. Wear resistance measurements were carried out using the Amsler method
with an A135 Amsler machine with the parameters:
sliding friction distance – 3000 m, constant load –
5 daN, 41Cr4 steel counter-sample and single immerse lubrication.
SEM micrographs of the surface of an untreated sample and a sample treated with HIPPB are
shown in Fig.1. Grain boundaries on the untreated
sample are clearly visible as a result of steel pro-
Fig.1. SEM surface morphology of AISI 316L samples.
duction process. After the modification process,
grain boundaries almost disappeared and features
of the mixed deposit-substrate material form can
be seen. Craters, cracks and other morphological
features were observed by SEM on the modified
surfaces. They are typical for melted and rapidly
solidified material known from previous investigations [8]. XRD spectra for initial and modified
material analysis show the FCC phase presence.
This is clearly recognized in the initial material –
austenitic stainless steel. In the case of modified
material peaks characteristic of FCC structure confirm that after remelting and alloying with REE
austenitic phases are still present in the surface
layer of steel. This result was observed in previous
investigations and explained by a very high cooling rate [8]. Two first peaks – diffraction patterns
of initial and material modified up to 1.2 and 2.01
80
at% REE are shown in Fig.2. The (200) peaks
shifting towards higher angles 2θ were observed,
what corresponds to a smaller lattice parameter of
identified austenitic phase. Lattice parameters de-
Fig.3. Changes in linear wear of AISI 316L samples.
Fig.2. First two peaks of GXRD spectra of AISI 316L
samples.
termined from these shifts were: a1 = 0.3575 nm
(AISI 316L initial material), a2 = 0.3537 nm (AISI
316L + 1.2 at% REE) and a3 = 0.3535 nm (AISI
316L + 2.01 at% REE). It should be taken into
consideration that theoretical austenite lattice parameter equal to a0 = 0.3582 nm [9]. It was suggested that very high cooling rate and very high
crystallization rate lead to obtain dispersed structure.
Figure 3 shows the dependence of linear wear
for initial and alloyed with REE materials. HIPPB
modified AISI 316L steel reveals a smaller value
of linear wear after each one part of wear measurements as compared with the initial material. Additionally: the presented results show a bigger improvement of tribological properties for higher
REE concentrations. Even small REE incorporation (0.23 at% REE) improved the tribological
properties of AISI 316L steel by about 25%.
The present authors supposed that the improvements of tribological properties are connected with
following findings: (i) enrichment of grain boundaries with REE, (ii) fine grains creation in the
modified material as a result of very high cooling
rate and (iii) nitrogen presence in the modified
layer.
In conclusion: (i) alloying of AISI 316L stainless steel with REE (Ce+La), using high intensity
pulsed plasma beams (HIPPB) lead to formation
of the remelted and enriched steel with active elements near the surface layer and (ii) obtained
modified surface layers showed improvement of
the tribological properties as compared with the
initial material.
References
[1]. Abreu C.M., Cristobal M.J., Novoa X.R., Pena G.,
Perez M.C., Rodriguez R.J.: Surf. Coat. Technol.,
158-159, 582-587 (2002).
[2]. Cleugh D., Blawert C., Steinbach J., Ferkel H., Mordike
B.L., Bell T.: Surf. Coat. Technol., 142-144, 392-396
(2001).
[3]. Cheng X.H., Xie C.Z.: Wear, 254, 415-420 (2003).
[4]. Jin F., Chu P.K., Xu Z., Zhao J., Zhu M., Fu R.K.Y.,
Tong H.: Surf. Coat. Technol., 201, 4357-4360 (2006).
[5]. Riffard F., Buscail H., Caudron E., Cueff R., Issartel
C., Perrir S.: Appl. Surf. Sci., 199, 107-122 (2002).
[6]. Picardo P., Chevalier S., Molins R., Viviani M., Caboche
G., Barbucci A., Sennour M., Amendola R.: Surf.
Coat. Technol., 201, 4471-4475 (2006).
[7]. Werner Z., Piekoszewski J., Szymczyk W.: Vacuum, 63,
701-708 (2001).
[8]. Sartowska B., Piekoszewski J., Waliś L., Senatorski J.,
Stanisławski J., Nowicki L., Ratajczak R., Kopcewicz
M., Szymczyk W., Nowotnik A.: Plasma Process Polym.,
4, S314-S318 (2007).
[9]. Saker A., Leroy Ch., Michel H., Frantz C.: Mater. Sci.
Eng., A 140, 702-708 (1991).
INAA AS A SOURCE OF INFORMATION FOR THE PROVENANCE
OF ALABASTER SCULPTURES
Tomasz Śliwa1/, Ewa Pańczyk
1/
Faculty of Geology, Geophysics and Environmental Protection, AGH University of Sciences
and Technology, Kraków, Poland
For the examination, characterization and analysis
of cultural heritage artefacts or art objects and
their component materials, a conservation specialist needs a palette of non-destructive and non-invasive techniques, in order to improve our knowledge concerning their elaboration, their evolution
and degradation during time, and to a give basis
for their restoration and conservation. Among various methods used for the examination of art ob-
jects, nuclear techniques are crucial due to their
high sensitivity and reproducibility.
In this paper, the basic attributes and limitations of
INAA (instrumental neutron activation analysis)
technique for analysis of alabaster sculptures are
described.
There are many works of art made of alabaster
the authors of which as well as the centres in which
they were created are unknown. The only criterion
81
used for dating a sculpture is the style of the epoch
or the artist. Nuclear methods, in particular neutron activation analysis (NAA) can furnish data
for estimation of the sculpture origin. By comparing the content of trace elements in alabaster form
deposits and in alabaster of the examined sculpture, it is possible to estimate where the sculpture
comes from, because the content of trace elements
in alabaster from different sources significantly
differs. For this purpose, a catalogue containing
data on the content of trace elements in alabaster
originating from various mines is necessary.
Alabaster is a massive crypto-crystalline form of
gypsum deposited by precipitation in inland seas
in the last Paleozoic-Permian period and the first
period of Mesozoic-Triassic period. Alabaster is a
pure substance with a very low trace element concentration [1].
Alabaster was used, particularly in the Middle
Ages as sculptor’s material mainly in Normandy,
Westfalen, North Netherlands and England. As
sculptor’s material, alabaster has excellent properties: it can be readily shaped, it permits to obtain
fine details, it is semitransparent, can be readily
gold-coated or polychromed [2]. Its disadvantages
are: brittleness and sensitivity to atmospheric agents.
The purpose of this research was to identify
historical Badenian alabaster deposits from the
Table 1. Description of analysed alabaster sculptures.
No.
Sculpture
Desciption
of sample
1
The Wawel Cathedral, Potocki’s Chapel, Bishop’s Padniewski figure
a_1
2
The Wawel Cathedral, Waza’s Chapel, fragment of cartouche
a_2
3
The Wawel Cathedral, Lipski’s Chapel, fragment of Andrzej Lipski tombstone (1)
a_3
4
The Wawel Cathedral, Lipski’s Chapel, fragment of Andrzej Lipski tombstone (2)
a_4
5
The Wawel Cathedral, Lipski’s Chapel, fragment of Cardinal Jan Aleksander Lipski
tombstone
a_5
6
The Basilica of Corpus Christi (Kraków), St. Stanisław Kazimierczyk Mausoleum,
Madonna with Child
a_6
7
The Cathedral Basilica (Tarnów) – Ostrogski’s tombstone
a_7
8
Parish church dedicated St. Cross (Zbylutowska Góra), Zbylitowski Family tombstone
a_8
9
Parish church (Dobromil), epitaph of child from Herbut Family
a_9
10
Parish church (Dobromil), fragment of sacrarium
a_10
11
Church of the Dominican Fathers (Lvov), tombstone monuments of Władysław Dzieduszycki,
Jan Swoszowski, Stanisław Włodek – figure in vestibule (pillow)
a_11
12
Jan Swoszowski, Stanisław Włodek – figure in vestibule (fragment of thigh)
a_12
13
Jan Swoszowski, Stanisław Włodek – figure in vestibule on the right side (pillow)
a_13
14
Jan Swoszowski, Stanisław Włodek – figure in vestibule on the left side (pillow)
a_14
15
Jan Swoszowski, Stanisław Włodek – figure in vestibule on the left side (pedestal)
a_15
16
Jan Swoszowski, Stanisław Włodek – figure in vestibule on the right side (pedestal)
a_16
17
St. Michael Archangel Ortodox Church (Lvov), St. Cross Altar, Jan Szolc-Wolfowicz
foundation
a_17
18
Latin Archbishop’s See (Lvov), Kampians Chapel, table
a_18
19
Latin Archbishop’s See (Lvov), Kampians Chapel, interior decoration (base of 1st pillar)
a_19
20
Latin Archbishop’s See (Lvov), High Sacristy, Altar of Family Zapała foundation
a_20
21
Latin Archbishop’s See (Lvov), High Sacristy, St. Joseph Chapel, St. Joseph Altar
a_21
22
Parish church (Rymanów), Jan and Sophia Sieniński tombstone (1)
a_22
23
a_22a
24
a_23
25
a_23a
26
Castle Chapel (Brzeżany), west crypt
a_24
27
Castle Chapel (Brzeżany), fragment of architectural framework
a_25
82
Ukrainian part of the Carpathian foredeep, which
served as a raw material for historical sepulchral
and figural statues from the Renaissance era to
the interwar period. Using the method of INAA,
24 samples of alabaster gypsum were examined
from, among others, the chapels of the Wawel
Cathedral, Lvov and Tarnów, as well as from the
parish churches of the Tarnów and Przemyśl dioceses. Small amounts of alabaster were collected
along with antique furnishings from the Roman
Catholic parishes around Lvov and the Orthodox
Church of St. Michael the Archangel in Lvov. Forty
five alabaster samples collected from natural outcrops and quarries that appear along the Dniester
Valley in the historic regions of Eastern Galicia,
Podolia and Bukovina served as reference material.
The samples are described in Tables 1 and 2.
Analysis of the samples was carried out by INAA
using standards of the elements to be determined.
Major components of alabaster (CaSO4*2H2O)
have low (n,γ) reaction cross-sections which is of
advantage for carrying out the analysis. By irradiating alabaster with thermal neutrons, its main component undergoes the nuclear reaction
46
Ca (n,γ) 47Ca → 47Sc
The radioisotope 47Ca has a half-life of 4.53 days
and emits gamma rays of energies 1290 and 800
keV. On the other hand, 47Sc with a half-life of 3.4
days emits gamma rays of an energy of 160 keV.
The reaction cross-section is 0.250 barn and the
natural abundance of 46Ca is 0.0033% [3].
The samples were sealed in quartz ampoules
and then packed together with standards of 48
elements. Each packet contained also Sc and Au
used as monitors of the thermal neutron flux.
The irradiation was carried out in the MARIA
reactor at Świerk (Poland), at a neutron flux of
8 x 1013 ncm–2s–1. The samples were irradiated for
24 h and cooled for 12 h. The radioactivity of the
samples was measured by means of an HP-Ge detector (ORTEC) coupled to a CANBERRA-System spectrometer, controlled by an IBM computer.
The analysis of gamma-ray spectra of the samples
was performed with the aid of the GENIE 2000
program.
A multi-parameter statistical analysis was performed to determine the degree of similarity between the studied objects (analysis of principal
components and cluster analysis) using the STATISTICA-8 program [3].
Forty eight elements were identified and determined in the samples examined. Out of 48 determined elements, only the elements identified
in all tested samples were selected for further
analysis. Elements such as Cd, Ga, Ho, Lu, Mo,
Ni, Rb, Se, Tb, Ta and Zr, the content of which in
the majority of analysed samples, was below the
method detection threshold, were disregarded.
The clustering analysis using STATISTICA (StatSoft) program was carried out to identify the similarity degree of analysed objects. The clustering analysis was carried out for standardized variables.
Results of this analysis are presented in Fig., which
clearly shows the division into two groups in which
Table 2. Description of studied alabaster deposits.
No. Localization of alabaster deposit
Sample
description
1
Kostriżiwka (1)
z_1
2
Kostriżiwka (2)
z_2
3
Dubowce (1)
z_3
4
Dubowce (2)
z_4
5
Werenczanka (1)
z_5
6
Werenczanka (2)
z_6
7
Łokutki (1)
z_7
8
Łokutki (2)
z_8
9
Szczerzec (1)
z-9
10
Szczerzec (2)
z_10
11
Szczerzec (3)
z_11
12
Czynków
z_12
13
Kriwa
z_13
14
Słoboda
z_14
15
Zagóreczko
z_15
16
Mamałyga
z_16
17
Podłuże
z_17
18
Głuszków
z_18
19
Skowiatyn
z_19
20
Wojniłów
z_20
21
Borszczów
z_21
22
Podkamień
z_22
23
Anadoły (1)
z_23
24
Anadoły (2)
z_24
25
Pałahicze (1)
z_25
26
Pałahicze (2)
z_26
27
Kudryńce (1)
z_27
28
Kudryńce (2)
z_28
29
Żurawno
z_29
30
Bochnia
z_30
31
Mielnica Podolska
z_31
32
Podillia
z_32
33
Oleszyw (1)
z_33
34
Oleszyw (2)
z_34
35
Krzywcze
z_35
36
Wasiuczyn
z_36
37
Łopuszka Wielka
z_37
38
Pohoryłówka
z_38
39
Kudryńce (Zamek)
z_39
40
Jezierzany
z_40
41
Pawlikówka
z_41
42
Czerwonogród
z_42
43
Kreszczatyk
z_43
44
Hołowczyńce
z_44
45
Kołokolin
z_45
46
Toutry
z_46
83
Fig. Cluster analysis for 73 objects (sculptures and deposits); describes 36 features equal number analysed elements,
standardized variables.
the objects are very similar. Probably, the applied
alabaster was obtained from the same source.
Several limitations and assumptions for the provenance studies of sculptures on the basis of elemental composition have to be kept in mind:
• We assume that alabaster used for sculpture is
homogeneous.
• The samples removed from sculpture are representative of its stone.
• Statistically a significant number of samples from
deposits is taken to the elemental analysis.
References
[1]. Beasley S.M.: The attribution of alabaster tomb carvings to Medieval schools. Analytical and typographical
problems. A further study. Post-graduate thesis. University of Bradford, 1978, unpublished.
[2]. Cheetman M.: English Medieval alabasters catalogue.
Victoria and Albert Museum, Oxford 1984.
[3]. Ligęza M., Pańczyk E., Rowińska L., Waliś L., Nalepa
B.: Nukleonika, 46, 2, 71-74 (2001).
POLLUTION CONTROL
TECHNOLOGIES LABORATORY
Research activities of the Pollution Control Technologies Laboratory concern the concepts
and methods of process engineering application to the environmental area. In particular, we
participate in research on the application of an electron accelerator in such environmental
technologies as flue gas and water treatment, wastewater purification, processing of different
industrial waste, etc.
The main aims of activity of the Laboratory are:
• development of new processes and technologies of environmental engineering,
• development of environmental applications of radiation technologies,
• promotion of nuclear methods in the field of environmental applications.
The activities of our group are both basic and applicable research. Among others, the most
important research fields are:
• development of electron beam flue gas treatment (EBFGT) technology,
• investigation of chemical reaction mechanisms and kinetics in gas phase irradiated by electron beam,
• study on the mechanism of removal of volatile organic compounds (VOCs) from flue gas by
electron beam excitation,
• process modelling.
The Laboratory is equipped with such research tools as:
• laboratory installation for electron beam flue gas treatment (flow rate up to 400 m3/h),
• gas chromatograph with a mass spectrometer,
• portable gas analyser (NOX, SO2, CO, O2, etc.).
In 2011, the research staff is involved in the following projects:
• “Dissemination and fostering of plasma-based technological innovation for environment
protection in Baltic Sea Region – PlasTEP” (project co-financed by ERDF).
• “Laboratory study on SO2 and NOx removal from marine diesel engines exhaust gases with
use of electron beam technology”.
• “Electron beam flue gas treatment pilot tests”.
The Laboratory is open to any form of cooperation. The most important partners of the
Laboratory are:
• Faculty of Chemical and Process Engineering, Warsaw University of Technology (Poland);
• International Atomic Energy Agency;
• Saudi ARAMCO (Saudi Arabia);
• A.P. Moeller and Maersk A/P (Denmark);
• EB Tech Co., Ltd. (South Korea);
• Technology Centre of Western Pomerania (Germany);
• Leibniz Institute for Plasma Science and Technology (Germany);
• Risø National Laboratory for Sustainble Energy, Technical University of Denmark (Denmark);
• Uppsala University, The Ångström Laboratory (Sweden);
• Kaunas University of Technology (Lithuania);
• Vilnius Gediminas Technical University (Lithuania);
• Robert Szewalski Institute of Fluid-Flow Machinery, Polish Academy of Sciences (Poland);
• West Pomeranian University of Technology (Poland);
• Ukrainian Engineering Pedagogic Academy (Ukraine).
86
MODELLING STUDY OF NOx REMOVAL IN FLUE GAS
IN THE PRESENCE OF C2H6 UNDER ELECTRON BEAM IRRADIATION
Yongxia Sun, Volodymyr Morgunov1/, Andrzej G. Chmielewski
Electron beam flue gas treatment (EBFGT) technology has demonstrated its efficiency in purification flue gases from SOx and NOx from coal and
oil fired boilers [1]. High removal efficiency of SO2
(> 95%) and NOx (> 70%) has been demonstrated and an industrial plant applying this process
has been built in Poland [2]. However, SO2 removal from off-gases by using electron beam (EB)
is relatively easy, but NOx removal needs higher
energy consumption. It demands a new method to
remove NOx with lower energy consumption. Our
previous work showed that NOx removal efficiency
was improved in the presence of alcohol [3]. In
this work we theoretically studied NOx removal in
the presence of C2H6 with the aid of computer
simulation.
The computer simulation of NOx removal in
flue gas under EB-irradiation was carried out by
using a self-developed computer code “ELO”, a
GEAR method was used. 883 reactions involving
94 species were considered for NOx + (air + CO2
+ H2O) + C2H6 (0-400 ppm) system, and 998 reactions involving 137 species were considered for
NOx + (air + CO2 + H2O) + 400 ppm C2H6 + 700
ppm SO2. Five main groups of reactions were included, the rate constants of reactions were mostly
taken from the literatures [4-6]. The units of rate
constant are 1/s, m3/mole·s and m6/mole2·s for the
first-, second- and third-order reactions, respectively.
When fast electrons from electron beams are absorbed in the carrier gas, they cause ionization
and excitation process of the nitrogen, oxygen,
CO2 and H2O molecules in the carrier gas. Primary
species and secondary electrons are formed.
The generation of active species under the electron beam is described by [6]:
dn i
xρ
= G ni D
i
dt
(1)
where: ni – concentration of the i-th component
[mole/m3], Gni – radiation yield of the i-th component of the gas [mole/J],
xi – mole fraction of the
.
i-th component, D – dose rate [J/(kg·s)], ρ – gas
density [kg/m3].
Kinetics of chemical reactions of species formed
during the gas irradiation with molecules of the
gas medium and with one another is described by
differential equations:
n
dn i
= n i ∑ k (n)
i ∏ nk
dt
n
k =1
(2)
For given initial concentrations:
ni(0) = ni0
(3)
where: ni – concentration of the i-th component
[mole/m3], ki(n) – the rate constant for n-order chemical reaction between the i-th and the k-compo-
Concentration [ppm]
General and Experimental Physics Department, Ukrainian Engineering Pedagogic Academy,
Kharkiv, Ukraine
Dose [kGy]
Fig.1. Experimental and calculation results of NOx removal
from flue gas vs. dose under EB-irradiation.
nents of gas, nk – concentration of the k-th component, ni0 – the initial concentration of the i-th
component. Calculations were made in the following conditions:
• NO = 494 ppm, NO2 = 38 ppm, CO2 = 7%,
H2O = 10-11% (v/v), O2 = 10%, N2 as balance,
T = 70oC (no any additives);
• NO = 494 ppm, NO2 = 38 ppm, CO2 = 7%,
T = 70oC (with presence of 100 and 400 ppm
C2H6, respectively);
• NO = 494 ppm, NO2 = 38 ppm, CO2 = 7%,
T = 70oC (with presence of 700 ppm SO2 and
400 ppm C2H6).
Figure 1 presents the calculation and experimental results of NOx removal in flue gas vs. dose
under EB-irradiation. Calculation results agree,
to some extent, with the experimental results [3].
NOx removal under the influence of additives is
presented in Fig.2. It is seen that NOx removal efficiency is slightly improved in the presence of
C2H6. The key reactions are listed below:
Removal efficiency [%]
1/
Dose [kGy]
Fig.2. Experimental and calculation results of NOx removal
from flue gas vs. dose under EB-irradiation in the presence
or absence of additives.
OH + C2H6 = C2H5• + H2O
(R1)
O2 + C2H5• = C2H5O2•
(R2)
2C2H5O2• = 2C2H5O• + O2
(R3)
C2H5O2• + NO = C2H5O• + NO2
(R4)
(R5)
C2H5O2• + NO + M = C2H5ONO2 + M
C2H5O2• + NO2 + M = C2H5O2NO2 + M (R6)
(R7)
NO2 + OH + M = HNO3 + M
The oxidation-reduction cycle between NO2 and
NO is toward the oxidation path and an increase
in NOx removal efficiency is favoured.
From calculation results, the following conclusions are drawn:
• Removal efficiency of NOx is increased by 3%
at a dose of 10.9 kGy in the presence of C2H6
when the concentration of C2H6 is in the range
of 100 to 400 ppm.
87
• Removal efficiency of NOx is decreased by
23.84% at a dose of 10.9 kGy in the presence of
400 ppm C2H6 and 700 ppm SO2. The SO2 presence decreases the removal efficiency of NOx
when ammonia is not added.
References
[1]. Basfar A.A. et al.: Fuel, 87, 8-9, 1446-1452 (2008).
[2]. Chmielewski A.G. et al.: Radiat. Phys. Chem., 71, 1-2,
439-442 (2004).
[3]. Chmielewski A.G. et al.: Radiat. Phys. Chem., 65, 4-5,
397-403 (2002).
[4]. Albritton, D.L.: At. Data Nucl. Data, 22, 1-101 (1978).
[5]. http://kinetics.nist.gov/kinetics/index.jsp.
[6]. Mätzing H.: Advances in chemical physics. Vol. LXXX.
John Wiley & Sons, Inc., New Jersey 1991, pp. 315-402.
EMISSION PROCESSES
IN THE BALTIC SEA REGION – PLASMA TECHNOLOGIES
IN ENVIRONMENTAL PROTECTION (PlasTEP)
Sylwia Witman, Andrzej Pawelec, Andrzej G. Chmielewski
Air pollution is one of the biggest environmental
problems, because the combustion products in the
form of volatile compounds of sulphur, nitrogen
are often transported along with the wind towards
regions distant from the place of generation. There,
reacting with the moisture contained in the atmosphere, these compounds form acids, causing acidification of the environment affecting the resources
of water and soil.
Transport, industry (metallurgy, cement and
chemicals), energy generation, heating and waste
incineration have the largest share in the production of gaseous air pollutants. Analysis of the main
sources of air pollution in the Baltic Sea Region
was conducted within the international project –
PlasTEP.
Mapping the specificity of NOx and SO2 emission in the Baltic Sea Region is the basis for further
discussions on possible implementation of plasma
pollution control technologies. Therefore the document presenting main sources of emission in certain countries has been elaborated. As a next step
of this work, an elaboration list of potential proTable 1. Annual SO2 and NOx emissions in the Baltic Sea
Region countries.
Country
Emission [t/year]
SO2
NOx
Finland
70 119
165 877
Estonia
69 333
34 393
Latvia
2 831
38 122
Lithuania
31 531
67 739
Poland
998 561
831 225
North Germany
842
6 190
Denmark
19 605
151 686
Sweden
30 521
154 403
cesses suitable for plasma technologies application
is foreseen.
According to PlasTEP project assumptions,
emission in the following countries was concerned:
Finland, Estonia, Latvia, Lithuania, Poland, North
Germany, Denmark and Sweden. The national
emissions of NOx and SO2 are presented in Table 1.
The highest emission were reported in Poland.
It is the biggest of all concerned countries (38.1
mln citizens). The lowest emissions were reported
in North Germany with 1.7 mln citizens. Therefore,
the total emission per capita will be a better indicator in order to compare emission in the Baltic
Sea Region countries. The emission of main inorganic pollutants per capita is presented in Table 2.
Table 2. Annual SO2 and NOx emissions per capita in the
Baltic Sea Region countries.
Country
Emission [kg/year]
SO2
NOx
Finland
13
31
Estonia
52
26
Latvia
1
17
Lithuania
9
20
Poland
26
22
North Germany
0.5
3.6
Denmark
4
28
Sweden
3
16
Average
15.4
22.8
Many problems associated with environmental
pollution may be solved by properly using electromagnetic phenomena. Technologies based on electricity are environmentally „clean” and therefore
wasteless, in contrast to most of the chemical technologies. Many of the newly created electromag-
88
netic technologies of air purification from gaseous
pollutants (processes in non-thermal plasma, laser
technologies, technologies using electron beam)
have already been applied on an industrial scale.
A progressive increase in demand for electricity
also brings challenges for the electricity industry
to develop more efficient technologies being in
comply with the requirements of environment.
The presented structure of emission opens new
possibilities for plasma technology for exhaust gas
purification.
Nowadays the improvement of efficiency of
electricity generation systems are realized through
the use of combined heat and electricity generation. With the proper use of various technologies,
the emissions of harmful compounds was partially
decreased, but still many problems are unsolved
and application plasma technologies for environment protection may improve this situation.
Non-thermal plasma, generated in barrier discharges, is used in the processes of sterilization
and disinfection of solid, liquid and gas media due
to its numerous advantages – the most important
being the lack of side effects as harmful to the environment waste products, the ability of plasma-chemical treatment at atmospheric pressure and
ambient temperatures. Survey in this field are con-
ducted by many scientific and research centres in
the world. The use of non-thermal plasma in the
agricultural and food industry for disinfection,
storage products, plant growth stimulation, seems
to be a competitive solution against conventional
chemical methods and fully justified to continue
the research in this area.
Research of plasma technologies for reducing
emissions in transport is also conducted in the
country and abroad. Mobile sources that use diesel
engines (very large emission of NOx) can use non-thermal plasma generated by electric discharges
which significantly reduces the negative impact on
the environment.
Thus, plasma technology can be used in:
• exhaust gases purification processes on a large-scale production (EB) and small boilers (plasma
created in discharges),
• removing harmful pollutants from exhaust gases
from industry,
• purification of exhausts from mobile sources.
The results of the PlasTEP project, in which the
(INCT) is involved, are the confirmation of the
importance of the research in the development of
plasma technologies for the environment.
Basic activity of the Stable Isotope Laboratory concern the techniques and methods of stable
isotope measurements by the use of an isotope ratio mass spectrometer – IRMS. Our activity
area concerns also the application to the environmental area: stable isotope composition of
hydrogeological, environmental, medical and food samples.
The main aims of activity of the Laboratory are:
• preparation and measurement of stable isotope composition of food and environmental
samples;
• new area of application of stable isotope composition for food authenticity control, environmental protection and origin identification.
The Laboratory is equipped with the following instruments:
• mass spectrometer – DELTAplus (FinniganMAT, Germany);
• elemental analyser Flash 1112NCS (Thermo Finnigan, Italy);
• GasBenchII (ThermoQuest, Germany);
• H/Device (ThermoQuest, Germany);
• gas chromatograph (Shimadzu, Japan);
• gas chromatograph with a mass spectrometer (Shimadzu, Japan);
• liquid scintillation counter (for 14C and tritium environmental samples) 1414-003 Guardian
(Wallac-Oy, Finland);
• portable gas analyser (N2O, CO2, CH4, H2S), (Nanosens, Poland).
Research staff of the Laboratory is involved in the following projects:
• “Formation of the data bank on original products for the juice sector, to supply requirements of the Polish market and producers, basing on the method of stable isotopes”
(Ministry of Science and High Education grant PBZ-MEiN NR12-0043-10/2010);
• “Differentiation of organically and conventionally produced foodstuff by the stable isotope
method”;
• accreditation process (isotopic method for food authenticity control);
• interlaboratory proficiency test FIT-PTS (food analysis using isotopic techniques – proficiency testing scheme).
Specific activity: industrial emission control of greenhouse gases by the use of isotopic composition and food authenticity control and origin identification.
The Stable Isotope Laboratory is open for any form of cooperation. We are ready to undertake any research and development task within the scope of our activity. Especially, we offer
our measurement experience, precision and proficiency in the field of stable isotope composition. Besides, we are open for any service in the area of food authenticity control by stable
isotope methods supported by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) methods.
Our Laboratory cooperates with the following
national partners:
• Inspekcja Jakości Handlowej Artykułów Rolno-Spożywczych,
• Urząd Ochrony Konsumenta,
• Krajowa Unia Producentów Soków,
• customs inspections,
• food export-import company,
• food control laboratories,
• private people – customers
and foreign partners:
• Eurofins Scientific Analytics (France),
• International Atomic Energy Agency (IAEA),
• Join Research Centre (Ispra, Italy),
• AgroIsoLab (Juelich, Germany),
• others isotopic laboratories.
91
STABLE ISOTOPES METHODS FOR JUICE AUTHENTICITY CONTROL
Ryszard Wierzchnicki
With the globalization of trade, quality control of
food products is gaining increasing importance
for ensuring consumer and producer protection.
Adulteration as an addition of the artificial (prohibited) components to natural products, a cheaper
product put into a place expensive one and mislabelling is still frequently meet fraud. The addition
of cheaper fruits, glucose syrup, acids, aromas and
water are typical examples of adulteration which
may occur in the juice production. The Polish market has started to speed with the latest challenges
facing the food industry with regard to food fraud.
This is connected with the economic politics of
EC in the agriculture sector of all EU countries.
Nowadays in Europe, stable isotope composition is probably one of the most important characteristic of juice for its authenticity control. The
standard method applied to determine the authenticity of juice is the measurement of δ13C of
sugar and pulp and δ18O of water (Table 1). The
ticity control. Important limitation of the application of isotopic method for juice authenticity
control is the lack of database of stable isotope
composition in fruits and vegetables of different
origin.
This Laboratory since many years is carrying
out a study of isotopic composition of food for the
elaboration and implementation of new IRMS
methods and database for some food products
from the Polish market. For testing of food products, we need extensive knowledge of the original
material. Our recent studies concern the intramolecular isotopic distribution pattern between the
juice components. The aim of the studies is the
extraction of chemical components and investigating their intermolecular relation with δ13C composition. The specific natural isotopic profile method
(SNIP-IRMS) [5] is based on multi-isotopic fingerprinting in which isotopic ratios are measured on
several components of the same product and their
Table 1. The isotopic methods accepted as international standards for juice authenticity control.
Product
Isotopic parameter
13
Fruit juice
sugar, C
Fruit juice
Method
Document
IRMS*
ENV 12140 (CEN/TC174N108) [1]
13
IRMS
ENV 12140 (CEN/TC174N108) [2]
2
IRMS
ENV 12141 (CEN/TC174N109) [3]
18
pulp, C
Fruit juice
water, H
Fruit juice
water, O
IRMS
ENV 12141 (CEN/TC174N109) [4]
Fruit juice
ethanol, (D/H)I, (D/H)II, R
SNIF-NMR**
AOAC method 995.17
IRMS
AOAC method 2004.01
13
Fruit juice
ethanol, C
* IRMS – isotope ratio mass spectrometry.
** SNIF-NMR – site-specific natural isotope fractionation determined by nuclear magnetic resonance.
difference between sugar and pulp isotopic composition is the reason to ascertain the addition of
sugar to tested juice. The oxygen isotopic ratio in
juice is directly related to the oxygen ratio of regional precipitation and groundwater which, in
turn, is linked to geographical origin of fruits. It is
possible to discriminate between natural and synthetic components (aromas, pigments, etc.) using
nitrogen and carbon isotopic composition. The use
of multicomponent and multielement approach is
studied, in which isotopic profile is built up for different food products in order to address authen-
intermolecular isotopic correlation is investigated.
The main components of juice are presented in
Table 2.
Nowadays, the role of the Stable Isotope Laboratory is the implementation of the SNIP-IRMS
method on the basis of original Polish fruits originated from important regions of fruit production.
In the future our Laboratory will check the compliance of both content and labelling of fruit juice
sold in the Polish marketplace. In the last year the
laboratory has taken part in Food Isotopic Techniques – Proficiency Testing Scheme organized by
Table 2. Basic chemical components of fruits and vegetables.
Basic components of fruits and vegetables
Content
[%]
Minor components of fruits and vegetables
Content
[mg]
Water
78-95
organic acids (citric, malic, tartaric)
< 100
Sugars (glucose, fructose, sucrose)
5-15
vitamins
< 80
Cellulose (texture)
0.4-5
enzymes
< 0.1
Starch
0.3-1
aromas
< 0.001
pigments
< 0.001
Fats
0.1-0.6
Proteins
0.3-1.8
Asch
0.3-1.0
92
the Eurofins Scientific Analytics, Nantes, France
and Bevabs office, JRC, Ispra, Italy. Isotopic composition of samples of wine, juice, honey and casein
were tested. Studies of this kind, using a multicomponent and multielement approach, concerning isotope profiles for different products, are prospected
for future needs of authenticity control of food.
This work is supported by the Polish Ministry
of Science and Higher Education under grant No.
NR12-0043-10/2010.
[2].
[3].
[4].
References
[1]. PN-ENV 12140 : 2004 Fruit and vegetable juices – Determination of the stable carbon isotope ratio (13C/12C)
[5].
of sugars from fruit juices – Method using isotope ratio
mass spectrometry.
PN-ENV 12141:2004 Fruit and vegetable juices – Determination of the stable oxygen isotope ratio (18O/16O)
of water from fruit juices – Method using isotope ratio
mass spectrometry.
PN-ENV 12142:2004 Fruit and vegetable juices – Determination of the stable hydrogen isotope ratio (2H/1H)
of water from fruit juices – Method using isotope ratio
mass spectrometry.
PN-ENV 113070:2004 Fruit and vegetable juices – Determination of the stable carbon isotope ratio (13C/12C)
in the pulp of fruit juices – Method using isotope ratio
mass spectrometry.
González J., Remaud G., Jamin E., Naulet N., Martin
G.G.: J. Agric. Food Chem., 47(6), 2316-2321 (1999).
STABLE ISOTOPE RATIO ANALYSIS TO CHARACTERIZE
CHOSEN SAMPLES OF POLISH HONEY
Kazimiera Malec-Czechowska, Ryszard Wierzchnicki
Since many years the activity of the Stable Isotope
Laboratory has been concentrated on the application of stable isotope mass spectrometry for environmental investigation and food authenticity control. In 2011, samples of Polish honey with a different floral type such as rape, linden, buckwheat,
honeydew and mixed floral (multiflorous) were
tested. The products were purchased in a local
shop in Warsaw. The investigated honeys were produced in apiarian farms situated in the Masuria
geographical region of Poland.
Honey is a sweet natural product, produced by
bees from flower nectar or from honeydew. Floral
honey is composed mainly of carbohydrates, fructose and glucose; but these sugars can be artificially added to falsify honey. Stable carbon isotope
ratio analysis (SCIRA) is used to demonstrate C4
(corn or cane) sugars in honey at a concentration
> 7%. The apparent C4 sugar content of the honey
is calculated using the following formula:
C4 sugars [%] = 100 x [δ13Cp – δ13Ch]/[δ13Cp – (-9.7)]
where: δ13Cp and δ13Ch – the δ13C values [‰] for
protein and honey, respectively; -9.7‰ – the average δ13C value for a corn syrup.
Proteins from honey were isolated according to
the AOAC Official Method 998.12 and own procedure [2]. Briefly, 10-12 g of a honey sample was
placed in a 50 ml centrifuge tube and 4 ml of distilled water was added and mixed. In another tube
about 2 ml of 10% sodium tungstate solution was
mixed thoroughly with 2 ml of 0.7 N sulphuric
acid. The solution was added to the centrifuge
tube and mixed with the solution containing the
sample of honey. The tube was heated in a water
bath at 80oC until visible flocks were formed (3-4
min). If no visible flocks were formed, or if the
supernatant remained cloudy 0.7 N acid in 2 ml
increments was added and repeated heating between additions. The sample was then centrifuged
at 1500 x g per 5 min and the supernatant removed.
The precipitate was washed with 50 ml of distilled
water, mixed and centrifuged. The washing procedure was repeated at least five times, until the su-
pernatant was clear. The precipitated protein was
dried in an oven at 60oC during at least 5 h and
transferred to a small tube before analysis.
Six parallel samples between 1.0 and 2.0 mg
each of the tested materials and each of two reference standards for δ15N and δ13C (B 2155 and
USGS-40) were transferred into tin capsules using our elemental analyser. Carbon and nitrogen
isotope analysis (δ13C and δ15N) were performed
on a DELTAplus mass spectrometer (Finnigan
MAT, Bremen, Germany), interfaced to elemental
analyser (elemental analyser Flash 1112 NCS –
Thermo Finnigan, Italy). In one measurement the
value for two isotopes were simultaneously obtained. The standard deviations of the values obtained from measurements were: 0.3‰ for δ15N
and 0.2‰ for δ13C. The values of the isotopic
ratios are expressed as δ and correspond to an
international standard (V-PDB for δ13C, and Air
for δ15N) respectively for carbon:
δ13C vsPDB
⎡ 13 C ⎤
⎡ 13 C ⎤
− ⎢ 12 ⎥
⎢ 12 ⎥
⎣ C ⎦SAMPLE ⎣ C ⎦STANDARD
=
∗1000 0 00
⎡ 13 C ⎤
⎢ 12 ⎥
⎣ C ⎦STANDARD
and for nitrogen:
δ15 N vsAIR
⎡ 15 N ⎤
⎡ 15 N ⎤
− ⎢ 14 ⎥
⎢ 14 ⎥
⎣ N ⎦SAMPLE ⎣ N ⎦STANDARD
=
∗1000 0 00
⎡ 15 N ⎤
⎢ 14 ⎥
⎣ N ⎦STANDARD
The carbon and nitrogen stable isotopes ratios in
honey and honey proteins with different floral
types such as lime tree, rape, buckwheat, multiflorous and honeydew are presented in Table and
in Fig.
Multielement stable isotope ratios (H, C, N, S)
of honey from different European regions were reported by A. Schellenberg [3]. In the frame of this
93
Table. The carbon and nitrogen stable isotopes ratios in honey and honey proteins for chosen Polish honey.
13
Code sample/honey type
15
Nprotein
-23.66
-25.14
4.26
MP2/Rape
-27.16
-27.55
1.09
MP3/Linden
-26.04
-26.45
4.08
MP4/Multiflorous
-26.91
-26.95
3.25
MP5/Linden
-23.72
-26.15
3.62
MP6/Buckwheat
-27.93
-27.27
3.85
MP7/Honeydew
-25.55
-26.13
3.03
MP8/Multiflorous
-26.39
-26.29
2.65
5
-15
2.5
-17.5
0
-20
δ13C
honey
δ13C honey
δ13C protein
δ13C
protein
δ15N protein
δ15N protein
-2.5
-22.5
-5
-25
-7.5
δ13C
δ15N
Cprotein
MP1/Multiflorous
study it was to test if honeys produced in regions
with different climatic and geological characteristics could be discriminated on the basis of the
isotopic data. Honey samples from twenty European regions including thirty samples from Poland
were collected. The δ13C and δ15N mean values of
the honey proteins for Poland honey were -26.2 ±
0.4 and 3.9 ± 0.9, respectively. The results obtained in our Laboratory show that the samples
coded as MP3/Linden, MP5/Linden, MP7/Honeydew and MP8/Multiflorous have δ13C and δ15N
-27.5
-10
-30
MP8
13
Choney
MP7
MP6
MP5
MP4
MP3
MP2
MP1
Fig. The carbon and nitrogen stable isotope ratios in honey
and honey proteins for chosen Polish honey.
values of the honey proteins within the range calculated by A. Schellenberg. The samples coded as
MP1/Multiflorous, MP2/Rape, MP4/Multiflorous
and MP6/Buckwheat have analysed values δ13C
and δ15N of the honey proteins beyond the definite
area. These divergences resulted probably from
the fact that the examined honeys originated only
from one region of Poland, while the honeys examined by A. Schellenberg originated from different
regions of Poland and different type of floral.
Until now, not much is known as to the investigation of geographical origin of honey from one
whole country. To our knowledge, there is only one
study where the determination of geographical
origin of Slovenian black locus, linden and chestnut honey was investigated by the analysis of some
physicochemical parameters and the stable carbon and nitrogen isotope ratios using isotope ratio
mass spectrometry [4]. On the other hand, the difference in the value δ13C for protein and honey for
the samples MP1/Multiflorous and MP5/Linden is
greater than 1‰ what is evident indication of
honey manipulation with C4 plant sugars such as
high fructose corn syrup (HFCS). The addition of
C4 plant sugars calculated on the basis of the formula is about 9.3% for MP1/Multiflorous honey,
and about 14.7% for MP5/Linden honey.
References
[1]. Padovan G.J., De Jong D., Rodrigues L.P., Marchini
J.S.: Food Chem., 82, 633-636 (2003).
[2]. White J.W.: J. AOAC Int., 75 (3), 543-548 (1992).
[3]. Schellenberg A. et al.: Food Chem., 121, 770-777
(2010)
[4]. Kropf U. et al.: Food Chem., 121, 839-846 (2010).
LABORATORY
FOR MEASUREMENTS
OF TECHNOLOGICAL DOSES
Laboratory for Measurements of Technological Doses (LMTD) was created in 1998 and accredited as testing laboratory in February 2004 (Polish Centre of Accreditation, accreditation
number: AB 461).
The actual accreditation range is:
• gamma radiation dose measurement by means of a Fricke dosimeter (20-400 Gy),
• gamma radiation dose measurement by means of a CTA film dosimeter (10-80 kGy),
• electron radiation dose measurement by means of a CTA film dosimeter (15-40 kGy),
• electron radiation dose measurement by means of graphite and polystyrene calorimeters,
• irradiation of dosimeters or other small objects with Co-60 gamma radiation to strictly defined doses,
• irradiation of dosimeters or other small objects with 10 MeV electron beams to strictly defined doses.
The secondary standard of the dose rate using by the LMTD is a Co-60 gamma source “Issledovatel” (cylindrical geometry, actual dose rate ~0.7 kGy/h, transit dose ~3 Gy). The source
was calibrated in April 2009, according to NPL (National Physical Laboratory, Teddington,
UK) primary standard. The uncertainty of the dose rate was estimated to be 2.9% (U, k = 2).
96
A STUDY OF FILMS: CTA, B3 AND PVC AS POTENTIAL DOSIMETERS
FOR DOSIMETRY AT LOW TEMPERATURES
Anna Korzeniowska-Sobczuk, Katarzyna Doner, Magdalena Karlińska
Sterilization of health care products, pharmaceutical and of tissue banking are important applications of radiation technology. The manufacturer
must document that the entire process is continuously under control and in compliance with national and international standards for radiation sterilization. Most of the dosimetry with films is based on
optical signal measurements [1-3]. All dosimetry
systems commonly used in the irradiation industry
are temperature sensitive. Radiation of low-temperature samples, must therefore take these dosimeter
temperature effects into consideration. Although
some information on temperature correction factors is available in the literature, the application
of a single correction factor is difficult because
there can be batch to batch differences in dosimeter
response and because temperature during the irradiation process itself is not constant throughout
the entire process. In a book, W. McLaughlin says
that “Irradiation temperature is, in fact, the most
important environmental factor contributing to
errors in absorbed dose estimation, and in radiation processing it is sometimes poorly determined
and difficult to correct for” [4].
The alanine dosimeter response has a small but
noticeable temperature dependence, and thus the
dosimeter temperature during irradiation must be
measured properly to correct this effect. The irradiation temperature coefficient is 0.23% per oC
[5], 0.185% per oC [6] or is 0.11% per oC [7]. The
reasons for differing values of temperature coefficient reported for different studies are not fully
understood, but may by due differences in measurement conditions.
The characteristics and dosimetric response of
thin film dosimetry after irradiation in room temperature are exactly known. CTA and B3 are films
widely use in routine dosimetry and were introduced into practice a few years ago [1, 2, 8, 9]. The
technical PVC film had been used as a routine
dosimeter at a sterilization plant of the Institute
of Nuclear Chemistry and Technology (INCT) for
many years [3, 6, 10-12].
In the present paper, we studied the response
of dosimeters after irradiation at a temperature of
-78oC (dry ice – solid CO2). Presented are the impact of the density of dry ice and other materials
on the reduction of the dosimetric response films.
In experiments three types of foil dosimeters were
used: CTA, B3, PCV with optical signal detection.
The film dosimeters were irradiated:
• with 10-MeV electron beams from an industrial
10-kW linear accelerator. The mean electron
energy measured by the wedge method was in
the range 9.6-9.8 MeV. The interrelation between the electron beam flux and the speed of
the conveyor delivering dosimeters under the
beam allowed keeping the dose at a specified
level. The dosimeters placed in dry ice were irradiated in the polystyrene phantoms. The dose
measurements were performed in a polystyrene or a graphite calorimetric dosimeters irradiated in the same experiment. Calorimetric
dosimeters and phantoms were produced at
the High Dose Radiation Laboratory – HDRL
(Risø, Denmark);
• in the gamma field of a reference 60Co source
Issledovatel (0.650 kGy/h), having the dose rate
traceable to a primary standard maintained by
the National Physical Laboratory – NPL (Teddington, UK);
• in the gamma field of 60Co source Gamma
Chamber 5000 (7.803 kGy/h), having the dose
rate measured using of a Fricke dosimeter.
Film dosimeters were placed in a glass-metal
thermos in the same position as during the measurements by determining the source using the
Fricke dosimeter. All irradiations in the 60Co source
were performed at the same packing geometry.
The mean temperature of irradiation was calculated as the average of temperatures before and
after the irradiation, which were measured with a
calibrated thermocouple.
The B3 and PVC films were heated immediately
after irradiation to accelerate the chemical reactions initiated by the ionizing radiation and playing
a role in the growth of the dosimetric signals. The
absorbance was measured by using a JASCO-V650
spectrophotometer UV/Vis. The wavelength and
absorbance scales were checked before each experiment by a calibrated reference standard.
During irradiation in the gamma source, sterilization dose (35 kGy) the impact was examined of
the density of the material being filled response
on the weakening of the responce of dosimetric
film. Summary of the results obtained is shown in
Table. For all investigated films, calibration curves
were constructed for the irradiation of highly en-
Table. The response of dosimeters irradiated in the Gamma Chamber 5000 to a dose of 35 kGy, at temperatures -78oC
(dry ice – solid CO2), and 25oC (room temperature) in dependence on the density fill material.
Nominal Measuring The response in dry ice
The response at room temperature A – Ao
The foil
A – Ao
thickness wavelength
dosimeters
[mm]
[nm]
d = 1.048 g/cm3
d = 0.842 g/cm3 d = 0.677 g/cm3 d = 0.07 g/cm3
CTA
0.128
280
0.1581 ± 3.4%
0.2604 ± 1.0%
0.2871 ± 1.7%
0.2492 ± 1.4%
B3
0.018
556
0.1944 ± 6.0%
0.3702 ± 2.0%
0.3979 ± 2.8%
0.3994 ± 1.9%
PCV
0.257
396
0.385 ± 0.8%
1.3009 ± 1.2%
1.3981 ± 0.7%
1.6247 ± 0.7%
ergetic electrons at the temperature of dry ice and
for a density of 0.75 g/cm3. The largest discrepancies were observed for CTA films, the convergence rate was 83% and the uncertainity measurement was 16.6%. Good results were obtained for
PVC and B3, the convergence rate was 94 and
96%, respectively. The uncertainity measurement
for the films PCV and B3 were 9.3 and 7.8%, respectively. The results are shown in Fig.
Fig. Calibration curves for irradiation with a 10 MeV electron beam from the accelerator at a temperature of dry ice
for the dosimetric films: (□) PCV, (♦) B3, (○) CTA.
Factor associated with the density (0.75-1.05
g/cm3, depending on the granulation of dry ice)
should be taken into account during irradiation in
dry ice. PVC and B3 are the potential dosimeters
that can be used for dosimetry at low temperatures and to process sterilization tissue. This requires further study.
References
[1].
[2].
[3].
ISO/ASTM 51275:2004(E). Standard practice for use
of a radiochromic film dosimetry system.
ISO/ASTM 51650:2005(E). Standard practice for use
of a cellulose triacetate system.
Bułhak Z.: Stosowanie dozymetrów foliowych w eksploatacji wielkiego źródła promieniowania – liniowego akceleratora elektronów LAE 13/6 (Use of foil
dosimeters in the exploitation of a large radiation
source – the electron linear accelerator LAE 13/6).
Instytut Badań Jądrowych, Warszawa 1975. Ph.D.
dissertation (in Polish).
[4].
97
McLaughlin W.L., Boyd A.W., Chadwick K.H., McDonald J.C., Miller A.: Dosimetry for radiation processing. Taylor & Francis, 1989, 251 p.
[5]. Sanchez-Mejorada G., Frias D., Negron-Mendoza A.,
Ramos-Bernal S.: Radiat. Meas., 43, 287-290 (2008).
[6]. Mehta K.: Appl. Radiat. Isot., 47, 11-12, 1155-1159
(1996).
[7]. Wieser A., Siegele R., Regulla D.F.: Appl. Radiat.
Isot., 40, 957-959 (1989).
[8]. Peimel-Stuglik Z.: Odpowiedź dozymetryczna nie barwionych folii z trioctanu celulozy (CTA) na promieniowanie gamma 60Co (Dosimetric response of untinted, commercially available CTA foils for 60Co
gamma rays). Instytut Chemii i Techniki Jądrowej,
Warszawa 2001. Raporty IChTJ. Seria B nr 11/2001
(in Polish).
[9]. Peimel-Stuglik Z., Fabisiak S.: Odpowiedź radiacyjna
folii PCW i folii B-3 na promieniowanie elektronowe
o energii 10 MeV w zakresie dawek 5-40 kGy (Dosimetric answer of PVC and B-3 films to electron
beams with energy 10 MeV in the range 5-40 kGy).
Instytut Chemii i Techniki Jądrowej, Warszawa 2005.
Raporty IChTJ. Seria B nr 4/2005 (in Polish).
[10]. Peimel-Stuglik Z., Fabisiak S.: Badanie czynników
wpływających na odpowiedź radiacyjną folii PCW
napromienianej w źródle kobaltowym (A study of influence factors affected dosimetric answer of PCV
films irradiated in 60Co source). Raporty IChTJ. Instytut Chemii i Techniki Jądrowej, Warszawa 2005.
Seria B nr 5/2005 (in Polish).
[11]. Peimel-Stuglik Z., Fabisiak S.: Rewalidacja metody
pomiaru dawki pochłoniętej promieniowania elektronowego dozymetrem foliowym z polichlorku winylu.
Cz.1. (Revalidation of the method used for measurement of electron beam absorbed dose by means
of a polyvinylchloride film dosimeter. Part 1). Instytut Chemii i Techniki Jądrowej, Warszawa 2007. Raporty IChTJ. Seria B nr 3/2007 (in Polish).
[12]. Peimel-Stuglik Z., Fabisiak S.: Rewalidacja metody
pomiaru dawki pochłoniętej promieniowania elektronowego dozymetrem foliowym z polichlorku winylu.
Cz.2. Krzywe kalibracyjne i post-efekty. (Revalidation of the method used for measurement of electron
beam absorbed dose by means of a polyvinylchloride
film dosimeter. Part 2. Calibaration curves and post-effects). Instytut Chemii i Techniki Jądrowej, Warszawa 2007. Raporty IChTJ. Seria B nr 4/2007 (in
Polish).
LABORATORY FOR DETECTION
OF IRRADIATED FOOD
The Laboratory for Detection of Irradiated Food was created in the Institute of Nuclear
Chemistry and Technology in 1994 and, after adoption of the quality assurance system, received its first accreditation certificate in 1999. From that time, it renders analytical service in
the field of detection of irradiated food to domestic and foreign customers in many countries.
During the last 10 years, more than 2000 food samples have been successfully examined. In
2010, the Laboratory received a new Accreditation Certificate of Testing Laboratory Nr AB 262
issued by the Polish Centre of Accreditation on 22.10.2010 valid until 24.10.2014. The integral
part of accreditation documentation is the Scope of Accreditation Nr AB 262 comprising the
list of detection methods which are in use. These are:
• detection of irradiated food containing bone by EPR spectroscopy – analytical procedures
based on PN-EN 1786:2000 standard;
• detection of irradiated food containing cellulose by EPR spectroscopy – analytical procedures based on PN-EN 1787:2001 standard;
• detection of irradiated food containing crystalline sugars by EPR spectroscopy – analytical
procedures based on PN-EN 13708:2003 standard;
• detection of irradiated food from which silicate minerals can be isolated using thermoluminescence – analytical procedures based on PN-EN 1788:2002 standard;
• detection of irradiated food using PSL (photostimulated luminescence) – analytical procedures based on PN-EN 13751:2009 standard.
The analytical activity of the Laboratory, to the orders of domestic and foreign customers
during the last 12 months, compiles the detection of irradiation in spices, herbal pharmaceuticals,
fruit and vegetable pulps, fresh fruits and vegetables, nuts, diary, mushrooms and fish. In parallel, the Laboratory develops new analytical
and measuring procedures making it possible
the detection of irradiation in complex food
articles containing typically low content of irradiated ingredient and minerals. The attention
was focused on the examination of wet samples
in L-band by EPR (electron paramagnetic
resonance) method and the effectiveness of
different procedures for mineral separation in
TL (thermoluminescence) method.
In the present year, 200 samples have been L-band electron paramagnetic resonance (EPR) spectroexamined which represented very different meter in the INCT designed and constructed in the Institute
groups of foodstuffs. As much as 14% of the of Telecomunication, Teleinformatics and Acoustics, Wrocław
total number of the samples were found to be University of Technology.
irradiated. The TL, EPR and PSL examination
of foodstuffs were executed for domestic firms and food control institutions as well as for
foreign customers in Germany, Italy, France, Denmark, Spain, the Untied Kingdom, Switzerland, Russia.
The Laboratory was invited in November 2011 to join the “Intercomparative exercise for
quality assurance on EPR and TL irradiated food detection method. 3rd round” organized by
the Food Technology Department of Spanish Agency for Food Safety and Nutrition with the
participation of specialized analytical laboratories from many countries.
100
INCT PARTICIPATES IN THE INTERCOMPARATIVE EXERCISE
FOR QUALITY ASSURANCE ON TL, PSL AND EPR IRRADIATED FOOD
DETECTION METHODS
Wacław Stachowicz, Magdalena Sadowska, Grażyna Liśkiewicz, Grzegorz P. Guzik
The National Center for Food (CNA) in Spain organized in 2011 an international intercomparative
study (3rd round) on the detection of food preserved by ionizing radiation with the use of standardized EPR (electron paramagnetic resonance),
TL (thermoluminescence) and PSL (photostimulated luminescence) methods and/or their own
protocols. The task of the present exercise was to
detect which of coded food samples was irradiated
and to distinct the samples irradiated with lower
and higher doses of radiation.
The CEN (European Committee for Standardization) standardized methods for the detection of
irradiated food by EPR, TL and PSL methods [1-5]
were validated with the use of model samples irradiated with doses equal or close to technological
doses recommended. Nowadays, food producers
and distributors tend to decrease irradiation doses
to the lowest acceptable levels assuring the intended preservation effect and microbial food safety.
Such “optimal” doses are markedly lower than
those recommended earlier. It is why in the present study low dose irradiated food samples were
examined, too.
In the present exercise twenty two laboratories
were involved from EU countries (France, Germany, Italy, Poland, Romania, Spain, United Kingdom) and from Turkey. Participating laboratories
are working on or are engaged in the detection of
irradiated food for customers or for the Official
Food Control System. Thirteen laboratories including the Laboratory for Detection of Irradiated
Food, Institute of Nuclear Chemistry and Technology (INCT) participated earlier (2010) in the
round 2nd intercomparative exercise in 2010, while
nine were new.
The samples
The following products were selected to be tested
throughout the study (Table 1):
• for TL method two samples of dried herbs,
oregano and green tea, coded as IE 3-1 and IE
3-2 and weighing about 50 g each;
• for PSL method four samples of dried spices,
curry, camomile, black pepper and rosemary,
coded as IE 3-3 to IE 3-6;
• for EPR method eight different samples as
chicken bone, pork bone, razor shell, clam shell,
walnut shell, cayenne, raisins, coded IE 3-7 to
IE 3-14.
Full list of the investigated products:
• chicken bone,
• pork bone
• walnut (shell),
• dried herbs,
• raisins (whole fruits),
• pepper,
• curry,
• cayenne,
Table 1. Samples prepared by the organizer to be analysed
in participating laboratories. Irradiation status is indicated.
Origin code
Sample
Irradiation dose
IE3-1
oregano
1 kGy
IE3-2
green tea
unirradiated
IE3-3
curry
1 kGy
IE3-4
camomile
1 kGy
IE3-5
pepper (black)
unirradiated
IE3-6
rosemary
unirradiated
IE3-7
chicken bone
unirradiated
IE3-8
pork bone
1 kGy
IE3-9
razor shell
unirradiated
IE3-10
clam shell
1 kGy
IE3-11
nut shell
1 kGy
IE3-12
cayenne
unirradiated
IE3-13
raisins
1 kGy
IE3-14
raisins
unirradiated
• camomile,
• rosemary,
• raizor shell,
• clam shell.
Organization of the study
The CNA Laboratory has prepared 14 test samples
irradiated and/or not irradiated to be delivered to
the participant by post for examination. Thus, each
of the participating laboratories analysed the following number of samples:
• two samples for TL method (each sample in duplicate);
• four samples for PSL method (each sample in
duplicate);
• eight samples for EPR method: two samples
containing cellulose, two containing crystallized
sugar, two samples of bones and two of molluscs.
All samples were coded with numbers.
Irradiation of samples
The samples analysed in the INCT for calibrated
irradiation were irradiated with the use of a 60Co
gamma source calibrated with a ferrous-ferric dosimeter (Fricke dosimeter). The dose rate was 0.95
kGy/h.
The CNA dosimetry was done using ECB dosimeters calibrated at the High Dose Reference Laboratory of Risø National Laboratory (Denmark),
which has traceability to the National Physical Laboratory (UK). The dose rate was 6.94 kGy/h.
EPR examination
The samples were examined in the INCT following the procedures adapted in the Laboratory for
Detection of Irradiated Food and based on those
recommended by the European standards:
• EN 1786 (chicken bones, pork bones, raizor
shell, clam shell);
• EN 1787 (walnut shell, cayenne);
• EN 13708 (raisins).
The EPR measurements have been done with the
use of a Bruker ESP 300 spectrometer in X-band.
The samples (ca. 2.5 cm high) were placed in 5 mm
101
Walnut shell and cayenne contain cellulose and
hence were expected to give rise to the specific
cellulose EPR signal. The criterion for the detection of irradiation in cellulose containing products
is the appearance of two satellite lines distanced
by 6 mT belonging to cellulose radical triplet (central line of this triple signal is overlapped by a
Table 2. EPR examination of investigated samples.
Origin number
Mass of sample [mg]
Name of sample
INCT result
Result as origin
IE 3-7
104.5
chicken bone
negative
negative
IE 3-8
75.8
pork bone
positive
positive
IE 3-9
309.1
raizor shell
negative
negative
IE 3-10
300.9
clam shell
positive
positive
IE 3-11
107.7
walnut (shell)
positive
positive
IE 3-12
75.1
cayenne
negative
negative
IE 3-13
103.1
raisins
positive
positive
IE 3-14
102.1
raisins
negative
negative
Wilmad glass sample tubes. The EPR measuring
conditions have followed those recommended in
the above-named standard documents.
PSL examination
The samples were examined with a SURRC PSL
screening system installed in this Laboratory following the procedures recommended in the European standard EN 13751. The samples (pepper,
curry, camomile, rosemary) were placed in 5 cm
diameter Petri-dishes. The PSL measuring conditions were adjusted as those recommended in the
above-named standard document.
Detection criteria
The criteria of the detection of radiation treatment were:
• identification of the EPR signal specific for irradiated samples,
• comparison of the PSL signal with the lower
and upper threshold values (T1 and T2) estimated for herbs and spices,
• identification of the TL signal based on the glow
ratio Glow 1/Glow 2 and the shape of Glow 1
within the range of temperatures 150-250oC for
mineral debris isolated from food samples.
strong quinone derivative signal). EPR signal recorded with radiation treated cayenne and walnut
shell was not specific enough to be qualified definitely as belonging to irradiated stuff. Nevertheless, a very weak shoulders in the EPR signal distanced by 6 mT allowed to conclude that walnut
shell could be irradiated. It was not the case with
cayenne which was qualified unirradiated. Both
qualifications were consistent with organizers data
as issued in the final report of the test.
Results of intercomparison study obtained
in the INCT Laboratory
A. EPR examination (Table 2):
• all non-irradiated samples were classified correctly,
• all irradiated samples were classified correctly.
B. PSL and TL examination (Table 3):
• all non-irradiated samples were classified correctly,
• all irradiated samples were classified correctly,
Conclusions
The standardized PSL and EPR methods for detection of radiation treatment of selected groups
of food are reliable and enable the detection of
Table 3. TL and PSL examination of investigated samples.
Origin
number
Name
of sample
Glow 1
– for fresh sample
Glow 2
– after control irradiation
INCT
result
Result
as origin
IE 3-1
oregano
2 923 366
3 893 179
positive
positive
IE 3-2
green tea
9 736
650 039
negative
negative
IE 3-3
curry
8 257 376
15 113 288
positive
positive
IE 3-4
camomile
88 282
119 194
positive
positive
IE 3-5
pepper
268
5 023
negative
negative
IE 3-6
rosemary
304
63 670
negative
negative
All samples investigated by the EPR method, with
the exception of walnut shell and cayenne, are
mentioned in relevant European standards as suitable for EPR examination whether irradiated.
food samples irradiated with 1 kGy. The PSL and
EPR methods for the detection of radiation treatment of selected groups of food are capable of
distinguishing low dose (1 kGy) and high dose
102
(7-10 kGy) irradiations. The investigated range of
doses covers that commercially adapted for radiation treatment of most of foodstuffs. However, at
doses lower than 1 kGy, like for example 0.5 kGy,
the sensitivity of EPR and PPSL methods was
found not sufficient resulting in the difficulty in
the qualification of samples. The best and most
reliable method for the detection of irradiation of
the investigated group of products was found the
TL method.
References
[1]. EN 13708:2003: Foodstuffs – Detection of irradiated
food containing crystalline sugar by ESR spectroscopy.
European Committee for Standardization (CEN),
Brussels.
[2]. PN-EN 1788:2001: Foodstuffs – Thermoluminescence
detection of irradiated food from which silicate minerals can be isolated. European Committee for Standardization (CEN), Brussels.
[3]. PN-EN 13751:2009: Foodstuffs – Detection of irradiated food using photostimulated luminescence. European Committee for Standardization (CEN), Brussels.
[4]. PN-EN 1786:2000: Foodstuffs – Detection of irradiated food containing bone – Method by ESR spectroscopy. European Committee for Standardization
(CEN), Brussels.
[5]. PN-EN 1787:2001: Foodstuffs – Detection of irradiated food containing cellulose by ESR spectroscopy. European Committee for Standardization (CEN), Brussels.
EFFECTIVENESS OF DIFFERENT PROCEDURES
OF MINERAL ISOLATION FROM IRRADIATED SPICES
SUITABLE FOR THERMOLUMINESCENCE DETECTION METHOD
Magdalena Sadowska, Wacław Stachowicz
Analytical methods suitable for the detection of
irradiated food have been developed to assure independent control of radiation preserved foodstuffs and to strengthen consumers confidence to
this relatively new method of food conservation
[1]. At present, the method most frequently used in
practice is thermoluminescence (TL) [2-4]. Substantial condition assuring high reliability of the
method is the isolation of mineral contaminants
from the tested food.
Thus, sensitivity and reliability of the detection
of irradiated food by thermoluminescence depends
on the effectiveness of mineral isolation from the
rest of food samples. Isolation procedure recommended by CEN (European Committee for Standardization) standard EN 1788:2002 [5] represents
a number of analytical steps including the main
one – density separation of the mineral fraction
from the organic remainder in sodium polytungstate water solution (d = 2.0 g/cm3). The product
most frequently undergoing examination whether
irradiated in analytical laboratories specialized in
the detection of radiation treatment of foodstuffs
are spices and seasonings in a pure state (leafs or
powders) or blended, while recently quite often
food products and diet supplements containing
spices and dried vegetables as additives as souses,
instant soups, phyto-pharmaceuticals and flavour
extracts. Usually, the content of mineral in such
products is extremely low and the application of
most effective and universal isolation procedure,
as that recommended in EN 1788:2002, is needed.
On the other hand, however, spices and dried vegetables in pure state or blended contain typically a
lot of mineral which could be isolated by a more
simple, less time consuming and inexpensive
method. In the present study the usefulness of such
methods of mineral isolation from this kind of
product was proven. As a subject of study, five commercial spices commonly used in the kitchen were
chosen. These were: dried basil leafs, powdered
onion, powdered garlic, powdered paprika and
powdered chili, all purchased in supermarkets. The
samples undergone preliminary control by applying a standard TL method (density separation) of
mineral isolation to prove whether irradiated. The
control was positive – none of the investigated
products was found irradiated. Samples were irradiated at a dose of 10 kGy (technological dose
adapted for spices) in a 60Co Gamma Chamber
(dose rate – 7.5 kGy/h) owned by the Centre for
Radiation Research and Technology, Institute of
Nuclear Chemistry and Technology (INCT). The
weight of each of the samples taken for TL examination was 25 g ± 2%.
The following mineral isolation procedures
were tested and subsequently compared:
• N – density isolation method recommended by
EN 1788:2002 lasting at least 2 h. A sample suspended in mineralized water undergoes ultrasound treatment for 10 min. Afterwards, it is
sieved wet through a 125 μm nylon net, treated
with sodium polytungstate water solution of the
density 2 g/cm3. Then, mineral debris was treated with 3 M hydrochloric acid, washed manifolds with water and centrifuged. Mineral deposit was taken from an ampoule, treated with
acetone, transferred to TL measuring cups and
dried.
• H – acid hydrolysis method lasting at least 2.5 h.
Sample suspended in water undergoes hydrolysis
with 6 M HCl for 2 h and is sieved wet through
a 125 μm nylon net. Mineral deposit taken from
the button of receiver bigger is centrifuged. The
isolated mineral debris is treated with acetone
and subsequently taken to TL measuring cups
and dried.
• P – wet sieving method lasting ca. 1 h. Sample
was stirred in demineralized water, sieved wet
through a 125 μm nylon net, while decanted
mineral deposit is taken from the button of the
vessel after removing the excess of water, treated with acetone and transferred to TL measuring cups.
• U – ultrasound method. Sample suspended in
mineralized water is for 10 min treated with
ultrasounds and then sieved wet through a 125
μm nylon sieving net. Mineral debris is taken
from the button of the vessel after removing of
excess water, treated with acetone and transferred to TL measuring cups, as above.
Minerals deposited on TL measuring cups isolated by four mineral separation procedures from
each of the five investigated products (test sample
weight – 25 g ± 2%) were weighed with an accuracy
of 0.0001 g. According to EN 1788:2002 standard,
the weight of mineral isolated from food that
103
silicates in it. However, this factor remains not
controllable and everything depends on recorded
data (counts of TL glow pulses/photons). Accord-
Fig.3. The normalized glow curves recorded with mineral
fraction isolated from irradiated garlic by four isolation
procedures tested: N – mineral separation, H – hydrolysis,
P – sieving, U – ultrasound treatment.
ingly, weighing of minerals is in practice not necessarily needed. Nevertheless, weighing of mineral
deposits in the present study is rational, indicating
how efficient was isolation procedure despite of its
composition.
fraction isolated from irradiated basil by four isolation procedures tested: N – mineral separation, H – hydrolysis, P –
sieving, U – ultrasound treatment.
guarantee the reliable TL detection of irradiation
lies between 0.1 and 5 mg. It is also recommended
to divide bigger mineral volumes to parts before
TL measurement. Low mineral weight below 0.1
mg is too low to proceed properly TL measure in
most cases. It is pertinent to note that a lower (0.1
mg) threshold value of mineral weight has only
empirical origin and was established on the ground
fraction isolated from irradiated paprika by four isolation
procedures tested: N- mineral separation, H – hydrolysis,
For each of the investigated spices, two TL
measurements were done in parallel. The intensity of thermoluminescence (the area below glow
curves) was measured within the range of temperature between 150 and 250oC. It is the region
where only radiation-induced thermoluminescence
appears.
fraction isolated from irradiated onion by four isolation
procedures tested: N – mineral separation, H – hydrolysis,
of a number of repeated measurements done with
selected model samples. The factor that influences
TL response of mineral deposit is the content of
fraction isolated from irradiated chili by four isolation procedures tested: N – mineral separation, H – hydrolysis, P –
sieving, U – ultrasound treatment.
104
In Figs. 1-5 the TL glow curves recorded with
mineral debris isolated from irradiated test products by four mineral isolation methods are compared.
As seen from the Table (column III), the highest volumes of mineral were isolated from garlic, a
little lower, but still high from paprika and chili,
but markedly lower from powdered onion. Isolation procedure based on sieving only result in the
lowest yield of mineral, lower than acceptable
threshold level (01 μg, see EN 1788:2002).
This parameter, however, is different from
sample to sample depending on the initial state of
product (cleaning/washing procedures).
Very interesting results were obtained when
TL intensities of Glow 1 (column IV) recorded
with mineral debris isolated by four different procedures from seven tested products were compared:
• Basil – the highest TL intensities were recorded
with mineral isolated by using hydrolysis (H)
and ultrasound treatment (U). The efficiency
of recommended mineral separation procedure
(N) was lower although still acceptable.
• Onion – positively the highest TL intensity was
obtained by using a density separation procedure, while the application of ultrasound delivered also a satisfactory result. However, hydrolysis
was found not suitable at all.
• Garlic – the highest TL intensities were obtained by the examination of mineral isolated with
the use of density separation and hydrolysis.
Both simplified isolation methods (sieving – P
and ultrasound treatment – U) were found also
efficient enough.
• Paprika – the most effective mineral isolation
was obtained by using hydrolysis (H) and simple
sieving (P). The effectiveness of two other isolation procedures was acceptable, too.
• Chili – the most efficient was mineral separation (N) and ultrasound treatment (U), while
the other two methods were effective, too.
From the above comparative study, it is clearly
seen that by the examination of dried spices and
Table. The results of TL examination of mineral debris isolated from irradiated (10 kGy).
Sample
number
Isolation
procedure*
Weight
of isolated mineral
[mg]
I
II
III
Glow 1 –
Glow 2 –
count number count number
150-250oC
150-250oC
IV
Glow ratio
Glow1/Glow2
TLGlow maxima
[oC]
V
VI
VII
BASIL
1
N
1.24
102 761 197
26 653 589
3.85
187
2
H
1.88
148 997 859
35 116 171
4.24
192
3
P
2.04
67 270 283
15 361 976
4.37
192
4
U
2.77
132 898 929
30 471 611
4.36
191
ONION
5
N
0.18
948 159
384 089
2.47
182
6
H
0.80
2 034
15 299
0.13
211
7
P
0.01
128 372
13 370
9.60
185
8
U
0.44
523 517
380 465
1.37
184
GARLIC
9
N
2.70
240 336 683
160 706 762
1.49
212
10
H
2.40
277 935 518
97 515 393
2.85
207
11
P
2.4
135 691 991
68 385 190
1.98
215
12
U
2.6
162 791 696
79 627 348
2.04
218
PAPRIKA
13
N
2.5
253 405 801
158 385 613
1.59
199
14
H
2.1
277 457 004
124 366 735
2.23
200
15
P
3.2
291 027 650
166 605 537
1.74
200
16
U
1.2
137 331 443
69 698 228
1.97
202
CHILI
17
N
1.6
238 175 443
131 728 313
1.81
198
18
H
1.3
175 049 815
58 646 969
2.98
205
19
P
1.8
161 833 118
73 704 992
2.19
206
20
U
1.9
191 628 642
92 256 991
2.07
199
* For more details see the text above.
vegetables the recommended density separation
procedure (N) does not dominate much over three
other isolation procedures tested including relatively simple sieving (P) and ultrasound treatment
(U). It is advisable to use these methods in analytical practice under the condition that for each
product the testing and validation of isolation procedures will be done in advance. It has to be pointed out that the recommended density separation
is not only a complex and time consuming procedure, but also the most expensive one.
References
[1]. FAO/WHO Codex Alimentarius. Vol. XVI. 1984.
105
[2]. Autio T., Pinjoja S.: Z. Lebensm. Untersuch. Forsch.,
191, 177-180 (1990), in German.
[3]. Calderon T., Rendell H.M., Beneitez P., Townsed P.D.,
Millan A., Wood R.: J. Food Sci., 59, 1070-1071 (1994).
[4]. Lesgards G., Fakirian A., Raffi J.: Thermoluminescence identification of irradiated food: LARQUA research. In: Detection methods for irradiated foods –
current status. Eds. C.H. McMurray, E.M. Stewat, R.
Gray, J. Pearce. Royal Society of Chemistry, Cambridge, UK 1996, pp. 158-167.
[5]. EN 1788:2002: Foodstuffs – Thermoluminescence detection of irradiated food from which silicate minerals
can be isolated. European Committee for Standardization (CEN), Brussels.
LABORATORY
OF NUCLEAR CONTROL SYSTEMS
AND METHODS
The main subject of the Laboratory activity in 2011 was the development of methods and apparatus, based generally on the application of ionizing radiation, and process engineering for
measurements and diagnostic purposes. The research programme of the Laboratory was focused on the following topics:
• development, construction and manufacturing of measuring devices and systems for industry,
medicine and protection of the environment;
• elaboration and implementation of wireless communication systems based on GPS or the
Internet for data acquisition and transmission;
• construction and laboratory testing of a gamma scanner for diagnostics of industrial installation;
• development of measuring equipments for other Institute laboratories and centers;
• development of a new leakage control method for testing of industrial installations during
their operation;
• identification and optimization of industrial processes using tracers and radiotracer methods;
• application of membrane processes of biogas separation and their enrichment in methane;
• elaboration and implementation on an industrial scale of new methods and technology of
biogas production by fermentation of agriculture substrates and by-products;
• hydrogen production from the synthesis gas using membrane separation.
In the field of elaboration and construction of new nuclear instrumentation the works
were directed towards radioactive contaminations, measurements of concentration of radon
daughters and wireless data transmission.
A radiometric stand based on the application of large area thin scintillators for alpha-,
beta- and gamma-radiation measurement, was constructed and tested for contamination detection in laboratory and industrial conditions.
The system for attached and unattached radon 222Rn decay products in air or water was
elaborated and tested in laboratory conditions. In the frame of realized R&D project, development of a new generation of mining radiometers was undertaken. The radiometer to be used
in mines where methane gas can be present, must satisfy the explosion proof conditions.
All realized and constructed instruments are prepared in the version with wireless transmission of results and their storage in memory of data acquisition system. The Wi-Fi (Wireless
Fidelity) and GSM (Global System for Mobile Communication) are used for data transmission
depending on the distance between the detector and control unit. The same type of measuring
equipment is used in a gamma scanner for diagnostics of large industrial installations.
108
THE RADIOMETRIC PROBES FOR INDUSTRIAL MEASURING SYSTEMS
Adrian Jakowiuk, Ewa Kowalska, Jan Pieńkos, Paweł Filipiak, Łukasz Modzelewski,
Jacek Palige, Janusz Kraś
In the frame of the development of new measuring systems a wireless probe (detector) was designed for measurements of ionizing radiation in
industrial and field conditions (Fig.1).
to determined the location and type of column
damage or disturbance of the process. The measurements is based on the simultaneous move of
the radiation source and scintillation probe on opposite sides of the tested column. The drive of
source and detector are on the ground (level zero).
Measuring diagram is shown in Fig.2 [1].
Fig.1. Probe for industrial radiometry.
Scintillation probe allows for the collection,
processing and storage of measurement results
through a dedicated steering software. These
probes have a built-in battery and are equipped
with a system for wireless communication to the
central unit of data acquisition. The detector consist of radiometric and electronic parts and is
equipped with a microcontroller that controls operation of communications systems and proper
operation of the probe.
The measurement results can be sent to a unit
of data collection using one of two transmission
channels in Wi-Fi for short measurement series
(up to 48 h) or through the GSM and the Internet
for long-term measurements.
Functional parameters of detector are the following:
• X-rays or gamma-radiation measurements in the
environment probes for quantum energy above
50 keV;
• possibility of continuous work with radioactive
isotopes 60Co, 137Cs, 241Am;
• possibility of probes work in vertical and horizontal positions also as hanging device in industrial and field conditions;
• active front surface – 20 cm2, side – 25 cm2;
• counts efficiency for isotope 137Cs: ≥ 20%;
• counts efficiency for isotope 60Co: ≥ 40%;
• manage of the probe work by a laptop or PDA;
• collection the measurements results of the
probe by using wireless communication (Wi-Fi,
GSM);
• power supply: built-in battery allows continuous operation of the probe during 10-14 days.
Possible connection with solar panels battery;
• range of operating temperatures: -10 to +40oC;
• dimension and weight: diameter – 9 cm (with
antennas φ12), length – 63 cm, weight – 7 kg.
Scintillation probes of this type can find application in the control and measuring the operation
parameters of various object and industrial installations. Such probes have been used in the gamma
scanner, which is used for identification of operation parameters of rectification columns in the
petrochemical industry.
The test column is screened by using radiation
sources 60Co or 137Cs. Based on the measurements
recorded in combination with archival measurements made on the same installation, it is possible
Fig.2. Functional diagram of a gamma scanner: Z – gamma-radiation source 137Cs, 555 MBg (15 mCi); SS – scintillation
probe with scintillate NaI(Tl) φ50 x 50 mm, equipped with
a wireless communication system, powered from a local
battery; NZ – drive shift of a source with a wireless control
system; NS – drive shift of the scintillation probe with a
wireless control system; PC – portable computer, a “notebook”, and a scanner program with a system of wireless
communication; P – fence; LP – leading rope; NL – tension
of the rope leading; KZ – wheel suspension of probe and
container with the source.
The designed system does not have a network
cable (with electric contact) for data transmission
from the probe (detector) to the control and data
processing unit, what is important for its use in the
petrochemical industry.
Test may be conducted during normal operation of installation and requires no intervention
within the diagnosed column. Realization of measurements requires only location on the external
parts of the installation, and using of lines to move
the source and detector in selected vertical sections of the installation. Typical scans obtained
during the experiments are shown in Fig.3.
Another application of this scintillation probe
type system is used for leak testing of industrial
objects using a unique method developed in the
(INCT) using radioactive tracer [2]. This kit consists of:
• four scintillation probes for the measurement
of gamma and beta radiation,
• multichannel impulse amplitude analyser,
• wireless system for information transmission
between the probe and the central unit,
• the software that controls work of the whole
set.
A scheme of leak testing is presented in Fig.4.
In the case of studying industrial objects, the
most important statement is the presence or ab-
series 1
series 3
series 4
109
probes S1 to S4. Based on the time elapsed from
the registration of radiation on individual probes,
the overall leak installation is calculated. When
none of the probes register growth radiation, the
Fig.4. A scheme of leak testing of industrial object.
installation is considered as a 100% air-tight. In
the case of a leak detection, the order methods for
leakage localization are applied [3].
References
Fig.3. Course of the scan test installation (distance between source and detector – 120 cm; series 1 – step of distance discretization – 1 cm, time per channel – 10 s; series
3 – step of distance discretization – 5 cm, time per channel
– 30 s; series 4 – step of distance discretization – 5 cm, time
per channel – 10 s.
sence of leak. The applied method is based on the
introduction of radioactive tracer (methyl bromide) to the controlled object, followed by continuous measurement of radiation values by using
[1]. Machaj B., Jakowiuk A., Świstowski E., Palige J.:
Gamma skaner GS-08. Instrukcja obsługi (Operation
manual of gamma scanner GS-08). Institute of Nuclear Chemistry and Technology, Warszawa 2011. Opracowanie wewnętrzne IChTJ nr 36/LTJ/11, in Polish.
[2]. Kraś J., Waliś L.: Lokalizacja nieszczelności w obiektach technologicznych przy użyciu metody znaczników
promieniotwórczych (Localization of leakages in technological objects using the method of radioactive
markers). Postępy Techniki Jądrowej, 42, 4 (1999), in
Polish.
[3]. Kraś J., Waliś L., Myczkowski S.: Doświadczenia z izotopowej kontroli szczelności obiektów technologicznych – aspekty techniczne i ekonomiczne (Experience
in isotope leak-proof control of engineering objects –
technical and economical aspects). In: Technika jądrowa w przemyśle, medycynie, rolnictwie i ochronie środowiska T.2. Raporty IChTJ. Seria A nr 2/2002. Instytut Chemii i Techniki Jądrowej, Warszawa 2002, pp.
373-379, in Polish.
MOBILE DOSIMETRIC GATE
Adrian Jakowiuk, Ewa Kowalska, Jan Pieńkos, Paweł Filipiak, Łukasz Modzelewski
Mobile dosimetric gate was constructed for the
purpose of continuous monitoring of radiation
background in places involving work with radioactive sources (possibility of contamination) and constant control of places with high concentration of
people (railway stations, airports, underground) in
order to detect an illegal transport of radioactive
isotopes. When comparing to similar devices [1-3],
mobile dosimetric gate is a stand-alone device,
able to work either indoors or outdoors. Current
measurements of background radiation can be received continuously or periodically by a computer
through wireless communication network Wi-Fi
[4]. Several gates, placed in different locations, can
be connected to the computer forming a monitoring network. The gate signals dangerous exceeding of the surrounding radiation background using light and sound signalling.
Principles of operation and construction
of the gate
The gate uses a scintillation probe containing a
sensitive to X- and gamma radiation integrated
detector with a NaI(Tl) scintillator, φ50 x 50 mm.
Pulses from the detector, shaped and amplified,
are sent to two measuring channels. In the first
channel, after the photomultiplier noise being cut
off, pulses go to the counter, where under the control of microcomputer are counted at specified
time intervals. The second measuring channel is
to analyse radiation registered by the probe, by
finding and positioning peaks in the spectrum recorded by the analyser. As a result, it is possible to
determine the probable isotope type which caused
the alarm. This channel runs continuously, but the
results are analysed only when the alarm counting
threshold is exceeded.
110
The gate works under the control of microcomputer, which manages the operation of the probe,
registers actual measurements in the memory,
launches the light and sound signalling (after exceeding alarm counting threshold) and sends information to the control centre about dangerous
breaches of the background.
The gate (Fig.1) consists of a long tube (φ15 x 70
cm) expanded in the lower part (φ33 x 30 cm). The
scintillation probe is located in the upper part. In
the middle part, electronics which registers measured radiation can be found. In the expanded part
there are batteries to power the electronics and a
signalling system (placed in the upper part). Thanks
to using the internal power, the designed gate is
mobile and easy to change location.
Measurement results and ways of presenting
Current measurement results of radiation background around the gate can be tracked on the
computer monitor, connected to the gate through
Wi-Fi network. Basic program panel to support
mobile dosimetric gate (Fig.2) displays digitally the
current (last 15 s) average number of background
counts in pulses per second and illustrates this
value graphically. There is also given a number of
exceedances of background for the set time range
of the measurement.
When turning the advanced panel on, the results
can be seen as graphs for a selected period of time.
Sample plot of background radiation measurements of four consecutive days is shown in Fig.3.
It is also possible to individually elaborate the
measurement results in different graphic programs
by transferring the results from the computer’s
memory (“Save to file” command). This is how the
results of an experiment carried out with a 60Co
source were illustrated. After establishing the back-
Fig.2. The main program window for mobile dosimetric gate.
Fig.1. Mobile dosimetric gate with a solar cell used to battery charging.
ground radiation (Fig.4, A area), a 1 μCi 60Co
source was placed at a distance of 30 cm from the
centre of the probe. The system responded by
turning on the alarm, rapid growth of background
indications and changed to one-second measurements (Fig.4, B area). After changing the distance
to 50 cm, the average measurement results are
shown again in five-second intervals (Fig.4, C
area).
The average background exceeding level followed by a sound and light threat signal and the
change of sending results to computer memory
111
Fig.3. The waveform of the background radiation measured in four consecutive days. The solid line – 1 h moving average
of the measured background.
every 1 s was set up to be 100 Bq. This value can
be changed on user’s request.
Exceeding the alarm threshold of radiation
around the gate, is a signal to carry out preliminary analysis of the radiation source (energy). The
second measuring channel containing a simple
analyser of the pulses amplitude is used. The operation of this system can be observed on the computer screen when you run advanced panel and
Rys.4. The measurement of dosimetric gate B_DOZ:A001
with 60Co source ca. 1 μCi: A – background radiation, B –
source at a distance of 30 cm, C – source at a distance of 50
cm from the centre of the probe. A, C – 5 s measurements,
B – 1 s measurements.
choose the option “Collect spectrum”. The image
of the spectrum changes every 5 s and after 1 min
(depending on the energy and the intensity of the
radiation reaching the gate’s head) it shows the
main peaks of the radiation source. The device
periodically calculates, for the main peaks occur-
ring in the spectrum, their location and their percentage in the spectrum. It can be then a basis for
determining the type of isotope which caused the
alarm threshold crossing. The position of the
peaks can be also checked manually by changing
the position of two cursors on the spectrum image.
The basic operational parameters of the gate
Mobile dosimetric gate is a sensitive detector
of X- and gamma radiation in its surrounding
from 50 keV energy. Detection area depends on
the energy and intensity of the radiation, but for
the most commonly used isotopes in industry and
medicine with an average activity over 200 μCi, is
about 2 m around the gate (if there are no natural
or artificial screens between the gate and the
source of radiation).
Efficiency of indications of the Gate for different incident radiation energies equals: over 90%
for 1200 keV, over 60% for 660 keV and about
30% for 60 keV.
Current measurement results of the gate can be
received and registered on a computer using Wi-Fi
wireless communication. The developed system
allows different ways of viewing the results from
different periods of time.
The gate turns the sound and light signalling,
when the radiation in surrounding area increases
by 100 Bq in relation to the fixed background.
Then, the 1 s long measurements are made and the
results are transmitted to the computer with the
same intervals.
When the computer is disconnected from the
network, the counts exceeding the background
are stored in the gate’s local memory and send to
the computer when the connection is established.
112
Several gates placed in different locations can
be connected via Wi-Fi network with a single computer creating a network monitoring
It is ensured that the continuous operation of
mobile dosimetric gate in normal conditions should
be equal to about 10 to 14 days without charging
the batteries. There is a possibility of connecting
the gate to the solar batteries power supply.
Mobile dosimetric gate was developed and made
within the project “New generation of intelligent
radiometric tools with wireless data transmission”
co-financed by the European Union from the European Regional Development Found.
References
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[3]. Stacjonarne monitory do kontroli pojazdów VM
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Journal of Chemical Crystallography, 41, 1988-1997 (2011).
84. Zagórski Z.
Nukleonika militarna – nieznane fakty z historii najnowszej (Military nucleonics – unknown facts from
the modern history).
Postępy Techniki Jądrowej, 54, 2, 22-25 (2011).
85. Zagórski Z.P.
Zimna fuzja raz jeszcze. [List do Redakcji] (Cold fusion once more – A Letter to the Editors).
Wiadomości Chemiczne, 1-2, 157-161 (2011).
86. Zagórski Z.P., Rajkiewicz M., Głuszewski W.
Radiacyjna modyfikacja elastomerów (Radiation modification of elastomers).
Przemysł Chemiczny, 6, 1191-1194 (2011).
87. Zhydachevskii Ya., Berkowski M., Warchoł S., Suchocki A.
Dosimetric properties of the 570 K thermoluminescence peak of YAlO3:Mn crystals.
Radiation Measurements, 46, 494-497 (2011).
119
BOOKS
1. Monitoring, control and effects of air pollution.
Ed. A.G. Chmielewski. InTech, Rijeka, Croatia 2011, 254 p.
2. Radiotracer applications in wastewater treatment plants.
Eds. L.E.B. Brandao, P. Brisset, A. Chmielewski, S. Genders, J.M. Griffith, J.-H. Jin, I.H. Khan, R. Kjellstrand, J. Palige, A. Pandit, H.J. Pant, Sung-Hee Jung, J. Thereska. Training Course Series no. 49. IAEA,
Vienna 2011, 93 p.
3. Samczyński Z., Dybczyński R.S., Polkowska-Motrenko H., Chajduk E., Pyszynska M., Danko B.,
Czerska E., Kulisa K., Doner K., Kalbarczyk P.
Preparation and certification of the new Polish reference material: Oriental Basma Tobacco Leaves
(INCT-OBTL-5) for inorganic analysis. Institute of Nuclear Chemistry and Technology, Warszawa 2011,
87 p.
4. Samczyński Z., Dybczyński R.S., Polkowska-Motrenko H., Chajduk E., Pyszynska M., Danko B.,
Preparation and certification of the new Polish reference material: Oriental Virginia Tobacco Leaves
(INCT-PVTL-6) for inorganic analysis. Institute of Nuclear Chemistry and Technology, Warszawa 2011,
88 p.
5. Sun Y.
Air organic pollutants destruction by using electron beam technology. Experimental and theoretical study.
LAP Lambert Academic Publishing, 2011, 152 p.
CHAPTERS IN BOOKS
1.
Bilewicz A., Bobrowski K., Chmielewski A.G., Marcinek A., Narbutt J., Przybytniak G., Szamrej-Foryś I.
Chemia radiacyjna, chemia jądrowa i radiochemia (Radiation chemistry, nuclear chemistry and radiochemistry).
In: Misja nauk chemicznych. Ed. B. Marciniec. Wydawnictwo Nauka i Innowacje, Warszawa 2011, p.
83-108.
2.
Bobrowski K.
Radiation-induced radicals and radical ions in amino AIDS and peptides.
In: Selectivity, control, and fine tuning in high-energy chemistry. Eds. D.V. Stass, V.I. Feldman. Research
Signpost, Trivandrum 2011, p. 41-68.
3.
Boguski J., Przybytniak G., Mirkowski K., Bojanowska-Czajka A., Nowicki A.
Starzenie radiacyjne kabli w elektrowniach jądrowych – wpływ antyutleniacza Irganox 1035 (Radiation
ageing of cables in nuclear power plants – influence of Irganox1035 antioxidant).
In: Modyfikacja polimerów. Stan i perspektywy w roku 2011. Ed. R. Steller. Wydawnictwo TEMPO s.c.,
Wrocław 2011, p. 207-210.
4.
Bojanowska-Czajka A.
Zastosowanie promieniowania jonizującego do rozkładu wybranych zanieczyszczeń organicznych wód
i ścieków (Application of ionizing radiation to the decomposition of selected organic impurities in waters
and professional sources).
In: Rola dokonań młodych naukowców a możliwości osiągnięcia sukcesu naukowego i zawodowego.
Vol. 2. Ed. M. Kuczer. Creativetime, Kraków 2011, p. 107-111.
5.
Brandenburg R., Barankova H., Bardos L., Chmielewski A.G., Dors M., Grosch H., Hołub M.,
Laan M., Mizeraczek J., Pawelec A., Stamate E.
Plasma-based depollution of exhausts: principles, state of the art, and future prospects.
In: Monitoring, control and effects of air pollution. Ed. A.G. Chmielewski. InTech, Rijeka, Croatia 2011,
p. 229-254.
6.
Chajduk E., Doner K., Polkowska-Motrenko H., Bilewicz A.
Opracowanie układu rozdzielczego Se-As i jego wykorzystanie w generatorze radionuklidów 72Se/72As
(Elaboration of a Se-As separation system and its use in a 72Se/72As generator).
Vol. 2. Ed. M. Kuczer. Creativetime, Kraków 2011, p. 128-130.
120
7.
Dybczyński R.
Neutronowa analiza aktywacyjna i jej zastosowania (Neutron activation analysis and its applications).
In: Nauka i przemysł – metody spektroskopowe w praktyce, nowe wyzwania i możliwości. Ed. Z. Hubicki.
Uniwersytet M. Curie-Skłodowskiej w Lublinie, Lublin 2011, p. 12-25.
8.
Hęclik K., Balawejder M., Kisała J., Mazurkiewicz W., Pogocki D.
Betulina i jej pochodne – triterpeny pochodzenia naturalnego o różnorodnej aktywności farmakologicznej (Betulin and its derivatives – triterpenes of natural origin and different pharmacological activity).
In: Nowoczesne metody analizy surowców rolniczych. Eds. Cz. Puchalski, G. Bartosz. Uniwersytet Rzeszowski, Rzeszów 2011, p. 523-533.
9.
Jakowiuk A.
Nowa generacja inteligentnych urządzeń radiometrycznych z bezprzewodową teletransmisją informacji
(New generation of inteligent radiometric facilitaties with a wireless transmission of information).
In: Nowe projekty rozwojowe. Wybrane projekty realizowane w ramach poddziałania 1.3.1 programu
„Innowacyjna gospodarka”. OPI, Warszawa 2011, p. 216-217.
10. Kalbarczyk P., Polkowska-Motrenko H.
Optymalizacja procesu rozpuszczania ThO2 napromienionego w reaktorze jądrowym (Optimization of
the dissolution process of ThO2 irradiated in a nuclear reactor).
Vol. 2. Ed. M. Kuczer. Creativetime, Kraków 2011, p. 161.
11. Kasztovszky Z., Kunicki-Goldfinger J.
Applicability of prompt gamma activation analysis to glass archaeometry.
In: Proceedings of the 37. International Symposium on Archaeometry. Ed. I. Turbanti-Memmi. Springer-Verlag, Berlin-Heidelberg 2011, p. 83-90.
12. Kruszewski M., Brzóska K., Brunborg G., Asare N., Dobrzyńska M., Dusińska M., Fjellsbø L.M.,
Georgantzopoulou A., Gromadzka-Ostrowska J., Gutleb A., Lankoff A., Magdolenová Z., Pran
E.R., Rinna A., Instanes C., Sandberg W.J., Schwarze P., Stępkowski T., Wojewódzka M., Refsnes M.
Toxicity of silver nanomaterials in higher eukaryotes.
In: Advances in molecular toxicology. Vol. 5. Ed. J.C. Fishbein. Elsevier B.V., Amsterdam 2011, p.
180-218.
13. Nowicki A., Przybytniak G., Mirkowski K.
Opracowanie kleju termotopliwego do instalacji ciepłowniczych (Developing of hot-melt adhesive for
hot-water installation).
In: Modyfikacja polimerów. Stan i perspektywy w roku 2011. Ed. R. Steller. Wydawnictwo TEMPO s.c.,
Wrocław 2011, p. 663-666.
14. Polkowska-Motrenko H., Kalbarczyk P., Chajduk E., Dudek J.
Oznaczanie uranu w torze aktywowanym neutronami w reaktorze Maria (Determination of uranium in
thorium neutron-activated in the reactor Maria).
In: Badania materiałowe na potrzeby elektrowni i przemysłu energetycznego. XVIII seminarium naukowo-techniczne, Zakopane, Poland, 28-30.06.2011. IAE, Otwock-Świerk 2011, p. 127-132.
15. Przybytniak G., Kornacka E.M., Fuks L., Walo M., Łyczko K., Mirkowski K.
Functionalization of polymer surfaces by radiation-induced grafting for separation of heavy metal ions.
In: Report of the 3. RCM on “Development of novel adsorbents and membranes by radiation-induced
grafting for selective separation purposes”, Budapest, Hungary, 6-10 December 2010. IAEA, Vienna
2011, p. 212-230.
16. Wójciuk K., Lewandowska H., Lewandowski W.
Zastosowanie radiolizy impulsowej oraz metod spektroskopowych w badaniach właściwości antyutleniających polifenoli występujących w żywności (Use of pulse radiolysis and spectroscopic method in the
studies of antioxidant properties of polyphenols).
In: Nauka i przemysł. Metody spektroskopowe w praktyce, nowe wyzwania i możliwości. Uniwersytet M.
Curie-Skłodowskiej w Lublinie, Lublin 2011, p. 214-222.
17. Zalewski M., Chmielewski A.G., Palige J., Roubinek O., Wawryniuk K., Usidus J., Kryłowicz A.,
Chrzanowski K.
Zagospodarowanie odpadów roślinnych i spożywczych do produkcji biogazu (Management of vegetable
and food waste for biogas production).
In: Człowiek a środowisko – w poszukiwaniu możliwej symbiozy. Kraków 2011, p. 151-157.
121
THE INCT PUBLICATIONS
1.
INCT Annual Report 2010.
Institute of Nuclear Chemistry and Technology, Warszawa 2011, 161 p.
2.
Lazurik V.M., Lazurik V.T., Popov G., Rogov Yu., Zimek Z.
Information system and software for quality control of radiation processing.
International Atomic Energy Agency/Collaborating Centre for Radiation Processing and Industrial
Dosimetry (Institute of Nuclear Chemistry and Technology), Warszawa 2011, 232 p.
3.
Samczyński Z., Dybczyński R.S., Polkowska-Motrenko H., Chajduk E., Pyszynska M., Danko B.,
Preparation and certification of the new Polish reference material: Oriental Basma Tobacco Leaves
(INCT-OBTL-5) for inorganic trace analysis.
4.
Samczyński Z., Dybczyński R.S., Polkowska-Motrenko H., Chajduk E., Pyszynska M., Danko B.,
Preparation and certification of the new Polish reference material: Polish Virginia Tobacco Leaves
(INCT-PVTL-6) for inorganic trace analysis.
5.
Polkowska-Motrenko H., Chajduk E., Dudek J., Skwara W., Pyszynska M.
Badanie biegłości ROŚLINY 10 – oznaczanie zawartości As, Cd, Cr, Cu, Hg, Pb, Se i Zn w cebuli suszonej (Allium cepa) (Proficiency test PLANTS 10 – determination As, Cd, Cr, Cu, Hg, Pb, Se and Zn in
dry onion powder).
Instytut Chemii i Techniki Jądrowej, Warszawa 2011. Raporty IChTJ. Seria B nr 1/2011, 28 p.
6.
Sadowska M.W., Stachowicz W.
Efektywność różnych procedur izolacji minerałów w metodzie termoluminescencji stosowanej do identyfikacji napromieniowanej żywności (Effectiveness of different procedures for mineral separation in
thermoluminescence method adapted for the detection of irradiated food).
7.
Zimek Z., Przybytniak G., Nowicki A., Mirkowski K., Roman K., Bułka S., Skajster J., Pujdak D.
Uruchomienie modelowego urządzenia do przewijania kabli i przewodów elektrycznych w procesie obróbki radiacyjnej w akceleratorze IŁU-6 (Testing set up for electrical cables and wires rewinding during
radiation processing based on ILU-6 electron accelerator).
CONFERENCE PROCEEDINGS
1.
Alaimo G., Alessi S., Enea D., Pitarresi G., Przybytniak G., Spadaro G., Tumino D.
The durability of carbon fiber/epoxy composites under hydrothermal ageing.
XII DBMC – International Conference on Durability of Building Materials and Components, Porto,
Portugal, 12-15.04.2011, 8 p.
2.
Chmielewski A.G., Berejka A.J.
Electron accelerators: a powerful tool for polymer processing.
Thermoset 2011: From Monomers to Components. Proceedings of the 2. International Conference on
Thermosets, Berlin, Germany, 21-23.09.2011, p. 29-31.
3.
Chmielewski A.G., Pawelec A., Witman S.
Technologia jednoczesnego usuwania SO2 i NOx z gazów odlotowych przy użyciu wiązki elektronów (Simultaneous technology of SO2 and NOx removal from exhaust gases using electron beam).
IX Konferencja „Dla miasta i środowiska – Problemy unieszkodliwiania odpadów”, Warszawa, Poland,
28.11.2011, p. 134-137.
4.
Chmielewski A.G., Urbaniak A., Harasimowicz M., Zalewski M.K., Wawryniuk K., Roubinek O.K.
Wzbogacanie biogazu w metan w kaskadzie modułów membranowych (Biogas enrichment in methane
with using mobile membrane cascade).
28.11.2011, p. 138-141.
122
5.
Chmielewski A.G., Urbaniak A., Zalewski M.K., Roubinek O.K., Wawryniuk K.
Membranowa separacja biogazu uzyskanego podczas fermentacji i kofermentacji odpadów lignocelulozowych (Membrane separation of biogas produced in fermentation and co-fermentation of lignocellulosic wastes).
28.11.2011, p. 181-183.
6.
Fuks L., Gniazdowska E., Koźmiński P., Mieczkowski J.
Novel technetium and rhenium complexes with the N-heterocyclic aldehyde thiosemicarbazones – potential radiopharmaceuticals.
7. International Symposium on Technetium and Rhenium – Science and Utilization, July 4-8, 2011,
Moscow, Russia. Book of proceedings. Eds. K.E. German, B.F. Myasoedov, G.E. Kodina, A.Ya. Maruk,
I.D. Troshkina. Publishing House GRANITSA, Moscow 2011, p. 339-342.
7.
Głuszewski W.
Maria Skłodowska-Curie prekursorka metody radiacyjnej sterylizacji (Maria Skłodowska-Curie as precursor of the method of radiation sterilization).
XI Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 20-21.10.2011,
p. I(1-6).
8.
Głuszewski W.
Oddziaływanie promieniowania jonizującego na materię (Interaction of ionization radiation with matter).
p. III(1-4).
9.
Gniazdowska E., Koźmiński P., Bańkowski K.
99m
Tc-labelled vasopressin analog d(CH2)5[D-Tyr(Et2),Ile4,Eda9]AVP as a potential radiopharmaceutical
for small-cell lung cancer (SCLC) imaging.
7. International Symposium on Technetium and Rhenium – Science and Utilization, July 4-8, 2011,
Moscow, Russia. Book of proceedings. Eds. K.E. German, B.F. Myasoedov, G.E. Kodina, A.Ya. Maruk,
I.D. Troshkina. Publishing House GRANITSA, Moscow 2011, p. 343-346.
10. Kałuska I.
Czy szykują się jakieś zmiany w przepisach związanych ze sterylizacją radiacyjną? (Are the changes in
rules of radiation sterilization in preparation?).
p. XIX(1-2).
11. Kałuska I.
Kwalifikacja procesowa ze szczegółowym omówieniem wyznaczania dawki sterylizacyjnej (Process qualification with particular discussion on the determination of sterilization dose).
p. VIII(1-4).
12. Kałuska I., Bułka S.
Analiza ryzyka procesu sterylizacji radiacyjnej (Analysis of the risk of radiation sterilization process).
p. X(1-2).
13. Kornacka E.M.
Rola opakowań w sterylizacji radiacyjnej (The role of package in radiation sterilization).
p. IX(1-6).
14. Korzeniowska-Sobczuk A.
Akredytowane Laboratorium Pomiarów Dawek Technologicznych (Accredited Laboratory for Measurements of Technological Doses).
p. XVII(1-2).
15. Kruszewski M.
Biologiczne działanie i ryzyko promieniowania jonizującego (Biological action and the risk of ionization
radiation).
p. IV(1-4).
123
16. Mehta K., Chmielewski A.G.
Stacje sterylizacji radiacyjnej wyposażone w izotopowe źródła promieniowania gamma (Stations of radiation sterillization equipped with isotope sources of gamma radiation).
p. XX(1-9).
17. Migdał W., Gryczka U.
Mikrobiologiczna dekontaminacja radiacyjna ziół i przypraw. Przepisy Unii Europejskiej (Microbiological radiation decontamination of herbs and spices. Regulations of the European Union).
p. XVIII(1-4).
18. Przybytniak G.
Modyfikacja materiałów polimerowych pod wpływem promieniowania jonizującego (Modification of
polymer materials under the influence of ionizing radiation).
p. XIII(1-4).
19. Rafalski A.
Kontrola dozymetryczna radiacyjnej sterylizacji wyrobów medycznych (Dosimetric inspection of radiation sterilization of medical appliances).
p. VII(1-5).
20. Stachowicz W.
Przegląd metod sterylizacji (A review of sterilization methods).
p. II(1-14).
21. Stachowicz W.
Samodzielne Laboratorium Identyfikacji Napromieniowanej Żywności (Laboratory for Detection of Irradiated Food).
p. XVI(1-6).
22. Walo M.
Nowe materiały polimerowe modyfikowane radiacyjnie (New polymeric materials modified by radiation).
p. XIV(1-4).
23. Zakrzewska-Trznadel G., Frąckiewicz K., Miśkiewicz A., Zielińska K., Herdzik-Koniecko I.,
Szczygłów K., Wołkowicz S.
Uranium supply from domestic resources in Poland.
Nuclear 2011: 4. Annual International Conference on Sustainable Development through Nuclear Research and Education, Pitesti, Romania, 25-27.05.2011, Session I, p. 161-166.
24. Zakrzewska-Trznadel G., Miśkiewicz A.
Membrane distillation as a method for liquid radioactive waste treatment.
Nuclear 2011: 4. Annual International Conference on Sustainable Development through Nuclear Research and Education, Pitesti, Romania, 25-27.05.2011, Session II, p. 161-167.
25. Zalewski M., Chmielewski A.G., Palige J., Roubinek O., Wawryniuk K., Chrzanowski K.,
Kryłowicz A., Usidus J.
Analiza pracy małej biogazowi dla przerobu traw i ich kiszonek (Analysis of operation of small biogas
plant using grasses and their silage).
28.11.2011, p. 142-144.
26. Zimek Z.
Akceleratory elektronów. Zastosowania dla potrzeb sterylizacji radiacyjnej (Electron accelerators. Applications for the need of radiation sterilization).
p. VI(1-4).
124
CONFERENCE ABSTRACTS
1.
Abbas K., Cydzik I., Simonell F., Krajewski S., Majkowska-Pilip A., Kasperek A., Bilewicz A.
Cyklotronowa produkcja 44Sc – nowego radionuklidu dla techniki PET (Cyclotron production of 44Sc –
a new radionuclide for PET techniques).
Ogólnopolska Konferencja Radiofarmaceutyczna, Łódź, Poland, 12-13.05.2011, p. 64.
2.
Barlak M., Piekoszewski J., Werner Z., Sartowska B., Waliś L., Starosta W., Kierzek J., Bocheńska K., Heller R., Wilhelm R., Kolitsch A., Pochrybniak C., Kowalska E.
High-temperature oxidation resistance of stainless steel doped with yttrium using ion implantation.
NUTECH-2011 International Conference on Development and Applications of Nuclear Technologies,
Kraków, Poland, 11-14.09.2011. Book of abstracts, p. 66.
3.
Barlak M., Piekoszewski J., Werner Z., Sartowska B., Waliś L., Starosta W., Kierzek J., Bocheńska K., Heller R., Wilhelm R., Kolitsch A., Pochrybniak C., Kowalska E.
Wettability of carbon and silicon carbide ceramics induced by their surface alloying with Ti, Zr and Cu
elements using high intensity pulsed plasma beams.
4.
Bartłomiejczyk T., Wojewódzka M., Grądzka I., Lankoff A., Iwaneńko T., Kruszewski M., Szumiel I.
The protective effect of iron chelator on DNA base damage in HepG2 cells treated with silver nanoparticles.
2. Congress of Biochemistry and Cell Biology, Kraków, Poland, 5-9.09.2011. Abstracts, p. 255.
5.
Bartosiewicz I., Chwastowska J., Chajduk E., Dudek J., Pyszynska M., Polkowska-Motrenko H.
Oznaczanie uranu i toru w materiałach geologicznych za pomocą spektrometrii mas z jonizacją w plazmie indukcyjnie sprzężonej (Determination of uranium and thorium in geological materials by means
of inductively coupled plasma – mass spectrometry).
ChemSession’11: VIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 13.05.2011.
Streszczenia, p. 21.
6.
Bayda M., Majchrzak M., Hug G.L., Burdziński G., Kciuk G., Bobrowski K., Marciniec B.,
Marciniak B.
Reactivity of arylene-silylene-vinylene polymers and their model compounds in the excited states.
Marie-Skłodowska-Curie Symposium on the Foundation of Physical Chemistry, Warszawa, Poland,
18-19.11.2011, p. 30.
7.
Biełuszka P., Frąckiewicz K., Herdzik-Konecko I., Miśkiewicz A., Szczygłów K., Wołkowicz S.,
Zakrzewska-Trznadel G., Zielińska B.
Nuclear power industry in Poland: analysis of uranium supply from low grade ores.
European Nuclear Young Generation Forum 2011, Praha, Czech Republic, 17-20.05.2011. Extended
abstracts, p. 65.
8.
Bobrowski K.
Radiation-induced oxidation processes in peptides and proteins relevant to oxidative stress.
5. European Young Investigator Conference, Frankfurt, Germany-Słubice, Poland, 22-26.06.2011. Book
of abstracts, p. 29.
9.
Bobrowski K., Hug G.L., Pędziński T., Kaźmierczak F., Wiśniowski P., Marciniak B.
●
OH-induced oxidation of Met-Met dipeptides: influence of geometric and steric factors.
27. Miller Conference on Radiation Chemistry, Tällberg, Sweden, 20-25.05.2011, P-44.
10. Bobrowski K., Hug G.L., Pędziński T., Kaźmierczak F., Wiśniowski P., Marciniak B.
●
OH-induced oxidation of Met-Met dipeptides: influence of geometric and steric factors.
14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 243-244.
11. Bobrowski K., Mozziconacci O., Kciuk G., Rusconi F., Mirkowski J., Wiśniowski P.B., Houee-Levin C.
Methionine residue acts as a prooxidant in the ●OH-induced oxidation of enkephalins.
COST Workshop CM603 Free Radicals in Chemical Biology, Zagreb, Croatia, 14-17.06.2011, p. 21.
12. Boguski J., Przybytniak G., Mirkowski K., Bojanowska-Czajka A.
Lifetime prediction of cables installed in nuclear power plants based on antioxidant decomposition in
insulations.
125
13. Bojanowska-Czajka A., Trojanowicz M., Soltan D., Kciuk G., Nałęcz-Jawecki G.
Radiolytic decomposition of diclofenac in water by gamma irradiation.
14. Brykała M., Deptuła A., Łada W., Olczak T., Wawszczak D., Smoliński T.
Badania nad otrzymywaniem dwutlenku uranu dotowanego torem za pomocą kompleksowej metody
zol-żel (CSGP) (Synthesis of uranium dioxide doped by Th by complex sol-gel process (CSGP)).
15. Brzóska K., Siomek A., Sochanowicz B., Oliński R., Kruszewski M.
Sod1 deficiency in mice results in increased NF-κB activity and altered expression of NF-κB related
genes.
Current Trends in Biomedicine Workshop: Molecular and Cellular Bases of Redox Signaling and Oxidative Stress: Implications in Biomedicine, Baeza, Spain, 2-4.11.2011, [1] p.
16. Brzóska K., Sochanowicz B., Grądzka I.
Conjugated linoleic acid sensitized human colon cancer HT-29 cells to X-radiation by impairing DNA
double strand break repair.
14. International Congress of Radiation Research, Warszawa, Poland, 28.08.-1.09.2011, p. 136.
17. Buczkowski M., Sartowska B., Starosta W.
Influence of ionising and UV radiation on template deposited microstructures of silver haloids.
18. Chajduk E., Danko B., Polkowska-Motrenko H.
Instrumental neutron activation analysis (INAA) for steel analysis and certification.
19. Chajduk E., Doner K., Polkowska-Motrenko H., Bilewicz A.
Badania układów rozdzielczych Se-As oraz ocena możliwości ich zastosowania do produkcji generatorów do Pozytonowej Tomografii Emisyjnej (Studies on separation systems for Se-As and evaluation of
the possibilities of their use to the production of generators for positron emission tomography (PET)).
I Ogólnopolska Konferencja Radiofarmaceutyczna, Łódź, Poland, 12-13.05.2011, p. 38.
20. Chajduk E., Dudek J., Danko B., Polkowska-Motrenko H., Skłodowska A.
Analiza chemiczna blaszek z welurów genueńskich (Elemental analysis of metal threads from Genoa
velvets).
Analiza zabytków w ochronie zabytków – Sympozjum, Warszawa, Poland, 8-9.12.2011, p. 27.
21. Chajduk E., Kalbarczyk P., Dudek J., Polkowska-Motrenko H.
Oznaczanie stosunków izotopowych uranu techniką ICP-MS (Determination of uranium isotope ratio
by ICP-MS).
XVI Konferencja: „Zastosowanie metod AAS, ICP-OES i ICP-MS w analizie środowiskowej”, Łódź,
Poland, 5-6.12.2011, p. 27.
Oznaczanie stosunków izotopowych uranu techniką ICP-MS (Determination of uranium isotope ratio
by ICP-MS).
Konferencja Naukowo-Techniczna: „Polska nauka i technika dla elektrowni jądrowych w Polsce”,
Mądralin, Poland, 13-14.01.2011, [1] p.
Oznaczanie stosunków izotopowych uranu techniką ICP-MS (Determination of isotope ratios of uranium by ICP-MS technique).
Konferencja naukowa: „Perspektywiczne cykle paliwowe energetyki jądrowej”, Mądralin, Poland,
13-14.06.2011, [1] p.
24. Chajduk E., Kalbarczyk P., Polkowska-Motrenko H.
Zastosowanie techniki ICP-MS do oznaczania stosunków izotopowych uranu (Application of ICP-MS
technique to the determination of isotope ratios of uranium).
54. Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i Techników
Przemysłu Chemicznego, Lublin, Poland, 18-22.09.2011. Materiały zjazdowe, p. 371.
126
25. Chajduk E., Polkowska-Motrenko H., Dybczyński R.
Zastosowanie neutronowej analizy aktywacyjnej do oznaczania metali szlachetnych (Application of neutron activation analysis to the determination of noble metals).
54. Zjazd Naukowy Polskiego Towarzystwa Chemicznego i Stowarzyszenia Inżynierów i Techników
Przemysłu Chemicznego, Lublin, Poland, 18-22.09.2011. Materiały zjazdowe, p. 81.
26. Chajduk E., Skwara W., Bartosiewicz I., Pyszynska M., Chwastowska J.
Ocena odpadów i produktów ubocznych przemysłu miedziowego jako źródła pierwiastków rzadkich
(Evaluation of wastes and by-products in the copper industry as a source of rare earth elements).
Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały Jubileuszowego XX Poznańskiego Konwersatorium Analitycznego, Poznań, Poland, 27-29.04.2011, p. 63.
27. Chmielewska D., Gryczka U., Migdał W., Daszewski W., Kuberka A., Chyrczakowska M.
Radiation treatment of library and archival collections for microbiological decontamination.
28. Chmielewska D., Starosta W.
Influence of ionizing radiation dose on size, distribution and properties of nanosilver particles embedded in different matrixes.
27. Miller Conference on Radiation Chemistry, Tällberg, Sweden, 20-25.05.2011, p. 51.
29. Chmielewska D., Starosta W.
Radiation synthesis of silver micro- and nanoparticles embedded in cotton fabric.
30. Chmielewska-Śmietanko D., Gryczka U., Migdał W., Daszewski W., Kuberka A.
Electron beam application to microbiological decontamination of library and archival collections.
International Meeting on Radiation Processing (IMRP), Montreal, Canada, 13-16.06.2011. Book of
abstracts, EA-13, p. 146.
31. Chmielewska-Śmietanko D., Sartowska B., Starosta W., Walo M.
Radiation synthesis of silver nanostructures in cotton matrix.
abstracts, HC-08, p. 212.
Chemistry for the nuclear energy of the future.
Electron accelerators application for wastewater treatment.
Gdańsk Workshop: “Progress in new methods of water and waste water cleaning”, Gdańsk, Poland,
4-5.07.2011, p. 6-7.
Nanotechnology and radiation chemistry.
abstracts, EA-01.02, p. 67-68.
Rola Rady ds. Atomistyki przy Prezesie Państwowej Agencji Atomistyki w przygotowaniu programu
badawczo-rozwojowego energetyki jądrowej (Role of the Council of Atomics, affiliated to the National
Atomic Energy Agency, in the preparation of a research – development programme for nuclear power
engineering in Poland).
36. Chmielewski A.G., Harasimowicz M., Palige J., Polak A., Roubinek O., Wawryniuk K., Zalewski M.
Wzbogacanie biogazu w metan przy wykorzystaniu mobilnej instalacji membranowej (Enrichment of
biogas in methane with using mobile membrane installation).
Streszczenia, P-115.
37. Chmielewski A.G., Licki J., Pawelec A., Zimek Z., Sun Y., Witman S.
Treatment of off-gases containing NOx by electron beam.
127
International Symposium on Nitrogen Oxides Emission Abatement NOEA 2011, Zakopane, Poland,
4-7.09.2011. Book of abstracts, p. 17.
38. Chmielewski A.G., Migdał W., Chmielewska-Śmietanko D., Gryczka U.
Biogas and radiation chemistry.
abstracts, EA-20, p. 153.
39. Chmielewski A.G., Pawelec A., Licki J., Witman S., Sun Y., Zimek Z.
Plasma processes including electron beam for off-gases purification.
12. Tihany Symposium on Radiation Chemistry, Zalakaros, Hungary, 27.08.-1.09.2011, p. 15.
40. Chmielewski A.G., Pawelec A., Licki J., Witman S., Zimek Z.
Electron beam treatment of high NOx concentration off-gases.
abstracts, EA-02.02, p. 69.
41. Chmielewski A.G., Polak A.
Wzbogacanie biogazu w metan w celu uzyskania produktu do zasilania sieci gazowych i wykorzystania
w silnikach samochodowych (Enrichment of biogas in methane to obtain a product to supply the gas
grid and to apply in motor-car engines).
Energia elektryczna, ciepło i gaz – perspektywą dla gminy, Minikowo, Poland, 11.03.2011. Materiały
konferencyjne, p. 1-4.
42. Chwastowska J., Chajduk E., Dudek J., Pyszynska M., Bartosiewicz I., Polkowska-Motrenko H.
Opracowanie optymalnych warunków roztwarzania materiałów do oznaczania U i Th metodą ICP-MS
(Elaboration of optimal conditions for the disgestion of materials for the determination of U and Th by
the ICP-MS method).
43. Chwastowska J., Skwara W., Dudek J., Pyszynska M., Sadowska-Bratek M.
Badanie wpływu nanocząsteczek srebra na organizmy żywe. Problemy analityczne (The study of influence of nano amounts of silver on living systems. The analytical problems).
44. Cieśla K.
Radiation modification of the physicochemical and functional properties of the polysaccharide films.
45. Cieśla K., Sartowska B.
Modification of the structure of the films prepared basing gamma irradiated starch examined by scanning electron microscopy.
46. Cieśla K., Sartowska B., Królak E., Głuszewski W.
Gamma irradiation influence on the structure of potato starch gels studied by SEM.
47. Dispenza C., Sabatino M.A., Niconov A., Chmielewska D., Spadaro G.
E-beam crosslinked, biocompatible functional hydrogels incorporating polyaniline nanoparticles.
48. Doner K., Polkowska-Motrenko H.
Ocena czystości chemicznej kompozytów WO3/ZrO2 wzbogaconych w izotop 186W wykonana metodą
NAA oraz ocena stopnia Lucji 188Re (Assessment of chemical purity WO3/zrO2 composites enriched in
the isotope 186W made by NAA and assess the degree of elution 188Re).
Streszczenia, P-16.
49. Dybczyński R.S.
Aktywacyjne metody analizy i ich znaczenie w nieorganicznej analizie śladowej (Activation methods od
analysis and their significance in trace analysis).
128
50. Dybczyński R.S, Danko B., Pyszynska M., Polkowska-Motrenko H.
Ilorazowa podstawowa pomiarowa procedura odniesienia (metoda definitywna) dla oznaczania żelaza
w materiałach biologicznych za pomocą radiochemicznej neutronowej analizy aktywacyjnej (Ratio primary reference measurements procedure for the determination of iron in biological materials by radiochemical neutron activation analysis).
5. Ogólnopolska Konferencja Naukowa: „Jakość w chemii analitycznej”, Mory k/Warszawy, Poland,
24-25.11.2011, p. 9.
51. Dybczyński R.S., Kulisa K.
Teoretyczne i praktyczne aspekty oznaczania ziem rzadkich w materiałach biologicznych i środowiskowych
za pomocą chromatografii jonowej (Theoretical and practical aspects of the determination of rare earth
elements in biological and environmental materials by ion chromatography).
II Konferencja Naukowa: „Monitoring i analiza wody. Chromatograficzne metody oznaczania substancji
i charakterze jonowym”, Toruń, Poland, 3-5.04.2011, p. 19.
52. Dybczyński R., Pyszynska M., Chajduk E.
Poszukiwanie nowej metody oddzielania śladowych ilości uranu od toru i 233Pa (Search for the new
method of the separation of the amounts of uranium from thorium and 233Pa).
13-14.06.2011, [1] p.
53. Filipiak P., Jakowiuk A., Bartak J., Machaj B., Pieńkos P., Kowalska E.
Laboratory automatic measuring system of gamma specimens.
54. Fuks L.
N-heterocyclic aldehyde thiosemicarbazones – ligands for the technetium and rhenium complexes, potential radiopharmaceuticals.
5. EuCheMS Conference on Nitrogen Ligands in Coordination Chemistry, Metal-Organic Chemistry,
Materials & Catalysis, Granada, Spain, 4-8.09.2011. Conference book, p. 147.
55. Fuks L., Gniazdowska E., Koźmiński P.
Novel technetium and rhenium complexes with the n-heterocyclic aldehyde thiosemicarbazones – potential radiopharmaceuticals.
7. International Symposium on Technetium and Rhenium – Science and Utilization, Moscow, Russia,
4-8.07.2011. Book of abstracts. Eds. K.E. German, B.F. Mysoedov, G.E. Kodina, I.D. Troshkina, T.
Sekine. Publishing House Granitsa, Moscow 2011, p. 148.
56. Fuks L., Gniazdowska E., Koźmiński P.
Technetium-99m complexed with n-heterocyclic aldehyde thiosemicarbazones – potential precursors of
the radiopharmaceuticals.
11. International Symposium on Applied Bioinorganic Chemistry, Barcelona, Spain, 2-5.12.2011, [1] p.
57. Głuszewski W.
Application of GC to study radiolysis of cultural heritage artefacts.
58. Głuszewski W.
Rok 2011 rokiem Marii Skłodowskiej-Curie (The year 2011 – the year of Maria Skłodowska-Curie).
59. Głuszewski W., Zagórski Z.P., Rajkiewicz M.
Modification of elastomers by ionizing radiation.
Radiation modification of elastomers.
Radiation modification of elastomers/Radiacyjna modyfikacja elastomerów.
XIV Międzynarodowa Konferencja Naukowo-Techniczna ELASTOMERY 2011: „Elastomery – innowacja i zrównoważony rozwój”, Warszawa, Poland, 23-25.11.2011, p. 118-119.
129
62. Gniazdowska E., Koźmiński P., Bańkowski K.
99m
Tc-labelled vasopressin analog d(CH2)5[D-Tyr(Et2),Ile4,Eda9]AVP as a potential radiopharmaceutical for small-cell lung cancer (SCLC) imaging.
7. International Symposium on Technetium and Rhenium – Science and Utilization, Moscow, Russia,
4-8.07.2011. Book of abstracts. Eds. K.E. German, B.F. Mysoedov, G.E. Kodina, I.D. Troshkina, T.
Sekine. Publishing House Granitsa, Moscow 2011, p. 149.
63. Grądzka I., Sochanowicz B., Brzóska K., Wojewódzka M., Sommer S., Wójciuk G., Gasińska A.,
Degen C., Jahreis G., Szumiel I.
Mechanism of HT-29 cells radiosensitization by conjugated linoleic acid: changes in lipid raft properties.
64. Grądzka I., Sochanowicz B., Brzóska K., Wojewódzka M., Sommer S., Wójciuk G., Gasińska A.,
Degen C., Jahreis G., Szumiel I.
Mechanism of HT-29 cells radiosensitization by conjugated linoleic acid: influence on double-strand
DNA break repair and lipid rafts properties.
2. Congress of Biochemistry and Cell Biology, Kraków, Poland, 5-9.09.2011. Abstracts, p. 80.
65. Guzik G.P.
Rozdzielanie i unieszkodliwianie odpadów promieniotwórczych z elektrowni jądrowych (Separation
and neutralisation of radioactive waste from nuclear power stations).
13-14.06.2011, [1] p.
66. Guzik G.P., Stachowicz W., Michalik J.
Study on radiation induced radicals giving rise to EPR signals employed for the detection of radiation
treatment in sugar containing food.
67. Ignasiak M., Pędziński T., Scuderi D., Filipiak P., Kciuk G., Houee-Levin Ch., Marciniak B.
Oxidation studies of methionine-containing peptides.
68. Jakowiuk A., Bartak J., Machaj B., Kowalska E., Filipiak P.
System pomiaru stężenia radonu w powietrzu i wodzie (System for measuring the concentration of
radon in air and water).
III Pomorska Konferencja z cyklu „Jakość powietrza”, Gdańsk, Poland, 7-8.04.2011, p. 45.
69. Jakowiuk A., Machaj B., Pieńkos P., Kowalska E., Filipiak P., Świstowski E.
Wireless system for radiometric measurements.
70. Jaworska A., Romm H., Oestreicher U., Thierens H., Vral A., Rothkamm K., Ainsbury E.,
Bendertitter H., Voisin P., Fattibene P., Lindholm C., Barquinero F., Sommer S., Woda K.,
Scherthan H., Beinke C., Vojnovic B., Trompier F., Bajinskis A., Wójcik A.
MULTIBIODOSE: multi-disciplinary biodosimetric tools to manage high scale radiological casualties.
71. Kalbarczyk P., Polkowska-Motrenko H., Chajduk E.
Study of thorium-uranium fuel cycle.
Wydzielanie uranu z dwutlenku toru napromieniowanego w reaktorze jądrowym (Separation of uranium from thorium dioxide irradiated in a nuclear reactor).
Wydzielanie uranu z dwutlenku toru napromieniowanego w reaktorze jądrowym (Separation of uranium from thorium dioxide irradiated in a nuclear reactor).
Sympozjum: „Bezpieczeństwo i ochrona radiologiczna w aspekcie budowy elektrowni jądrowej w Polsce”, Warszawa, Poland, 6.06.2011, [1] p.
130
74. Kałuska I., Zimek Z., Sadło J.
Comparison trials in dosimetry.
abstracts, TE-06, p. 219.
75. Kaźmierczak U., Banaś D., Bogowicz M., Braziewicz J., Buraczewska I., Choiński J., Czerwiński
M., Czub J., Jaskóła M., Korman A., Kruszewski M., Lankoff A., Szefliński Z., Wojewódzka M.,
Wójcik A., Wrzesień M.
Investigation of bystander responses in CHO-K1 cells irradiated by 12C ions.
76. Kciuk G.
Electron transfer in dipeptides containing methionine and tyrosine.
77. Kciuk G., Bobrowski K., Mirkowski K., De la Fuente J.R., Aliaga C.
Spectral and kinetic properties of transient species derived from 2-methyl-3-azaoxoisoaporphine in organic solvents.
78. Kciuk G., Bobrowski K., Mirkowski K., De la Fuente J.R., Aliaga C.
Spectral and kinetic properties of transient species derived from quinoxaline-derivatives in irradiated
organic solvents.
79. Kisała J., Kumięga P., Balawejder M., Hęclik K., Pogocki D.
Linuron contaminated water detoxification by ozonolysis and Fenton reaction.
Risk Factors of Food Chain – 11. International Conference, Iwonicz, Poland, 5-6.09.2011, p. 44.
80. Kocia R., Grodkowski J., Mirkowski J.
Excited states of p-terphenyl in selected ionic liquid under electron pulses irradiation.
81. Kocia R., Grodkowski J., Mirkowski J., Szreder T., Nyga M., Sulich A.
Inicjowana radiacyjnie redukcja CO2 w środowisku wybranej cieczy jonowej (Radiation-induced reduction of CO2 in a medium of a selected ionic liquid).
82. Kornacka E.M., Zagórski Z.P.
Ionizing radiation assisted, abiotic formation of methane.
ESF-COST High-Level Research Conference on Systems Chemistry III, 23-28.10.2011 and Systems
Chemistry, COST Action CM0703 Meeting – Chembiogenesis 2011, 27-30.10.2011, Heraklion-Crete,
Greece. Abstracts, p. 37.
83. Kornacka E.M., Zagórski Z.P.
Radiation chemistry of DNA as origins of life connection.
Origins 2011: ISSOL and Bioastronomy Joint International Conference, Montpellier, France, 3-8.07.2011.
Program and abstracts, [1] p.
84. Korzeniowska-Sobczuk A., Doner K., Karlińska M.
Accredited Laboratory for Measurement of Technological Doses (LMTD).
85. Kosno K., Celuch M., Mirkowski J., Pogocki D.
Dwa oblicza nikotyny (Two faces of nicotine).
86. Krajewski S., Kasperek A., Bilewicz A., Abbas K., Cydzik I., Simonell F.
Cyclotron production of 44Sc – new radionuclide for PET technique.
EU COST Action D38 Final Meeting, Oxford, Great Britain, 13-15.09.2011, [1] p.
87. Kruszewski M., Brzóska K., Stępkowski T., Wojewódzka M., Wójciuk G., Wójciuk K., Lankoff A.,
Dusińska M., Dobrzyńska M., Gromadzka-Ostrowska J., Brunborg G.
131
Nanosilver induced changes in cellular signal transduction in HEPG2 cells.
EEMS – European Environmental Mutagen Society Annual Meeting, Barcelona, Spain, 4-7.07.2011,
p. 100.
88. Kruszewski M., Buraczewska I., Lankoff A., Sommer S., Wojewódzka M.
Radiobiologia w służbie energetyki jądrowej (Radiobiology for nuclear industry).
89. Kruszewski M., Grądzka I., Bartłomiejczyk T., Iwaneńko T., Lankoff A., Dusińska M., Brunborg G., Dobrzyńska M., Gromadzka-Ostrowska J., Wojewódzka M.
In vitro and in vivo toxicity of silver nanoparticles.
9. International Comet Assay Workshop, Kusadasi, Turkey, 13-16.09.2011, p. 42.
90. Kubera H., Melski K., Assman K., Głuszewski W., Zimek Z., Czaja-Jagielska N.
Changes in properties of hydrobiodegradable film based on aliphatic-aromatic copolymers treated by
ionizing radiation.
91. Łyczko K., Łyczko M., Herdzik-Koniecko I., Zielińska B.
Nowa metoda rozpuszczania tlenku toru (New dissolution method of thorium oxide).
92. Migdał W., Chmielewska-Śmietanko D., Dubiel M.
Możliwości wykorzystania materiałów lignocelulozowych do produkcji biogazu (Possibilities of application lignocellulose materials for biogas production).
Energia elektryczna, ciepło i gaz – perspektywą dla gminy, Minikowo, Poland, 11.03.2011. Materiały
konferencyjne, p. 5-6.
93. Migdał W., Ptaszek M., Gryczka U., Orlikowski L.B.
Możliwość wykorzystania technologii radiacyjnych w ochronie roślin przed chorobami (Possibility of
application radiation technologies in protection of plants against diseases).
51. Sesja Naukowa Instytutu Ochrony Roślin Państwowego Instytutu Badawczego, Poznań, Poland,
17-18.02.2011. Streszczenia, [2] p.
94. Migdał W., Ptaszek M., Orlikowski L., Gryczka U.
Influence of electron beam irradiation on the growth of Phytophthora cinnamoni and its control in
substrates.
abstracts, EA-21, p. 153-154.
95. Miśkiewicz A., Zakrzewska-Trznadel G.
Radiotracers as an effective tool for membrane processes investigation.
96. Miśkiewicz A., Zakrzewska-Trznadel G.
Using of isotopes produced from radionuclide generators as tracer for membrane installation investigation.
6. International Conference on Tracers and Tracing Methods, TRACER 6, Oslo, Norway, 6-8.06.2011.
Abstracts, [1] p.
97. Narbutt J.
Ekstrakcyjne wydzielanie pierwiastków transuranowych z wypalonego paliwa jądrowego (Solvent extraction separation of transuranium elements from spent nuclear fuel).
98. Nichipor H., Yacko S., Sun Y., Chmielewski A.G., Zimek Z., Bułka S.
Degradation mechanism of benzene in air under electron beam irradiation.
4. Central European Symposium on Plasma Chemistry, Zlatibor, Serbia, 21-25.08.2011. Book of abstracts. Eds. M.M. Kuraica, B.M. Obradović, p. 107-108.
99. Nyga M., Grodkowski J., Kocia R., Mirkowski J.
Różnice wartości stałej równowagi w cieczach jonowych w porównaniu do klasycznych rozpuszczalników
(Differences in the values of equillibrium constant in ionic liquids compared to classical solvents).
132
100. Nyga M., Hug G.L., Mirkowski J., Szreder T., Grodkowski J.
Equilibrium reactions in ionic liquids.
101. Nyga M., Hug G.L., Mirkowski J., Szreder T., Grodkowski J.
Generation of oxidizing radicals and their reactivity in ionic liquids with the same anion.
102. Orlikowski L.B., Gryczka U., Ptaszek M., Migdał W.
Activity of e-beam irradiation in the control of Rhizoctonia solani.
103. Pitarević Svedružić L., Rončević S., Chajduk E.
Spectrometric analysis of lanthanides in archeological ceramics.
IX International Congress of Young Chemists ‘YoungChem 2011’, Cracow, Poland, 12-16.10.2011, [1] p.
104. Polkowska-Motrenko H.
Jądrowe metody analizy. Znaczenie dla metrologii chemicznej (Nuclear analytical techniques – importance for chemical metrology).
Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków. Materiały Jubileuszowego XX Poznańskiego Konwersatorium Analitycznego, Poznań, Poland, 27-29.04.2011, p.
27-28.
105. Polkowska-Motrenko H., Chajduk E.
Przypisanie wartości właściwościom materiałów do badań w programie Rośliny (Assigment of property
values in the procifiency test scheme Plants).
24-25.11.2011, p. 19.
106. Polkowska-Motrenko H., Fuks L., Kalbarczyk P., Pyszynska M.
Przygotowanie materiałów do badań biegłości laboratoriów oznaczających pierwiastki radioaktywne
w środowisku i żywności (Preparation of materials for proficiency tests of laboratories determining
radioactive elements in the environment and food).
107. Polkowska-Motrenko H., Fuks L., Kalbarczyk P., Skotniczna M.
Program badań biegłości dla placówek specjalistycznych prowadzących pomiary skażeń promieniotwórczych w ramach monitoringu radiacyjnego kraju (Proficiency test scheme for radiochemical laboratories forming the radiation monitoring network in Poland).
Sympozjum: „Bezpieczeństwo i ochrona radiologiczna w aspekcie budowy elektrowni jądrowej w Polsce”, Warszawa, Poland, 6.06.2011, [1] p.
Program badań biegłości dla placówek specjalistycznych prowadzących pomiary skażeń promieniotwórczych w ramach monitoringu radiacyjnego kraju (Proficiency test scheme for radiochemical laboratories forming the radiation monitoring network in Poland).
24-25.11.2011, p. 19.
109. Polkowska-Motrenko H., Kalbarczyk P., Chajduk E., Łyczko K.
Badania produktów napromieniania ThO2 (Studies on the irradiation products of ThO2).
13-14.06.2011, [1] p.
110. Przybytniak G.
Degradacja kabli i przewodów niskiego napięcia wykorzystywanych w elektrowniach jądrowych (Degradation of low-voltage cables and wires applied in nuclear power plants).
111. Przybytniak G.
Radiation-induced effects in polyesters – influence of chemical structure and morphology.
133
112. Przybytniak G., Nowicki A., Boguski J.
Starzenie polimerów stosowanych jako warstwy izolacyjne i osłony w kablach (Ageing of polymers applied as insulating layers and shields in cables).
113. Przybytniak G., Zimek Z., Nowicki A., Mirkowski K., Boguski J.
Selection of the materials for radiation cross-linked cables.
114. Ritter S., Pignalosa D., Lee R., Hartel C., Durante M., Sommer S., Nikoghosyan A., Debus J.
mBAND analysis of aberrations reveals marked differences between cells exposed in vitro and in vivo
to X-rays or C-ions.
115. Sadło J., Michalik J., Strzelczak G., Lewandowska-Szumieł M., Sterniczuk M.
Carbon-centered radicals in γ-irradiated bone substituting biomaterials based on hydroxyapatite.
III Spotkanie Użytkowników Systemów Firmy Bruker w Polsce, Poznań, Poland, 27-28.09.2011, p. 70.
116. Samczyński Z.
Determination of uranium(VI) and thorium(IV) in technological phosphoric acid solutions.
117. Samczyński Z., Dybczyński R.S., Polkowska-Motrenko H., Chajduk E., Pyszynska M., Danko
B., Czerska E., Kulisa K., Kalbarczyk P., Doner K.
Nowe polskie materiały odniesienia dla nieorganicznej analizy śladowej (New Polish reference materials
for inorganic trace analysis).
5. Ogólnopolska Konferencja Naukowa: „Jakość w chemii analitycznej”, Mory k/Warszawy, 24-25.11.2011,
p. 21.
118. Sartowska B., Orelovitch O.L., Presz A., Apel P.Yu., Blonskaya I.V.
Nanopores with controlled profiles in track-etched membranes.
119. Sartowska B., Piekoszewski J., Waliś L., Barlak M., Starosta W., Pochrybniak C.
Poprawa odporności na wysokotemperaturowe utlenianie stali AISI 316L przez stopowanie pierwiastkami ziem rzadkich przy wykorzystaniu intensywnych impulsów plazmowych (Improvement of high
temperature oxidation resistance of AISI 316L steel by alloying with rare earth elements using intense
pulses).
120. Sartowska B., Piekoszewski J., Waliś L., Starosta W., Barlak M., Ratajczak R., Kopcewicz M.
Application of nuclear techniques for materials surface characterisation: own investigations examples.
121. Skłodowska A., Polkowska-Motrenko H., Danko B., Dudek J., Chajduk E.
INAA and other analytical techniques in cultural heritage – elemental analysis of metal threads from
silk velvet in Wilanów Museum-Palace.
122. Smoliński T., Deptuła A., Chmielewski A.G.
Methods of immobilization of radioactive elements in Synroc materials.
Kraków, Poland, 11-14.09.2011. Book of abstracts, [1] p.
123. Smoliński T., Deptuła A., Chmielewski A.G.
Nowoczesne metody neutralizacji odpadów radioaktywnych w materiałach typu SYNROC (Modern
neutralization methods of radioactive wastes immobilized in SYNROC materials).
134
124. Sommer S., Buraczewska I., Grądzka I., Szumiel I., Kruszewski M.
On the role of biological dosimetry in nuclear power industry safety assurance.
1. International Nuclear Energy Congress, Warszawa, Poland, 23-24.05.2011, [2] p. <http://nuclear.itc.
pw.edu.pl/eng/proceedings>
125. Sommer S., Kowalska M., Szymańska M., Buraczewska I., Kruszewski M.
Inter-laboratory comparison of ionising radiation dose reconstruction by the dicentric assay in Poland.
19. Nuclear Medical Defence Conference, Munich, Germany, 16-19.05.2011. Supplement to MCIF 2/4,
p. 20-21.
126. Sommer S., Lankoff A., Wojewódzka M., Buraczewska I., Szumiel I., Kruszewski M.
Development of multiparameter biodosimetry test for triage of casualties in a large scale radiological
event.
p. 20.
127. Sommer S., Nasonova E., Kruszewski M., Ritter S.
Aneuploidy of individual human chromosomes in m-FISH assay.
p. 20.
128. Starosta W., Sartowska B., Pawlukojć A., Waliś L., Buczkowski M.
Metal-organic framework materials (MOF) and their applications.
129. Steczek Ł., Kiegel K., Zakrzewska-Trznadel G.
Application of Calix[6]arene for extraction of uranium(VI) from water solution.
1. International Conference on Methods and Materials for Separation Processes: Separation Science –
Theory and Practice 2011, Kudowa Zdrój, Poland, 5-9.06.2011, [1] p.
130. Steczek Ł., Zakrzewska-Trznadel G.
Design of liquid membranes with calixarenes as carriers for separation of uranium from aqueous solutions.
XXVIII Membrane Summer School, Smardzewice, Poland, 11-15.09.2011, p. 78.
131. Steczek Ł., Zakrzewska-Trznadel G., Kiegiel K.
Synthesis of Calix[6]arenes as carriers for separation of uranium from aqueous solutions.
132. Sterniczuk M., Michalik J., Sadło J., Strzelczak G.
Paramagnetic centers generated radiolytically in molecular sieves exposed to carbon monoxide.
III Spotkanie Użytkowników Systemów Firmy Bruker w Polsce, Poznań, Poland, 27-28.09.2011, p. 69.
Paramagnetyczne produkty radiolizy tlenku węgla stabilizowane w sitach molekularnych (Paramagnetic
products of carbon monoxide radiolysis in molecular sieves).
Radiolitically generated paramagnetic centers in molecular sieves with adsorbed carbon monixide.
EUROMAR 2011 - Magnetic Resonance Conference, Frankfurt am Main, Germany, 21-25.08.2011, p. 85.
Radiolitically generated paramagnetic centers in molecular sieves with adsorbed carbon monoxide.
136. Stępkowski T., Bartłomiejczyk T., Grądzka I., Iwaneńko T., Męczyńska-Wielgosz S., Kruszewski M.
Oxidative stress related effects in HepG2 and A549 cells treated with silver nanoparticles.
Current Trends in Biomedicine Workshop: Molecular and Cellular Bases of Redox Signaling and Oxidative Stress: Implications in Biomedicine, Baeza, Spain, 2-4.11.2011, [1] p.
137. Strzelczak G., Pogocki D., Bobrowski K.
EPR study of dipeptides containing tyrosine.
135
138. Sulich A., Grodkowski J., Mirkowski J., Kocia R., Foreman M.
Benzophenone as a probe in the pulse radiolysis of cyclohexanone and 1-octanol, diluents for procedures in minor actinides extraction.
Radioliza impulsowa wybranych ligandów i rozpuszczalników, proponowanych do procesu SANEX
w przetwórstwie zużytego paliwa jądrowego (Pulse radiolysis of selected ligands and solvents proposed
for the SANEX process in reprocessing of spent nuclear fuels).
Studies on improving radiation stability of substances applied in the recycling of a spent nuclear fuel.
141. Sun Y., Chmielewski A.G.
Overview of multiple pollutants treatment by using electron beam technology.
4. Central European Symposium on Plasma Chemistry, Zlatibor, Serbia, 21-25.08.2011. Book of abstracts. Eds. M.M. Kuraica, B.M. Obradović, p. 27-28.
142. Szczygłów K., Zakrzewska-Trznadel G., Frąckiewicz K.
Metody pozyskiwania uranu ze złóż występujących w Polsce (Methods of recovery uranium from low
grade ores in Poland).
143. Śmietanko-Chmielewska D.K., Chmielewski A.G.
Application of ionizing radiation for metal nanoclusters synthesis.
144. Thierens H., Vral A., Romm H., Oestreicher U., Barnard S., Rothkamm K., Ainsbury E., Sommer S., Beinke C., Wójcik A.
The automated micronucleus assay as a reliable biodosimetric tool for population triage in large scale
radiation accidents.
145. Trojanowicz M., Bojanowska-Czajka A., Gumiela M., Męczyńska S., Kruszewski M., Nałęcz-Jawecki G.
Hyphenated ionizing radiation based AOP methods for decomposition of toxic pollutants in waters.
abstracts, EA-02.04, p. 70.
146. Walo M., Przybytniak G.
Polyurethane biomaterial modified with electron beam radiation.
147. Walo M., Przybytniak G., Akkas Kavakli P., Barsbay M., Güven O.
Functionalization of polyurethane surface by radiation-induced graft polymerization.
148. Walo M., Przybytniak G., Mirkowski K.
Radiacyjna modyfikacja poli(estrouretanów) (Radiation modification of poly(estrourethanes)).
149. Wawryniuk K., Chmielewski A.G., Palige J., Roubinek O., Zalewski M.
Procesy membranowe oczyszczania gazu syntezowego (Membrane processes of the synthesis gas purification).
150. Węgierek-Ciuk A., Arabski M., Lisowska H., Banasik-Nowak A., Kędzierawski P., Florek A.,
Gozdz S., Wójcik A., Lankoff A.
Relationship between acute reactions to radiotherapy, micronucleous yields in lymphocytes and SNP
polymorphisms in XRCC1, XRCC3, OGG1 genes in cervix cancer patients treated by external beam
radiotherapy.
136
151. Witman S., Pawelec A., Chmielewski A.G.
Technologie plazmowe w ochronie środowiska (Plasma technology for environment protection).
152. Wojewódzka M., Iwaneńko T., Bartłomiejczyk T., Lankoff A., Kruszewski M.
The gamma-H2AX assay – an effective alternative for the comet assay in biodosimetry?
9. International Comet Assay Workshop, Kusadasi, Turkey, 13-16.09.2011, p. 73.
153. Wojewódzka M., Lankoff A., Kruszewski M.
The optimisation of a finger-prick blood collection method for the gamma-H2AX assay: potential application in population triage.
154. Wójcik A., Bajinskis A., Romm H., Oestreier U., Thierens H., Vral A., Rothkamm K., Ainsbury E.,
Bendertitter M., Fattibene P., Jaworska A., Lindholm C., Barquinero F., Sommer S., Woda K.,
Scherthan H., Vojnovic B., Trompier F.
Multi-disciplinary biodosimetric tools to manage high scale radiological casualties – MULTIBIODOSE.
1. International Nuclear Energy Congress, Warszawa, Poland, 23-24.05.2011, [2] p. <http://nuclear.itc.
pw.edu.pl/eng/proceedings>
155. Wójcik A., Bajinskis A., Romm H., Oestreier U., Thierens H., Vral A., Rothkamm K., Ainsbury E.,
Bendertitter M., Fattibene P., Jaworska A., Lindholm C., Whitehouse C., Barquinero F., Sommer S., Woda K., Scherthan H., Vojnovic B., Trompier F.
MULTIBIODOSE: multi-disciplinary biodosimetric tools to manage high scale radiological casualties.
p. 15.
156. Wójciuk G., Wójciuk K., Kruszewski M.
Biokoniugaty des-acyl greliny z wybranymi radionuklidami jako potencjalne radiofarmaceutyki (Bioconjugates des-acyl ghrelin analogs with chosen radionuclides as potential radiopharmaceuticals).
157. Zagórski Z.P., Kornacka E.M.
Connections of radiation research to origins of life.
Critical analysis of attempts leading to the experimental confirmation of Panspermia hypothesis.
ESF-COST High-Level Research Conference on Systems Chemistry III, 23-28.10.2011 and Systems
Chemistry, COST Action CM0703 Meeting – Chembiogenesis 2011, 27-30.10.2011, Heraklion-Crete,
Greece. Abstracts, p. 49.
Ionizing radiation assisted, abiotic formation of methane.
Origins 2011: ISSOL and Bioastronomy Joint International Conference, Montpellier, France, 3-8.07.2011.
Program and abstracts, [1] p.
Składowisko odpadów w kopalni soli w USA – wizja lokalna (Waste storage in a salt mine in the USA
– a local visit).
161. Zakrzewska-Trznadel G.
Implementing public participation approaches in radioactive waste disposal.
162. Zakrzewska-Trznadel G.
Projekty badawcze wsparciem energetyki jądrowej w kraju (Research projects as support for nuclear
energy in the country).
137
163. Zakrzewska-Trznadel G., Frąckiewicz K., Zielińska B., Herdzik-Koniecko I., Biełuszka P.,
Miśkiewicz A., Szczygłów K., Wołkowicz S., Strzelecki R., Kiegel K.
Analysis of uranium supply from domestic resources.
Kraków, Poland, 11-14.09.2011. Book of abstracts, [1] p.
164. Zakrzewska-Trznadel G., Frąckiewicz K., Zielińska K., Herdzik-Koniecko I., Miśkiewicz A.,
Szczygłów K., Biełuszka P., Chajduk E., Oszczak A.
Metody pozyskiwania uranu z rud występujących w Polsce (Methods for obtaining uranium from ores
occurring in Poland).
165. Zakrzewska-Trznadel G., Harasimowicz M., Miśkiewicz A., Jaworska A.
The hybrid system for liquid low-level radioactive waste treatment with application of membrane
processes.
166. Zakrzewska-Trznadel G., Miśkiewicz A., Fuks L., Kulisa K.
Concentration of liquid radioactive waste using biopolymer-enhanced ultrafiltration.
167. Zalewski M., Chmielewski A.G., Palige J., Roubinek O., Wawryniuk K., Chrzanowski K., Kryłowicz A., Usidus J.
Instalacja do wytwarzania biogazu z odpadów rolniczo-spożywczych (Installation for production of biogas
from agricultural and food waste).
168. Zimek Z., Przybytniak G., Nowicki A.
Optimization of electron beam crosslinking of wire and cable insulation.
SUPPLEMENT LIST OF THE PUBLICATIONS IN 2010
1.
Biełuszka P., Zakrzewska-Trznadel G.
Zagęszczanie i oczyszczanie roztworów uranu za pomocą metod membranowych (Concentration and
purification of uranium solutions by means of membrane methods).
ChemSession’10: VII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 14.05.2010.
2.
Deptuła A., Brykała M., Łada W., Olczak T., Wawszczak D., Modolo G., Daniels H., Chmielewski A.G.
Synthesis of uranium and thorium dioxides by Complex Sol-Gel Processes (CSGP).
Proceedings of the First ACSEPT International Workshop, Lisbon, Portugal, 31.03.-2.04.2010, [10] p.
3.
Harasimowicz M., Chmielewski A.G., Palige J., Roubinek O., Zalewski M., Urbaniak A.
Zastosowanie kaskady membranowych modułów separacyjnych do wzbogacania biogazu w metan (Application of separation membrane module cascade for biogas enrichment in methane).
VIII Konferencja „Dla miasta i środowiska – problemy unieszkodliwiania odpadów”, Warszawa, Poland,
29.11.2010. Materiały konferencyjne, p. 66-68.
4.
Koss U., Bilewicz A., Czerwiński A.
Otrzymywanie beznośnikowego 186Re z naświetlonych neutronami tarcz Re2(CO)10 i Re(CO)5Cl z wykorzystaniem efektu Szilarda-Chalmersa (Obtaining of carrier-free 186Re from neutron-irradiated
Re2(CO)10 and Re(CO)5Cl targets, using the effect of Szilard-Chalmers).
ChemSession’10: VII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 14.05.2010.
5.
Krygowski T.M., Oziminski W.P., Palusiak M., Fowler P.W., McKenzie A.D.
Aromaticity of substituted fulvene derivatives: substituent-dependent ring currents.
Physical Chemistry Chemical Physics, 12, 10740-10745 (2010).
138
6.
Kubera H., Melski K., Ziajka A., Głuszewski W., Zimek Z.
Influence of ionizing irradiation on polymers sleeves using for sterilization of medical utensils.
Zeszyty Naukowe Uniwersytetu Ekonomicznego w Poznaniu, 160, 43-49 (2010).
7.
Majkowska A., Bilewicz A.
Macrocyclic complexes of scandium radionuclides as precursors for diagnostic and therapeutic radiopharmaceuticals.
In: Application of radiotracers in chemical, environmental and biological sciences. Vol. 3. Eds. S. Lahiri,
M. Maiti, S.K. Das. Saha Institute of Nuclear Physics, Kolkata 2010, p. 324-326.
8.
Majkowska-Pilip A., Pruszyński M., Bilewicz A., Loktionova N., Rösch F.
Labeling and stability of 46Sc-DOTATATE and 44Sc-DOTATATE radiobioconjugates.
COST D38 Action: Metal-based systems for molecular imaging applications. Annual Meeting, Thessaloniki, Greece, 20-22.06.2010, [1] p.
9.
Musijowski J., Szostek B., Koc M., Trojanowicz M.
Determination of fluoride as fluorosilane derivative using reversed-phase HPLC with UV detection for
determination of total organic fluorine.
Journal of Separation Science, 33, 2636-2644 (2010).
10. Oszczak A.
Paliwo jądrowe. Przerób wypalonego paliwa (Nuclear fuel and reprocessing).
Materiały Krakowskiej Konferencji Młodych Uczonych, Kraków, Poland, 23-25.09.2010. Sympozja i Konferencje KKMU no. 5, p. 131-136.
11. Oziminski W.P., Garnuszek P., Mazurek A.P.
Theroretical modeling of Pt-histamine complex hydrolysis and interactions with guanine and adenine.
5. Central European Conference “Chemistry towards biology”, Primošten, Croatia, 8-11.09.2010. Book
12. Oziminski W.P., Krygowski T.M.
Substituent effects in exocyclically substituted fulvene derivatives.
Central European School on Physical Organic Chemistry, Przesieka, Poland, 8-12.06.2010, p. 39.
13. Oziminski W.P., Krygowski T.M., Fowler P.W., Soncini A.
Aromatization of fulvene by complexation with lithium.
Organic Letters, 12, 21, 4880-4883 (2010).
14. Trojanowicz M.
Chromatographic and capillary electrophoretic determination of microcystins.
Journal of Separation Science, 33, 359-371 (2010).
15. Trojanowicz M., Latoszek A., Poboży E.
Analysis of genetically modified food using high-performance separation methods.
Analytical Letters, 43, 1633-1679 (2010).
NUKLEONIKA
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NUKLEONIKA
THE INTERNATIONAL JOURNAL OF NUCLEAR RESEARCH
EDITORIAL BOARD
Andrzej G. Chmielewski (Editor-in-Chief, Poland), Krzysztof Andrzejewski (Poland), Janusz Z. Beer
(USA), Jacqueline Belloni (France), Grażyna Bystrzejewska-Piotrowska (Poland), Gregory R.
Choppin (USA), Hilmar Förstel (Germany), Andrei Gagarinsky (Russia), Andrzej Gałkowski
(Poland), Evgeni A. Krasavin (Russia), Marek Lankosz (Poland), Stanisław Latek (Poland), Sueo
Machi (Japan), Dan Meisel (USA), Jacek Michalik (Poland), Heino Nitsche (USA), Robert H.
Schuler (USA), Christian Streffer (Germany), Irena Szumiel (Poland), Alexander Van Hook
(USA)
CONTENTS OF No. 1/2011
1.
Editorial – 2011 – the Year of Maria Skłodowska-Curie
2.
Implanted manganese redistribution in Si after He+ irradiation and hydrogen pulse plasma treatment
Z. Werner, C. Pochrybniak, M. Barlak, J. Piekoszewski, A. Korman, R. Heller, W. Szymczyk, K. Bocheńska
3.
Targetry and radiochemistry for no-carrier-added production of 117,118m,119,120m,122Sb
M. Sadeghi, M.R. Aboudzadeh Rovais, M. Enferadi, P. Sarabadani
4.
Application of a neuro-fuzzy model for neutron activation analysis (NAA)
H. Khalafi, M.S. Terman, F. Rahmani
5.
Self-absorption correction and efficiency calibration for radioactivity measurement of environmental
samples by gamma-ray spectrometry
R. Misiak, R. Hajduk, M. Stobiński, M. Bartyzel, K. Szarłowicz, B. Kubica
6.
Treatment with silver nanoparticles delays repair of X-ray induced DNA damage in HepG2 cells
M. Wojewódzka, A. Lankoff, M. Dusińska, G. Brunborg, J. Czerwińska, T. Iwaneńko, T. Stępkowski,
I. Szumiel, M. Kruszewski
7.
Preparation and evaluation of a [66Ga]gallium chitosan complex in fibrosarcoma bearing animal models
A. Pourjavadi, M. Akhlaghi, A.R. Jalilian
8.
Preparation and primary evaluation of 66Ga-DTPA-chitosan in fibrosarcoma bearing mice
M. Akhlaghi, A. Pourjavadi
9.
The effect of external wedge on the photoneutron dose equivalent at a high energy medical linac
S.M. Hashemi, G. Raisali, M. Taheri, A. Majdabadi, M. Ghafoori
10. Performance of a plastic scintillator and GM pancake tubes as alpha and beta contamination detectors
in dosimetric stand
B. Machaj, J. Mirowicz, E. Kowalska
11. Seasonal variation of the elemental composition of particulate matter collected in a small town near
Warszawa, Poland
L. Samek, M. Lankosz
12. Effect of ionizing radiation on the properties of PLA packaging materials
K. Melski, H. Kubera, W. Głuszewski, Z. Zimek
13. Evaluation and benchmarking of gamma dose rate employing different nuclear data libraries for MCNP
code at the decommissioning stage of Ignalina NPP
G. Stankunas, A. Tonkunas, R. Pabarcius
14.
68
Ge/68Ga radioisotope generator as a source of radiotracers for water flow investigations
J. Palige, A. Majkowska, I. Herdzik, S. Ptaszek
140
NUKLEONIKA
Proceedings of the 9th Kudowa Summer School “Towards Fusion Energy”, 8-12 June 2010,
Kudowa Zdrój, Poland
1.
Editorial – 9th Kudowa Summer School “Towards Fusion Energy”
2.
Generation and diagnostics of fast electrons within tokamak plasmas
M.J. Sadowski
3.
Studies on fast electron transport in the context of fast ignition
D. Batani
4.
Diagnostics and scaling of fusion-produced neutrons in PF experiments
H. Schmidt
5.
Laser-induced ablation: physics and diagnostics of ion emission
L. Torrisi
6.
Measurements of electron and ion beams emitted from the PF-1000 device in the upstream and downstream direction
R. Kwiatkowski, E. Skladnik-Sadowska, K. Malinowski, M.J. Sadowski, K. Czaus, J. Zebrowski, L. Karpinski,
M. Paduch, M. Scholz, I.E. Garkusha, P. Kubeš
7.
Optical emission spectroscopy of plasma streams in PF-1000 experiments
K. Jakubowska, M. Kubkowska, E. Skladnik-Sadowska, K. Malinowski, A.K. Marchenko, M. Paduch,
M.J. Sadowski, M. Scholz
8.
Creation of linear DC plasma generator for pyrolysis/gasification of organic materials
A. Tamošiūnas, V. Grigaitienė, P. Valatkevičius
9.
Real-time diagnostics of fast light ion beams accelerated by a sub-nanosecond laser
D. Margarone, J. Krása, A. Picciotto, J. Prokupek
10. CVD diamond detectors for fast alpha particles escaping from the tokamak D-T plasma
I. Wodniak, K. Drozdowicz, J. Dankowski, B. Gabańska, A. Igielski, A. Kurowski, B. Marczewska, T. Nowak,
U. Woźnicka
11. Ponderomotive self-focusing of a short laser pulse under a plasma density ramp
N. Kant, S. Saralch, H. Singh
12. Conceptual design of Light Impurity Monitor for Wendelstein 7-X
I. Książek, R. Burhenn, J. Musielok
13. Post-acceleration of ions from the laser-generated plasma
L. Giuffrida, L. Torrisi
14. Carbon equation of state at high pressure: the role of the radiative transport in the impedance mismatch
diagnostics
A.A. Aliverdiev, D. Batani, R. Dezulian, T. Vinci
15. Localized plasma polarimetry based on the phenomenon of normal mode conversion
Yu.A. Kravtsov, B. Bieg
16. Possible accuracy of the Cotton-Mouton polarimetry in a sheared toroidal plasma
Yu.A. Kravtsov, J. Chrzanowski
17. On the study of ion cyclotron waves in a cylindrical magnetized plasma
N.G. Zaki
18. Post-recoil thermal annealing study of
compounds
L. Nassan, B. Achkar, T. Yassine
177
Lu,
169
Yb,
175
Yb,
166
Ho and
153
Sm in different organometallic
Special Issue on the 100th Anniversary of the Nobel Prize in Chemistry to Maria Skłodowska-Curie
1.
Marie Skłodowska-Curie: teacher, mentor, research center founder, and “la Patronne”
D.C. Hoffman
NUKLEONIKA
141
2.
Historic landmarks in radiation chemistry since early observations by Marie Skłodowska-Curie and Pierre
Curie
J. Belloni
3.
Synthesis of heaviest nuclei and heaviest chemical elements
A. Sobiczewski
4.
Isotope effects in chemistry
W.A. Van Hook
5.
Chemistry for the nuclear energy of the future
A.G. Chmielewski
1.
Clastogenic effects in human lymphocytes exposed to low and high dose rate X-ray irradiation and vitamin C
M. Konopacka, J. Rogoliński
2.
Routine simultaneous production of no-carrier-added high purity 64Cu and 67Ga
A.H. Al Rayyes, Y. Ailouti
3.
Production of 166Ho and 153Sm using hot atom reactions in neutron irradiated tris(cyclopentadienyl)
compounds
L. Nassan, B. Achkar, T. Yassine
4.
Production of 18F by proton irradiation of C6H6NF and C6H5NF2
E. Běták, R. Mikołajczak, J. Staniszewska, S. Mikołajewski, E. Rurarz, J. Wojtkowska
5.
Preparation, quality control and biodistribution studies of 165Dy-chitosan for radiosynovectomy
S. Shirvani-Arani, A. Mahmoodabadi, A. Bahrami-Samani, A.R. Jalilian, M. Mazidi, H. Afarideh,
M. Ghannadi-Maragheh
6.
Computer simulation of temperature distribution on a solid target for 201Tl production
M.R. Aboudzadeh Rovais, K. Yousefi, K. Ardaneh, M. Mirzaii
7.
Monte Carlo study on a new concept of a scanning photon beam system for IMRT
A.M. Wysocka-Rabin, G.H. Hartmann
8.
Simulation of computed tomography (CT) images using a Monte Carlo approach
A.M. Wysocka-Rabin, S. Qamhiyeh, O. Jäkel
9.
Effects of warmness and spatial nonuniformity of plasma waveguide on periodic absolute parametric
instability
N.G. Zaki, A.H. Bekheit
10. Instrumental neutron activation analysis (INAA) for steel analysis and certification
H. Polkowska-Motrenko, E. Chajduk, B. Danko
11. Large area scintillation detector for dosimetric stand with improved light collection
B. Machaj, J. Mirowicz, E. Kowalska
12. A real-valued genetic algorithm to optimize the parameters of support vector machine for classification
of multiple faults in NPP
F.Z. Amer, A.M. El-Garhy, M.H. Awadalla, S.M. Rashad, A.K. Abdien
13. Radiation-heterogenic processes of hydrogen accumulation in water-cooled nuclear reactors
A. Garibov
14. Experimental research on the effects of radioactive waste repository upon groundwaters
A. Zagorskis, V. Verikaitė
15. Electron beam decomposition of pollutant model compounds in aqueous systems
T.-M. Ting, K.Z.M. Dahlan
16. Effectiveness of electron beam irradiation in the control of some soilborne pathogens
L.B. Orlikowski, W. Migdał, M. Ptaszek, U. Gryczka
17. Natural radioactivity in building materials in Iran
S. Mehdizadeh, R. Faghihi, S. Sina
142
NUKLEONIKA
18. Development of an automation system for iodine-125 brachytherapy seed encapsulated by Nd:YAG
laser welding
S.L. Somessari, A. Feher, F.E. Sprenger, M.E.C.M. Rostelato, F.E. da Costa, W.A.P. Calvo
19. Leakage test evaluation used for qualification of iodine-125 seeds sealing
A. Feher, M.E.C.M. Rostelato, C.A. Zeituni, W.A.P. Calvo, S.L. Somessari, J.A. Moura, E.S. Moura,
C.D. Souza, P.R. Rela
20. An intraoral cone system for a Neptun 10PC linear accelerator
P. Shokrani, M. Soltani
21. Effect of magnetic field on the corrosion of iron as studied by positron annihilation
R. Pietrzak, R. Szatanik
22. In memoriam – Professor Antoni M. Dancewicz
Information
INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY
NUKLEONIKA
Dorodna 16, 03-195 Warszawa, Poland
phone: +48 22 504 11 32; fax: +48 22 811 15 32; e-mail: [email protected]
Abstracts and full texts are available on-line at http://www.nukleonika.pl
INTERVIEWS IN 2011
143
INTERVIEWS IN 2011
1. Chmielewski A.G.
Projekt atomowy – pierwsza elektrownia jądrowa w Polsce (The atomic project – the first power station in
Poland). W Pionie i na Poziomie. Aktualności ULMA Construccion Polska SA, 1(9), 8-10 (2011).
2. Chmielewski A.G.
Indeks cen uranu wzrósł o 75 proc. w ciągu roku (The index of uranium prices increased by 75% within
one year). Puls Biznesu, www.pb.pl, 20.02.2011.
3. Chmielewski A.G.
Sytuacja reaktora Fukushima (Situation in the Fukushima nuclear reactor). TVN, 15.03.2011.
4. Chmielewski A.G.
Truszczak D.: Sytuacja reaktora Fukushima (Situation in Fukushima reactor). Program I Polskiego Radia,
16.03.2011.
5. Chmielewski A.G.
Feder A.: Program “Era Wynalazków”, TVP Info, 20.11.2011.
6. Chmielewski A.G.
Truszczak D.: Atomowa czy zielona? (Nuclear or green?). Wieczór z Jedynką. Program I Polskiego Radia,
07.12.2011.
7. Kruszewski M.
Szmidt B.: Wiadomości. Program IV Polskiego Radia (TOK FM), 16.03.2011.
8. Lankoff A.
Truszczyńska B.: Katastrofa w elektrowni jądrowej Fukushima w Japonii (The catastrophe in the nuclear
power plant Fukushima). Wieczór Naukowy. Program I Polskiego Radia, 16.03.2011.
9. Lankoff A.
Husberg Å.: Maria Skłodowska-Curie – woman of science. www.nobelmuseum.se/en/marie-sklodowska-madame-curie, 16.09.2011.
144
PATENTS
1. Sposób otrzymywania terapeutycznych ilości radionuklidu 177Lu (Method for obtaining therapeutic quantities of the 177Lu radionuclide)
A. Bilewicz, E. Iller
Polish Patent 209169
2. Sposób otrzymywania dwuwolframianu itrowo-potasowego oraz nanokompozytu tego dwuwolframianu
dotowanego iterbem (Method for obtaining yttrium-potassium ditungstate and nanocomposite of this
compound doped with ytterbium)
A. Deptuła, W. Łada, T. Olczak, D. Wawszczak, M. Borowiec, H. Szymczak, W. Diakonow, M. Barański
Polish Patent 209170 (with the Institute of Physics, Polish Academy of Sciences)
3. Sposób otrzymywania warstw ochronnych z dwutlenku tytanu (TiO2) albo tytanu litu (Li2TiO2) na katodach niklowych (Method of production protective coatings made of titanium dioxide (TiO2) or lithium
titanate (Li2TiO2) on nickel cathodes)
W. Łada, A. Deptuła, D. Wawszczak, E. Simonetti, A. Sabazia, M. Brocco
Polish Patent 209414
4. Sposób otrzymywania napełniaczy o strukturze montmorylonitu (Method for obtaining fillers of montmorillonite structure)
Z. Zimek, I. Legocka, K. Mirkowski, A. Nowicki, G. Przybytniak
Polish Patent
5. Sposób modyfikowania srebrem pigmentów mineralnych i tkanin (Method for modification of mineral
pigments and fabrics with silver)
A. Łukasiewicz, D. Chmielewska, L. Waliś, J. Michalik
Polish Patent
6. Method and equipment for simultaneous removal of acidic inorganic pollutants and volatile organic compounds from stream of flue gases
A.G. Chmielewski, A. Pawelec, B. Tymiński, J. Licki, A.A. Basfar
Saudi Arabia Patent No. 2810 (with King Abdulaziz City for Science and Technology)
PATENT APPLICATIONS
1. Radiofarmaceutyk terapeutyczny znakowany radionuklidami radu oraz sposób jego wytwarzania (Therapeutic radiopharmaceutical labelled with radionuclides of radium and method for its obtaining)
A. Bilewicz, A. Kasperek
P-394340
2. Sposób otrzymywania sferycznych ziaren trójtlenku itru (Method for obtaining spherical grains of yttrium
trioxide)
A. Deptuła, W. Łada, D. Wawszczak, E. Iller, L. Królicki, J. Ostyk-Narbutt
P-394645
3. Sposób i układ transportu i mieszania zawiesiny biomasy w hydrolizerze i fermentorze (Method and system
of transport and mixing of biomass suspension in a hydrolyser and fermenter)
A. Kryłowicz, J. Usidus, K. Chrzanowski, A.G. Chmielewski
P-395860
4. Sposób selektywnego wydzielania uranu i protaktynu z materiału zawierającego tor (A selective extraction of uranium and protactinium from material containing thorium)
P. Kalbarczyk, H. Polkowska-Motrenko, E. Chajduk
P-396564
145
5. Sposób pozyskiwania i separacji cennych pierwiastków metali, zwłaszcza z ubogich rud uranowych oraz
ścieków radioaktywnych (Method for separation and obtaining of valuable metals particularly from low-grade uranium ores and radioactive effluents)
G. Zakrzewska-Trznadel, A. Jaworska-Sobczak, A. Miśkiewicz, W. Łada, E. Dłuska, S. Wroński
P-397379
6. Sorbent for receiving radionuclide arsenic-72, production of this sorbent and its use
H. Polkowska-Motrenko, A. Bilewicz, K. Doner, E. Chajduk
European Patent Application No. EP12152024.1
7. A selective extraction of uranium and protactinium from material containing thorium
P. Kalbarczyk, H. Polkowska-Motrenko, E. Chajduk
European Patent Application No. EP12152025.8
8. Method of dissolution of thorium oxide
K. Łyczko, M. Łyczko, I Herdzik, B. Zielińska
European Patent Application
9. Method of dissolution of thorium oxide
K. Łyczko, M. Łyczko, I. Herdzik, B. Zielińska
Indian Patent Application
146
CONFERENCES ORGANIZED AND CO-ORGANIZED
BY THE INCT IN 2011
1.
SPOTKANIE POLSKIEJ GRUPY ROBOCZEJ PROJEKTU IPPA FP7 EU (POLISH NATIONAL GROUP MEETING IN THE FRAME OF IPPA FP7 EU PROJECT), 5 APRIL
2011, WARSZAWA, POLAND
Organized by the Institute of Nuclear Chemistry and Technology, Institute of Atomic Energy
Organizing Committee: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc., professor in INCT, Barbara
Zielińska, Ph.D., Agnieszka Miśkiewicz, M.Sc., Bogumiła Mysłek-Laurikainen, Ph.D., Ewelina
Miśta, M.Sc.
2.
SEMINAR ON THE EXCHANGE OF INFORMATION ON NUCLEAR SAFETY AND
RADIOLOGICAL PROTECTION WITH PARTICIPATION OF GOVERNMENT DELEGATIONS OF AUSTRIA AND POLAND, 25-26 MAY 2011, WARSZAWA, POLAND
Organized by the Institute of Nuclear Chemistry and Technology
3.
SPOTKANIE POLSKIEJ GRUPY ROBOCZEJ PROJEKTU IPPA FP7 EU (POLISH NATIONAL GROUP MEETING IN THE FRAME OF IPPA FP7 EU PROJECT), 1 JULY
2011, WARSZAWA, POLAND
Organized by the Institute of Nuclear Chemistry and Technology, Institute of Atomic Energy
Miśta, M.Sc.
4.
PlasTEP SUMMER SCHOOL AND TRAINING COURSE IN WARSAW/SZCZECIN, 25
JULY-5 AUGUST 2011, WARSZAWA/SZCZECIN, POLAND
Organized by the Institute of Nuclear Chemistry and Technology; Faculty of Electrical Engineering,
West Pomeranian University of Technology
Organizing Committee: Andrzej Pawelec, Ph.D., Sylwia Witman, M.Sc., Marcin Hołub, Ph.D.
5.
WORKSHOP “CURRENT TRENDS IN RADIATION CHEMISTRY RESEARCH”, 26
AUGUST 2011, WARSZAWA, POLAND
Organizer: Prof. Krzysztof Bobrowski, Ph.D., D.Sc.
6.
INTERNATIONAL CONFERENCE ON DEVELOPMENT AND APPLICATIONS OF NUCLEAR TECHNOLOGIES NUTECH-2011, 11-14 SEPTEMBER 2011, KRAKÓW, POLAND
Organized by the Institute of Nuclear Chemistry and Technology; Faculty of Physics and Applied
Computer Science, AGH University of Science and Technology
Organizing Committee: Prof. Marek Lankosz, Ph.D., D.Sc., Dariusz Węgrzynek, Ph.D., D.Sc., Marek
Ciechanowski, Ph.D., Zdzisław Stęgowski, Ph.D., Joanna Chwiej, Ph.D., Joanna Dudała, Ph.D.,
Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc., Wojciech Migdał, Ph.D., D.Sc., Wojciech Głuszewski,
Ph.D., Piotr Urbański, Ph.D., D.Sc.
7.
SPOTKANIE POLSKIEJ GRUPY REFERENCYJNEJ PROJEKTU IPPA FP7 EU (POLISH
REFERENCE GROUP MEETING IN THE FRAME OF IPPA FP7 EU PROJECT), 20
SEPTEMBER 2011, WARSZAWA, POLAND
147
Organized by the Institute of Nuclear Chemistry and Technology, National Centre for Nuclear Research
Miśta, M.Sc.
8.
XI SZKOŁA STERYLIZACJI I MIKROBIOLOGICZNEJ DEKONTAMINACJI RADIACYJNEJ (XI TRAINING COURSE ON RADIATION STERILIZATION AND HYGENIZATION), 20-21 OCTOBER 2011, WARSZAWA, POLAND
Organizing Committee: Zbigniew Zimek, Ph.D., Iwona Kałuska, M.Sc., Andrzej Rafalski, Ph.D.,
Wojciech Głuszewski, Ph.D.
9.
RER/8/014 COORDINATION MEETING ON RADIATION ENGINEERED NANOSTRUCTURES – SUPPORTING RADIATION SYNTHESIS AND THE CHARACTERIZATION
OF NANOMATERIALS FOR HEALTH CARE, ENVIRONMENTAL PROTECTION AND
CLEAN ENERGY APPLICATIONS, 16-18 NOVEMBER 2011, WARSZAWA, POLAND
Organized by the International Atomic Energy Agency, Institute of Nuclear Chemistry and Technology
Organizing Committee: Andrei Chupov, Agnes Sáfrány, Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.,
Wojciech Starosta, Ph.D., Marek Buczkowski, Ph.D.
10. PIERWSZE WARSZTATY W RAMACH PROJEKTU IPPA FP7 EU (1st WORKSHOP
IN THE FRAME OF IPPA FP7 EU PROJECT), 24 NOVEMBER 2011, WARSZAWA,
POLAND
Organized by the Institute of Nuclear Chemistry and Technology, National Centre for Nuclear Research
Miśta, M.Sc.
11. IX KONFERENCJA “DLA MIASTA I ŚRODOWISKA – PROBLEMY UNIESZKODLIWIANIA ODPADÓW” (IX CONFERENCE ON “FOR THE CITY AND ENVIRONMENT
– PROBLEMS OF WASTE DISPOSAL), 28 NOVEMBER 2011, WARSZAWA, POLAND
Organized by the Warsaw University of Technology, Institute of Nuclear Chemistry and Technology
(PlasTEP project), Solid Communal Waste Utilization Plant (Warszawa), Gdańsk University of
Technology
Organizing Committee: Maria Obrębska, Ph.D., Michał Kalita, Ph.D., Agata Urbaniak, M.Sc., Sylwia Witman, M.Sc.
148
Ph.D. THESES
1. Maroor Raghavan Ambikalmajan Pillai, Ph.D.
Studies on radioimmunoassays for thyroid and related hormones
University of Mumbai, India, 1986
Nostrification: Institute of Nuclear Chemistry and Technology, 25.02.2011
2. Kamil Brzóska, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Aktywność szlaku NF-κB w warunkach permanentnego stresu oksydacyjnego: wnioski z badań na modelu
myszy pozbawionych cytozolowej dysmutazy ponadtlenkowej (SOD1) (NF-κB signalling pathway activity
under conditions of chronic oxidative stress: lessons from cytosolic superoxide dismutase (SOD1) deficient mice)
supervisor: Prof. Marcin Kruszewski, Ph.D., D.Sc.
Institute of Biochemistry and Biophysics, Polish Academy of Sciences, 10.05.2011
3. Sylwia Męczyńska-Wielgosz, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Wpływ tlenku azotu i nadtlenoazotynu na konformację i aktywność białek zawierających żelazo (The influence of nitric oxide and peroxynitrite on conformation and activity of iron containing proteins)
Institute of Nuclear Chemistry and Technology, 30.06.2011
4. Karolina Ewa Wójciuk, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Rola wysokocząsteczkowych ligandów w powstawaniu dinitrozylowych kompleksów żelaza (Role of high-molecular ligands in the formation of dinitrosyl complexes of iron)
5. Gabriel Kciuk, M.Sc. (Industrial Chemistry Research Institute, Warszawa, Poland)
Wpływ grup funkcyjnych aminokwasów na mechanizmy reakcji rodnikowych w peptydach zawierających
tyrozynę (Influence of functional groups of neighbouring amino acids on the mechanism of radical reactions occurring in peptides containing tyrosine)
supervisor: Prof. Krzysztof Bobrowski, Ph.D., D.Sc.
6. Danuta Wawszczak, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Synteza kompleksową metodą zol-żel kompozytów ZrO2, TiO2, SiO2 na bazie tlenków wolframu, ich badania strukturalne, przykładowe zastosowania (A complex method for the synthesis of sol-gel composites
ZrO2, TiO2, SiO2 on the basis of tungsten oxides)
supervisor: Edward Iller, Ph.D., D.Sc., professor in NCBJ
D.Sc. THESES
1. Maroor Raghavan Ambikalmajan Pillai, Ph.D. (Bhabha Atomic Research Centre, Trombay, Mumbai,
India)
Metallic radionuclides and therapeutic radiopharmaceuticals
EDUCATION
149
EDUCATION
Ph.D. PROGRAMME IN CHEMISTRY
The Institute of Nuclear Chemistry and Technology holds a four-year Ph.D. degree programme for
graduates of chemical, physical and biological departments of universities, for graduates of medical
universities and to engineers in chemical technology and material science.
The main areas of the studies are:
• chemical aspects of nuclear energy,
• radiation chemistry and biochemistry,
• chemistry of radioelements,
• isotopic effects,
• radiopharmaceutical chemistry,
• analytical methods,
• chemistry of radicals,
• application of nuclear methods in chemical and environmental research, material science and protection of historical heritage.
The candidates accepted for the mentioned programme will be employed in the Institute. The candidates can apply for a doctoral scholarship. The INCT offers accommodation in 10 rooms in the guesthouse for Ph.D. students not living in Warsaw.
During the four-year Ph.D. programme, the students participate in lectures given by senior staff
from the INCT, University of Warsaw and the Polish Academy of Sciences. In the third year, the Ph.D.
students are obliged to prepare a seminar related to the various aspects of nuclear energy. Each year
the Ph.D. students are obliged to deliver a lecture on topic of his/her dissertation at a seminar. The final
requirements for the Ph.D. programme graduates, consistent with the regulation of the Ministry of
Science and Higher Education, are:
• submission of a formal dissertation, summarizing original research contributions suitable for publication;
• final examination and public defense of the dissertation thesis.
In 2011, the following lecture series were organized:
• “The physical foundations of nuclear energy. Radioactivity, its application and elements of radiation
protection” – Prof. Ludwik Dobrzyński, Ph.D., D.Sc. (National Centre for Nuclear Research, Świerk,
Poland);
• “Adsorbents and their part in environmental protection, in industry and in analytical chemistry:
classical approach and the trends of the current studies” – Krystyna Cieśla, Ph.D., D.Sc., professor in
INCT (Institute of Nuclear Chemistry and Technology, Warszawa, Poland);
• “Automatization and miniaturization of instrumentation in chemical analysis” – Prof. Marek Trojanowicz, Ph.D., D.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland).
The qualification interview for the Ph.D. programme takes place in the mid of September. Detailed
information can be obtained from:
• head: Prof. Aleksander Bilewicz, Ph.D., D.Sc.
(phone: +48 22 504 13 57, e-mail: [email protected]);
• secretary: Dr. Ewa Gniazdowska
(phone: +48 22 504 11 78, e-mail: [email protected]).
TRAINING OF STUDENTS
Country
Number
of participants
Period
Adam Mickiewicz University
Faculty of Law and Administration
Poland
1
2 weeks
Korea Nuclear Energy Foundation
Korea
4
one-day course
Institution
150
EDUCATION
Country
Number
of participants
Period
Philippines
1
2 weeks
Faculty of Chemistry
Poland
3
3 weeks
Warsaw University of Life Sciences
Faculty of Human Nutrition and Consumer Sciences
Poland
42
one-day course
Faculty of Chemical and Process Engineering
Poland
8
one-day practice
Faculty of Chemistry
2
1 month
Poland
2
1.5 month
Faculty of Materials Science and Engineering
15
one-day course
Poland
2
1 month
Faculty of Physics
15
one-day course
Poland
20
one-day practice
WAT Military University of Technology
Poland
4
1.5 month
Zespół Szkół Samochodowych i Licealnych nr 3
im. I.J. Paderewskiego
Poland
16
one-day course
Institution
Philippine Nuclear Research Institute
151
RESEARCH PROJECTS GRANTED
BY THE NATIONAL SCIENCE CENTRE
IN 2011
1.
The influence of nitric oxide and peroxynitrite on conformation and activity of iron containing
proteins.
2.
Novel technetium and rhenium complexes with the N-heterocyclic aldehyde thiosemicarbazones
– the potential radiopharmaceuticals.
supervisor: Leon Fuks, Ph.D.
3.
Provenance and chronology studies of selected silver coins minted in the Polish and Central
Europe coinages by means of chemical composition, sources of raw materials and technology.
supervisor: Lech Waliś, Ph.D.
4.
Synthesis and physicochemical properties of conjugates technetium-99m complexes with n-octanoyl-[Ser3]-ghrelin(1-6) peptide as potential diagnostic radiopharmaceuticals.
supervisor: Przemysław Koźmiński, M.Sc.
5.
Radiochemical separation of arsenic from selenium and its potential usage in generator 72Se/72As
construction.
supervisor: Ewelina Chajduk, Ph.D.
6.
Glass in Central Europe from the late-medieval times to the end of the pre-industrial era.
Chemical composition.
supervisor: Jerzy Jakub Kunicki-Goldfinger, Ph.D.
7.
Complexes of 44Sc as precursors of radiopharmaceuticals for molecular imaging.
supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc.
8.
Participation of radiation chemistry in systems chemistry, especially in prebiotic chemistry.
supervisor: Prof. Zbigniew P. Zagórski, Ph.D., D.Sc.
9.
Radiosensitizing effect of conjugated linoleic acid (CLA) on the colon adenocarcinoma cells
HT-29 investigation of the mechanism of double-strand DNA break (DSB) repair delay.
supervisor: Iwona Grądzka, Ph.D.
10. Radiation-induced radical processes in model amino acid and polypeptide molecules.
DEVELOPMENT PROJECTS GRANTED
BY THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT
IN 2011
1.
New detection systems for the control of dosimetric stands.
supervisor: Bronisław Machaj, Ph.D.
2.
A new generation of mining radiometers for the measurement of radon decay products.
supervisor: Jakub Bartak, Eng.
3.
A plant for the liquid radioactive waste treatment in research institutes and organizations using radioactive substances.
supervisor: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc., professor in INCT
4.
Obtaining of carrier-free-scandium-47 – a radionuclide for therapeutic radiopharmaceuticals.
152
5.
Labelling of biomolecules with At-211 –- obtaining of therapeutic radiopharmaceuticals for
nuclear medicine.
supervisor: Monika Łyczko, Ph.D.
6.
Preparation of a hot-melt adhesive for the insulation of joints in preinsulation pipes used in
heating installations.
supervisor: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT
7.
Radiation sterilized substrata for plant cultivation inoculated with selected microorganisms.
supervisor: Wojciech Migdał, Ph.D., D.Sc., professor in INCT
8.
Formation of the data bank on original products for the juice sector, to supply requirements of
the Polish market and producers, basing on the method of stable isotopes.
supervisor: Ryszard Wierzchnicki, Ph.D.
9.
Elaboration of the synthesis procedure of a receptor diagnostic radiopharmaceutical for breast
cancer, of the type Her-2, imaging lapatinib labelled with technetium-99m.
supervisor: Ewa Gniazdowska, Ph.D.
10. A mobile membrane installation for the enrichment of gas in methane (project INITECH).
supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.
11. Technical project of high-performance installation for obtaining and management of biogas
(project INITECH).
INTERNATIONAL PROJECTS CO-FUNDED
BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION
IN 2011
1.
Functionalization of polymer surfaces by radiation grafting for the separation of heavy metals
including radioactive lanthanides.
2.
Developing of an advanced industrial gamma scanning system with wireless data acquisition.
supervisor: Jacek Palige, Ph.D.
3.
Supporting radiation synthesis and the characterization of nanomaterials for health care, environmental protection and clean energy applications.
supervisor: Dagmara Chmielewska-Śmietanko, M.Sc.
4.
Enhancing quality control methods and procedures for radiation technology.
supervisor: Iwona Kałuska, M.Sc.
5.
Radiation supporting synthesis and curing of nanocomposites suitable for practical applications.
6.
Ageing diagnostic and prognostic of low voltage C and I cables.
7.
Multi-disciplinary biodosimetric tools to manage high scale radiological casualties.
supervisor: Sylwester Sommer, Ph.D.
8.
Implementing public participation approaches in radioactive waste disposal.
supervisor: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc., professor in INCT
9.
Synthesis and research on new metal-organic framework coordination compounds of light sblock metal ions with heterocyclic ligands.
supervisor: Wojciech Starosta, Ph.D.
10. Formation, investigations and characterization of new nanostructured porous and composite
materials.
supervisor: Bożena Sartowska, Ph.D.
153
STRATEGIC PROJECT
“NEW TECHNOLOGIES SUPPORTING DEVELOPMENT
OF SAFE NUCLEAR ENERGY”
1. Scientific problem no. 3: Principles to secure fuel needs for the Polish nuclear energy
2. Scientific problem no. 4: Development of techniques and technologies aiding the management of
spent nuclear fuel and radioactive wastes
supervisor: Leon Fuks, Ph.D.
3. Scientific problem no. 5: Participation criteria of the Polish industry in the development of nuclear
energy. Study of the case
4. Scientific problem no. 6: Development of methods securing nuclear safety and radiological protection for the current and future needs of nuclear energy
STRATEGIC PROJECT
“ADVANCED TECHNOLOGIES FOR GAINING ENERGY”
1. Scientific problem no. 3: Elaboration of a technology of coal gasification for highly efficient production of fuel and electric energy (coordinated by the Institute for Chemical Processing of Coal)
• Studies on the processes of membrane purification of synthesis gas
2. Scientific problem no. 4: Elaboration of integrated technologies for production of fuels and energy from biomass, agriculture waste and others (coordinated, in part, by the University of Warmia
and Mazury in Olsztyn)
• Concentration of methane in biogas formed during fermentation and co-fermentation of
lignocellulose (4.2.1.C)
• Studies on the degradation efficiency of lignocellulose materials under the influence of ionizing radiation (4.4.A)
supervisor: Wojciech Migdał, Ph.D., D.Sc., professor in INCT
• Design work on a biogas-plant (2.1.B)
supervisor: Jacek Palige, Ph.D.
IAEA RESEARCH CONTRACTS IN 2011
1. Functionalization of polymer surfaces by radiation grafting for separation of heavy metals including radioactive lanthanides.
No. 14431
principal investigator: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT
2. Radiation supporting synthesis and curing of nanocomposites suitable for practical applications.
No. 16666
3. Laboratory and feasibility study for industrial waster wate effluent treatment by radiation.
No. 16454
principal investigator: Zbigniew Zimek, Ph.D.
154
IAEA TECHNICAL AND REGIONAL CONTRACTS IN 2011
1. Developing of an advanced industrial gamma scanning system with wireless data acquisition.
POL/0/010
2. Supporting radiation synthesis and the characterization of nanomaterials for health care, environmental protection and clean energy applications.
RER/8/014
3. Enhancing quality control methods and procedures for radiation technology.
RER/8/017
4. Using nuclear techniques for the characterization and preservation of cultural heritage artefacts
in the European Region.
RER/8/015
PROJECTS WITHIN THE FRAME
OF EUROPEAN UNION FRAME PROGRAMMES
IN 2011
1. FP7 Integrated Project: Actinide recycling by separation and transmutation (ACSEPT).
principal investigator: Prof. Jerzy Narbutt, Ph.D., D.Sc.
2. FP7 Collaborative Project: Multidisciplinary biodosimetric tools to manage high scale radiological casulaties (MULTIBIODOSE).
principal investigator: Sylwester Sommer, Ph.D.
3. FP7 – EURATOM, FUSSION: Ageing diagnostic and prognostic of low voltage C and I cables
(ADVANCE).
4. FP7 – EURATOM, FUSSION: Implementing public participation approaches in radioactive
waste disposal (IPPA).
principal investigator: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc., professor in INCT
5. FP7 – EURATOM, FUSSION: New MS linking for an advanced cohesion in Euratom research
(NEWLANCER).
principal investigator: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc., professor in INCT
EUROPEAN REGIONAL DEVELOPMENT FUND:
BALTIC SEA REGION PROGRAMME
1. Dissemination and fostering of plasma based technological innovation environment protection in
BSR PlasTEP.
INTERNATIONAL RESEARCH PROGRAMMES IN 2011
1. European cooperation in the field of scientific and technical research. COST CM0703 Systems
chemistry – Chemistry and molecular sciences and technologies. Participation of radiation
chemistry in systems chemistry, especially in prebiotic chemistry.
supervisor: Prof. Zbigniew Zagórski, Ph.D., D.Sc.
2. European cooperation in the field of scientific and technical research. COST ACTION CM 0603
– Free radicals in chemical biology.
3. European cooperation in the field of scientific and technical research. COST D38 – Metal based
probes for imaging applications. Complexes of 44Sc as precursors of radiopharmaceuticals for
molecular imaging.
155
4. Polish-Norwegian Research Fund – Impact of nanomaterials on human health: lessons from in
vitro and animal models.
5. European cooperation in the field of scientific and technical research. COST Action BM 0607
Targeted radionuclide therapy.
STRUCTURAL FUNDS:
OPERATIONAL PROGRAMME INNOVATIVE ECONOMY
1. Centre of Radiochemistry and Nuclear Chemistry – meeting the needs for nuclear power and
nuclear medicine.
supervisor: Roman Janusz, M.Sc.
2. Analysis of the possibilities of uranium supply from indigenous resources in Poland
supervisor: Grażyna Zakrzewska-Trznadel, Ph.D., D.Sc.
3. Analysis of the effects of utilization of thorium in a power reactor
supervisor: Prof. Jacek Michalik, Ph.D., D.Sc.
4. New generation of electrical wires modified by radiation.
supervisor: Zbigniew Zimek, Ph.D.
5. A multiparameter “Triage” test for assessment of radiation exposure to the general population.
6. A new generation of radiometric devices with wireless transmission of information.
supervisor: Adrian Jakowiuk, M.Sc.
156
1.
Adliene Diana, Department of Physics, Kaunas University of Technology, Lithuania, 16-18.11.2011.
2.
Alessis Sabina, University of Palermo, Italia, 14-18.02.2011.
3.
Alkin Ahmet, TUPRAS, Turkey, 05.04.2011.
4.
Amilcar Antonio, Polytechnic Institute of Bragança, Portugal, 29.11.-02.12.2011.
5.
Benea Vasile, Institute of Applied Physics, Academy of Sciences of Moldova, Republic of Moldova,
16-18.11.2011.
6.
Brisut Patrick, International Atomic Energy Agency, Austria, 12-15.12.2011.
7.
Cantser Valeriu, National Council for Accreditation and Attestation, Republic of Moldova, 16-18.11.2011.
8.
Chitho Pavayno Feliciano, Philippine Nuclear Research Institute, Philippines, 01.09.-30.11.2011.
9.
Chupor Andrey, International Atomic Energy Agency, Austria, 15.11.2011.
10. De la Fuente Julia, University of Chile, Chile, 25.10.-14.11.2011.
11. Dogan Alisan, TUPRAS, Turkey, 05.04.2011.
12. Gabulov Ibrahim, Institute of Radiation Problems, Azerbaijan National Academy of Sciences, Azerbaijan, 16-18.11.2011.
13. Garibov Adil, Institute of Radiation Problems, Azerbaijan National Academy of Sciences, Azerbaijan,
15.11.2011.
14. Guidez Joel, Atomic Energy and Alternative Energies Commission (CEA), France, 13.03.2011.
15. Guven Olgun, Department of Chemistry Hacettepe University, Turkey, 16-18.11.2011.
16. Hoveé-Levin Chantal, University of Paris-Sud 11, Orsay, France, 25-31.08.2011.
17. Hyun Jin Kim, Embassy of the Republic of Korea, 26.05.2011.
18. Jaksic Milko, Division of Experimental Physics, Ruđer Bošković Institute, Croatia, 16-18.11.2011.
19. Kalugin Oleg N., Kharkiv National University, Ukraine, 20-26.02.2011.
20. Kovac Peter, BIONT a.s., Slovakia, 16-18.11.2011.
21. Krkljes Aleksandra, Vinča Institute of Nuclear Sciences, Serbia, 16-18.11.2011.
22. Letournol Eric, VIVIRAD, France, 05.04.2011.
23. Lyssukhin Sergey, National Nuclear Center of the Republic of Kazakhstan (NNC), Kazakhstan,
16-18.11.2011.
24. Maningas Aurelio, Philippine Nuclear Research Institute, Philippines, 01.09.-30.11.2011.
25. Morgunov Volodymir, Kharkiv National University, Ukraine, 05-15.12.2011.
26. Ristova Mimoza, Faculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University in
Skopje, Republic of Macedonia, 16-18.11.2011.
27. Sabatino Maria Antonella, University of Palermo, Italy, 14-18.02.2011.
28. Schay Zoltan, Institute of Isotopes Co., Ltd., Hungarian Academy of Sciences, Hungary, 16-18.11.2011.
29. Seanh Wan Baek, Embassy of the Republic of Korea, 26.05.2011.
30. Spadaro Giuseppe, University of Palermo, Italy, 14-18.02.2011.
31. Sueo Machi, Japan, 14-17.09.2011.
32. Tan Erdal, Turkish Atomic Energy Commission (TAEK), Turkey, 05.04.2011.
33. Tchelidze Tamar, Tbilisi State University, Georgia, 16-18.11.2011.
34. Tetsuro Majimy, Osaka University, Japan, 27-31.08.2011.
35. Tulsi Mukherjee, Bhabha Atomic Research Centre, India, 25.08.-02.09.2011.
36. Vnul Suat, Turkish Atomic Energy Commission (TAEK), Turkey, 05.04.2011.
37. Wischart James F., Brookhaven National Laboratory, USA, 25.08.-02.09.2011.
38. Yeunje Oh, Embassy of the Republic of Korea, 26.05.2011.
39. Ylli Fatos, Centre of Applied Nuclear Physics, Albania, 16-18.11.2011.
40. Young Mi Nam, Korean Atomic Energy Research Institute, Republic of Korea, 09.03.2011.
157
158
1.
Tomasz Białopiotrowicz, Ph.D., D.Sc. (Maria Curie-Skłodowska University, Lublin, Poland)
Swobodna energia powierzchniowa i kąt zwilżania jako parametry określające stan energetyczny powierzchni (The surface free energy and contact angle as parameters determining energetic state of a
surface)
2.
Krystyna Cieśla, Ph.D., D.Sc., professor in INCT (Institute of Nuclear Chemistry and Technology,
Warszawa, Poland)
Chemia w żywności: zagrożenia czy ulepszenie. Rola dodatków funkcjonalnych w kształtowaniu cech
współczesnej żywności (Chemical substances in food: impendence or improvement. The weight of functional additives as the agents modifying the properties of the contemporary food)
3.
Izabela Cydzik, M.Sc. (Joint Research Centre, European Commission, IHCP Nanobioscience
Unit, Ispra, Italy)
Production of radioactive nanoparticles for biological studies
4.
Nasir Hamodi, M.Sc. (Nuclear Fuel Group, University of Manchester, United Kingdom)
Manufacturing TRISO particles from kernel to a nuclear fuel element used in high temperature reactor
(HTR)
5.
Prof. Oleg N. Kalugin (V.N. Karazin Kharkiv National University, Ukraine)
Computer modelling nanomaterials: possibilities and perspectives
6.
Prof. Zbigniew Karpiński, Ph.D., D.Sc. (Institute of Physical Chemistry, Polish Academy of
Sciences, Warszawa, Poland)
Katalityczne wodoroodchlorowanie tetrachlorometanu na katalizatorach platynowych (Catalytic hydrogen-dechlorination of tetrachloromethane on platinum catalysts)
7.
Robert Kołos, Ph.D., D.Sc. (Institute of Physical Chemistry, Polish Academy of Sciences, Warszawa, Poland)
Kilka nienasyconych cząsteczek łańcuchowych o znaczeniu astrochemicznym: teoria, eksperyment, obserwacje (A few unsaturated chain molecules of astrochemical importance: theory, experiment, observations)
8.
Seweryn Krajewski, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Metaloorganiczne i chelatowe kompleksy 105Rh i 103mRh jako potencjalne prekursory radiofarmaceutyków terapeutycznych (Organometallic and chelate compexes of 105Rh and 103mRh as potential precursors
of therapeutic radiopharmaceuticals)
9.
Prof. Doron Lancet (Weizmann Institute of Science, Rehovot, Israel)
Life’s origin: complex networks right from day one
10. Małgorzata Nyga, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Generowanie rodników utleniających i ich reaktywność w wytypowanej grupie cieczy jonowych (Generation of oxidizing radicals and their reactivity in selected group of ionic liquids)
11. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Chemia dla energetyki jądrowej przyszłości (Chemistry for the nuclear energy of the future)
12. Marcin Sterniczuk, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Centra paramagnetyczne generowane radiacyjnie w sitach molekularnych z zaadsorbowanym tlenkiem
węgla (Radiation generated paramagnetic centres in molecular sieves with adsorbed carbon oxide)
13. Prof. Ion Tiginyanu (Academy of Sciences of Moldova)
Novel nanomaterials based on inorganic nanostructured membranes
14. Marta Walo. M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Rola segmentów giętkich w radiacyjnej modyfikacji poli(estrouretanów) (The role of soft segments in
radiation modification of poly(ester-urethanes))
159
LECTURES AND SEMINARS DELIVERED OUT OF THE INCT
IN 2011
LECTURES
1.
Bilewicz A.
Wyzwania stojące przed kształceniem w zakresie chemii dla enegetyki jądrowej w Polsce (Challenges of
education and training in chemistry for nuclear energy in Poland).
Francusko-Polska Konferencja „Chemia dla energetyki jądrowej przyszłości” (French-Polish Symposium “Chemistry for the nuclear energy of the future”), Montpellier, France, 05.04.2011.
2.
Bobrowski K.
Chemia radiacyjna w Polsce: 100 lat po odkryciu Marii Skłodowskiej-Curie (Radiation chemistry in
Poland: 100 years after Maria Skłodowska-Curie’s discovery).
Seminarium „Maria Skłodowska-Curie: naukowe dziedzictwo i współczesne polskie badania” (Seminar
“Maria Skłodowska-Curie: scientific heritage and contemporary Polish research”), Brussels, Belgium,
09-11.06.2011.
3.
Bobrowski K.
Radiation-induced electron transfer in enkephalins.
ESF Conference in partnership with LFUI “Charge transfer in biosystems”, Obergugl, Austria,
17-22.07.2011.
4.
Bobrowski K.
Radiation chemistry in Poland: 100 years after Maria Skłodowska-Curie’s discovery.
Workshop “Current trends in radiation chemistry research”, Warszawa, Poland, 26.08.2011.
5.
Bobrowski K.
From retinal polyenes to peptides and proteins: radiation chemistry approach.
Colloque Chimie sous Rayonnement: l’Heritage de Marie Curie, Paris, France, 14-17.11.2011.
6.
Buczkowski M.
Influence of ionising and UV radiation on template deposited nano-/microstructures of silver haloids.
RER/8/014 Coordination Meeting on Radiation Engineered Nanostructures – Supporting Radiation
Synthesis and the Characterization of Nanomaterials for Health Care, Environmental Protection and
Clean Energy Applications, Warszawa, Poland, 16-18.11.2011.
7.
Chmielewski A.G., Polak A., Palige J., Harasimowicz M., Zalewski M., Wawryniuk K., Roubinek O.
Nowe rozwiązania technologiczne biogazowni – współpraca polskiej nauki z przemysłem (New technologic
solution of biogas-works – cooperation of the Polish science and industry).
Konferencja „Energia elektryczna, ciepło i gaz – perspektywą dla Gminy”, Minikowo, Poland, 11.03.2011.
8.
Chmielewski A.G.
Przyszłość energetyczna świata (The future of energy of the world).
Mazowieckie Forum Nauczycieli Przedmiotów Przyrodniczych „Poznać chemię. Zrozumieć przyrodę”,
Warszawa, Poland, 16.03.2011.
9.
Chmielewski A.G.
Chemia dla energetyki jądrowej przyszłości (Chemistry for nuclear energy of the future).
Role of the Polish R&D institutions, academic organizations and industry in the development of nuclear
energy in Poland.
1st International Nuclear Energy Congress, Warszawa, Poland, 23-24.05.2011.
Chemia dla energetyki jądrowej przyszłości (Chemistry for nuclear energy of the future).
160
Chemia w rozwoju i postępie cywilizacji – Konferencja w Senacie Rzeczpospolitej Polskiej z okazji Międzynarodowego Roku Chemii IYC 2011 i Roku Marii Skłodowskiej-Curie MSC-100, Warszawa, Poland,
07.06.2011.
Fossil, fissile and renewable energy sources, they role in sustainable country development.
Conference “Scientific support to a competitive European carbon economy: energy, transport and emerging technologies”, Warszawa, Poland, 07.06.2011.
Electron beam generated plasma flue gas treatment.
17th Romanian International Conference on Chemistry and Chemical Engineering, Sinaia, Romania,
07-10.09.2011.
Chemia radiacyjna i radiochemia w Polsce – sto lat później (Radiation chemistry and radiochemistry in
Poland – 100 years later).
Konferencja „Historia badań radiacyjnych w Polsce”, Warszawa, Poland, 14.11.2011.
15. Cieśla K.
Application of ionizing radiation for preparation of edible and biodegradable nanostructured packaging
materials based on polysaccharides.
16. Deptuła A., Brykała M., Łada W., Olczak T., Wawszczak D., Modolo G., Daniels H.
Badania na syntezą tlenków uranowych za pomocą kompleksowej metody zol-żel (CSGP) (Synthesis of
uranium oxides by complex sol-gel processes (CSGP)).
Konferencja Naukowo-Techniczna „Polska nauka i technika dla elektrowni jądrowych w Polsce”,
Mądralin, Poland, 13-14.01.2011.
17. Deptuła A., Brykała M., Łada W., Wawszczak D., Olczak T.
Synthesis of uranium oxides doped by Th by complex sol-gel processes (CSGP).
ACSEPT 3rd Annual Meeting, Manchester, Great Britain, 04-07.04.2011.
18. Głuszewski W.
Radiacyjne metody modyfikacji elastomerów (Radiation methods for modification of elastomers).
Seminarium poświęcone tematyce tworzyw sztucznych, Poznań, Poland, 22.03.2011.
Wpływ prac Marii Skłodowskiej-Curie na rozwój technik radiacyjnych (Impact of the work of Maria
Skłodowska-Curie on the development of radiation techniques).
Konferencja „Maria Skłodowska-Curie. Dwukrotna noblistka i jej wkład w powstanie nowych dziedzin
nauki”, Warszawa, Poland, 24.03.2011.
20. Głuszewski W.
Maria Skłodowska-Curie prekursorką radiacyjnych metod konserwacji dzieł sztuki (Maria Skłodowska-Curie precursor radiation method of preservation art work).
XII Beskidzki Festiwal Nauki i Sztuki, Bielsko-Biała, Poland, 27-28.05.2011.
Od Marii Skłodowskiej-Curie do radiacyjnych metod konserwacji obiektów o znaczeniu historycznym
(From Maria Skłodowska-Curie to radiation methods of conservation of historical objects).
Konferencja „Wybitne odkrycia źródłem inspiracji dla wynalazców – w 100-lecie II nagrody Nobla Marii
Skłodowskiej-Curie”, Warszawa, Poland, 17.06.2011.
22. Głuszewski W.
Prezentacja wystawy poświęconej 100. rocznicy nagrody Nobla przyznanej Marii Skłodowskiej-Curie
(Presentation of the exibition, devoted to the anniversary of the Noble Prize for Maria Skłodowska-Curie).
3rd International Nuclear Energy Forum, Warszawa, Poland, 18-19.10.2011.
23. Głuszewski W.
Od Marii Skłodowskiej-Curie do radiacyjnej modyfikacji polimerów dla energetyki jądrowej (From
Maria Skłodowska-Curie to radiation modification of polymers for nuclear power).
3rd International Nuclear Energy Forum, Warszawa, Poland, 18-19.10.2011.
161
Wydzielanie uranu z dwutlenku toru napromieniowanego w reaktorze jądrowym (Separation of uranium from thorium dioxide irradiated in nuclear reaction).
Sympozjum „Bezpieczeństwo i ochrona radiologiczna w aspekcie budowy elektrowni jądrowej w Polsce”,
25. Kałuska I.
Radiation sterilization – operational experience.
IAEA Technical Cooperation Regional Project – RER/8/017 “Enhancing quality control methods and
procedures for radiation technology” – IAEA Regional Training Course on Feasibility Studies for the
Establishment of Radiation Processing Facilities, Zalakaros, Hungary, 28.08.-02.09.2011.
26. Kałuska I.
Radiation sterilization – QA/QC requirements and programs.
27. Kałuska I.
Inter-comparison trials in dosimetry.
28. Kciuk G.
Electron transfer in dipeptides containing methionine and tyrosine.
29. Krajewski S., Bilewicz A., Łyczko K.
Dicarbonyl and cyclopentadienyl 105Rh complexes as precursors for therapeutic radiopharmaceuticals.
Working Group and MC Meeting of COST Action BM0607 “Targeted radionuclide therapy”, Innsbruck/Igls, Austria, 08-09.04.2011.
30. Kruszewski M., Buraczewska I., Lankoff A., Wojewódzka M., Sommer S.
Dozymetria biologiczna w Centrum Radiobiologii i Dozymetrii Biologicznej Instytutu Chemii i Techniki
Jądrowej (Biological dosimetry in the Centre of Radiobiology and Biological Dosimetry, Institute of
Nuclear Chemistry and Technology).
31. Kruszewski M.
Nanosilver panaceum or Pandora box?
32. Lankoff A.
Mechanizmy popromiennej śmierci komórkowej (Mechanisms of radiation-induced cell death).
Kurs specjalistyczny z radiobiologii, Kielce, Poland, 07-10.11.2011.
33. Lankoff A.
Mechanizmy powstawania popromiennych uszkodzeń DNA i ich naprawa (Mechanisms of radiation-induced DNA damage and repair).
Kurs specjalistyczny z radiobiologii, Kielce, Poland, 07-10.11.2011.
34. Nyga M.
Generation of oxidizing radicals and their reactivity in a selected group of ionic liquids.
35. Ostyk-Narbutt J.
Co może wnieść Polska do współpracy międzynarodowej w zakresie chemii dla energetyki jądrowej?
(What can Poland contribute into international collaboration on chemistry for nuclear power?).
Program badań biegłości dla placówek specjalistycznych prowadzących pomiary skażeń promieniotwórczych w ramach monitoringu radiacyjnego kraju (Proficiency testing scheme for laboratories forming radiation monitoring network).
162
37. Przybytniak G.
Radiation chemistry of polymers. Top-down and bottom-up apporaches.
38. Przybytniak G.
Effect of ionizing radiation on epoxy resin based composites.
39. Sartowska B., Piekoszewski J., Waliś L., Barlak M., Brunelli K., Starosta W., Senatorski J.
Alloying the near surface layer of stainless steel with rare earth elements (REE) using intensity pulsed
plasma beams (HIPPB).
XIV International Conference on Electron Microscopy, Wisła, Poland, 26-30.06.2011.
Biologiczne skutki promieniowania jonizującego (Biological effects of ionizing radiation).
Konferencja „PoRa na Marię. Promieniotwórczośc wokół nas”, Warszawa, Poland, 09.11.2011.
Biologiczne skutki promieniowania jonizującego (Biological effects of ionizing radiation).
II Forum Nauczycieli Przedmiotów Przyrodniczych „PoRa na Marię. Promieniotwórczość wokół nas”,
Ciechanów, Poland, 23.11.2011.
42. Starosta W.
Metal-organic framework materials as templates for nanomaterials synthesis. Synthesis and characterization methods.
43. Sterniczuk M., Michalik J.
Silownie jądrowe oparte na reaktorach PWR i BWR (Types of nuclear reactors – PWR and BWR systems).
Konferencja Naukowo-Techniczna „Polska nauka i technika dla elektrowni jądrowych w Polsce”,
Mądralin, Poland, 13-14.01.2011.
44. Walo M.
Radiation modification of polyurethane biomaterials.
45. Wołkowicz S., Miecznik J., Strzelecki R., Zakrzewska-Trznadel G., Polkowska-Motrenko H.
Uranium resources of Poland.
IAEA Technical Meeting on Uranium Provinces and Mineral Potential Modeling, Vienna, Austria,
20-22.06.2011.
46. Zagórski Z.P.., Kornacka E.M.
Historia badań radiacyjnych w Polsce po II wojnie światowej (The history of radiation research in Poland
after the World War II).
Konferencja „Historia badań radiacyjnych w Polsce”, Warszawa, Poland, 14.11.2011.
47. Zakrzewska-Trznadel G., Frąckiewicz K., Herdzik-Koniecko I., Kiegiel K., Gajda D., Chajduk E.
Leaching of uranium ores from Polish deposits.
Third General Assembly of the Sustainable Nuclear Energy Technology Platform, Warszawa, Poland,
29-30.11.2011.
48. Zakrzewska-Trznadel G., Biełuszka P., Zielińska B., Oszczak A., Chajduk E.
Membrane processes for the uranium recovery from aqueous solutions.
Third General Assembly of the Sustainable Nuclear Energy Technology Platform, Warszawa, Poland,
29-30.11.2011.
163
SEMINARS
1.
Brykała Marcin
Chemia paliw jądrowych (Nuclear fuel chemistry).
Warsaw University of Technology, Faculty of Power and Aeronautical Engineering, Warszawa, Poland,
30.03.2011.
2.
Chmielewski Andrzej G.
Chemia i inżynieria chemiczna w energetyce jądrowej (Chemistry and chemical engineering in nuclear
technologies).
Łódź University of Technology, Łódź, Poland, 07.03.2011.
3.
Plazma generowana wiązką elektronów w technologiach ochrony środowiska (Electron-beam-generated
plasma in technologies for the protection of environment).
Rzeszów University of Technology, Rzeszów, Poland, 09.12.2011.
4.
Inżynieria chemiczna i procesowa w energetyce jądrowej (Chemical and process engineering in nuclear
technologies).
Rzeszów University of Technology, Rzeszów, Poland, 09.12.2011.
5.
Chemia w energetyce jądrowej (Chemistry for nuclear power).
Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Kraków, Poland,
14.12.2011.
6.
Doner Katarzyna
Promieniowanie w nas i wokół nas (Radiation in us and around us).
Maria Skłodowska-Curie Museum, Warszawa, Poland, 18.09.2011.
7.
Głuszewski Wojciech
Od Marii Skłodowskiej-Curie do współczesnych zastosowań chemii radiacyjnej (From Maria Skłodowska-Curie to modern applications of radiation chemistry).
8.
Krajewski Seweryn
Przyroda sama tworzy reaktor? Reaktor w Oklo – stworzony w naturalnych warunkach (Does nature
create reactor by itself? Reactor in Oklo – created in natural conditions).
9.
Lankoff Anna
Maria Skłodowska-Curie – woman of science.
Noble Museum, Stockholm, Sweden, 16.09.2011-31.01.2012.
10. Smoliński Tomasz, Chmielewski Andrzej G.
A jednak, mimo wszystko, energetyka jądrowa? (In spite of everything, nuclear power?).
Warsaw University of Technology, Faculty of Chemical and Process Engineering, Warszawa, Poland,
19.09.2011.
164
AWARDS IN 2011
AWARDS IN 2011
1.
Preparation of nanocomposite tungsten-zirconium, potential material for radionuclide generators
W-188/Re-188
Special award of the Croatian Association of Inventors at the XIV Moscow International Salon of Inventions and Innovation Technologies “Archimedes-2011”, Moscow, Russia, 05-08.04.2011
Edward Iller, Danuta Wawszczak, Andrzej Deptuła, Marcin Konior, Wiesława Łada, Tadeusz
Olczak
2.
Diploma of the Ministry of Science and Higher Education for the project “Method of bioceramic material production”
Wiesława Łada, Andrzej Ignaciuk, Andrzej Deptuła, Michał Kozłowski, Tadeusz Olczak
3.
Diploma of the Ministry of Science and Higher Education for the project “Method for obtaining uranium dioxide in the form of spherical and irregular grains”
Andrzej Deptuła, Marcin Brykała, Andrzej G. Chmielewski, Danuta Wawszczak, Wiesława
Łada, Tadeusz Olczak
4.
Application of GC to study radiolysis of cultural heritage artefacts
The Best Poster Presentation Award at the International Conference on Development and Applications
of Nuclear Technologies NUTECH-2011, Kraków, Poland, 11-14.09.2011
Wojciech Głuszewski
5.
Method of production protective coatings made of titanium dioxide (TiO2) or lithium titanate (Li2TiO2)
on nickel cathodes
Gold Medal at the V International Warsaw Invention Show IWIS 2011, Warszawa, Poland, 03-05.11.2011
Wiesława Łada, Andrzej Deptuła, Danuta Wawszczak, Elisabetta Simonetti, Marco Brocco
6.
Method of production protective coatings made of titanium dioxide (TiO2) or lithium titanate (Li2TiO2)
on nickel cathodes
Special Prize of Scientific School of Causality at the International Trade Fair “Ideas – Inventions – New
Products” IENA-2011, Nuremberg, Germany, 27-30.10.2011
Wiesława Łada, Andrzej Deptuła, Danuta Wawszczak, Elisabetta Simonetti, Marco Brocco
7.
Officer’s Cross of Order of Polonia Restituta conferred by the President of Poland for outstanding
achievements in the scientific, didactic and social work and for the popularization of science in Poland
and in the world
Irena Szumiel
8.
First degree award of Director of the Institute of Nuclear Chemistry and Technology for the chapter
“Chemistry of sulfur-centered radicals” in the book “Recent trends in radiation chemistry”
Krzysztof Bobrowski
9.
Second degree award of Director of the Institute of Nuclear Chemistry and Technology for five publications on the structure and dynamics of charge transfer (CT) complexes published in international journals
with high IF
Andrzej Pawlukojć
10. Third degree award of Director of the Institute of Nuclear Chemistry and Technology for five publications on the properties of new complexes of uranium, lead, zinc and lithium with a pyridazine-carboxylic
ligand published in “Acta Crystallographica”
Janusz Leciejewicz, Wojciech Starosta
11. Distinction of the first degree of Director of the Institute of Nuclear Chemistry and Technology for the
achieved progress in the preparation of thesis and professional activity
Marcin Sterniczuk
12. Distinction of the second degree of Director of the Institute of Nuclear Chemistry and Technology for
the achieved progress in the preparation of thesis and professional activity and participation in the
preparation and realization of research projects
Paweł Kalbarczyk
AWARDS IN 2011
165
13. Distinction of the second degree of Director of the Institute of Nuclear Chemistry and Technology for
the achieved progress in the preparation of thesis and professional activity and participation in the
preparation and realization of research projects
Przemysław Koźmiński
166
A
Abbas Kamel 42
Apel Pavel 77
B
Banasik-Nowak Anna 59
Bańkowski Krzysztof 43
Barlak Marek 79
Barsbay Murat 28
Bartłomiejczyk Teresa 58, 59
Bartosiewicz Iwona 47, 68
Bilewicz Aleksander 42
Blonskaya Irina 77
Bobrowski Krzysztof 64
Bojanowska-Czajka Anna 23, 64
Brunborg Gunnar 58
Brykała Marcin 48, 51
Brzóska Kamil 60
Bulgheroni Antonio 42
Buraczewska Iwona 59
C
Celuch Monika 20, 23
Chajduk Ewelina 47, 68
Chmielewski Andrzej G. 51, 86, 87
Chwastowska Jadwiga 47, 68
Cieśla Krystyna 31
Cydzik Izabela 42
D
Degen Christian 60
Deptuła Andrzej 48, 51
Doner Katarzyna 96
Dusinska Maria 58
F
Filipiak Paweł 108, 109
Frąckiewicz Kinga 47
G
Gajda Dorota 47
Głuszewski Wojciech 31
Gniazdowska Ewa 43
Grądzka Iwona 58, 60
Grodkowski Jan 19
Gumiela Magdalena 64
Guven Olgun 28
Guzik Grzegorz P. 100
J
Jahreis Gerhard 60
Jakowiuk Adrian 108, 109
Janik Ireneusz 20
Jaworska-Sobczak Agnieszka 45
K
Karlińska Magdalena 96
Kavaklı Pınar Akkas 28
Kciuk Gabriel 64
Kiegiel Katarzyna 47
Kisała Joanna 23
Kocia Rafał 19
Kornacka Ewa Maria 30
Korzeniowska-Sobczuk Anna 96
Kosno Katarzyna 20, 23
Kowalska Ewa 108, 109
Koźmiński Przemysław 43
Krajewski Seweryn 42
Kraś Janusz 108
Kruszewski Marcin 57, 58
Kulisa Krzysztof 23
L
Lankoff Anna 57, 58, 59
Leciejewicz Janusz 73
Lewandowska-Szumieł Małgorzata 26
Lisowska Halina 59
Liśkiewicz Grażyna 100
Ł
Łada Wiesława 48, 51
Łyczko Krzysztof 41
Łyczko Monika 41
M
Majkowska-Pilip Agnieszka 42
Malec-Czechowska Kazimiera 92
Michalik Jacek 25, 26
Miecznik Jerzy B. 47
Mirkowski Jacek 19, 20
Miśkiewicz Agnieszka 45
Modzelewski Łukasz 108, 109
Morgunov Volodymyr 86
N
Nałęcz-Jawecki Grzegorz 64
Narbutt Jerzy 39
Nyga Małgotrzata 19
H
Harasimowicz Marian 45
Herdzik-Koniecko Irena 39, 41
O
Olczak Tadeusz 48, 51
Orelovitch Oleg 77
I
Iwaneńko Teresa 58, 59
P
Palige Jacek 108
Pańczyk Ewa 80
Pawelec Andrzej 87
Piekoszewski Jerzy 79
Pieńkos Jan 108, 109
Pochrybniak Cezary 79
Pogocki Dariusz 20, 23
Pokorska Irena 79
Polkowska-Motrenko Halina 68
Presz Adam 77
Przybytniak Grażyna 28
Pyszynska Marta 68
S
Sadło Jarosław 25, 26
Sadowska Magdalena 100, 102
Sartowska Bożena 77, 79
Senatorski Jan 79
Siekierski Sławomir 39
Simonell Federica 42
Smoliński Tomasz 48, 51
Sochanowicz Barbara 60
Sommer Sylwester 59
Stachowicz Wacław 100, 102
Starosta Wojciech 73, 79
Sterniczuk Marcin 25, 26
Strzelczak Grażyna 25, 26
Strzelecki Ryszard 47
167
Sulich Agnieszka 19
Sun Yongxia 86
Szreder Tomasz 19
Szumiel Irena 58, 59, 60
Ś
Śliwa Tomasz 80
T
Trojanowicz Marek 64
W
Waliś Lech 79
Walo Marta 28
Wawszczak Danuta 48, 51
Wewiór Iwona 59
Węgierek-Ciuk Aneta 59
Wierzchnicki Ryszard 91, 92
Witman Sylwia 87
Wojewódzka Maria 57, 58
Wołkowicz Stanisław 47
Wójciuk Grzegorz 60
Z
Zagórski Zbigniew Paweł 30
Zakrzewska-Trznadel Grażyna 45, 47
Zaza Fabio 51
Zielińska Barbara 41

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