annual report 2015 - Instytut Chemii i Techniki Jądrowej

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ISSN 1425-204X
ANNUAL REPORT
2015
INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY
60th Anniversary
of the former Institute of Nuclear Research (IBJ)
1955-2015
ANNUAL REPORT
2015
INSTITUTE
OF NUCLEAR CHEMISTRY
AND TECHNOLOGY
EDITORS
Prof. Jacek Michalik, Ph.D., D.Sc.
Ewa Godlewska-Para, M.Sc.
© Copyright by the Institute of Nuclear Chemistry and Technology, Warszawa 2016
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 (2011-2015)
9
10
ORGANIZATION SCHEME
12
SCIENTIFIC STAFF
13
PROFESSORS
13
SENIOR SCIENTISTS (Ph.D.)
13
CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY
15
RADIATON-INDUCED SELF-REPAIRING EPOXY RESINS – CONCEPTION AND FIRST EXPERIMENTS
G. Przybytniak, A. Nowicki, K. Mirkowski
17
THE PROPERTIES AND IONIZING RADIATION EFFECTS IN THE STARCH-PVA FILMS PREPARED
BASED ON VARIOUS SUBSTRATES
K. Cieśla, A. Abramowska, M. Buczkowski
20
PROTECTIVE EFFECTS OF LIGNIN SULPHONATE IN CELLULOSE RADIOLYSIS
W. Głuszewski, H. Kubera, K. Kozera
23
DEDICATED RF DRIVING GENERATOR FOR LINEAR ACCELERATOR BASED ON PLL FREQUENCY
SYNTHESIZER UNDER MPU CONTROL
S. Bułka, Z. Zimek
25
CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY
27
ACTINIDE COMPLEXATION WITH A HYDROPHILIC SO3-Ph-BTP LIGAND, STUDIED
BY LIQUID-LIQUID DISTRIBUTION
J. Narbutt, Ł. Steczek, M. Rejnis, I. Herdzik-Koniecko
29
NOVEL PROCEDURE FOR THE REMOVAL OF THE RADIOACTIVE METALS FROM AQUEOUS WASTES
BY THE MAGNETIC CALCIUM ALGINATE
L. Fuks, A. Oszczak, W. Dalecka
32
PREPARATION OF URANIUM CARBIDE BY THE COMPLEX SOL-GEL PROCESS
M. Rogowski, M. Brykała, D. Wawszczak, W. Łada, T. Olczak, A. Deptuła, T. Smoliński, P. Wojtowicz
36
RESEARCH TOWARDS A NEW REPOSITORY FOR LOW- AN INTERMEDIATE-LEVEL RADIOACTIVE
WASTE IN POLAND
A. Miśkiewicz, G. Zakrzewska-Kołtuniewicz, W. Olszewska, L. Lankof, L. Pająk
40
TACRINE DERIVATIVE LABELLED WITH Ga FOR PET DIAGNOSIS
E. Gniazdowska, P. Koźmiński, E. Mikiciuk-Olasik, P. Szymański, K. Masłowska
43
COMPUTATIONALLY ASSISTED LOW-WAVENUMBER SPECTROSCOPY OF HYDROGEN-BONDED
SUPRAMOLECULAR SYNTHONS
K. Łuczyńska, K. Drużbicki, K. Łyczko, J.Cz. Dobrowolski
46
THE RECOVERY OF VALUABLE METALS FROM FLOWBACK FLUIDS AFTER HYDRAULIC FRACTURING
OF POLISH GAS-BEARING SHALES
G. Zakrzewska-Kołtuniewicz, D. Gajda, A. Abramowska, A. Miśkiewicz, K. Kiegiel
50
68
CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY
TOWARD THE DEVELOPMENT OF TRANSCRIPTIONAL BIODOSIMETRY FOR THE IDENTIFICATION
OF IRRADIATED INDIVIDUALS AND ASSESSMENT OF ABSORBED RADIATION DOSE
K. Brzóska, I. Grądzka, B. Sochanowicz, M. Kruszewski
53
54
GENOTOXICITY OF SILVER NANOPARTICLES IN LEUKOCYTES AND ERYTHROCYTE PRECURSORS
AFTER ORAL OR INTRAVENOUS ADMINISTRATION TO RATS
I. Grądzka, I. Wasyk, T. Iwaneńko, S. Sommer, I. Buraczewska, K. Sikorska, T. Bartłomiejczyk,
K. Dziendzikowska, J. Gromadzka-Ostrowska, M. Kruszewski
55
WEAK EFFECT OF HALLOYSITE ON HUMAN LUNG CARCINOMA A549 CELLS AND THEIR NORMAL
COUNTERPART – BEAS-2B CELLS
S. Męczyńska-Wielgosz, I. Grądzka, M. Wojewódzka, I. Wasyk, T. Bartłomiejczyk, L. Zapór
57
IMPACT OF SELECTED TYPES OF CARBON NANOMATERIALS ON DNA REPAIR AND CLONOGENIC
SURVIVAL IN VITRO
M. Kowalska, A. Węgierek-Ciuk, M. Kruszewski, H. Lisowska, S. Męczyńska-Wielgosz, T. Iwaneńko,
M. Wojewódzka, A. Lankoff
58
FORMATION OF GLUTATHIONYL DINITROSYL IRON COMPLEXES PROTECTS AGAINST IRON
GENOTOXICITY
H. Lewandowska, J. Sadło, S. Męczyńska-Wielgosz, T.M. Stępkowski, I. Szumiel, G. Wójciuk, M. Kruszewski
59
LABORATORY OF NUCLEAR ANALYTICAL METHODS
61
CHROMATOGRAPHIC DETERMINATION OF SELECTED PERFLUOPRINATED ORGANIC COMPOUNDS
AND TOTAL ORGANIC FLUORINE IN NATURAL WATERS AND MILK SAMPLES
M. Trojanowicz, M. Koc, K. Chorąży
62
OPTIMIZATION OF SAMPLE PROCESSING IN AUTOMATED FLOW PROCEDURE FOR ICP-MS
DETERMINATION OF 90Sr AND 99Tc
K. Kołacińska, E. Chajduk, J. Dudek, Z. Samczyński, A. Bojanowska-Czajka, M. Trojanowicz
66
STABILITY TESTING OF NEW POLISH CERTIFIED REFERENCES MATERIALS FOR INORGANIC
TRACE ANALYSIS BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY
I. Kużelewska, H. Polkowska-Motrenko, Z. Samczyński
70
LABORATORY OF MATERIAL RESEARCH
73
METAL ORGANIC FRAMEWORK COMPOSITE MATERIALS WITH POLYMER OR CERAMIC BASE
B. Sartowska, W. Starosta, O. Orelovitch, P. Apel, M. Buczkowski
75
ARCHAEOMETRICAL STUDY OF MEDIAEVAL SILVER COINS FROM POLAND AND CENTRAL EUROPE
BY PROMPT-GAMMA ACITIVATION ANALYSIS
E. Pańczyk, L. Waliś, Zs. Kasztovszky, B. Maróti, M. Widawski, W. Weker
77
POLLUTION CONTROL TECHNOLOGIES LABORATORY
81
INVESTIGATION ON THE HIGH INLET CONCENTRATION OF NOx REMOVAL UNDER ELECTRON
BEAM IRRADIATION
J. Licki, E. Zwolińska, S. Bułka, A.G. Chmielewski, Y. Sun
83
OPTIMIZATION OF PROCESS PARAMETERS INFLUENCING THE REMOVAL OF SO2 AND NOx
DURING ELECTRON BEAM FLUE GAS TREATMENT PROCESS BY MATHEMETICAL MODELLING
IN MATLAB
E. Zwolińska, V. Gogulancea, V. Lavric, Y. Sun, A.G. Chmielewski
85
STABLE ISOTOPE LABORATORY
STUDY OF ISOTOPIC COMPOSITION OF CO2 IN SPARKLING DRINKS
R. Wierzchnicki
LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES
VALIDATION OF METHODS FOR MEASURING THE DOSE USING CALORIMETERS
A. Korzeniowska-Sobczuk, M. Karlińska
LABORATORY FOR DETECTION OF IRRADIATED FOOD
INVESTIGATION WITH THERMOLUMINESCENCE AND PHOTOLUMINESCENCE METHODS
OF IRRADIATED DIET SUPPLEMENTS AND THEIR VEGETAL COMPONENTS
M.W. Sadowska, G.P. Guzik, W. Stachowicz, G. Liśkiewicz
LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS
89
90
93
94
97
99
103
HYBRID NUCLEAR TECHNIQUES IN THE MULTIPHASE FLOW INVESTIGATIONS
J. Palige, O. Roubinek, A. Dobrowolski, W. Ołdak, W. Sołtyk
PUBLICATIONS IN 2015
104
106
ARTICLES
106
BOOKS
114
CHAPTERS IN BOOKS
114
THE INCT PUBLICATIONS
118
CONFERENCE PROCEEDINGS
119
CONFERENCE ABSTRACTS
120
SUPPLEMENT LIST OF THE PUBLICATIONS IN 2014
129
NUKLEONIKA
132
POSTĘPY TECHNIKI JĄDROWEJ
141
INTERVIEWS IN 2015
144
THE INCT PATENTS AND PATENT APPLICATIONS IN 2015
145
PATENTS
145
PATENT APPLICATIONS
145
CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2015
147
Ph.D./D.Sc. THESES IN 2015
150
Ph.D. THESES
150
D.Sc. THESES
150
EDUCATION
151
Ph.D. PROGRAMME IN CHEMISTRY
151
TRAINING OF STUDENTS
152
MASTER’S AND BACHELOR’S DISSERTATIONS
152
RESEARCH PROJECTS AND CONTRACTS
153
RESEARCH PROJECTS GRANTED BY THE NATIONAL SCIENCE CENTRE
IN 2015
153
PROJECTS GRANTED BY THE NATIONAL CENTRE FOR RESEARCH
AND DEVELOPMENT IN 2015
153
APPLIED RESEARCH PROGRAMME OF THE NATIONAL CENTRE
FOR RESEARCH AND DEVELOPMENT IN 2015
154
INTERNATIONAL PROJECTS CO-FUNDED BY THE MINISTRY OF SCIENCE
AND HIGHER EDUCATION IN 2015
154
STRATEGIC PROJECT “TECHNOLOGIES SUPPORTING DEVELOPMENT
OF SAFE NUCLEAR POWER ENGINEERING”
155
IAEA RESEARCH CONTRACTS IN 2015
155
IAEA TECHNICAL AND REGIONAL CONTRACTS IN 2015
156
PROJECTS WITHIN THE FRAME OF EUROPEAN UNION FRAME
PROGRAMMES IN 2015
156
OTHER INTERNATIONAL RESEARCH PROGRAMMES IN 2015
156
PROJECTS GRANTED BY THE FOUNDATION FOR POLISH SCIENCE IN 2015
157
ERASMUS+ PROGRAMME
157
THE NCBR STRATEGIC RESEARCH PROJECT “TECHNOLOGIES
SUPPORTING DEVELOPMENT OF SAFE NUCLEAR POWER ENGINEERING”
158
LIST OF VISITORS TO THE INCT IN 2015
160
THE INCT SEMINARS IN 2015
161
LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2015
162
LECTURES
162
SEMINARS
164
AWARDS IN 2015
166
INDEX OF THE AUTHORS
170
GENERAL INFORMATION
7
GENERAL INFORMATION
In 1955, Poland decided to start a national nuclear energy programme 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 at Warsaw Żerań, which became the interdisciplinary Institute of Nuclear Chemistry and Technology (INCT) in 1983.
In 2015, the Institute of Nuclear Chemistry and Technology (INCT) together with
the National Centre for Nuclear Research (NCBJ) and the Radioactive Waste Management
Plant (RWMP) – the successors of the Institute of Nuclear Research (IBJ), celebrated the
IBJ’s 60th anniversary. For this occasion the main ceremonial meeting under auspicies
of the President of Poland took place on June 11, 2015 in Royal Castle in Warsaw. The
workers of the above-mentioned institutions and guests from the government and other
research institutions participated in the meeting. The outstanding scientists working in the
field of nuclear physics, chemistry and engineering were awarded with the highest state
distinctions by the President’s representative (Officer’s Cross of the Order of the Rebirth
of Poland, Knight’s Cross of the Order of the Rebirth of Poland, Silver Cross of Merit,
Bronze Cross of Merit). The Medals for Long-Time Service, Honorary Medals of Merit for
Economic Development in the Polish Republic and Pro Masovia commemorative medals
were also given. Out of this main event the more local jubilee ceremonies took place in
Żerań and Świerk. The emeritus and present workers of the INCT were invited for picnic
on the premises of the INCT. On the jubilee occasion the NCBJ and INCT organized together the scientific meeting “60th Anniversary of IBJ: Nuclear physics and chemistry for
medicine”.
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 the pulse radiolysis method. With its nine electron
accelerators in operation and with the 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 with 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 the EPS Pomorzany with the accelerators power
over 1 MW is the biggest radiation processing facility ever built.
The Institute represents the Polish Government in the Euroatom Fuel Supply Agency,
in Fuel Supply Working Group of Global Nuclear Energy Partnership and in Radioactive
Waste Management Committee of the Nuclear Energy Agency (Organisation for Economic Co-operation and Development).
The INCT Scientific Council has the 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 2015 three Ph.D. and one D.Sc. theses were defended.
The Institute won one of the ten projects granted in the action 2 of Erasmus+ programme. This project “Joint innovative training and teaching/learning program in enhancing
development and transfer of application of ionizing radiation in materials processing” is intended to fill up the gap of education quality between different region of EU countries.
8
GENERAL INFORMATION
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.
The INCT is editor of the scientific journal “Nukleonika” (www.nukleonika.pl) and
the scientific-information journal “Postępy Techniki Jądrowej” (www.ptj.waw.pl).
In 2013, the Evaluation Committee of Scientific Units in the Ministry of Science
and Higher Education conferred the INCT cathegory A+.
The INCT is the leading institute in Poland regarding the implementation of nuclear energy related EU projects. Its expertise and infrastructure was the basis for participation in FP7-EURATOM grants:
• ASGARD: Advanced fuels for generation IV reactors: reprocessing and dissolution;
• RENEB: Realizing the European Network in Biodosimetry;
• ARCADIA: Assessment of regional capabilities for new reactors development through
an integrated approach;
• EAGLE: Enhancing education, training and communication processes for informed
behaviors and decision-making related to ionizing radiation risks;
• PLATENSO: Building a platform for enhanced societal research related to nuclear energy
in Central and Eastern Europe;
• SACSESS: Safety of actinide separation processes;
• TALISMAN: Transnational access to large infrastructure for a safe management of actinide;
• UCARD-2 WP4: Applications of accelerators: The industrial and environemntal applications of electron beams.
In 2015, the INCT scientists published 80 papers in scientific journals registered in
the Philadelphia list, among them 53 papers in journals with an impact factor (IF) higher
than 1.0. Four scientific books and 39 chapters were written by the INCT research workers.
The following annual awards of the INCT Director-General for the best publications in 2015 were granted:
• first degree team award to Ewa Gniazdowska, Przemysław Koźmiński, Leon Fuks for
a series of three original and valuable publications concerning the investigations of
radiopharmaceuticals;
• second degree team award to Jacek Boguski, Leon Fuks, Ewa M. Kornacka, Krzysztof
Łyczko, Krzysztof Mirkowski, Andrzej Nowicki, Grażyna Przybytnik, Jarosław Sadło,
Marta Walo, Zbigniew P. Zagórski, Zbigniew Zimek for a series of twelve publications
dedicated to radiation chemistry;
• third degree team award to Grażyna Zakrzewska-Kołtuniewicz, Katarzyna Kiegiel, Łukasz Steczek, Irena Herdzik-Koniecko, Ewelina Chajduk, Jakub Dudek for a series of
four publications dedicated to obtaining uranium ores for fabrication of nuclear fuel.
In 2015, the research teams in the INCT were involved in the organization of 13 scientific meetings.
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. Grażyna Zakrzewska-Kołtuniewicz,
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./Yongxia Sun, Ph.D.,
D.Sc., professor in INCT
• Laboratory for Detection of Irradiated Food
Wacław Stachowicz, Ph.D./Grażyna Liśkiewicz
• Laboratory for Measurements of Technological
Doses
Anna Korzeniowska-Sobczuk, M.Sc.
1.
Prof. Grzegorz Bartosz, Ph.D., D.Sc.
University of Łódź
5.
Institute of Nuclear Chemistry and Technology
2.
Prof. Aleksander Bilewicz, Ph.D., D.Sc.
6.
Andrzej Chwas, M.Sc.
Ministry of Economy
3.
Prof. Krzysztof Bobrowski, Ph.D., D.Sc.
(Vice-chairman)
7.
Jadwiga Chwastowska, Ph.D., D.Sc., professor
in INCT
4.
Marcin Brykała, Ph.D.
8.
Krystyna Cieśla, Ph.D., D.Sc., professor in INCT
10
Jakub Dudek, Ph.D.
23. Prof. Jacek Michalik, Ph.D., D.Sc.
10. Prof. Rajmund Dybczyński, Ph.D., D.Sc.
24. Wojciech Migdał, Ph.D., D.Sc., professor
in INCT
9.
11. Prof. Zbigniew Florjańczyk, Ph.D., D.Sc.
(Chairman)
Warsaw University of Technology
25. Prof. Jarosław Mizera, Ph.D., D.Sc.
12. Prof. Zbigniew Galus, Ph.D., D.Sc.
University of Warsaw
26. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc.
13. Prof. Henryk Górecki, Ph.D., D.Sc.
Wrocław University of Technology
27. Andrzej Pawlukojć, Ph.D., D.Sc., professor
in INCT
14. Prof. Leon Gradoń, Ph.D., D.Sc.
15. † Jan Grodkowski, Ph.D., D.Sc., professor
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)
19. Prof. Anna Lankoff, Ph.D., D.Sc.
20. Prof. Marek Wojciech Lankosz, Ph.D., D.Sc.
AGH University of Science and Technology
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
31. Prof. Janusz Rosiak, Ph.D., D.Sc.
Technical University of Łódź
32. Lech Waliś, Ph.D.
33. Maria Wojewódzka, Ph.D.
21. Prof. Janusz Lipkowski, Ph.D., D.Sc.
Institute of Physical Chemistry, Polish Academy
of Sciences
34. Prof. Grażyna Zakrzewska-Kołtuniewicz, Ph.D.,
D.Sc.
(Vice-chairman)
22. Zygmunt Łuczyński, Ph.D.
Institute of Electronic Materials Technology
35. Zbigniew Zimek, Ph.D.
HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (2011-2015)
1. Prof. Sławomir Siekierski, Ph.D.
2. Prof. Zbigniew Szot, Ph.D., D.Sc.
3. Prof. Irena Szumiel, Ph.D., D.Sc.
4. † Prof. Zbigniew Paweł Zagórski, Ph.D., D.Sc.
1.
Prof. Aleksander Bilewicz, Ph.D., D.Sc.
5.
2.
Prof. Krzysztof Bobrowski, Ph.D., D.Sc.
6.
Tomasz Ciach, Ph.D., D.Sc., professor in WUT
3.
Prof. Ewa Bulska, Ph.D., D.Sc.
7.
Prof. Jan Czesław Dobrowolski, Ph.D., D.Sc.
4.
Sylwester Bułka, M.Sc.
8.
Prof. Rajmund Dybczyński, Ph.D., D.Sc.
9.
Prof. Zbigniew Florjańczyk, Ph.D., D.Sc.
(Chairman)
10. Prof. Zbigniew Galus, Ph.D., D.Sc.
11. Prof. Janusz Gołaszewski, Ph.D., D.Sc.
University of Warmia and Mazury
12. Prof. Henryk Górecki, Ph.D., D.Sc.
Wrocław University of Technology
13. Edward Iller, Ph.D., D.Sc., professor in NCBJ
National Centre for Nuclear Research
14. Michał Jamróz, Ph.D., D.Sc., professor in INCT
15. Prof. Marek Janiak, Ph.D., D.Sc.
Military Institute of Hygiene and Epidemiology
16. Rafał Kocia, Ph.D.
17. Prof. Marcin Kruszewski, Ph.D., D.Sc.
(Vice-chairman)
18. Krzysztof Kulisa, Eng.
19. Prof. Anna Lankoff, Ph.D., D.Sc.
20. Prof. Marek Wojciech Lankosz, Ph.D., D.Sc.
AGH University of Science and Technology
21. Prof. Jacek Michalik, Ph.D., D.Sc.
22. Wojciech Migdał, Ph.D., D.Sc., professor
in INCT
11
23. Prof. Jarosław Mizera, Ph.D., D.Sc.
24. Prof. Jan Namieśnik, Ph.D., D.Sc.
Gdańsk University of Technology
25. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc.
26. Andrzej Pawlukojć, Ph.D., D.Sc., professor
in INCT
27. Halina Polkowska-Motrenko, Ph.D., D.Sc.,
professor in INCT
(Vice-chairman)
28. Marek Pruszyński, Ph.D.
29. Grażyna Przybytniak, Ph.D., D.Sc., professor
in INCT
30. Prof. Janusz Rosiak, Ph.D., D.Sc.
Technical University of Łódź
31. Yongxia Sun, Ph.D., D.Sc., professor in INCT
32. Prof. Marek Trojanowicz, Ph.D., D.Sc.
33. Lech Waliś, Ph.D.
34. Maria Wojewódzka, Ph.D.
35. Prof. Grażyna Zakrzewska-Kołtuniewicz, Ph.D.,
D.Sc.
(Vice-chairman)
HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (2015-2019)
1. Prof. Sławomir Siekierski, Ph.D.
2. Prof. Zbigniew Szot, Ph.D., D.Sc.
3. Prof. Irena Szumiel, Ph.D., D.Sc.
12
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
SCIENTIFIC STAFF
13
SCIENTIFIC STAFF
PROFESSORS
1.
Bilewicz Aleksander
radiochemistry, inorganic chemistry
2.
Bobrowski Krzysztof
radiation chemistry, photochemistry, biophysics
3.
Chmielewski Andrzej G.
chemical and process engineering, nuclear
chemical engineering, isotope chemistry
13. Michalik Jacek
radiation chemistry, surface chemistry, radical
chemistry
14. Migdał Wojciech, professor in INCT
chemistry, science of commodies
15. Ostyk-Narbutt Jerzy
radiochemistry, coordination chemistry
4.
Cieśla Krystyna, professor in INCT
physical chemistry
16. Pawlukojć Andrzej, professor in INCT
chemistry
5.
Dobrowolski Jan Cz.
physical chemistry
17. Pogocki Dariusz, professor in INCT
radiation chemistry, pulse radiolysis
6.
Dybczyński Rajmund
analytical chemistry
7.
Gniazdowska Ewa, professor in INCT
chemistry
8.
Grigoriew Helena, professor in INCT
solid state physics, diffraction research
of non-crystalline matter
9.
Jamróz Michał, professor in INCT
chemistry, physics
18. Polkowska-Motrenko Halina, professor in INCT
19. Przybytniak Grażyna, professor in INCT
radiation chemistry
20. Siekierski Sławomir
physical chemistry, inorganic chemistry
21. Sun Yongxia, professor in INCT
chemistry
10. Kruszewski Marcin
radiobiology
22. Szumiel Irena
cellular radiobiology
11. Lankoff Anna
biology
23. Trojanowicz Marek
12. Lipkowski Janusz
physical chemistry
24. Zakrzewska-Kołtuniewicz Grażyna
process and chemical engineering
SENIOR SCIENTISTS (Ph.D.)
1.
Bartłomiejczyk Teresa
biology
6.
Brzóska Kamil
biochemistry
2.
Boguski Jacek
chemistry
7.
Chajduk Ewelina
chemistry
3.
Bojanowska-Czajka Anna
chemistry
8.
Danilczuk Marek
chemistry
4.
Borowik Krzysztof
chemistry
9.
Dobrowolski Andrzej
chemistry
5.
Brykała Marcin
chemistry
10. Dudek Jakub
chemistry
14
SCIENTIFIC STAFF
11. Fuks Leon
chemistry
34. Rafalski Andrzej
radiation chemistry
12. Głuszewski Wojciech
chemistry
35. Rode Joanna
chemistry
13. Grądzka Iwona
biology
36. Roubinek Otton
chemistry
14. Herdzik-Koniecko Irena
chemistry
37. Sadło Jarosław
chemistry
15. Kciuk Gabriel
chemistry
38. Samczyński Zbigniew
16. Kiegiel Katarzyna
chemistry
39. Sartowska Bożena
material engineering
17. Kocia Rafał
chemistry
40. Sochanowicz Barbara
biology
18. Kornacka Ewa
chemistry
41. Sommer Sylwester
radiobiology, cytogenetics
19. Koźmiński Przemysław
chemistry
42. Stachowicz Wacław
radiation chemistry, EPR spectroscopy
20. Kunicki-Goldfinger Jerzy
conservator/restorer of art
43. Starosta Wojciech
chemistry
21. Latek Stanisław
nuclear physics
44. Sterniczuk Macin
chemistry
22. Lewandowska-Siwkiewicz Hanna
chemistry
45. Strzelczak Grażyna
radiation chemistry
23. Łyczko Krzysztof
chemistry
46. Szreder Tomasz
chemistry
24. Łyczko Monika
chemistry
47. Waliś Lech
material science, material engineering
25. Majkowska-Pilip Agnieszka
chemistry
48. Walo Marta
chemistry
26. Męczyńska-Wielgosz Sylwia
chemistry
49. Warchoł Stanisław
solid state physics
27. Miśkiewicz Agnieszka
chemistry
50. Wawszczak Danuta
chemistry
28. Nowicki Andrzej
organic chemistry and technology,
high-temperature technology
51. Wierzchnicki Ryszard
chemical engineering
29. Ostrowski Sławomir
chemistry
30. Palige Jacek
metallurgy
31. Pawelec Andrzej
32. Pruszyński Marek
chemistry
33. Ptaszek Sylwia
52. Wiśniowski Paweł
radiation chemistry, photochemistry, biophysics
53. Wojewódzka Maria
radiobiology
54. Wójciuk Grzegorz
chemistry
55. Wójciuk Karolina
chemistry
56. Zimek Zbigniew
electronics, accelerator techniques, radiation
processing
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, stopped-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 five 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,
• stopped-flow experimental set-up,
• EPR spectroscopy for solid material investigation,
• pilot installation for polymer modification,
• laboratory experimental stand for removal of pollutants from gas phase,
• laboratory of polymer characterization,
• pilot facility for radiation sterilization, polymer modification 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.
17
RADIATON-INDUCED SELF-REPAIRING EPOXY RESINS – CONCEPTION
AND FIRST EXPERIMENTS
Grażyna Przybytniak, Andrzej Nowicki, Krzysztof Mirkowski
Some metals, ceramics, polymers and their composites damaged through thermal, mechanical,
ionizing radiation, ballistic or other means, have
the ability to self-repairing, i.e. to heal and restore
the substance to its original set of properties. This
process is especially important when materials are
located in unavailable for service places, such as
space, nuclear installation, underwater equipment,
etc.
In the past, we studied curing of epoxy resins
supported by ionizing radiation in which the treatment provided materials of high glass transition temperatures, flexural strength comparable to thermally
cured ones and of advantageous mechanical parameters. Enhanced toughness and unusual long-term
stability make the resins usable under harsh/degradable conditions for many years. In order to obtain
a good-quality material, usually photoinitiator is
applied at the concentration lower than 1%. The
final product shows better features than the resins
based on amine hardeners [1-3].
Radiation treatment is usually considered as a
cold processing during which thermal effects are
small and do not influence the final functionality
of the products. Contrary to this usually legitimate
assumption, radiation-induced cationic polymerization is characterized by the substantial thermal
effect which is a consequence of two following phenomena: conversion of supplied radiation energy
into the heat (insignificant effect that increases
temperature to less than 50oC) and generation of
heat during exothermic polymerization process
which, in some cases, increases temperature to almost 300oC.
According to the analysis proposed by Coqueret
et al. [4], the second process initially is dominated by the combination of radicals in the viscous
liquid which, with increasing conversion degree,
is being replaced gradually by the monomolecular
occlusion of residual active centres due to mobility restrictions.
The polymerization based on accelerator technique used in former work [5] shows some restrictions with respect to limited penetration of electron beam (EB). However, when gamma or X-rays
are applied as radiation sources, even thick products can be cured. Then, the radiation processing
Scheme 1. Formulae of cationic initiator Rhodorsil 2074
used for radiation-induced curing (p-methyl-p-cumyl-iodonium (tetrakis(pentafluorophenyl))borate, IPB) [4].
might be used for the large structures applied in
aeronautic, transport industry or marine. The dose
necessary to reach complete curing of the resins
is about tenfold lower for gamma treatment than
for EB irradiation [6]. Generally, as curing involves
chain reactions, the dose required for the process
is usually lower than in the case of typical polymer
crosslinking resulting from radical recombination.
Gamma irradiation is considered to be specially
suitable for curing; however, due to low dose rates,
the process is much time consuming than the EB
treatment.
Schemes 1 and 2 show reactants used in our
work. DGEBA was supplied by Sigma-Aldrich,
whereas Epidian 5 and Epidian 6 were obtained
from Z. Ch. Sarzyna-Organika, Poland. Gamma
irradiation was performed in Gamma Cell 5000
chamber at a dose rate of 6 kGy/h. The cationic
initiator IPB was used for polymerization of several bisphenol based resins. The mechanism of activation of the initiator by ionizing radiation is
presented in Scheme 3. Weakly bound with anion
protons produced continuously during the exposure to ionizing radiation, participate in the initiation of exothermic chain reaction. Simultaneously
with reaction progress, the glassy phase grows
(vitrification) limiting polymerization rate which
eventually results in the termination of the process
due to diffusion problems.
Scheme 2. Formulae of epoxy resins used in our works. Depending on the “n” value the formulae mean: diglycidyl ether
of bisphenol A (DGEBA), n = 0, or commercial epoxy resins Epidian 5, Epidian 6, mixture of various amounts of compounds with n = 0 and n = 1.
18
Scheme 3. Mechanism of initiation of ionic polymerization by irradiated initiator in the form of iodonium salt. Irreversible
reaction of radicals’ recombination supports the creation of strong complex acid. Chemical structure of the initiator is
simplified for clarity.
Syntheses of polymer microcapsules containing epoxy resin were conducted according to the
literature methods [7], and chemicals used were
supplied by Sigma-Aldrich.
In order to estimate the effects related to the
absorption of radiation energy by the walls of the
chamber and absorption by the resin, thermal
measurements were conducted for the chamber
fects predominantly initiate polymerization in the
presence of the initiator. The conclusion confirms
thermogram recorded by DSC method showing
intensive thermal curing of the system above
170oC (Fig.2).
Several commercially available materials were
investigated under the same conditions. At constant dose rate and the same concentration of
cationic initiator, the radiation polymerization effects depend on the type of epoxy resin. It seems
that induction time of the process is a function of
the contribution of epoxy groups. The content of
epoxy groups in the resins decreases in the following order: DGEBA > Epidian 6 > Epidian 5.
The induction time of curing is changing in the
Fig.1. Thermal effects for the selected resins irradiated in
a Gamma Chamber 5000 at a dose rate of 6.0 kGy/h.
loaded with epoxy resin free from initiator and for
different resins containing 1 wt% of initiator IPB
(Fig.1). The diagrams indicate that even after 6 h,
the temperature in the loaded chamber is less than
45oC if the resin is free from initiator, and has not
reached equilibrium yet. On the basis of these results, it was assumed that ionizing radiation ef-
Fig.2. Thermogram of DGEBA, Epidian 5 and Epidian 6 in
the presence of 1% initiator IPB; heating rate – 5oC/min.
opposite direction which reveals that the beginning of polymerization is strongly influenced by
the availability of oxirane units. The data suggest
that the acceptable level of impurities inhibiting
the initiation is not the only factor influencing induction time which naturally is proportional to
the dose absorbed. The accumulation of active
centres to the critical level is also associated with
the population of epoxy rings, and both variables
influence the beginning of polymerization. Then,
the dominant driving force of the reaction progress is the heat emitted gradually in the exothermic reaction causing autoacceleration of the
process.
The results were confronted with the exothermic effects of the thermally cured resins (Fig.2).
The data obtained using these two procedures
seem to be in correlation: the shorter the induction
time of radiation-induced processes, the higher the
temperature of thermal polymerization. The trends
observed are difficult to interpret in terms of various contributions of epoxy groups. The activation
of the initiator in the primary stage of the processes
does not depend on the type of oligomers used
but on the nature of energy deposited (radiation
or thermal). It can be assumed that in the model
DGEBA, the deficiency of proton donors hinders
the beginning of the process which results in the
shift of thermal effects towards higher temperatures observed in Fig.2, whereas in Epidians, having hydroxyl groups, these barriers are abolished.
Hydroxyl group content is higher in Epidian 5
than in Epidian 6 which is reflected by the position of peaks in the thermograms recorded by calorimetric method.
The above results allowed us to propose a self-repairing system of crosslinked epoxy resins. The
liquid epoxy resin as a healing material is incorporated in the form of microcapsules into cured
epoxy resin. The healing agent is released upon
crack intrusion. Polymerization of the healing agent
is then triggered by contact with an embedded
catalyst, bonding the crack faces. The idea of the
process is demonstrated in Fig.3.
It was assumed that:
• initiator cannot react with epoxy resin of microcapsules during curing,
19
Fig.3. Concept of self-repairing epoxy resin: A – cured
epoxy resin contains microcapsules with liquid epoxy
resin and non-active initiator; B – after irradiation, the
initiator forms active species; C – crack introduced into
the material, liquid resin released from microcapsules fills
crack; D – after contact with active form of initiator, epoxy
resin yields polymerized material that bonds the crack surfaces.
• walls of microcapsules should be chemically
inert and thermally resistant,
• healing agent from microcapsules should be
able to polymerize in contact with initiator dispersed in the crosslinked resin,
• during manufacturing objects should be insusceptible to elevated temperatures.
Taking into account these limitations, “exotic”
systems of healing agents for epoxy resins were
proposed in the past, e.g. dicyclopentadiene and
Grubbs’ catalyst (high price), or high excess of
typical multifunctional amines used for curing resulting in poor properties of epoxy resin [8].
Our proposal meets the above requirements,
is cheap and simple. Inactivated IPB does not react with epoxy resins, is stable in contact with
matrix to 170oC and after irradiation reacts with
epoxy groups at room temperature with high degree of conversion. Relationships presented in Fig.1
suggest that the best repairing medium is DGEBA.
Our first attempts to obtain microcapsules on the
basis of urea-formaldehyde resin result in relatively high distribution of particles (Fig.4).
The experiments will be continued based on
other components prone to create microcapsule
Fig.4. SEM images of the particles constructed from urea-formaldehyde resin microcapsules containing epoxy resin.
20
shells constructed from hydrophobic-hydrophilic
hybrid structures, e.g. 2,6-dimethylphenol.
The work reported was co-funded by the International Atomic Energy Agency (CRP F22051,
Research Contract no. 16666) and the Polish Ministry of Science and Higher Education (Contract
no. 3141/IAEA/2014).
[4].
[5].
References
[1]. Degrand, H., Cazaux, F., Coqueret, X,, Defoort, B.,
Boursereau, F., & Larnac, G. (2003). Thermal effects
on the network structure of diglycidylether of bisphenol-A polymerized by electron-beam in the presence
of an iodonium salt. Radiat. Phys. Chem., 68 (5),
885-891. DOI: 1016/S0969-806X(03)00208-1.
[2]. Alessi, S., Parlato, A., Dispenza, C., De Maria, M., &
Spadaro, G. (2007). The influence of the processing
temperature on gamma curing of epoxy resins for the
production of advanced composites. Radiat. Phys.
Chem., 76 (8-9), 1347-1350. DOI: 10.1016/j.radphyschem.2007.02.029.
[3]. Alessi, S., Dispenza, C., Fuochi, P.G., Corda, U., Lavalle, M., & Spadaro, G. (2007). E-beam curing of epoxy-based blends in order to produce high-performance
[6].
[7].
[8].
composites. Radiat. Phys. Chem., 76 (8–9), 1308-1311.
DOI: 10.1016/j.radphyschem.2007.02.021.
Coqueret, X., Krzeminski, M., Ponsaud, P., & Defoort, B. (2009). Recent advances in electron-beam
curing of carbon fiber-reinforced composites. Radiat.
Phys. Chem., 78 (7-8), 557-561. DOI: 10.1016/j.radphyschem.2009.03.042.
Pitarresi, G., Alessi S., Tumino D., Nowicki, A., & Spadaro, G. (2014). Interlaminar fracture toughness behavior of electron-beam cured carbon-fiber reinforced
epoxy-resin composites. Polym. Composites, 35 (8),
1529-1542. DOI: 10.1002/pc.22806.
Singh, A., Saunders, C.B., Barnard, J.W., Lopata, V.J.,
Kremers, W., McDougall, T.E., Chung, M., & Tateishi, M.
(1996). Electron processing of fibre-reinforced advanced
composites. Radiat. Phys. Chem., 48 (2), 153-170. DOI:
10.1016/0969-806X(95)00424-V.
White, S.R., Sottos, N.R., Geubelle, P.H., Moore, J.S.,
Kessler, M.R., Sriram, S.R., Brown, E.N., & Viswanathan, S., (2001). Autonomic healing of polymer composites. Nature, 409 (15 Feb), 794-797. DOI: 10.1038/
35057232.
Yuan, l., Gu, A., Nutt, S., Wu, J., Lin, Ch., Chen, F., &
Liang G. (2013). Polym. Adv. Technol., 24, 81-89. DOI:
10.1002/pat.3053.
THE PROPERTIES AND IONIZING RADIATION EFFECTS
IN THE STARCH-PVA FILMS PREPARED BASED ON VARIOUS SUBSTRATES
Krystyna Cieśla, Anna Abramowska, Marek Buczkowski
The increasing problem of the non-degradable
plastic waste induces the interest in substitution
of traditional packaging by the biodegradable materials based on the mixed systems composed from
a variety of natural polymers (polysaccharides or
proteins) as well as from polysaccharides and artificial biodegradable polymer.
Starch appears to be the appropriate source for
the preparation of cheap biodegradable packaging [1-7]. However, films prepared based on natural starches alone have rather moderate mechanical properties and resistance to moisture. Therefore, for the purpose of improving the properties
of starch films, various methods are applied as follows: using the modified starches, blending starch
with other natural polymer or with the artificial
biodegradable polymer and applying various physical and chemical treatments. PVA can be used for
packaging purposes and is known to be the appropriate polymer for blending with starch [3, 6]. Simultaneously, radiation techniques appear to be the
perspective methodology for the modification of
polymers and biopolymers (including the films).
A possible desired modification of the film’s structure and properties [1, 2, 4-7] as well as the potential for packing the products subjected to radiation decontamination [1, 6] lead to the interest in
studies dealt with ionizing radiation influence on
the biodegradable films.
Our previous results have already shown that
using the irradiated starch enables to obtain the
films with better functional properties as compared to those prepared based on the native starch
[1, 2, 4, 5]. Moreover, studies concerning the
preparation of the starch-PVA films and the examination of irradiation effects were already carried
out and have shown the ability for modification
of the films’ properties by modifying their composition and irradiation [6].
The purpose of the present work constitutes
the selection of the best substrates for the preparation of the films in the starch-PVA system in
the case when the synthesis is supported or followed by ionizing radiation. Accordingly, the studies
were carried out dealing with the effect of using
various preparation techniques of PVA and starch,
and the effect was studied of gamma irradiation on
the resulting films’ properties.
Four selected PVAs (products of Sigma and
of Alfa Aesar) characterized by various molecular masses (PVA1 – 145 kDa, PVA2 – 90 kDa,
PVA3 – 60 kDa and PVA4 – 15-30 kDa) were used
for the films’ preparation. Moreover, two cornstarches such as SC3 (Sigma) and SC2 (Cerestar)
and two potato starches such as S8 (Sigma) and
S7 (commercial, local market) were applied. Commonly, the starches contain ca. 23% of amylose.
These starches were degraded on the way of irradiation with a dose of 10 kGy (in purpose to reduce their viscosity [2]). In addition, the high-amylose cornstarch (SC4, Sigma) was applied
(native and pre-irradiated using the same dose of
10 kGy).
Films characterized by a starch:PVA ratio
equal to 60:40 were prepared by solution casting
method. Some syntheses were also done applying
starch:PVA (50:50) composition. Glycerol was introduced at the level of 30% (in relation to the
joint starch-PVA mass). The films were dried, peeled from the substrate and irradiated. The films
were conditioned during couple of days at the
relative humidity of 43% before testing.
0 kGy
25 kGy
25 kGy
100
80
60
40
20
16
14
0
12
PVA1
PVA2
PVA3
PVA4
Fig.3. Wetting angle of the starch:PVA (40:60) films containing SC3 and various PVAs, non-irradiated and irradiated with gamma rays applying a dose of 25 kGy.
10
8
6
4
2
0
PVA1
PVA2
PVA3
PVA4
Fig.1. Tensile strength of the starch:PVA (40:60) films
containing SC3 and various PVAs, non-irradiated and irradiated with gamma rays applying a dose of 25 kGy.
In the first step, studies of the effect of application of the various PVAs on the properties of
starch-PVA films, i.e. non-irradiated and irradiated were carried out. Pre-irradiated cornstarch
SC3 (absorbed dose of 10 kGy) was selected as a
starch component.
The results (Figs.1-4) have shown that application of PVA1 (characterized by the highest molecular mass) enables to obtain the films with the
best properties as compared to the application of
other PVAs. This was observed directly after synthesis as well as after subsequent irradiation. These
200
Elongation at break [%]
0 kGy
0 kGy
No particular effect of irradiation with the absorbed dose of 25 kGy on tensile strength of the
films containing PVA1 was noticed, while decrease
in this parameter was observed in the cases of all
other films. Decreases in flexibility and in wetting
angle were detected after the irradiation in cases
of all the compositions. However, only a slight decrease in wetting angle was noticed in the case of
the films based on PVA1, and these films have still
revealed the best mechanical parameters (tensile
strength and elongation at break) and the higher
contact angle. Moreover, these films revealed the
lowest swelling parameter, and this parameter has
decreased additionally after the radiation treatment, contrary to all the other compositions (no
effect in the case of PVA2 and increase in swelling
in the cases of PVA3 and PVA4), (Fig.4). Furthermore, it was found that the films containing PVA
with the low molecular mass contain more low
450
25 kGy
180
350
160
300
140
120
100
80
200
150
100
40
50
20
0
PVA1
PVA2
PVA3
PVA4
Fig.2. Elongation at break of the starch:PVA (40:60) films
containing SC3 and various PVAs, non-irradiated and irradiated with gamma rays applying a dose of 25 kGy.
25 kGy
250
60
0
0 kGy
400
swelling [%]
Tensile strength [MPa]
18
films have revealed the highest tensile strength
accompanied by a relatively high flexibility (Figs.1
and 2) and the highest wetting angle as compared
to the other ones (Fig.3); although the films containing PVA3 were also characterized by the high
contact angle.
Wetting angle [°]
Irradiation was carried out with Co-60 gamma
rays in nitrogen at ambient temperature in the
Gamma Chamber GC 5000 applying a dose rate of
5.00 kGy/h. Irradiation of the films were carried
out using doses of 25 kGy and 10 kGy.
Mechanical tests were carried out using Inström testing machine [2]. The wetting (contact)
angle measurements (enabling to evaluate the hydrophilic/hydrophobic properties) were done using the instrument constructed in the Department
of Nuclear Methods of Materials Engineering,
(INCT) with the method described in Ref. [2].
The other parameter determined in relation to the
films’ hydrophilicity was the capability for swelling in water.
21
PVA1
PVA2
PVA3
PVA4
Fig.4. Swelling in water related to the dry mass of the
starch:PVA (40:60) films containing SC3 and various PVAs,
non-irradiated and irradiated with gamma rays applying a
dose of 25 kGy.
22
molecular fractions (probably moisture) already
before swelling in water. In addition, phase separation was observed in the starch-PVA films formed
using PVA4 component. Therefore, it can be concluded that PVA1 constitutes the best substrate
for the films’ preparation.
the native SC4 starch were characterized by rather
moderate properties, and their swelling capability
was very high. The next in sequence after the films
containing SC4 (10 kGy) were the films containing the pre-irradiated cornstarch SC3. The films
containing both potato starches (S7 and S8) were
Table 1. Comparison of the mechanical properties of the starch:PVA (40:60) films prepared using PVA1 and various
starches, non-irradiated and irradiated with gamma rays applying absorbed doses of 10 kGy and 25 kGy. Conventionally,
the pre-irradiated starches (gamma rays, 10 kGy) were applied for the films’ preparation.
Reference (0 kGy)
Starch
Irradiated
tensile strength [MPa]
 l [%]
SC2
17.6 ±1.4
125 ±27
SC3
19.9 ±1.3
206 ±20
SC4
20.4 ±1.4
224 ±38
S7
14.7 ±1.6
139 ±8
S8
20.0 ±1.2
138 ±4
SC4
(0 kGy, non-irradiated)
17.5 ±1.1
185 ±42
Accordingly, PVA1 was used as the PVA component in the next step of the studies dealing
with the effect of application of various preparations of starch on the properties of the starch-PVA
films, non-irradiated and irradiated. The results
are shown in Table 1 and in Figs.5 and 6.
The films obtained using the starch subjected
to pre-irradiation (10 kGy) were characterized by
the best properties. These films revealed the highest mechanical resistance (Table 1), the highest
wetting angle (Fig.5) and not very high swelling
parameter. Simultaneously, the films containing
100
0 kGy
10 kGy
10
15.8 ±1.1
170 ±25
25
18.1 ±1.1
169 ±20
10
19.1 ±3.0
191 ±30
25
19.9 ±2.4
186 ±9.64
10
20.8 ±1.3
232 ±33
25
19.0 ±1.2
188 ±39
10
13.9 ±0.8
139 ±6
25
12.9 ±0.7
141 ±9
10
19.1 ±0.7
133 ±10
25
19.2 ±1.0
132 ±13
10
16.9 ±1.3
139 ±27
25
15.9 ±0.7
184 ±25
characterized by worst properties as compared to
the films containing all the cornstarches. In particular, a strong swelling was observed in the case
of these starches (similar to the case of the native
cornstarch SC4); due to the low stability in water,
the swelling parameter was not determined for the
majority of these films, especially the irradiated
ones. Only in some cases, gamma irradiation with
a dose of 25 kGy induces a very slight deterioration of the mechanical properties of the films,
while irradiation with a dose of 10 kGy has no
impact on these properties. A small decrease in
wetting angle was noticed in the majority of the
25 kGy
600
90
80
0 kGy
10 kGy
25 kGy
500
70
60
Swelling [%]
Wetting angle [°]
 l [%]
dose [kGy] tensile strength [MPa]
50
40
400
300
200
30
20
100
10
0
0
SC2
(10kGy)
SC3
(10kGy)
SC4
(10kGy)
S7
(10kGy)
S8
(10kGy)
SC4
(0kGy)
Fig.5. Wetting angle of the starch:PVA (40:60) samples
containing SC3 and various PVAs, non-irradiated and irradiated with gamma rays applying doses of 25 kGy or 10 kGy.
SC2 (10kGy) SC3 (10kGy) SC4 (10kGy) S7 (10kGy)
S8 (10kGy)
Fig.6. Swelling in water related to the dry mass of the
sample of the starch:PVA (40:60) samples containing SC3
and various PVAs, non-irradiated and irradiated with gamma rays applying a dose of 25 kGy.
cases (Fig.5), but simultaneously, a decrease in the
swelling parameters can be concluded in the cases
of all the pre-irradiated cornstarches – SC2, SC3
and SC4 (Fig.6).
Accordingly, it can be concluded that the use
of PVA1 (characterized by the highest molecular
mass) and pre-irradiated high amylose cornstarch
enables to prepare the starch:PVA (40:60) films
characterized by the best properties, as well before
as after irradiation. However, the standard pre-irradiated cornstarch SC3 can also be considered
as the promising substrate, particularly when the
high cost of the SC4 starch is taken into account.
The obtained results also suggest that the films
obtained in the starch-PVA system can be applied
for the products predicted for radiation decontamination.
The work was sponsored in the frame of IAEA
Research Contract No. 17493 (CRP F2206).
References
[1]. Cieśla, K. (2009). Przekształcenia struktury nadcząsteczkowej w polimerach naturalnych inicjowane promieniowaniem jonizującym. Warszawa: Instytut Chemii i Techniki Jądrowej, 223 p.
23
[2]. Cieśla, K., Nowicki, A, & Buczkowski, M. (2010) Preliminary studies of the influence of starch irradiation
on physicochemical properties of films prepared using
starch and starch-surfactant systems. Nukleonika, 55,
2, 233-242.
[3]. Tang, X., & Alavi, S. (2011). Recent advances in starch,
polyvinyl alcohol based polymer blends, nanocomposites and biodegradability. Carbohydr. Polym., 85, 1-16.
[4]. Cieśla, K., Watzeels, N., & Rahier, H. (2014). Effect of
gamma irradiation on thermophysical properties of
plasticized starch and starch surfactant films. Radiat.
Phys. Chem., 99, 18-22.
[5]. Cieśla, K., & Sartowska, B. (2016). Modification of
the microstructure of the films formed by gamma irradiated starch examined by SEM. Radiat. Phys. Chem.,
118, 87-95.
[6]. Abramowska, A., Cieśla, K.A., Buczkowski, M.J., Nowicki, A., & Głuszewski, W.J. (2015). The influence of
ionizing radiation on the properties of starch-PVA films.
Nukleonika, 60, 3, 669-677. doi: 10.1515/nuka-2015-0088.
[7]. Ryzhkova, N., Jarzak, U., Schäffer, A., Bämer, M., &
Swiderek, P. (2011). Modification of surface properties
of thin polysaccharide films by low energy electron exposure. Carbohydr. Polym., 83, 608.
PROTECTIVE EFFECTS OF LIGNIN SULPHONATE
IN CELLULOSE RADIOLYSIS
Wojciech Głuszewski, Hieronim Kubera1/, Klaudia Kozera2/
1/
Warsaw University of Technology, Faculty of Production Engineering, Warszawa, Poland
2/
Warsaw University of Technology, Faculty of Chemistry, Warszawa, Poland
The issue of the use of ionizing radiation for the
preservation of objects of significant cultural heritage is still valid despite extensive scientific literature on the subject [1]. A unique feature is the
possibility of disinfestations and disinfections of
a very large number of objects in a short (express)
time by radiation techniques [2]. For this purpose,
both the electron beam (EB) and gamma radiation
are used worldwide [3]. In particular, radiation
techniques are an interesting offer for conserva-
tors dealing with objects made of paper. The issue
of radiation resistance of cellulose is also important from the point of view of packaging materials
and preventive sterilization of postal items that
could potentially be a source of bacteriological
terrorist attack [4, 5].
If the protective phenomena in radiation chemistry of polymers generally are defined as processes
to restrain their degradation (deterioration of mechanical properties), it is necessary to consider
Table 1. The radiolytic yield of hydrogen emission and oxygen uptake. Irradiation was carried out in air at room temperature.
Lignin sulphonate [%]
G(H2) [mol/J]
G(-O2) [mol/J]
EB (15 000 kG/h)
gamma rays (5 kGy/h)
EB
gamma rays
0
0.168
0.163
1.444
1.746
0.6
0.129
0.116
1.150
1.533
5.3
0.100
0.092
0.888
1.398
10
0.100
0.082
0.747
1.206
16
0.088
0.079
0.715
1.191
20
0.087
0.074
0.604
1.165
25
0.082
0.067
0.542
1.115
30
0.073
0.066
0.498
1.009
43
0.072
0.065
0.267
0.882
50
0.065
0.061
0.217
0.588
100
0.064
0.057
0.057
0.061
24
several possible ways to achieve this goal. The protective effect may be the result of electron transfer
or the transfer of positive holes to the scavengers.
This is the basic mechanism that prevents chemical changes in the polymer. We can also explain
the protective effect of energy transfer from the
excited molecule to the aromatic additives. The
concept of such a transfer mechanism is very interesting and could be explained by the ability of
aromatic ring to dissipate energy. Protective additives may also react with free radicals, thereby
competing with the processes of crosslinking and
oxidation. It should be noted, however, that the
network structure of a polymer material is often
advantageous from the standpoint of mechanical
properties.
The study pointed out the protective effect of
lignin in the cellulose radiolysis. We have studied
the protective effects by gas chromatography (GC).
The prepared samples contained various percentage of lignin sulphonate (produced during the
processing of wood pulp) in the cellulose. Sulphonate cellulose was dissolved in water and soaked
in the paper. The paper web was dried. Lignin content was determined by weight. They were used as
the cellulose Whatman paper. An aromatic compound was lignin sulphonate (produced by Borregaard, Norway). The samples were irradiated at
room temperature, in the air atmosphere. Table 1
shows radiation yields of hydrogen and absorbed
oxygen in a function of the content of the aromatic
compound in the paper.
porated in that case in the thermal degradation
process, and that phenomenon is also outside the
scope of the paper.
On the contrary, in the radiolytic decomposition at room temperatures and even under cryogenic conditions, hydrogen is the main constituent of the gas phase above any hydrogen-bearing
products. For instance, in the case of all polymers,
hydrogen dominates over the concentration of low
molecular weight debris of the degraded polymers.
In the specific case of radiolysis cellulose/lignin
sulphonate mixture, the latter constituent had protective effect due to the high contribution of aromatic rings (Fig.1). It is confirmed both by the volume of hydrogen emitted and oxidation consumption capacity. Quantitatively, the data also reveal
the influence of dose rate on radiolysis and postradiation oxidation. The use of electron beam (15 000
kGy/h) instead of gamma rays (5 kGy/h) greatly
reduces oxidation of the cellulose (Fig.2).
Fig.2. Oxygen yield as a function of the content of lignin
sulphonate.
It is worth noticing that gas chromatography
in the proposed system can be a convenient tool
for assessing oxidation of polymers also in classical chemistry.
References
Fig.1. Hydrogen yield as a function of the content of lignin
sulphonate.
Detachment of gaseous hydrogen from any hydrogen-bearing material (from inorganics to polymers) at ambient temperature is unknown in the
conventional chemistry. Hydrogen can appear at
room temperature when generated by biological
metabolic processes, outside the topic of the present paper. At elevated temperature, gaseous hydrogen can appear over polymers heated to high
temperatures, well above the melting or decomposition temperature. Free H2 formation is incor-
[1]. Głuszewski, W., Boruc, B., Kubera, H., & Abbasowa,
D. (2015). The use of DRS and GC to study the effects
of ionizing radiation on paper artifacts. Nukleonika,
60, 665-668.
[2]. Głuszewski, W. (2015). Features of radiation conservation of high collections of objects about of historical
interest J. Herit. Conserv., 41, 84-91.
[3]. Głuszewski, W., Cieśla, K., Zimek, Z., & Kubera, H.
(2014). Peculiar features of radiation treatment of the
packaging materials. Towaroznawcze Problemy Jakości, 4, 11-17.
[4]. Głuszewski, W. (2015). Niewidzialne ale pracowite.
Packaging Polska, 5, 24-15.
[5]. Głuszewski, W. (2015). Unikatowe cechy radiacyjnej
konserwacji dużych zbiorów obiektów o znaczeniu historycznym. Postępy Techniki Jądrowej, 58, 1, 19-23.
25
DEDICATED RF DRIVING GENERATOR FOR LINEAR ACCELERATOR
BASED ON PLL FREQUENCY SYNTHESIZER UNDER MPU CONTROL
Sylwester Bułka, Zbigniew Zimek
The experience gained during over ten years’ operation of the LAE 10 accelerator shows a limited
reliability of microwave klystron driving generators. The output power needed from the unit does
not exceed 20 mW. The problems concern usually
malfunction of generators’ output amplifier stage,
it was observed highly elevated chassis temperature after several hours of operation. Probably that
was the reason for last failure: damage of the non-volatile EEPROM containing generator’s output
stage calibration data. In addition, the services refused to fix the device which was too obsolete.
This situation led us to design a low cost, easy
serviceable, dedicated RF generator equipped with
external amplification/matching module. The basis
for the construction was GaP monolithic integer-N
synthesizer and voltage controlled oscillator (VCO)
in one Analog Devices ADF4360 chip [1].
A typical frequency range for LAE 10 accelerator is 1.8174 GHz which should be tuned with
100 kHz step ±0.3 MHz span. The selected integrated synthesizer of ADF4360-x series is designed
for a centre frequency of 1750 MHz (version 3 denoted in its symbol).
As shown in Fig.1, the internal circuitry determining the output frequency consists of:
• VCO tuned with the analog signal from phase
comparator;
• dual-modulus prescaler. It takes the clock from
the VCO and divides it down to a manageable
frequency for the CMOS A and B counters. The
prescaler is programmable. It can be set in software to 8/9, 16/17, or 32/33 and is based on a
synchronous 4/5 core, along with the A and B
counters, enabling the division ratio, N, to be
realized (N = BP + A);
• A and B counters, in conjunction with the dual-modulus prescaler, make it possible to generate
output frequencies that are spaced only by the
reference frequency divided by R. The VCO frequency equation is as follows:
fVCO = [(P  B) + A]  fREFIN/R
where: fVCO – the output frequency of the VCO,
P – the preset modulus of the dual-modulus
prescaler (8/9, 16/17, or 32/33), B – the preset
divide ratio of the binary 13-bit counter (from 3
to 8191), A – the preset divide ratio of the binary
5-bit swallow counter (from 0 to 31), fREFIN – the
external reference frequency oscillator.
The practical values of the counters selected for
the assumed performance are as follows: A = 30,
B = 567, P = 32. They give n = 18 174 which
Fig.1. Internal structure of ADF4360 frequency synthesizer chip.
26
The user interface of the controller is simplified
and contains the minimum number of necessary
functions that are sufficient to manage the generator: frequency up/down, signal level up/down
controls and safety button RF POWER ON/OFF.
As shown in Fig.4, the generator is located in
one of the accelerators’ control racks and is easily
operable by the user during the machine tune-up
procedure. Right from the generator control panel,
there is RF power amplifier which provides a correct microwave power level to the klystron and additionally is equipped with reflected power ferrite
isolator for operation reliability.
Fig.2. The configuration of ADF4360 as local oscillator.
together with fREFIN = 10 000 MHz external reference oscillator frequency provides 1817.400 tuned
±0.300 MHz with 0.100 MHz step.
Alphanumerical LCD
Display
Port A
RF Power
Amplifier
RF OUT
ATTINY 2313
Port B
Pre-Amp.
ADF4360
PLL Synth.
Board
Control Panel
Fig.3. LAE 10 accelerator driving RF generator block diagram.
As shown in Fig.2, a typical hardware configuration recommended by the manufacturer as local
Fig.5. Plot from RF spectrum analyser.
As shown in Fig.5, the generator is tested with
the RF spectrum analyser for the linearity of frequency sweep step, and the plot from its screen
displays the spectra of the output signal during
the routine tuning of accelerator. The peaks are
sharp with well-defined frequency step, at least
30 dB distant from noise level, and there is no
trace of spurs (frequency modulation VCO parasitic spectrum components).
Fig.4. LAE 10 driving RF generator placement in accelerator control rack.
oscillator is realized using the EVAL printed board
[2], which can be provided with the chip. It contains 10,000 MHz crystal reference oscillator, PLL
phase detector filter circuitry, 3.3 V and 5 V power
stabilizers.
The control of the chip is via simplified (unidirectional) SPI bus.
Before ADF4360 starts operation, the appropriate data for the counters, dividers and VCO operation mode must be transmitted into the chip.
For this purpose, the single chip AVR ATTINY2313
[3] microcontroller was used (Fig.3).
References
[1]. ADF4360-3 integrated synthesizer and VCO datasheet. (2003). Analog Devices, Inc. Rev. 0, C04437-0-11/03(0).
[2]. Evaluation board for ADF4360-3 integrated VCO &
frequency synthesizer EVAL-ADF4360-3EB1. (2003).
Analog Devices, Inc. REV.PrC 08/03.
[3]. 8-bit AVR microcontroller with 2K bytes in-system
programmable flash ATtiny2313 datasheet. (2004).
ATMEL. 2543DS-AVR-03/04.
CENTRE FOR RADIOCHEMISTRY
AND NUCLEAR CHEMISTRY
Chemical issues of nuclear power and radiopharmaceutical chemistry – the two top domains
of applied radiochemistry and nuclear chemistry – remained the main areas of the research
activity of the Centre for Radiochemistry and Nuclear Chemistry in 2015. The research projects of the Centre were financed in the form of grants from the National Centre for Research
and Development (NCBR) and the National Science Centre (NCN), as well as in the form of
funding the Institute’s statutory research and international collaboration from the Ministry
of Science and Higher Education. International resources included the European Commission (FP7 Euratom, Fission) and other (IAEA, COST).
The teams of three Centre laboratories (Radiochemical Separation Methods, Membrane
Processes and Technologies, and Sol-Gel Technology) continued their studies on radioactive
waste management, and on special nuclear materials. In this respect, the Sol-Gel Technology
team continued the execution of the European Collaborative Project ASGARD, contributing
to the development of new types of MOX nuclear fuels based on uranium oxides and carbides. The work was accompanied by research on the synthesis of another potential nuclear
fuel, mixed thorium-uranium dioxide in the form of microspheres. The Radiochemical Separation team continued the research on actinide/lanthanide separation by solvent extraction,
in the frame of the European Collaborative Project SACSESS (Safety of actinide separation
processes). Cooperation with the CEA Marcoule, on actinide complexes with hydrophilic,
polyheterocyclic-N-dentate ligands used for actinide stripping from the organic phase, was
continued on the basis of bilateral research agreement and other common projects. The aim
of the study was to get thermodynamic characteristics of the complexes of actinide cations
from Th to Am, at different oxidation levels (+3 to +6) with the newly synthesized (Karlsruhe
Institute of Technology-Institute for Nuclear Waste Disposal – KIT-INE), tri- and tetra-N-dentate hydrophilic ligands – SO3-Ph-BTP and SO3-Ph-BTBP, especially the determination of
stability constants of these complexes in acidic aqueous solutions. Advanced quantum chemical calculations, which allowed explaining the reason of actinide selectivity of some ligands
used for solvent extraction separation of actinides from lanthanide fission products, were
performed.
The knowledge based on molecular modelling may allow to design and synthesize novel,
more selective ligands for such separations. Calculations of Eu(III) and Am(III) complexes
in phenanthroline (Phen) with using DFT/B3LYP/6-31G**, were carried out in the frame of
the NCN grant OPUS. Recovery of uranium and accompanying metals from various types of
industrial wastes like phosphogypsum or waste from flotation of copper ores was studied in
the scope of the IAEA CRP.
Various aspects related to the management and storage of spent nuclear fuel and radioactive wastes formed in the course of exploitation of nuclear power plants, with a special emphasis on the Polish Nuclear Power Programme, were studied. Within the statutory research,
novel methods were examined by the Membrane Processes group, for the separation of radionuclides and heavy-metal ions, based on hybrid processes (membrane filtration combined
with sorption or complex formation, and micellar-enhanced ultrafiltration), as the basis for
further technological advancement for radioactive waste processing. Micellar-enhanced ultrafiltration was studied as a method for purification of reactor coolant with boric acid recovery.
The application of advanced membrane systems in nuclear desalination was tested within
the frame of the IAEA CRP. The possibility of application of such methods as reverse osmosis
and membrane distillation, for desalination as well as radioactive waste treatment within
nuclear power plants (NPPs), was proved. Basic research on the phenomena occurring during the operation of membrane units was continued in the scope of the NCN research project
on the development of sensitive methods for studying concentration polarization and membrane fouling. The combination of radiotracers with optic techniques like SEM (scanning
electron microscopy), FT-IR/PAS (Fourier-transform infrared/photoacoustic spectroscopy)
has brought data for the future elaboration of the methodology of testing membrane units.
The Centre actively participated in European initiatives of the development of new nuclear reactors including those of Generation IV – ALFRED and ALLEGRO. Evaluation of the
potential of European institutions to participate in such initiatives was performed in the scope
of PLATENSO and ARCADIA Euratom projects.
Great attention was paid to social and societal implications of nuclear energy and applications of ionizing radiation. These aspects were studied with international consortia in the
frame of Euratom projects PLATENSO and EAGLE. Social and socio-economic effects of
implementation of the Polish Nuclear Power Programme with the development of macroeconomical tools for assessment were studied within the IAEA CRP in cooperation with the
Ministry of Economy. On request of this ministry, the implementer of the Polish Nuclear
Power Programme, other projects were developed, like elaboration of a methodology to evaluate the safety and identify the optimal location of shallow repository for low- and intermediate-level radioactive waste, and obtaining uranium from unconventional resources.
Research on radiopharmaceutical chemistry (Laboratory of Radiopharmaceuticals Synthesis
and Studies) was focused on obtaining and studying novel potential radiopharmaceuticals,
both diagnostic and therapeutic. Novel biomolecules, derivatives of tacrine, substance P, and
lapatinib, as well as antibiotics used in medical treatment of bacterial infections, were labelled
with 99mTc or 68Ga, resulting in potential diagnostic tools for Alzheimer’s disease, glioma brain
tumours, breast cancer and diabetic foot, respectively. A part of the research was carried out
in cooperation with the Department of Pharmaceutical Chemistry and Drug Analyses, Medical
University of Łódź. The 99mTc-labelled antibiotics were used in medical experiments in the
Department of Nuclear Medicine, Medical University of Warsaw.
New methods for cyclotron productions of diagnostic radionuclides, both SPECT (99mTc)
and PET (43Sc, 44Sc, 72As) were developed in cooperation with the Heavy Ion Laboratory of the
University of Warsaw, and the National Centre for Nuclear Research – POLATOM, within two
projects awarded by the NCBR. Also potential therapeutic radiopharmaceuticals were obtained and studied. Peptides and proteins were labelled with alpha emitters (211At, 225Ac and
223
Ra) via functionalized soft-metal chelates (metal bridge), and by the use of functionalized
nanoparticles such as nanozeolites and gold nanoclusters. The synthesized bioconjugates
exhibit high receptor affinity and high radiotoxicity. Nanobodies labelled with either beta or
alpha emitters were studied in cooperation with the Vrije Universiteit, Brussels. Studies on the
use of alpha emitters to destroy very resistant cancer stem cells, initiated in 2014 in cooperation with the JRC Institute of Transuranium Elements, Karlsruhe, will be continued, supported
from the Foundation for Polish Science.
The interest in energy related issues and our expertise in separation methods allowed building the industrial consortium capable to develop a research project devoted to elaboration of
the technology for treatment of fluids after hydraulic fracturing of shale with water reuse and
recovery of valuable metals. The project awarded by the NCBR in the course of the Blue Gas
competition will enable to expand the expertise of the Centre to new areas of competence.
One D.Sc. degrees (habilitations) has got approval last year; two teams of the Centre were
awarded with Director’s prize for publications.
The international and national scientific cooperation of the Centre was successfully continued and enhanced, making the Centre teams desired partners not only on the national scale,
but also over the European research area.
The Centre participated in organization of several meetings, conferences and seminars,
among them the SACSESS project conference “Towards safe and optimized separation processes, a challenge for nuclear scientists” and the seminar on the possibility of implementation of Gen III/IV systems in NMS and approaches for public participation in the decision
making process in the Ministry of Economy.
The scientists of the Centre were involved in activities of large number of organizations,
societies, and editorial boards of scientific journals in the country and abroad.
29
ACTINIDE COMPLEXATION WITH A HYDROPHILIC SO3-Ph-BTP LIGAND,
STUDIED BY LIQUID-LIQUID DISTRIBUTION
Jerzy Narbutt, Łukasz Steczek, Magdalena Rejnis, Irena Herdzik-Koniecko
Recycling of actinides from spent nuclear fuel by
their selective separation followed by transmutation in fast reactors will optimize the use of natural uranium resources and minimize the long-term
hazard from high-level nuclear waste. This ap-
been developed which exhibit a very high selectivity for trivalent actinides (An) over lanthanides:
bis-triazinyl derivatives of pyridine (BTP), of bi-pyridine (BTBP) and of 1,10-phenantroline (BTPhen)
[4] (Fig.1).
A
C
B
Fig.1. Structural formulae of bis-triazinyl ligands: (A) R-BTP (R – aliphatic group), (B) CyMe4-BTBP and (C)
CyMe4-BTPhen.
proach focused on the closing the nuclear fuel
cycle, should drastically reduce the potential long-term threat to humans and the environment from
the radiotoxic nuclear waste. The new technologies
will make the nuclear energy sustainable, enabling
its broader development worldwide. This will reduce the global CO2 emissions, in line with the
agreement on the last UN Climate Change Conference (Paris, December 2015). Developing of an
energy mix with a significant contribution from
the zero-emission nuclear energy is the only real
option for our country (Polish Nuclear Power Programme, 2014) whose energy production is based
mainly on fossil fuels which can hardly be replaced
by renewable energy sources (wind, hydro, solar)
because of our geographical conditions [1].
To meet the challenge that nuclear energy has
become sustainable, extensive research is carried
out worldwide on improving technologies of reprocessing spent nuclear fuel. Basing on the strategy of Partitioning and Transmutation, the actinides separated (“partitioned”) from the spent fuel
will be transmuted into much shorter-lived and
stable nuclides by high energy (fast) neutrons,
e.g. in fast nuclear reactors of Generation IV [2].
Various options, hydro- and pyrometalurgical, are
being developed and tested for the actinide partitioning [3]. The most promising hydrometalurgical (solvent extraction) technologies utilize completely incinerable poly-N-dentate polyheterocyclic
‘CHON’ ligands which eagerly extract trivalent
f-electron metal ions from aqueous HNO3 solutions. Because the separation of americium from
lanthanide fission products is an indispensable
condition for the actinide transmutation [2, 4],
novel lipophilic bis-[1,2,4]-triazinyl ligands have
Apart from the AnIII/LnIII separation with the
use of the above lipophilic extractants (e.g. in the
regular SANEX process [3, 4]), another option
has been proposed – to selectively strip the AnIII
ions from the loaded organic phase to nitric acid
solutions using hydrophilic AnIII-selective ligands
[4]. Such a ligand, 2,6-bis(5,6-di(sulphophenyl)1,2,4-triazin-3-yl)pyridine (SO3-Ph-BTP, Fig.2),
was synthesized and studied as an actinide-selective stripping agent by Geist and coworkers [5].
Later on, the usefulness of this anionic ligand for
the separation of americium(III) from lanthanides
Fig.2. Structural formula of the SO3-Ph-BTP4– anion.
(in the innovative-SANEX process [3, 4]) was
demonstrated in a laboratory-scale test carried out
in a multistage counter-current system [6]. Also
other sulphonated bis-1,2,4-triazine ligands, hydrophilic derivatives of BTBP and BTPhen appeared
effective complexing reagents for separating actinides(III) from lanthanides(III) via selective formation of aqueous actinide complexes [7, 8].
The knowledge of complexing properties of the
novel ligands towards actinides allows us to predict their usefulness for solvent extraction sep-
30
arations. The studies on the extraction system
N,N,N’,N’-tetraoctyl-diglycolamide (TODGA)/
SO3-Ph-BTP4– + HNO3 made possible to conclude that only two Am3+–SO3-Ph-BTP4– complexes (1:1 and 1:2) co-existed in the aqueous
phase [5]. Though no stability constants of these
complexes have been reported, such data are available for the analogous complexes of Cm3+ (chemical properties of which are very similar to those of
Am3+), determined using time-resolved laser fluorescence spectroscopy (TRLFS). Moreover, not
two but three (also 1:3) Cm3+–SO3-Ph-BTP4–
complexes have been found in a separate dilute
aqueous solution of pH 3 [9].
To conclude on the complex formation of
Am3+ ions with the SO3-Ph-BTP4– (L4–) ligand in
the aqueous phase and to determine the stability
constants of the complexes, we studied the dependence of two-phase distribution of Am3+ on
the concentration of the free ligand, [L4–]. The
system consisted of 0.1 M TODGA in 5 vol%
octanol-kerosene (the organic phase) and the
SO3-Ph-BTP ligand (0.03 mM to 5 mM in total)
in HNO3/NaNO3 solutions of various acidities
(0.02 M to 1 M) at a constant 1 M nitrate concentration. The concentrations of Am in both phases
at equilibrium at 25oC were measured radiometrically (241Am tracer) [10].
We based in this study on a simple model of
Mn+ extraction in the system consisting of two
competing ligands: lipophilic (TODGA) and hydrophilic (L) in both liquid phases. It assumed
the formation of some consecutive hydrophilic
M–L complexes solely in the aqueous phase. The
distribution ratio of Am3+ in the system studied,
D = CAm,org/CAm,aq, can be expressed as:
for the Am3+ complexation by NO3– anions in the
aqueous phase:
W
 D0

4 i
 j
[L
]
1
1





L,i
 D
    NO3, j [NO3 ]  (3)


j1
j1

k
The [L4–] values were calculated as the functions of the total concentrations of L, CL,tot, and
HNO3, [H+], assuming the protonation constant
of L4–, KH,1, to be an adjustable value which ensured the best fit of the calculated (3) to the
corresponding experimental (D0/D – 1) values in
the whole range of the CL,tot and [H+] variables
[10]. This “best fit” value, log KH,1 = 0.5 was equal
to the literature value determined from UV-Vis
spectra [10].
In each region of L4– concentration where a
complex of a given stoichiometry predominates,
Eq. (3) can be simplified and expressed in the
logarithmic form:
r


D

log  0  1  log 1    NO3, j [NO3 ] j  
 D

j1

 (4)
4
 i log [L ]  log L,i
Two such regions have been found in the experiment, corresponding to the two Am3+–L4– complexes, 1:1 and 1:2 (Fig.3). Their stability constants, have been calculated by extrapolation of
the straight lines to the value log [L4–] = 0, and
correcting the result on the complexation of Am3+
by nitrates [10]. This way, the disagreement of
S
D
[Am(TODGA) (NO ) ]
j
j1
3 3 org
W
k
j1
i 1
[Am3 ]   [Am(NO3 )3j  j ]   [AmL3i 4i ]
(1)
where, in the absence of L, we have D = D0
S
D0 
[Am(TODGA) (NO ) ]
j
j1
W
3 3 org
[Am3 ]   [Am(NO3 )3j  j
(2)
j1
Fig.3. Log (D0/D – 1) for Am3+ against log [L4–] in the
system studied at a constant 1 M nitrate concentration
and the HNO3 concentration equal to: () 1 M, () 0.5 M,
() 0.15 M, and (●) 0.02 M, at 25oC. The “best-fit” straight
lines with the slopes of 1.00 and 2.00 are shown.

The competition for Am3+ ions between the
lipophilic (TODGA) and the hydrophilic (L4–) ligands leads to the decrease of the D values with
increasing L concentration. Moreover, a significant increase in the D values with increasing
HNO3 concentration is observed, which is undoubtedly due to an increase in the protonation
of L4– in the examined range of acidity as the protonated LH3– ligand does not complex metal ions
in the aqueous phase.
The known solvent extraction (distribution)
method of determination of stability constants of
metal complexes with hydrophilic ligands [11]
was applied. The log (D0/D – 1) values were plotted as a function of log [L4–], which also accounts
the results obtained using the two-phase distribution and monophasic spectroscopy methods has
been confirmed. In particular, no evidence has
been found for the existence of the 1:3 complex in
the aqueous phase of the two-phase system, in
spite of much higher free SO3-Ph-BTP4– concentration than that in the monophasic system where
the 1:3 Cm3+ complex had been detected (Table 1).
31
for uranyl and thorium under the experimental
conditions. The stability constants of these 1:1
complexes have been arranged in the following
order: U(VI)  Th(IV) < Am(III) < Pu(IV).
This report is based on the research carried
out in parts within (i) the statutory research of
the Institute of Nuclear Chemistry and Technology (INCT); (ii) the Cooperation Agreement pro-
Table 1. Conditional stability constants of the consecutive M3+–L4– (SO3-Ph-BTP4–) complexes in aqueous solution (SX
– solvent extraction).
M3+
Cm
3+
Am
3+
Method
Solution
TRLFS
0.001 M HClO4
SX
1 M (H,Na)NO3
Log 1
Log2
Log 3
Reference
 1  10
5.4 ±0.1
9.3 ±0.2
12.2 ±0.3
[9]
 2  10
4.35 ±0.07
7.67 ±0.06
no
[10]
[L−4], [M]
−3
−2
To explain this unexpected result, we have formulated a hypothesis that heteroleptic complexes
can be formed in the two-phase system studied,
lipophilic and extractable from the acidic aqueous
phase, e.g. [Am(TODGA)2(SO3-Ph-BTP)]– extractable as an ion pair with the TODGA·H+ cation
[10]. The search of such hypothetical species has
already been started by TRLFS in cooperation with
Dr. Geist’s team [12]. Preliminary results obtained
in a monophasic system, using a hydrophilic homologue of TODGA: N,N,N’,N’-te-traethyl-diglycolamide (TEDGA), allow to detect two unknown
heteroleptic complexes Cm(III)/TEDGA/SO3-Ph-BTP (1:1:1 and 1:2:1) in dilute slightly acidic
aqueous solutions. Unfortunately, no such complexes have been found so far in the organic phase
of the two-phase solvent extraction system containing TODGA [12]. The research is going on. It
is worth mentioning that also other authors postulated a possible formation of extractable mixed solvates Ln(NO3)3-(TEDGA)n-DMDOHEMA
(where n = 1 or 2, and DMDOHEMA is a lipophilic malonamide), as a reasonable interpretation of the observed co-extraction of hydrophilic
TEDGA with the lightest lanthanides in similar
systems [13, 14].
If the above hypothesis proves to be true one
will need to take the following actions: (i) elaborate the expanded model of solvent extraction of
metal ions in systems containing two competing
ligands, lipophilic and hydrophilic; (ii) validate the
values of stability constants of numerous metal
complexes determined by this method and included in the tables and text books; and (iii) design new hydrophilic ligands which do not form
heteroleptic actinide complexes with TODGA. The
latter task can be of significant practical importance because it can greatly increase the effectiveness of stripping certain metal ions from loaded organic phases by the hydrophilic complexing
agents.
Using the same two-phase distribution method
we also studied complexation of some other actinides: U(VI) [15], Th and Pu(IV); by the SO3-Ph-BTP4– ligand. The same two-phase extraction
system was applied (at some different TODGA
concentrations). Both 1:1 and 1:2 complexes of
all the metals studied were detected in the acidic
aqueous phases, with the 1:1 species dominating
ject 31/CA/2014 “Coordination of actinides with
hydrophilic ligands” – the bilateral agreement
between the INCT and the French Alternative
Energies and Atomic Energy Commission (CEA,
Marcoule, France); and (iii) the TALISMAN, Collaborative Project Grant co-funded by the European Commission, JRP no. TALI-C06-15 “TRLFS
search of heteroleptic Cm(III)/Eu(III) complexes
with TODGA and SO3-Ph-BTP ligands in solvent
extraction systems” studied in the Karlsruhe Institute of Technology-Institute for Nuclear Waste
Disposal (KIT-INE, Karlsruhe, Germany).
The cooperation with our colleagues: Marie-Christine Charbonnel and Philippe Moisy (CEA,
Marcoule), as well as Christoph Wagner, Andreas
Geist and Petra J. Panak (KIT-INE) is kindly acknowledged.
References
[1]. Narbutt, J. (2016). New trends in the reprocessing
of spent nuclear fuel. Separation of minor actinides
by solvent extraction. Annales UMCS, Ser. AA (Chemistry), in press.
[2]. Salvatores, M., & Palmiotti, G. (2011). Radioactive
waste partitioning and transmutation within advanced
fuel cycles: Achievements and challenges. Prog. Part.
Nucl. Phys., 66, 144-166.
[3]. Bourg, S., Geist, A., & Narbutt, J. (2015). SACSESS
– the EURATOM FP7 project on actinide separation
from spent nuclear fuels. Nukleonika, 60, 809-814.
[4]. Panak, P.J., & Geist, A. (2013). Complexation and
extraction of trivalent actinides and lanthanides by
triazinylpyridine N-donor ligands. Chem. Rev., 113,
1199-1236.
[5]. Geist, A., Müllich, U., Magnusson, D., Kaden, P.,
Modolo, G., Wilden, A., & Zevaco, T. (2012). Actinide(III)/lanthanide(III) separation via selective
aqueous complexation of actinide(III) using a hydrophilic 2,6-bis(1,2,4-triazin-3-yl)pyridine in nitric
acid. Solvent Extr. Ion Exch., 30, 433-444.
[6]. Wilden, A., Modolo, G., Kaufholz, P., Sadowski, F.,
Lange, S., Sypula, M., Magnusson, D., Müllich, U.,
Geist, A., & Bosbach, D. (2015). Laboratory-scale
counter-current centrifugal contactor demonstration
of an innovative-SANEX process using a water soluble BTP. Solvent Extr. Ion Exch., 33, 91-108.
[7]. Lewis, F.W., Harwood, L.M., Hudson, M.J., Geist,
A., Kozhevnikov, V.N., Distler, P., & John, J. (2015).
Hydrophilic sulfonated bis-1,2,4-triazine ligands are
highly effective reagents for separating actinides(III)
from lanthanides(III) via selective formation of aqueous actinide complexes. Chem. Sci., 6, 4812-4821.
32
[8]. Kaufholz, P., Sadowski, F., Wilden, A., Modolo, G.,
Lewis, F.W., Smith, A.W., & Harwood L.M. (2015).
TS-BTPhen as a promising hydrophilic complexing
agent for selective Am(III) separation by solvent extraction. Nukleonika, 60, 815-820.
[9]. Ruff, C.M., Müllich, U., Geist, A., & Panak, P.J.
(2012). Complexation of Cm(III) and Eu(III) with
hydrophilic 2,6-bis(1,2,4-triazin-3-yl)-pyridine studied
by time-resolved laser fluorescence spectroscopy.
Dalton Trans., 41, 14594-14602.
[10]. Steczek, Ł., Rejnis, M., Narbutt, J., Charbonnel,
M.-C., & Moisy, P. (2016). On the stoichiometry and
stability of americium(III) complexes with a hydrophilic SO3-Ph-BTP ligand, studied by liquid-liquid
extraction. J. Radioanal. Nucl. Chem. DOI 10.1007/
s10967-015-4663-7.
[11]. Stary, J. (1967). The use of solvent extraction of
metal chelates for the investigation of complexation
in aqueous solutions. In D. Dyrssen, J.-O. Liljenzin
& J. Rydberg (Eds.), Solvent Extraction Chemistry
– Proceedings of the International Conference held
[12].
[13].
[14].
[15].
at Gothenburg Sweden (pp. 1-10). Amsterdam:
North-Holland Publ.
Herdzik-Koniecko, I., Wagner C., Geist, A., Panak,
P.J., & Narbutt J. (2016). On the formation of heteroleptic complexes in an innovative-SANEX system.
In Sustainable Nuclear Energy Conference (SNEC),
Nottingham, UK, 12-14 April 2016 (submitted).
Chapron, S., Marie, C., Arrachart, G., Miguirditchian,
M. & Pellet-Rostaing, S. (2015). New insight into
the americium/curium separation by solvent extraction using diglycolamides. Solvent Extr. Ion Exch.,
33, 236-248.
Pacary, V., Burdet F., & Duchesne, M.-T. (2012). Experimental and modeling extraction of lanthanides
in system HNO3-TEDGA-{DMDOHEMA-HDEHP}.
Procedia Chem., 7, 328-333.
Steczek, L., Narbutt, J., Charbonnel, M.-Ch., & Moisy,
Ph. (2015). Determination of formation constants of
uranyl(VI) complexes with a hydrophilic SO3-Ph-BTP
ligand, using liquid-liquid extraction. Nukleonika,
60, 809-813.
NOVEL PROCEDURE FOR THE REMOVAL OF THE RADIOACTIVE METALS
FROM AQUEOUS WASTES BY THE MAGNETIC CALCIUM ALGINATE
Leon Fuks, Agata Oszczak, Wanda Dalecka
Radioactive wastes produced either from the civil
or the military nuclear industry, as well as from nuclear medicine, still create many problems. They
are dangerous both to human life and to the natural environment. The majority of low- and medium-level wastes contain different - and -emitters and a very small amount of actinides with
specific activity below 107 kBq/m3. These wastes
require pretreatment both to fulfil the norms for
releasing them into the water flows and to minimize the volume of radioactive materials to be
stored in the disposal sites. According to the recommendations for the drinking water published
by the European Union, radioactivity concentrations obtained from different radionuclides present in water intended for human consumption
may range from 0.5 Bq/L to 11 Bq/L, with the
exception of this originating from carbon-14 (240
Bq/L) [1].
Until now, adsorption technology has been considered as one of the most effective methods for
the removal of metal ions from water because it is
convenient and easy to design and to operate. The
adsorption processes with various adsorbents,
among other these of the biological and waste
materials origin, have been recently extensively
studied (e.g. [2-4]). It could be used most effectively in the metal concentration range below 100
mg/L, where other techniques are ineffective or
costly [5]. Thus, the development of novel, effective and low-cost adsorbents and the adsorption
procedures are welcome.
Among the most common biosorbents currently used for industrial metal-bearing effluents are
alginates, biopolymers of alginic acid extracted
from different types of algae or from two forms of
bacteria, Pseudomonas and Azotobacter. It was
found that calcium alginate exhibits relatively
higher uptake rate and distribution coefficient of
Am3+ than the other metals ions [6]. However, the
separation of the metal-loaded sorbent from the
purified solution is often a problem to overcome.
So the use of magnetic sorbents (in the following
called magsorbents, MS) to solve this technical
problem has received significant attention in recent years (e.g. [6-12]). These magnetic materials
may be tailored to fix specific pollutants in wastewater.
As a result, MS may become one of the promising methods for the removal of pollutants. This
process does not generate secondary waste and
consequently produces no additional pollution.
Moreover, this approach is particularly adapted
when the conditions of separation are complex,
e.g. when polluted water contains solid additives.
Usually, purification of the aqueous metal solutions by means of sorption is realized in the
two-stage batch process. First, sodium alginate is
added to water and particles of the magnetic material are suspended. Then, the above suspension
is added drop-wise into the sodium-alginate solution for cross-linking and preparing the MS beads.
Finally, sorption is generally performed by batch
process or in the adsorption columns.
A detailed literature inspection on the purification of the wastewater containing heavy metals
has shown that when the polyvalent metal ions
exist at relatively high concentrations in the aqueous media (i.e. above 100 ppm), sodium-alginate
solution may be directly dispensed into the solution circulating in a loop to produce the alginate
gels in situ that contain these metals [13]. Despite
the fact that the method seems to be perspective,
a series of studies performed in the group headed
by L.K. Jang has not been undertaken. The objective of the present study was to investigate a novel
variant of the procedure proposed by Jang with
application of the calcium alginate beads as MS
for the treatment of the radioactive liquid wastes,
i.e. containing radioactive metals in the trace
amounts.
Till now, the most frequently used compounds
as the magnetic cores were the hematite (iron(III)
oxide, Fe2O3) and the magnetite (mixed iron(II)/
iron(III) oxide, Fe3O4). In contrast, in the present
study, carbonyl iron has been used. Carbonyl iron
is a highly pure iron, prepared by chemical decomposition of purified iron pentacarbonyl. It is
commonly used in electronics for the production
of the magnetic high-frequency coils and as a component of the radar-absorbing materials. Carbonyl
iron is also used in powder metallurgy and in pharmaceutics for treating iron deficiency and as an
iron dietary supplement. If bought in bulk, the
price may be significantly smaller than 5 USD per
1 kg [14].
Synthesis of the alginate beads with simultaneous
sorption of the radionuclides
Magnetic calcium alginate (MS) beads were
prepared by the following procedure [15]: homogenous sodium-alginate solution with a concentration of 0.02 g/mL was prepared. Different amounts
of the carbonyl iron were added to the sodium-alginate solution and the suspension was stirred for
90 min in room temperature. Obtained homogenous solution, constantly stirred, was dropped using a peristaltic pump into the aqueous solution
of the radionuclides after the addition of calcium
chloride (CaCl2; different amounts). Stirring of the
solution containing the synthesized grains of sorbent was continued for 2 h.
33
Initial and equilibrium radioactivity concentrations [Bq/L] (quotient of the activity of a material
and the volume of this material) of the radionuclides in the solutions were determined radiometrically using a Perkin Elmer 2480 Wizard2® Automatic Gamma Counter.
In the following, results of our studies were
presented in terms of decontamination factor, YM
(ratio of activity prior to and after the decontamination of radioactively contaminated objects,
wastewater, air, etc. [16]).
Effect of the calcium chloride concentration
In the present study, prior to the combined gelation-sorption process, calcium chloride has been
added in the concentrations ranging from 5 g to
25 g per each litre of the decontaminated solution.
Obtained values of decontamination factor for
caesium(I), strontium(II), europium(III) and americium(III) radionuclides are presented in Fig.1.
It can be seen that for all metals studied, YM
does not depend significantly on the calcium chloride concentration. These values are about 100, 72
and 29% for americium(III), europium(III) and
strontium(II), respectively, while the lack of sorption for caesium(I).
Effect of the iron concentration
Obtained values of decontamination factor for
caesium(I), strontium(II), europium(III) and americium(III) radionuclides for different amounts of
iron added are presented in Fig.2. In the present
study, calcium chloride has been added in the
constant amount of 25 g per each litre of the decontaminated solution.
Fig.1. Effect of the calcium chloride concentration on the decontamination factors for the radionuclides sorbed by the
magnetic alginate spheres.
34
Fig.2. Effect of iron concentration in the sodium-alginate solution on the decontamination factors for the radionuclides
sorbed by the magnetic alginate beads.
Fig.3. Effect of pH on the decontamination factors for the radionuclides sorbed by the magnetic alginate spheres.
35
Table 1. Thermal decomposition of the composite sorbent.
T [oC]
30
50
100
150
200
250
300
400
450
500
600
700
800
900
M [%]
100
99.7
96.5
93.1
90.4
76.8
64.2
55.0
50.7
48.6
36.5
30.1
29.7
29.2
It can be seen that for all metals studied, YM
does not depend significantly on the amount of
the iron added and are similar to these mentioned
above. It means that the magnetic characteristic of
the obtained MS, which depends on the amount
of iron present in the inner core, is the main limit
of the procedure.
Effect of the acidity of the aqueous solution
The initial acidity of the solution is one of
the decisive factors determining the efficiency of
metal uptake from aqueous solutions. It affects
both surface of the sorbent and speciation of the
metal ion in solution which, additionally, depends
on the concentration of the metal. To study the
acidic dependence of sorption, pH was adjusted
in the range from about 1.5 to about 7. The results are presented in Fig.3. It can be seen that
uptake of the metals oscillates slightly around the
plateau being 99.9 ±0.2% for americum(III), 74.0
±1.6% for europium(III), 32.2 ±3.7% for strontium(II), while caesium(I) is not sorbed within the
whole range of the acidity.
Thermogravimetric studies of the sorbent
Performing thermal analyses were important
taking into account that in the industrial processes, heat is commonly used, and the thermal
decomposition of MS may yield a decreased solid
radioactive waste mass. It is a textbook knowledge that organic matter breaks down into small
molecular components if heated and does not recombine on cooling. Carbon dioxide, carbon monoxide and steam, with small quantities of acids,
aldehydes and volatile solids, are found as main
thermal decomposition products of the carbohydrates [17].
For this purpose, thermogravimetric studies
have been performed in the temperature range of
20-950oC. Raw material of the sorbent has been
studied. Table 1 presents main results obtained. It
can be seen that total mass loss of the sorbent is
about 70%; however, already in temperatures below 450oC, the sorbent loses about 50% of its mass.
The analysis of the pattern of the metal uptake,
as well as more results, will be published soon.
Conclusions
One-step procedure for the decontamination of
the radioactive wastes applying calcium alginate
with the magnetic inner-core from the iron carbonyl
was found to be effective for the solutions containing americium(III), europium(III) and strontium(II)
radionuclides. The purification efficiency depends
on the cation charge.
The magnetic sorbent is sufficiently stable to
have practical application in the treatment of wastewaters, and its mass, when the radionuclide was
loaded, can be diminished by heating below 450oC.
[2].
[3].
[4].
[5].
[6].
[7].
[8].
[9].
[10].
[11].
[12].
[13].
References
[14].
[1]. Council Directive 2013/51/EURATOM of 22 October 2013 laying down requirements for the protec-
[15].
tion of the health of the general public with regard
to radioactive substances in water intended for human consumption. Official Journal of the European
Union, L296/12. Retrieved 25 January 2016, from
http://eur-lex.europa.eu/legal-content/EN/TXT/
?uri=CELEX%3A32013L0051.
Song, W., Xu, X., Tan, X., Wang, Y., Ling, J.Y., Gao,
B.Y., & Yue, Q.Y. (2015). Column adsorption of perchlorate by amine-crosslinked biopolymer based
resin and its biological, chemical regeneration properties. Carbohyd. Polym., 115, 432-438.
Kalaivani, S.S., Vidhyadevi, T., Murugesan, A., Thiruvengadaravi, K.V., Anuradha, D., Sivanesan, S., &
Ravikumar, L. (2014). The use of new modified
poly(acrylamide) chelating resin with pendent benzothiazole groups containing donor atoms in the
removal of heavy metal ions from aqueous solutions.
Water Resour. Ind., 5, 21-35.
Kabiri, S., Tran, D.H.N., Aitalhi, T., & Losic, D.
(2014). Outstanding adsorption performance of graphene-carbon nanotube aerogels for continuous oil
removal. Carbon, 80, 523-533.
Schiewer, S. & Volesky, B. (1995). Modelling of the
proton-metal ion exchange in biosorption. Environ.
Sci. Technol., 29, 3049-3058.
Banerjee, A., & Nayak, D. (2007). Biosorption of
no-carrier-added radionuclides by calcium alginate
beads using ‘tracer packet’ technique. Bioresource
Technol., 98, 2771-2774.
Zhou, Y.-T., Nie H.-L., Branford-White, C., He, Z.-Y.,
& Zhu, L.-M. (2009). Removal of Cu2+ from aqueous solution by chitosan-coated magnetic nanoparticles modified with alpha-ketoglutaric acid. J. Colloid
Interface Sci., 330, 29-37.
Huang, G., Yang, C., Zhang, K., & Shi, J. (2009). Adsorptive removal of copper ions from aqueous solution using cross-linked magnetic chitosan beads.
Chinese J. Chem. Eng., 17, 960-966.
Tran, H.V., Tran, L.D., & Nguyen, T.N. (2010). Preparation of chitosan/magnetite composite beads and
their application for removal of Pb(II) and Ni(II) from
aqueous solution. Mater. Sci. Eng. C, 30, 304-310.
Monier, M., Ayad, D.M., Wei, Y., & Sarhan, A.A.
(2010). Preparation and characterization of magnetic chelating resin based on chitosan for adsorption of Cu(II), Co(II), and Ni(II) ions. React. Funct.
Polym., 70, 257-266.
Wang, J.-S., Peng, R.-T., Yang, J.-H., Liu, Y.-C., & Hu,
X.-J. (2011). Preparation of ethylenediamine-modified
magnetic chitosan complex for adsorption of uranyl
ions. Carbohyd. Polym., 84, 1169-1175.
Hu, X.-J., Wang, J.-S., Liu, Y.-G., Li, X., Zeng, G.-M.,
Bao, Z.-l., Zeng, X.-X., Chen, A.-W., & Long, F.
(2011). Adsorption of chromium (VI) by ethylenediamine-modified cross-linked magnetic chitosan resin:
Isotherms, kinetics and thermodynamics. J. Hazard.
Mater., 185, 306-314.
Jang, L.K., Geesey, G.G., Lopez, S.L., Eastman, S.L.,
& Wichlacz, P.L. (1990). Use of gel-forming biopolymer directly dispensed into a loop fluidized bed reactor to recover dissolved copper. Water Res., 24,
889-897.
http://www.alibaba.com/showroom/carbonyl-ironpowder.html.
Ani, I., Nur, S.M.I., Nursia, H., Effaliza, M., & Ngomsik, A.-F. (2012). Synthesis of magnetic alginate beads
36
based on maghemite nanoparticles for Pb(II) removal in aqueous solution. J. Ind. Eng. Chem., 18,
1582-1589.
[16]. European Nuclear Society. Decontamination factor.
Retrieved January 25, 2016, from https://www.euro-
nuclear.org/info/encyclopedia/d/decontaminationfactor.htm.
[17]. Puddington, I.E. (1948). The thermal decomposition
of carbohydrates. Can. J. Res., Sect. B, 26, 415-431.
PREPARATION OF URANIUM CARBIDE
BY THE COMPLEX SOL-GEL PROCESS
Marcin Rogowski, Marcin Brykała, Danuta Wawszczak, Wiesława Łada, Tadeusz Olczak,
Andrzej Deptuła, Tomasz Smoliński, Patryk Wojtowicz
The main goal of the Institute of Nuclear Chemistry and Technology (INCT) which works on the
synthesis of uranium carbide (UC) by the complex sol-gel process (CSGP) was to use ascorbic
acid (ASC) as a carbon substrate for carbide materials [1, 2]. In the CSGP method, ascorbic acid
is a complexing agent and occurs in sol and gels’
particles. So if the conditions of thermal treatment are chosen accordingly, it will be possible to
engage ascorbic acid to produce uranium carbide.
In short, the processes leading from the gel stage
to uranium carbide can be presented as follows:
T, inert atmosphere
[UO3-ASC]gel  UO2-x-C
Ar / H 2
T, vacuum or Ar

 UO2-C 
 UC
The gel sample (molar ratio UO3:ASC 1:0.82)
was thermally treated. First, it was carbonized at
T = 700oC in Ar/5% H2 to UO2-C and then it
underwent carbothermic reduction in vacuum at
T = 1600oC. It results from the X-ray diffraction
(XRD) analysis that the main product was uranium carbide with an additional UO phase. No
phases with higher contents of carbon and oxygen were detected. In addition, a series of sols in
which the molar ratio of UO3 to ASC were from
1:0.9 to 1:1.9 was produced. For sols with a molar
ratio  1.5, ammonia was added to pH  3.75, in
order to eliminate the gels’ tendency to form a hard
crust. The dried microspheres of gels are spherical with dense surface. Below, there are examples
of the scanning electron microscopy (SEM) pictures of gels with varying scope UO3:ASC (Figs.1
and 2).
Microspheres with molar ratio up to 1.3 look similar. In Fig.1A,B,D there are visible bright areas on
the particle surface. The reasons for that are electric charges, even though the samples consisted
A
B
C
D
Fig.1. SEM images of dried uranyl-ascorbate gels. Different UO3:ASC molar ratio: halved particle 1:0.9 (A), 1:1.1 (B),
halved particle 1:0.82 (C), 1:1.3 (D).
B
A
A
37
B
C
Fig.2. SEM images of dried uranyl-ascorbate gels. Different UO3:ASC molar ratio: 1:1.5 (A), 1:1.7 (B), 1:2 (C).
of sputtered carbon. The surface of the microspheres is usually smooth. But for a higher content of ascorbic acid (Fig.1D), a significantly noticeable deterioration of the particle quality may
be observed. There are numerous cracks and delaminations. In the case of gels containing ammonia (Fig.2A), the particle surface is smoothed
and worsened again, at yet a higher content of ascorbic acid (Fig.2B). There are also visible dimples
on the surface, whose image resembles a golf ball
(Fig.2C).
Obviously, the appearance and shape of gel particles in a large extent determine the appearance
of particles after the heat treatment.
Powders of gels were reduced in the furnace
(Nabertherm VHT series) to obtain uranium carbide in one cycle. Figure 3 shows a programme of
a thermal process for preparing uranium carbide.
In the beginning, powders of gels were carbonized
by heating them in argon up to 300oC (1.5oC·min–1)
and then up to 900oC (3oC·min–1). Afterwards, atmosphere was shifted to the mixture Ar+5% H2
Fig.3. Programme of thermal treatment of uranyl-ascorbate gels.
38
Fig.4. Powders after thermal treatment of uranyl-ascorbate gels with different UO3:ASC molar ratio.
and being held for 4 h. The obtained mixture of
UO2-C was then heated in vacuum up to 1400oC
(5oC·min–1). The carbothermic reduction towards
most all the microspheres were externally and internally cracked (Fig.5); perhaps because the heating rate for these samples was too high. For the
sample 1:1.3 (Fig.5D), the obtained particles had
most cracks (Fig.1D).
For the samples 1:0.82 and 1:0.9, there are clearly
visibly shaped large crystallites of size 0.5-4 m
(Fig.6A,B). For the remaining samples, meaning
those with a higher carbon content, the crystallites are smaller, have a size lower than 100 nm
and are not clearly separated (Fig.6C).
Samples for the XRD analysis were coated with
silicone immediately after the removal from the
furnace. This was a protection from oxidation and
moisture. The results of the analysis revealed low
levels of UO2 (database: JCPDS 41-1422) in the
1:0.9 sample, probably formed during the prepara-
A
B
C
D
E
F
Fig.5. SEM images of microspheres after carbothermic reduction. Different UO3:ASC molar ratio: 1:0.82 (A), 1:0.9 (B),
1:1.1 (C), 1:1.3 (D), 1:1.5 (E), 1:1.7 (F).
final UC was carried out for 4 h in vacuum (0.2
mbar). Cooling of the samples took place in a
vacuum at a rate 10oC·min–1. Loose, dark-grey
powders were obtained (Fig.4) and then were
analysed by the SEM and the XRD techniques.
The SEM analysis reveals some differences in
morphology of particles. It should be noted that
the microspheres are partially destroyed during
sample’s preparation for the analysis. That means
their strength is not very high. Unfortunately, al-
A
B
tion of the sample for analysis. Significant amount
of UO2 was observed for the sample 1:0.82, which
indicates an insufficient carbon amount during the
carbothermic reduction. For samples with a molar
ratio higher than 1:1.1, only UC (JCPDS 09-0214)
and UC2 (JCPDS 06-0372) were detected. Also,
the UC2 amounts increased with increasing molar
ratio of UO3:ASC. In Fig.7, examples of diffractograms on a 2-theta scale for different samples of
UO3:ASC are shown.
C
Fig.6. SEM images of microspheres after carbothermic reduction. Different UO3:ASC molar ratio: 1:0.82 (A), 1:0.9 (B),
1:1.5 (C).
39
A
B
C
D
Fig.7. XRD diffractograms of samples after carbothermic reduction. Different UO3:ASC molar ratio: 1:0.82 (A), 1:0.9 (B),
1:1.1 (C), 1:1.7 (D).
40
The XRD results indicate that the proper
amount of ascorbic acid to UO3 for UC synthesis
is in the range 1:0.9-1.0.
References
[1]. Brykała, M., & Rogowski, M. (2015). Sposób wytwarzania węglika uranu o ziarnach sferycznych i nieregu-
larnych jako prekursora paliwa do reaktorów nowej,
IV generacji. Polish Patent Application P-414768.
[2]. Brykala, M., Rogowski, M., & Olczak, T. (2015). Carbonization of solid uranyl-ascorbate gel as an indirect
step of uranium carbide synthesis. Nukleonika, 60, 4,
921-925.
RESEARCH TOWARDS A NEW REPOSITORY
FOR LOW- AND INTERMEDIATE-LEVEL RADIOACTIVE WASTE
IN POLAND
Agnieszka Miśkiewicz, Grażyna Zakrzewska-Kołtuniewicz, Wioleta Olszewska, Leszek Lankof1/,
Leszek Pająk1/
1/
The Mineral and Energy Economy Research Institute, Polish Academy of Sciences, Kraków, Poland
The issue of radioactive waste management appeared in Poland in 1958, when the first research
reactor was put into operation at the Institute for
Nuclear Research in Świerk. Since then, there has
been a large increase of applications of radioactive isotopes in different areas of science and industry. All those activities generate a waste, which
requires special handling (collection, processing,
solidification, transportation, storage and disposal).
Radioactive waste of low and medium activity,
produced in Poland, is collected, processed, solidified and prepared for disposal by the state-owned
public utility – Radioactive Waste Management
Plant (RWMP). Subsequently, the waste is disposed
in the National Radioactive Waste Repository
(NRWR) in Różan site. The repository is a near-surface disposal site dedicated for processed
short-lived, low- and intermediate-level radioactive waste and sealed radioactive sources.
The amount of all waste collected in Poland
every year is relatively not big; for example, in 2010,
the total collected volume of stable waste was
51.3 m3 and 36.1 m3 of liquid radioactive waste.
Low-level waste (LLW) constituted a volume of
87 m3, while small amount of intermediate-level
waste (ILW) and alpha radioactive constituted
about 1.1 m3. In addition, 17 500 smoke sensors
and 5300 sealed radioactive sources were collected. All this radioactive waste after the selection
and preparation were placed in containers and, in
this form, were disposed in Różan repository.
According to the present expectations, this repository is foreseen to be completely filled by
2025. Therefore, Poland faces the challenge of
choosing a location for the new surface disposal
site for low- and intermediate-level radioactive
waste.
Issues related to the new repository are, among
other topics concerning the radioactive waste management, discussed in recently developed document entitled “The National Plan of Radioactive
Waste and Spent Nuclear Fuel Management”. This
document has been prepared in accordance with
the provisions of the Atomic Law Act, as well as
the guidelines to the Council Directive 2011/70/
Euratom of 19 July 2011, establishing Community
frameworks in regard to responsible and safe
management of spent nuclear fuel and radioactive waste. The national plan is a result of cooperation between several institutions involved in
the management of radioactive waste and spent
nuclear fuel, also considering experiences of other
countries.
According to this plan, there is a need to build
a new surface repository taking into account the
needs arising from the development of the Polish
Nuclear Power Programme. It is planned that the
new repository will be put into operation after
2024 and will be operated by the year 2144. This
repository will accumulate low- and intermediate-level short-lived waste originating from their
applications in medicine and industry and, in the
case of the introduction of the Polish Nuclear
Power Programme, the waste produced during the
operation of nuclear power plants (NNPs). The
amounts of waste of various applications estimated according to “The National Plan of Radioactive
Waste and Spent Nuclear Fuel Management” are
shown in Table 1.
The issue of a new repository is also the objective of the research project entitled “Study the
Table 1. The projected amounts of short-lived low- and intermediate-level waste for storage at new repository.
Waste source
Volume of waste by 2050
[m3]
Volume of waste by 2144
[m3]
From two NPP operation
16 500
54 000
From decommissioning of two NPP
N.A.
67 500
From medical and industrial application
1 520
12 000
From decommissioning of Maria research reactor
and research laboratories
1 595
20 000
methodology to evaluate the safety and identifying the optimal location for surface repository for
low and intermediate level waste” carried out by
consortium consisting of research institutes (Polish
Geological Institute-National Research Institute
– PGI-NRI; Institute of Geophysics of the Polish
Academy of Sciences – IGF PAS; the Mineral and
Energy Economy Research Institute of the Polish
Academy of Sciences – MEERI PAS; Institute of
Nuclear Chemistry and Technology – INCT), geological company – Geoprojekt Szczecin Ltd. and
Radioactive Waste Management Plant. The main
objective of the project is to select the optimal
location for the surface repository. Implementing
this target must be preceded by many intermediate
steps, which include:
• the preparation of projects of geological works;
• field tests;
• the development of numerical models of the
2D layer system in order to simulate the migration of radionuclides in the geological environment for different scenarios of releases;
• monitoring project of the future repository,
taking into account the specificity of location;
• geological-engineering documentation for each
of the three locations.
Finally, for the optimal location, methodology
for the safety assessment will be proposed.
Radionuclides, constituents of the waste stored
in the repository, may move into the aquatic environment as a result of the natural evolution of the
environment and the slow degradation of barriers.
3
H, 60Co, 90Sr, 137Cs – due to their activity, radiotoxicity and mobility in the environment – and
the half-life, represent a group of significant radionuclides that should be taken into account when
safety case for the surface repository is elaborated.
As was mentioned above, in the new repository in
Poland, waste from NPP will also be stored; however, in this moment, neither the technology nor
the type of the first NPP in Poland was selected
yet. From this reason, to assess a safety of the repository, it is necessary to make simulations with
assumptions based on the available literature data.
When assessing the activity of radioactive waste
delivered to the new repository, as an example,
waste from the economic simplified boiling water
reactor (ESBWR) from GE Hitachi was used [1].
A list of the dominant radionuclides for the ESBWR
reactor is given in Table 2.
According to this list, the group of significant
radionuclides stored in the surface repository
41
should also include 134Cs and 51Cr. However, taking into account relatively short half-life of the
51
Cr, this nuclide will have no impact on the total
activity of potential effluents from the repository
during the operation and after its closure.
In addition to the type and activity of radionuclides, the exposure associated with the possible
release to the environment will depend on rate of
their release and the rate of migration in the environment. The parameter which allows estimating
the possibility of migration of a particular radionuclide in aqueous solution in contact with the
solid phase in the surroundings of radioactive
waste repository is the partition coefficient (Kd).
Due to the variety of parameters that affect
the migration of radionuclides, which include: the
nature of the soil and suspended particles, mutual
impact of radionuclides and other contaminants,
sorption/desorption processes, bacteriological activity, physicochemical properties of groundwater
and the half-life of the radionuclides, the use of
partition coefficient in models of transport of radionuclides is always some estimation [2]. Therefore, for more thorough calculations, it is preferable to determine the Kd values for the particular
type of soil in the laboratory or field, but such
tests are very time consuming.
Partition coefficient is defined as the ratio of
equivalent concentrations of the studied component in the two-phase system: a sorbent (soil)-the
aqueous phase (ground water):
Kd 
Cs
Cw
where Cs is a concentration of compound adsorbed per unit of sorbent (soil) [mol/kg] and Cw
is a concentration of compound in the liquid
phase at equilibrium [mol/L].
Thus, the Kd is associated with the distribution
of the compound between the solid and the aqueous phase. There are several methods used to determine the Kd value, which include laboratory
methods, methods based on measurements in the
field (in situ) and computational methods. Each
of these methods has advantages and disadvantages, as well as a set of assumptions to calculate
the Kd values based on experimental data. Therefore, it is expected that the Kd values measured by
various methods can be different. The values of Kd
for the group of radionuclides dominated in the
waste, which will be stored in the surface repository of radioactive waste, are given in Table 3.
Table 2. Dominant radionuclides in solid waste from ESBWR type reactor.
Half-life
of radionuclide
Energy
[keV]
Activity in the ESBWR reactor
[Bq]
The fraction of total activity
of solid waste
[%]
Cr
27.7 d
5, 320 ()
503  106
20.4
Co
5.3 y
318 (),
1173, 1333 ()
325  106
13.2
Cs
30.1 y
512 (),
662 ()
130  106
5.3
Cs
2.06 y
658 ()
38.2  106
1.5
Radionuclide
51
60
137
134
42
Table 3. Value of Kd for different type of soil, determined using different methods.
Radionuclide
The range of Kd [L/kg]
H
0 [3]
Kd [L/kg]
sand
silt
7 [4]
3
0 [5]
26 [4]
0.04 [6]
Cr
51
Co
60
clay
4 [4]
0 [5]
1.7-1 729 [6]
1 000 [3]
0.07-9 000 [6]
60 [4]
1 300 [4]
550 [4]
20 [3]
15 [4]
0.05-190 [6]
27 [5]
134
200 [3]
0.2-10 000 [6]
70 [7]
160 [5]
400 [7]
5 000 [5]
137
200 [3]
0.2-10 000 [6]
70 [7]
160 [5]
400 [7]
5 000 [5]
90
Sr
Cs
Cs
There are many issues to consider when measuring Kd values and in selecting these values from
the literature, among others, choice of simple or
more complex test systems, the variability of site
conditions (soil), issues related to the content of
gravel or creation of colloids. Crawford et al. [8]
summed up the uncertainty in the measurements
of the Kd values using the data in the literature.
These include the reasons for the uncertainty of the
Kd values, such as random errors, mineralogical
variability of soil samples, the methodological defects of measurement and interpretation of results
and the uncertainty associated with specific hydrological and geochemical conditions (difficulty in
determining the actual flow path and the type of
rocks encountered during water flow by fractured
rock). Consequently, the properties of the material
are averaged, and therefore, the resulting Kd values
are subject to have burdened with some errors. In
addition, the state of geochemical parameters in
the future cannot be accurately determined due to
the temporary effects of the flow.
The issue of migration of radionuclides has
been the subject of research conducted at the
Fig.1. Discretization scheme with area location in the coordinate system and the boundary conditions of the model [9].
20 [4]
110 [4]
300 [5]
INCT, and some of the results have been published [9]. The aim of studies was a simulation of the
migration of radionuclides in environment, near
the radioactive waste repositories. The example
of radionuclide migration in geosphere concerns
hypothetical release of radionuclide in saturated
porous media from a constant source. The computational abilities of TOUGH2 simulator was a
subject of the work. Simulator uses finite differential method for multiphase and multicomponent modelling in porous and fractured media in
unstable conditions [10]. Discretization scheme,
area localization in the coordinate system and the
boundary conditions of the model are shown in
Fig.1.
Two types of geological formations were distinguished in the modelled area – the permeable
and impermeable ones. The numeric calculations
were carried out for isothermal conditions using
the module (Equation of State) EOS7R intended
for modelling the transport of radionuclides in geological media. In the study, the migration of 137Cs
radionuclide was modelled. Caesium radionuclide
source was located approximately in the centre of
the modelled area (Fig.1). The source generates
parallel radionuclides and water. The rate of source
is 0.1 kg of caesium per year and 10 kg of water
Fig.2. The range of isosurface of 10–9 mass fraction concentration of 137Cs after 100 years from the beginning of radionuclide release from the source and groundwater flow rate.
per hour. Parallel generation of radionuclides and
water simulates permeation of contaminated leachate into saturated geological formation.
In Figs.2 and 3, the calculation results of the
contamination propagation after 100 years are presented. The extent of caesium contamination plum
of 10–9 mass fraction concentration ranges up to
500 m in 100 years.
Fig.3. The concentration of 137Cs mass fraction after 100
years from the beginning of radionuclide release from the
source.
The aim of the calculations was to test the
computational capabilities of the TOUGH2 simulator used for modelling radionuclide contamination propagation in the geological environment
taking into account the decay of radionuclides in
time.
Despite the simplicity of the model, the presented problem confirms the possibility of using
this software for modelling complex, three-dimensional issues related to the subject.
References
[1]. Energoprojekt Warszawa. (2013). Wariantowa koncepcja programowo-przestrzenna składowiska odpadów promieniotwórczych. Unpublished report, Warszawa.
43
[2]. Krupka, K.M., Kaplan, D.I., Whelan, G., Serne, R.J.,
& Mattigod, S.V. (1999). Understanding variation
in partition coefficient, Kd, values. Review of geochemistry and available Kd values for cadmium,
cesium, chromium, lead, plutonium, radon, strontium,
thorium, tritium (3H), and uranium. United States
Environmental Protection Agency, Office of Air and
Radiation Protection, 341 p. (EPA 402-R-99-004B).
[3]. Nair, R.N., & Krishnamoorthy, T.M. (1999). Probabilistic safety assessment model for near surface radioactive waste disposal facilities. Environ. Model.
Softw., 14, 447-460.
[4]. Heuel-Fabianek, B. (2014). Partition coefficients (Kd)
for the modelling of transport processes of radionuclides in groundwater. Julich: Forschungszentrum
Jülich, 51 p. (Berichte des Forschungszentrums Julich
4375).
[5]. Generic repository studies. Generic post-closure performance assessment. (2003). Harwell, UK: United
Kingdom Nirex Limited, 225 p. (Nirex Report no.
N/080).
[6]. Sheppard, M.I., & Tibault, D.H. (1990). Default soil
solid/liquid partition coefficients, Kds, for four major soil types: a compendium. Health Phys., 59(4),
471-482.
[7]. Schwartz, M.O. (2012). Modelling groundwater contamination above a nuclear waste repository at Gorleben, Germany. Hydrogeol. J., 20, 533-546.
[8]. Crawford, J., Neretnieks, I., & Malmström, M. (2006).
Data and uncertainty assessment for radionuclide
Kd partitioning coefficients in granitic rock for
use in SR-Can calculations. Swedish Nuclear Fuel
and Waste Management Co., 117 p. (SKB Rapport
R-06-75).
[9]. Olszewska, W., Miśkiewicz, A., Zakrzewska-Kołtuniewicz, G., Lankof, L., & Pająk, L. (2015). Multibarrier system preventing migration of radionuclides
from radioactive waste repository. Nukleonika, 60, 3,
557-563.
[10]. Pruess, K., Oldenburg, C., & Moridis, G. (2012).
TOUGH2 user’s guide, Version 2. Berkeley, California: Earth Sciences Division, Lawrence Berkeley National Laboratory, University of California, 197 p.
TACRINE DERIVATIVE LABELLED WITH 68Ga FOR PET DIAGNOSIS
Ewa Gniazdowska, Przemysław Koźmiński, Elżbieta Mikiciuk-Olasik1/, Paweł Szymański1/,
Katarzyna Masłowska2/
1/
Medical University of Łódź, Department of Pharmaceutical Chemistry, Drug Analyses
and Radiopharmacy, Łódź, Poland
2/
University of Warsaw, Faculty of Physics, Warszawa, Poland, on leave
Tacrine (1,2,3,4-tetrahydro-9-acridinamine – TAC)
is an oral medicament used to treat patients with
Alzheimer’s disease (AD) – the most common
form of dementia. There is no cure for this disease
and worsens as it progresses leading to death [1, 2].
Tacrine belongs to the class of drugs which are
cholinesterase inhibitors [3, 4]. Cholinesterase inhibitors inhibit the action of acetylcholinesterase
(AChE), the enzyme responsible for the degeneration of acetylcholine. Acetylcholine is one of
several neurotransmitters in central nervous system (CNS) – chemicals which nerve cells use to
communicate with one another. Reduced level of
acetylcholine in the brain is believed to be responsible for some of the symptoms of AD. By block-
ing the enzyme that hydrolyses acetylcholine, the
concentration of acetylcholine in the brain increases, resulting in the improvement in thinking
and alleviation of the clinical symptoms of the
disease [5, 6]. Tacrine in the form of monohydrochloride was the first drug approved by the United
States Food and Drug Administration in 1993 for
palliative treatment of AD. Tacrine and its analogues labelled with diagnostic radionuclide (e.g.
125
I, 11C) were also studied from the point of view
of their application as potential diagnostic agent
able to define the specific site of action in the
brain [7, 8]. However, the use of tacrine is limited
due to its significant incidence of hepatotoxicity,
cardiovascular system impairment and mild cogni-
44
The coupling reactions between DOTA-NHS
(1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid mono-N-hydroxysuccinimidyl ester)
and the three tacrine derivatives were performed
tive benefits, but does not alter the course of the
disease [9]. Therefore, the search for new tacrine
analogues is still of interest for scientists involved
in AD research [10, 11].
O
HO
O
N
N
OH
N
N
O
A)
A
BB)
NH2
HN
(CH2)n
N
a: n=7
b: n=8
c: n=9
O
O
N
68
N
O
Ga
O
N
O
O
C)
C
NH
(CH2)n
HN
N
(CH2)n
N
DOTA-TACd
2a-2c.
NH2(CH2)nTAC
1a-1c.
N
OH
NH
HN
O
HO
68Ga-DOTA-TACd
3a-3c.
Fig.1. A – Structure of tacrine derivatives containing different number of CH2 groups (n = 7-9) in aliphatic chain, B –
structure of DOTA-tacrine derivatives, C – structure of 68Ga-DOTA-TACd radioconjugates.
The aim of this work was to synthesize three
radioconjugates (Fig.1C, Table 1) containing the
68
Ga-DOTA complex and different tacrine derivatives (TACd, Fig.1A, Table 1) as the biologically
active molecules. The choice of the radioconjugate with the highest lipophilicity (blood-brain
barrier can be crossed by compounds of sufficiently high lipophilicity [12]) and the determination
of physicochemical properties of this radioconjugate are important from the radiopharmaceutical
point of view [13]. The tacrine derivatives used in
syntheses contained in aliphatic chain: seven CH2
groups (n = 7, TACd-7), eight CH2 groups (n = 8,
TACd-8) and nine CH2 groups (n = 9, TACd-9).
It was expected that TACd labelled with 68Ga may
serve as a diagnostic receptor radiopharmaceutical, used in PET method, for the diagnosis of AD
at the very early stage of the disease.
in DMF at 50oC and in the presence of Et3N
(Scheme 1). The molar ratio of the reagents used
in the coupling reactions was 1.3:1:4, respectively.
Crude DOTA-TACd-n products (Fig.1B, Table 1)
were purified on a semi-preparative HPLC column
and lyophilized, with the yield  85%.
MS of DOTA-TACd-4: m/z: calcd. – 697.88, found
– 698.46 [M+H+].
– 712.49 [M+H+].
– 726.47 [M+H+].
The 68Ga-DOTA-TACd radioconjugates (Table
1) were synthesized according to the following
procedure: to the vial containing about 50 g of
lyophilized DOTA-TACd, 300 L of acetate buffer
(pH = 5.89) and 50100 L of concentrated solution of 68GaCl3 from the 68Ge/68Ga generator
Table 1. Physicochemical properties of synthesized conjugates and radioconjugates.
MS analyses
Compound
RT [min]
Mw calcd.
[g/mol]
Mw found [M + H+]
[g/mol]
log P
TACd-7
11.78
311.5
−
−
TACd-8
12.36
325.5
−
−
TACd-9
13.01
339.3
−
−
DOTA-TACd-7
11.45
697.88
698.46
−
DOTA-TACd-8
12.04
711.91
712.49
−
DOTA-TACd-9
12.60
725.93
726.47
−
68
Ga-DOTA-TACd-7
12.26
−
−
-2.52 ±0.01
68
Ga-DOTA-TACd-8
12.62
−
−
-2.02 ±0.01
68
Ga-DOTA-TACd-9
13.20
−
−
-1.52 ±0.01
13.10
793.6
794.37
−
Ga-DOTA-TACd-9
45
O
NH2
N
O
O
HO
O
N
N
N
N
OH
O
O
OH
HN
(CH2)n
HO
+
(CH2)n
HN
O
N
N
N
N
N
O
OH
N
N
H
O
+
HO
N
O
O
O
OH
O
Scheme 1. Coupling reaction of DOTA with tacrine derivatives.
(70100 MBq) were added. The reaction mixture
was heated for 30 min at 95oC, and the reaction
progress was checked by HPLC method. The radiochemical yield of the synthesized conjugate was
higher than 98%.
In order to verify the identity of the 68Ga-DOTA-TACd-9 radioconjugate synthesized in n.c.a. scale,
the non-radioactive reference compound – the
Ga-DOTA-TACd-9 conjugate – was prepared in
milligram scale, isolated by HPLC method and
characterized by MS analysis (Table 1).
MS of Ga-DOTA-TACd-9: m/z: calcd. – 793.6,
found – 794.37 [M+H+].
The lipophilicity of 68Ga-DOTA-TACd-n radioconjugates isolated from the reaction mixture
(using HPLC method) was characterized by the
determination of the logarithms of their partition
coefficients, log P, in the n-octanol/PBS (pH 7.40)
system (Table 1). The stability of the chosen
68
Ga-DOTA-TACd-9 isolated radioconjugate was
investigated both as a function of time and in
challenge experiments (in the presence of excess of
histidine or cysteine), as well as in human serum
and cerebrospinal fluid.
Conditions of HPLC system were the following: Phenomenex Jupiter Proteo semi-preparative
column (4 m, 90 Å, 250  10 mm), UV/Vis detector (220 nm); elution conditions: solvent A –
water with 0.1% TFA (v/v), solvent B – acetonitrile with 0.1% TFA (v/v); gradient – 0-20 min
20% to 80% of solvent B, 20-35 min 80% solvent
B; 2 mL/min.
The HPLC chromatograms of the compounds
DOTA-TACd-9 (UV/Vis detection, RT = 12.60
Fig.2. The HPLC analyses of the reaction mixtures after
the synthesis of DOTA-TACd-9 (A), 68Ga-DOTA-TACd-9
(B) and Ga-DOTA-TACd-9 (C) compounds prepared in
this study.
min), 68Ga-DOTA-TACd-9 (gamma detection, RT
= 13.20 min) and Ga-DOTA-TACd-9 (UV/Vis
detection, RT = 13.10 min), synthesized in this
study, are shown in Fig.2. The conjugate 68Ga-DOTA-TACd-9 was formed with high yield and
purity. The non-radioactive reference conjugate
Ga-DOTA-TACd-9 isolated from the reaction mixture was characterized by MS. Almost the same
RT values of 68Ga-DOTA-TACd-9 and Ga-DOTA-TACd-9 conjugates confirmed the existence in
n.c.a. scale of the 68Ga-DOTA-TACd-9 conjugate
in the reaction mixture.
The determined lipophilicity values of 68Ga-DOTA-TACd-n radioconjugates increased with
increasing number of CH2 groups (from 7 to 9) in
the aliphatic chain and were in the range from
-2.52 to -1.52 (Table 1), which indicates hydrophilic character of the designed compounds. However, the log P values of 68Ga-DOTA-TACd-n radioconjugates can be easily modified using macrocyclic ligand DOTA in the form of the DOTA-tris(tBu)ester.
The studied 68Ga-DOTA-TACd-9 conjugate exhibited high stability. After about 5 h of incubation
in 10 mM histidine or cysteine solution or in human serum, as well as in cerebrospinal fluid, the
obtained HPLC chromatograms have shown mainly the existence of only one radioactive species in
the solution, with the retention time characteristic
for the studied radioconjugate. Thus, we can consider that the 68Ga-DOTA-TACd-9 radioconjugate
does not undergo the ligand exchange reactions
with amino acids or other strongly competing
natural ligands containing SH or NH groups. In
the case of studies on stability in human serum
and in cerebrospinal fluid, the protein components were precipitated using ethyl alcohol and
the radioactivity of both the supernatant and precipitate (protein) fractions was measured. 68Ga-DOTA-TACd-9 conjugate showed to be stable
also in human serum and cerebrospinal fluid – the
percentage of 68Ga-DOTA-TACd-9 conjugate,
which has been bound by the serum or by cerebrospinal fluid components, was in the range of
2-10%, while about 90% of the studied conjugate
remained in the liquid phase in unchanged form.
In conclusion, one can say that the physicochemical properties of the 68Ga-DOTA-TACd-9
conjugate can be an important basis for further
consideration of this conjugate as a potential diagnostic radiopharmaceutical. From the viewpoint of application in nuclear medicine, it is important to note that the 68Ga-DOTA-TACd-n
conjugates can be easily synthesized in hospital
46
laboratories using previously prepared lyophilized
kit formulations and the portable 68Ge/68Ga generator. 68Ga-DOTA-TACd-9 can be a useful tool
for the diagnosis of early stage of AD.
The work has been supported by the statutory
activity of the Institute of Nuclear Chemistry and
Technology (INCT). The authors thank Prof. S.
Siekierski (INCT) for the valuable discussion and
review of the text.
[6].
[7].
[8].
References
[1]. Ewers, M., Sperling, R.A., Klunk, W.E., Weiner, M.W.,
& Hampel, H. (2011). Neuroimaging markers for
the prediction and early diagnosis of Alzheimer’s
disease dementia. Trends Neurosci., 34, 430-442.
[2]. Petrella, J.R., Coleman, R.E., & Doraiswamy, P.M.
(2003). Neuroimaging and early diagnosis of Alzheimer disease: A look to the future. Radiology, 226,
325-336.
[3]. Mehta, M., Adem, A., & Sabbagh, M. (2012). New
acetylcholinesterase inhibitors for Alzheimer’s disease. Int. J. Alzheimer’s Dis., 2012, Article ID 728983,
8 p.
[4]. Szymański, P., Lázničková, A., Lázniček, M., Bajda,
M., Malawska, B., Markowicz, M., & Mikiciuk-Olasik, E. (2012). 2,3-Dihydro-1H-cyclopenta[b]quinoline derivatives as acetylcholinesterase inhibitors—
synthesis, radiolabeling and biodistribution. Int. J.
Mol. Sci., 13, 10067-10090.
[5]. Szymański, P., Żurek, E., & Mikiciuk-Olasik, E.
(2006). New tacrine-hydrazinonicotinamide hybrids
as acetylcholinesterase inhibitors of potential inter-
[9].
[10].
[11].
[12].
[13].
est for the early diagnostics of Alzheimer’s disease.
Pharmazie, 61, 4, 269-273.
Szymański, P., Markowicz, M., & Mikiciuk-Olasik,
E. (2011). Synthesis and biological activity of derivatives of tetrahydroacridine as acetylcholinesterase
inhibitors. Bioorg. Chem., 39, 138-142.
Kabalka, G.W., & Akula, M.R. (1999). Synthesis of
7-[123I]Iodotacrine: a potential SPECT agent to map
acetylcholine esterase. J. Labelled Compd. Radiopharm., 42, 959-964.
Tavitian, B., Pappata, S., Bonnot-Lours, S., Prenant,
C., Jobert, A., Crouzel, C., & Di Giamberardino, L.
(1993). Positron emission tomography study of [11C]
methyl-tetrahydroaminoacridine (methyl-tacrine) in
baboon brain. Eur. J. Pharmacol., 236, 229-238.
Davis, K.L., & Pochwik, P. (1995). Tacrine. Lancet,
345, 8950, 625-630.
Musiał, A., Bajda, M., & Malawska, B. (2007). Development of acetylcholinesterase inhibitors for Alzheimer’s disease treatment. Curr. Med. Chem., 14,
2654-2679.
Tumiatti, V., Minarini, A., Bolognesi, M.L., Milelli,
A., Rosini, M., & Melchiorre, C. (2010). Tacrine derivatives and Alzheimer’s disease. Curr. Med. Chem.,
17, 1825-1838.
Ambikanandan, M., Ganesh, S., Aliasgar, S., & Shrenik, P.S. (2003). Drug delivery to the central nervous system: a review. J. Pharm. Pharm. Sci., 6(2),
252-273.
Welch, M.J., & Redvanly, C.S. (2003). Handbook of
radiopharmaceuticals: radiochemistry and applications. West Sussex, England: John Wiley and Sons
Ltd.
COMPUTATIONALLY ASSISTED LOW-WAVENUMBER SPECTROSCOPY
OF HYDROGEN-BONDED SUPRAMOLECULAR SYNTHONS
Katarzyna Łuczyńska1,2/, Kacper Drużbicki2,3,/ Krzysztof Łyczko1/, Jan Cz. Dobrowolski1/
Institute of Nuclear Chemistry and Technology, Warszawa, Poland
Joint Institute for Nuclear Research, Frank Laboratory of Neutron Physics, Dubna, Russia
3/
Adam Mickiewicz University, Faculty of Physics, Poznań, Poland
1/
2/
The formation of molecular architectures driven
by specific interactions such as hydrogen-bonds
(H-bonds) has been one of the most important
areas of research in structural chemistry over the
last few decades. For the purpose of crystal engineering, the term supramolecular synthons has
been proposed, as referring to “building blocks”
that control the molecular aggregation on a large
scale [1]. In that sense, donor-acceptor type organic complexes appear to be of vital importance,
being related both to the proton and electron
transfer phenomena. Of these, the family of anilic
acids was found to be particularly interesting [2-6].
From the scientific perspective, it is thus important to deeper examine the crystallographic structures and competing intermolecular interactions
therein. To this end, multiple complexes of heterocyclic aromatic amines with bromanilic and chloranilic acids have been synthesized. An extensive
physical-chemical characterization of these systems was conducted thanks to the long-term collaboration with the Joint Institute for Nuclear Research (JINR) in Dubna, Russia. Thanks to this collaboration, we can provide a novel complementary
approach to study low-energy vibrational excitations in molecular crystals by combining state-of-the-art theoretical calculations in the framework
of solid-state density functional theory (DFT) with
time-domain terahertz (TDs-THz) and inelastic
neutron scattering (INS) spectroscopy. Here we report the case study of (1:1) co-crystal of bromanilic
acid and 2,6-dimethylpyrazine (BrA:2,6-DMP) [7].
This report is constructed as follows. First, we
acquaint the reader with the basic principles of
this rather unique experimental methodology. Then
we illustrate the research on low-wavenumber
vibrational dynamics using BrA:2,6-DMP as an
example.
In the well-established middle-infrared or Raman spectroscopy, one can routinely probe internal
molecular vibrations that can generally be attributed to the presence of particular atoms or functional groups. These experiments are usually performed at higher wavenumbers, since access to the
spectral range below 150 cm–1 is technically difficult. However, the terahertz features give the most
unique fingerprint arising from complex vibrations
of the entire molecules or from vibrations that can
47
be ascribed to long-range inter-molecular vibrations (external modes).
Terahertz radiation can be loosely defined as
the frequency between 0.1-10 THz (< 300 cm–1)
and was called the “THz gap”, since one could
not access this region efficiently for a long time.
Nowadays, this gap is filled thanks to the photoconductive and electro-optic emitters, which have
given rise to the so-called time-domain terahertz
spectroscopy. A simplified scheme of a typical
TDs-THz setup is illustrated in Fig.1A. In principle, in TDs-THz electron-hole pairs are generated in a semiconducting crystal (e.g. GaAs) using
an ultra-short femtosecond pulse (e.g. < 100 fs
from Ti:Sapphire laser). These photo-excited charge
carriers are further accelerated by an applied electric field, emitting THz radiation. According to
Fig.1A, the a small portion of light is directed on
the THz receiver through an optical delay line,
tional to the factor k  2/. Therefore, a radiation of several thousand Å (), which is used in
Raman and infrared spectroscopy is only a few
thousandths of that of a typical Brillouin zone dimension. As a consequence, Raman, IR or TDs-THz
refer to the Brillouin zone-centre phonons (-point
vibrations), where the selection rules are constrained by the symmetry of each normal mode [9]. In
contrast, there is no such constraint in INS. Additionally, the spectral intensity is defined here in
a simple way, as it is directly proportional to the
amplitude of atomic motion and incoherent neutron scattering cross-section of an atom (inc),
which is an isotope-specific property independent
of its chemical environment. Since the cross-section value for hydrogen (80 barns) is far greater
that of all other elements (typically ca. 5 barns),
the INS spectrum emphasizes the modes that involve substantial hydrogen motion [9].
A
B
Fig.1. A simplified scheme of the TDs-THz (A) and INS (B) spectrometers used throughout this work. The labels in
figure B stands for: 1 – the sample, 2 – filters, 3 – collimators, 4 – 3He detectors (INS and QENS), 5 – a pyrolytic graphite
analyser, 6 – a single crystal QENS analyser, 7 – a detector for high intensity diffraction, 8 – a detector for high resolution
diffraction, 9 – spectrometer shielding, 10 – an Ni-coated mirror neutron guide in a vacuum tube, 11 – a vacuum neutron
guide [8].
acting as the probe beam in the time-domain. The
pump beam shines onto the THz emitter, resulting in a continuous spectrum covering the range
of ~0.1-3 THz (3-100 cm–1). The emitted radiation
follows an optical path and passes the sample
placed in a transparent matrix (e.g. HDPE). In the
TDs-THz experiment, we observe a delay of the
signal due to sample absorption. The reference distance is therefore scanned by an optical delay line
using the probe signal. Optionally, the Fourier
transform (FT) is performed, converting the spectrum from the time- into the frequency domain.
TDs-THz probes the absorption of terahertz
radiation due to vibrational excitations, where the
transition probability is constrained by the same
selection rules as in infrared spectroscopy. The
transition arises from the interaction of the electric component of the photon with the electronic
cloud of the system. Alternatively, the low-wavenumber vibrational excitation may be induced by
an inelastic collision of the nucleus with an uncharged, non-zero mass particle, that is the neutron, which is then called inelastic neutron scattering.
The major differences between vibrational neutron and optical spectroscopy arise from the neutron’s mass which leads to the significant transfer
of both energy and momentum. The accessible
wavevectors in the momentum space are propor-
Thanks to the long-term collaboration with
the JINR, employees of the Institute of Nuclear
Chemistry and Technology actively participate in
the experiments conducted at the IBR-2 neutron
source, including INS measurements with the
NERA spectrometer. The simplified scheme of
NERA has been given in Fig.1B (see [8] for more
details). In brief, NERA is an inverted-geometry
spectrometer, which means that the final energy
of the scattered neutrons is fixed, and the wavelength spectrum of polychromatic incident neutrons is analysed according to the de Broglie relation by the time of flight on the ~110 m path. The
scattered neutrons are Bragg reflected from a pyrolytic graphite analyser and higher-order reflections beyond (002) are suppressed by cooled filters
so as to define the final energy of scattered neutrons at Ef as 4.65 meV. The spectrometer consists
of two symmetrical sections, A and B, which both
consist of eight chambers of 3He detectors for INS
measurements. The spectrometer is also intended
for simultaneous measurements of INS, QENS
(quasi-elastic neutron scattering) and NPD (neutron powder diffraction), fully covering the low-wavenumber range [8].
BrA:2,6-DMP was synthesized and structurally characterized with a low-temperature (100 K)
single-crystal X-ray diffraction (using the SuperNova Dual Source single-crystal diffractometer).
48
The molecular structure of the system containing
BrA and 2,6-DMP in a 1:1 molar ratio, is presented in Fig.2.
Fig.2. The geometry of hydrogen-bonded synthon formed
in a (1:1) co-crystal of BrA and 2,6-DMP.
The studied system can be described as a supramolecular superstructure built by the hydrogen-bonded ···2,6-DMP···BrA··· chains, formed by
alternating molecules, which are propagated toward the crystallographic axis a. The neighbouring acid and base molecules are linked into chains
by a pair of non-equivalent intermolecular hydrogen bonds. The system crystallizes in the monoclinic, centrosymmetric P21/c (C2h5) space group,
with four molecules equivalent by symmetry per
unit cell. The molecular chains in the crystal are
arranged in the opposite directions (anticlinic configuration), where the associated polarization vectors compensate each other, resulting in a centrosymmetric structure.
The low-wavenumber vibrational response was
probed by combining TDs-THz (Teraview TPS
3000) and INS spectroscopy (NERA) [8]. The experimental spectra are collected in Fig.3 and compared with the results of the first-principles calculations for solid-state.
In 2015, we optimized the numerical procedure for predicting low-wavenumber optical and
neutron spectra in the framework of density functional perturbation theory (DFPT), by taking periodic boundary conditions into account [10, 11]. We
have adopted the ab initio simulation method,
based on the plane-wave pseudopotential approach
as implemented in CASTEP code [12]. In brief,
DFPT provides analytical solutions for the calculation of lattice dynamics in solids, where the ionic
displacement along with an external electric field
are treated as perturbations acting on the equilibrium crystal structure. The example analysis of the
A
BrA:2,6-DMP crystal clearly illustrates that the
aforementioned methodology is capable of accurately predicting the position and intensity of both
the optical and INS spectra as well as identifying
the normal modes of vibration in the THz region,
as well as identify the normal modes of vibration
in the THz region of both optical and INS spectra.
As illustrated in Fig.3, the highly-accurate numerical methodology allows one to achieve a very
good match with the experimental spectra, allowing
for more complete interpretation of such a challenging spectral range. In Table 1, the full analysis
of the external modes has been delivered.
By employing theoretical calculations it was
also possible to probe the influence of the long-range dipole-coupling on the optical spectrum,
which has been shown to be of importance as it
significantly affects the TDs-THz band intensities
(see LO and TO components in Fig.3).
By inspection of these data, one can find, for
example, that the most intense spectral feature in
the TDs-THz can be attributed to the hydrogen
bridge stretching, that is, the lowest-energy hydrogen-bond mode, which in fact cannot be studied
with any other technique. One can also note that
the analysed spectra could be generally divided into
two parts, namely that above and below 50 cm–1.
While the upper range engages multiple librational
modes of co-molecules, the lower part expresses the
highly collective nature of the related vibrations,
which involve rotational (screwing) and translational motions (breathing, shearing) of the whole
hydrogen-bonded chains.
While the INS intensity is generally driven by
hydrogen contributions due to its large scattering
cross-section, the spectrum mainly reflects the contributions coming from the methyl groups, that is,
the 2,6-DMP counterpart. Such modes are not visible on their own in optical vibrational spectroscopy, since their motion does not affect the dipole
moment (nor polarizability), but are the most intense in INS spectroscopy. By contrast, the most
intense features in the TDs-THz spectrum can be
associated with partially charged oxygen atoms,
whose motion affects the polarization in the crystal cell, that is, the BrA moieties.
B
Fig.3. Theoretical (PBE) and experimental low-wavenumber (A) TDs-THz (298 K) and (B) INS (10 K) spectra of
BrA:2,6-DMP (1:1) co-crystal.
49
Table. 1. Collection of experimentally identified TDs-THz and INS wavenumbers ( [cm–1]) for the BrA:2,6-DMP (1:1)
complex along with a tentative band assignment. The experimental data are presented against the results of the plane-wave DFT lattice dynamics calculations (fixed-cell PBE/1050 eV data) as divided into the transverse (TO) and longitudinal (LO) optical components.
Theory – PBE
[]
LO
TO
Experiment
THz
INS
Tentative mode assignment
 [cm ]
–1
Bu
107.7
Bg
Bu
92.9
92.4
90
Bg
84.5
75
74.1
73.6
68
Bu
68.5
67.9
63
Au
66.9
66.9
Bu
66.0
65.3
C6O4H2 )
DMP lib.  bcBrA(oop  Br
+ transl. DMP  b)
C6O4H2 )
C6O4H2 )
CH3)DMP
DMP lib.  ab; BrA lib.  ac
68
BrA···DMP  ab (+ – – +)BrA(oop  Br
BrA···DMP  ab (+ – – +);
58
50
BrA···DMP  ab (+ – + –)BrA(oop  Br
C6O4H2 )
C6O4H2 )
Bu
56.3
56.1
52
Breathing mode  b ()BrA(oop  Br
Au
48.3
48.3
44
ScrewingDMP  ab (+ + + +)
Ag
46.8
Au
36.0
36.0
Bu
34.6
34.6
Ag
31.1
Bg
29.5
Au
27.1
Ag
27.1
C6O4H2 )
BrA···DMP  ab (+ + + +)
59
57.7
; DMP lib.  ab; CH3)DMP
DMP lib.  bcCH3)DMPBrA(oop  Br
79
Bu
C6O4H2 )
DMP lib.  acCH3)DMP
82
80.7
Ag
BrA(oop  Br
N···O (BrA(oop  Br
89
85.1
84.5
N···O (BrA  ab; transl. DMP  a); CH3)DMP
97
99.4
Ag
Bu
104.7
39
ScrewingDMP  ab (+ – + –)
Shearing BrA  a (+ – – +)
ScrewingBrA  bc (+ – + –)
33
24
20
Chain shearing BrA  a (+ + – –)
Chain shearing BrA  c (+ – + –)
Chain shearing BrA  c (+ – – +)
Chain shearing  c (+ + – –)
22.8
This research was supported in part by PL-Grid
Infrastructure (grant IDs: phd2013, phd2014).
K. Łuczyńska and K. Drużbicki gratefully acknowledge the financial support of the Polish Government Plenipotentiary for the JINR in Dubna
(grants no. 118-8/1069-5/2014; 44/27-01-2015/
7/1121/5) along with OMUS scholarship for the
outstanding young scientists at the JINR.
[6].
[7].
References
[1]. Desiraju, G.R. (1995). Supramolecular synthons in
crystal engineering – A new organic synthesis. Angew.
Chem., 34, 2311-2327. DOI: 10.1002/anie.199523111.
[2]. Horiuchi, S., & Tokura, Y. (2008). Organic ferroelectrics. Nat. Mater., 7, 357-366. DOI: 10.1038/nmat2137.
[3]. Horiuchi, S., Kumai, R., & Tokura, Y. (2007). Supramolecular ferroelectric realized by collective proton
transfer. Angew. Chem., 46, 3497-3501. DOI: 10.1002/
anie.200700407.
[4]. Horiuchi, S., Noda, Y., Hasegawa, T., Kagawa, F., &
Ishibashi, S. (2015). Correlated proton transfer and
ferroelectricity along alternating zwitterionic and nonzwitterionic anthranilic acid molecules. Chem. Mater.,
27, 6193-6197. DOI: 10.1021/acs.chemmater.5b0295.
[5]. Kobayashi, K., Horiuchi, S., Kumai, R., Kagawa, F.,
Murakami, Y., & Tokura, Y. (2012). Electronic ferroelectricity in a molecular crystal with large polariza-
[8].
[9].
[10].
[11].
tion directing antiparallel to ionic displacement. Phys.
Rev. Lett., 108, 23, 237601-237605. DOI: 10.1103/
PhysRevLett.108.237601.
Adam, M.S., Parkin, A., Thomas, L.H., & Wilson, C.C.
(2010). Bifurcated hydrogen-bonded synthons in molecular complexes of picolines with chloranilic acid.
CrystEngComm, 12, 917-924. DOI: 10.1039/B912539F.
Łuczyńska, K., Drużbicki, K., Łyczko, K., & Dobrowolski, J.Cz. (2015). Experimental (X-ray, 13C CP/
MAS NMR, IR, RS, INS, THz) and solid-state DFT
study on (1:1) co-crystal of bromanilic acid and 2,6-dimethylpyrazine. J. Phys. Chem. B, 119, 6852-6872.
DOI: 10.1021/acs.jpcb.5b03279.
Natkaniec, I., Chudoba, D., Hetmanczyk, Ł., Kazimirov, V.Yu., Krawczyk, J., Sashin, I., & Zalewski, S.
(2014). Parameters of the NERA spectrometer for
cold and thermal moderators of the IBR-2 pulsed reactor. J. Phys., Conf. Ser., 554, 012002. DOI: 10.1088/
1742-6596/554/1/012010.
Parker, S.F., & Haris, P.I. (2008). Inelastic neutron
scattering spectroscopy of amino acids. Spectroscopy,
22, 297-307. DOI: 10.3233/SPE-2008-0354.
Baroni, S., Giannozzi, P., & Testa, A. (1987). Green’s-function approach to linear response in solids. Phys.
Rev. Lett., 58, 1861-1864. DOI: 10.1103/PhysRevLett.58.1861.
Gonze, X. (1997). Dynamical matrices, born effective
charges, dielectric permittivity tensors, and inter-
50
atomic force constants from density-functional perturbation theory. Phys. Rev. B, 55, 10337-10354. DOI:
10.1103/PhysRevB.55.10355.
[12]. Clark, S.J., Segall, M.D., Pickard, C.J., Hasnip, P.J.,
Probert, M.J., Refson, K., & Payne, M.C. (2005). First
principles methods using CASTEP. Z. Kristallogr.,
220, 567-570. DOI: 10.1524/zkri.220.5.567.65075.
THE RECOVERY OF VALUABLE METALS FROM FLOWBACK FLUIDS
AFTER HYDRAULIC FRACTURING OF POLISH GAS-BEARING SHALES
Grażyna Zakrzewska-Kołtuniewicz, Dorota Gajda, Anna Abramowska, Agnieszka Miśkiewicz,
Katarzyna Kiegiel
Shale gas is natural gas that we use every day for
cooking or heating. This name does not describe
the special type of resources, but it is used to emphasize specific properties of the rock where gas
is accumulated. The shale gas is extracted from
these rocks using special exploration and production technologies, namely, hydraulic fracturing.
The fracturing fluid is pumped under high pressure into the borehole. The fluid pumping rate
typically ranges from 8 m3/min to 18 m3/min, and
the pumping pressure might be as high as 800
bars. The hydraulic action of the fracturing fluid
crushes the rock formations and creates fractures.
This fluid is typically slurry of water, proppants
and other chemical additives. The rocks contain
various metals that can be extracted by fracturing
fluids.
Institute take an action to develop the new project that will create the prototype of installation
that can be used for the treatment of flowback
fluids from hydraulic fracturing of Polish gas-bearing shales. In this paper, the initial results of
the studies on the examination of composition
and purification of flowback fluids are presented.
The fracturing fluids are very diverse in terms
of chemical composition, depending on the borehole and fracturing technology applied. However,
they consist of components such as water (more
than 90%), proppants (quartz sand/resin-coated
quartz sand/other high-resistance proppants, e.g.
zirconium oxide), natural polymers (derivatives of
Indian guar beans: Xantham gum, E415; guar
gum, E412), crosslinkers (boron, titanium and
zirconium compounds), buffers (inorganic acids
Table 1. The composition of selected fracking fluid used in Poland.
Ingredients
Maximum ingredients
concentration
[%mass]
Ingredients
Maximum ingredients
concentration
[%mass]
Water
94.535
Proppant
4.667
Hydrotreated light distillate
0.0274
Alcohols, C12-15, ethoxylated
0.0027
Choline chloride
0.0795
2-Butoxyethanol
0.0272
Isopropanol
0.0274
Ethoxylated C11 alcohol
0.0274
Ethoxylated alcohol
0.0183
Sasol DHR 200
0.0169
Lutensol TO-8
0.0001
Propylene carbonate
0.0002
Elementis Bentone® 150
0.0008
Guar gum powder
0.0151
Propylene glycol
0.0003
Formic acid
0.0002
Ammonium persulphate
0.0016
Hydrochloric acid 15%
0.4741
By-product of shale gas production is the huge
amounts of toxic fluids. These fluids are characterized by high salinity and contain heavy metals,
inter alia, also rare earth metals, radioactive elements and organic matter.
Pyrocat Catalyse World, Institute of Nuclear
Chemistry and Technology and Polish Geological
and bases, e.g. hydrochloric acid, ammonium bisulphate), natural biocides, stabilizers (sodium
chloride, calcium chloride, isopropanol), surfactants (amines, glycol ethers), viscosity breakers
(lithium hypochlorite, sulphates, peroxides), clay
and shale inhibitors – phosphonates, polyglycols,
gelling agents (polymers, hydroxyethylcellulose,
Table 2. The content of main elements [mg/L] found in selected flowback fluid samples.
Examined sample
Cl
Na
K
Li
Mg
Ca
Ba
Sr
Cs
B1
100 000
10 000
900
1 500
2 000
20 000
n.d
800
60
L1
65 400
23 740
489
12
849
7 836
212
1 159
n.d
n.d. – not determined.
guar gum). The example of composition of the
fracking fluid, which was used in Poland, is reported in Table 1 [1].
Hydraulic fluid works as a lixiviant for many
minerals found in shales [2], and different minerals
are leached during the hydraulic fracturing process.
Flowback fluid typically contains large amounts
51
the environment, they must be treated prior to
further use or final disposal as treated sewage
that can be introduced into water or ground. The
removal of heavy metals is one of the aims of processing. In addition, the separation of valuable
metals from the solution can improve the profitability of the proposed technology.
Table 3. The content of trace elements [mg/L] found in selected flowback fluid samples.
Examined sample
U
La
V
Y
Mo
Mn
B1
3.5
12.4
1.3
1.3
2
9.7
L1
n.d
n.d
< 0.1
n.d
< 5·10–3
9.4
of salt, various quantities of metals including heavy
metals and rare earth metals, and small amounts
of naturally occurring radioactive elements and
organic matters. The flowback fluid composition
can vary depending on the location and the method
of fracturing. The constituents of two flowback
fluids (B1 and L1) from fracturing in two locations in Poland are given in Tables 2, 3 and 4.
The content of Na+, Ca2+ and Cl– in flowback
fluid is high. Compared to these ions, the other
ions, such as Sr2+ and Cs+, occur in low concentration. Moreover, the fluid contains moderate concentration of organic materials, at 100-254 mg/L.
The conductivity of the flowback fluid samples
is high on the level 130 mS/cm and pH is in the
range 5.4-8.2.
The characteristics of presented fluids undoubtedly show that to reduce negative effects on
The combined treatment scheme of membrane
and ion exchange processes that can be used to
treat flowback fluids from shale gas wells being
Table 4. The content of organic and inorganic carbon
[mg/L] found in selected flowback fluid samples (TOC –
total organic carbon, TIC – total inorganic carbon).
Examined sample
TOC
TIC
B1
108
14
L1
254
152
drilled in Poland was shown in Fig.1. At the beginning, the fluid should be pretreated with using
the depth filters. In this process, turbidity is significantly reduced from 0.2 NTU to > 0.2 NTU. There
Fig.1. The possible scheme for the treatment of fluids after hydraulic fracturing.
52
is also a reduction of the organic carbon content
of about 20%.
The filtration by the activated carbon bed, oxidation by Fenton reaction and ozonation are much
more suitable for the treatment of aqueous solution with high organic content. Then, the adequate
sequence of cation and anion exchange resins will
allow to separate rare earth elements and uranium.
The main result of the project will be the elaboration of cheap and efficient technology which
allows the treatment and reuse of flowback fluids
and recovery of valuable metals. The design and
construction of the mobile installation which can
demonstrate the feasibility of technology at full
scale will complete the studies.
References
[1]. Organizacja Polskiego Przemysłu Poszukiwawczo-Wydobywczego. http://www.opppw.pl.
[2]. Chermak, J.A., & Schreiber, M.E. (2014). Mineralogy
and trace elements geochemistry of gas shales in the
USA: Environmental implications. Int. J. Coal Geol.,
126, 32-44.
CENTRE FOR RADIOBIOLOGY
AND BIOLOGICAL DOSIMETRY
Studies carried out in 2015 focused on implementation of new biodosimetric tools that have
been developed in the frame of the strategic research project “Technologies supporting development of safe nuclear power engineering” from the National Centre for Research and Development (SP/J/6/143 339/11), as well as in the “Development of a multi-parametric triage approach for an assessment of radiation exposure in a large-scale radiological emergency” funded
in the frame of the Operational Programme Innovative Economy (POIG 01.03.01-14-054/09).
A new approach based on the identification a panel of genes that expression changes in response to ionizing radiation has been elaborated toward the development of transcriptional
biodosimetry.
The Centre also participates in the Coordination Action project RENEB founded within
the 7th EU Framework Programme EURATOM – Fission. The project is aimed at establishing a sustainable European network in biological dosimetry involving 23 organizations from
16 EU countries. Their competence has been identified by a survey carried out in 2009 and
proofed by the interlaboratory comparison in 2011. The project will significantly improve the
response capabilities in the case of a large-scale radiological emergency. An operational network has been created, based on coordination of the existing reliable and proven methods in
biological dosimetry. This will guarantee the highest efficiency in processing and scoring of
biological samples for fast, reliable results implemented in the EU emergency management.
We take part in WP1, WP3 and WP4 of the RENEB project. Besides dicentric assay, micronuclei assay and histone -H2AX assay, which are implemented and calibrated in the Centre,
other two methods of biological dosimetry are being introduced in the frame of RENEB: PCC
and FISH-translocation assay. The Institute of Nuclear Chemistry and Technology (INCT) is
the leader organization of Task 4.1 of WP4 “Infrastructure, transport, linking to first responders, disaster management units” and is the only Polish partner of the project. The results obtained in the frame of the RENEB project were described in several publications and
presented at international conferences.
An important research topic for the last few years has been the oxidative stress, its molecular and cellular mechanisms in mammalian cells exposed to ionizing radiation and/or
nanomaterials and its role in development of neurodegenerative diseases. In particular, the
impact of nanoparticles on the cellular signalling activated by tumour necrosis factor was
studied in the frame of the project UMO-2014/13/D/NZ7/00286 and the role of nanoparticles in response of microglia cells to -amyloid was studied in the frame of the project
UMO-2013/11/N/NZ7/00415.
54
TOWARD THE DEVELOPMENT OF TRANSCRIPTIONAL BIODOSIMETRY
FOR THE IDENTIFICATION OF IRRADIATED INDIVIDUALS
AND ASSESSMENT OF ABSORBED RADIATION DOSE
Kamil Brzóska, Iwona Grądzka, Barbara Sochanowicz, Marcin Kruszewski
Biological dosimetry is the quantification of exposure to ionizing radiation by means of measurable biological changes (biological indicators) that
take place in the biological system. Based on such
indicators, cases of individual exposure to ionizing radiation can be detected and possible consequences of the exposure predicted. This enables
the planning of adequate medical treatment, when
information from physical dosimetry is not available.
The most frequently used and the best established method of biological dosimetry at present
is the dicentric chromosome assay, which is poorly suitable for a mass casualties scenario. This gives
rise to the need for the development of new, high-throughput assays for rapid identification of the
subjects exposed to ionizing radiation. In the present study, we tested the usefulness of gene expression analysis in blood cells for biological dosimetry.
The schematic representation of the experiment
is shown in Fig.1. Human peripheral blood from
Fig.1. Schematic representation of the experimental procedure.
three healthy donors was X-irradiated with doses
of 0 (control), 0.6, and 2 Gy. The mRNA level of
16 genes (ATF3, BAX, BBC3, BCL2, CDKN1A,
Fig.2. Cluster analysis of 36 blood samples based on Ct values of GADD45A, CDKN1A, BBC3, BAX, DDB2, GDF15,
TNFSF4, FDXR.
DDB2, FDXR, GADD45A, GDF15, MDM2, PLK3,
SERPINE1, SESN2, TNFRSF10B, TNFSF4, and
VWCE) was assessed by reverse transcription
quantitative PCR 6, 12, 24, and 48 h after exposure
with ITFG1 and DPM1 used as reference genes.
The panel of radiation-responsive genes was selected comprising GADD45A, CDKN1A, BAX, BBC3,
DDB2, TNFSF4, GDF15, and FDXR.
Among radiation-responsive genes, a significant difference between samples irradiated with
0.6 Gy and 2 Gy was observed only for TNFSF4.
For the other genes, significant differences were
observed between irradiated samples and control
samples, but not between samples irradiated with
different doses, even though a positive correlation
between the dose and mRNA level was observed.
This lack of a sharp difference between samples
irradiated with different doses is reflected in the
cluster analysis, where one of the samples irradiated with 2 Gy is grouped with 0.6 Gy samples
(Fig.2). This result is in agreement with the data
published by other authors, from which it appears
that gene expression analysis performs better in
distinguishing between irradiated and non-irradiated samples than in predicting the actual absorbed dose (e.g. [1-3]). Cluster analysis showed
that Ct values of the selected genes contained
sufficient information to allow discrimination between irradiated and non-irradiated blood samples.
The samples were clearly grouped according to the
absorbed doses of radiation and not to the time
interval after irradiation or to the blood donor.
55
Thus, in the present study, we have selected and
tested a new panel of radiation-responsive genes
proving its usefulness for biological dosimetry purposes. Our results confirm that the analysis of expression of a carefully selected group of genes can
provide sufficient information to discriminate between irradiated and non-irradiated blood samples.
The full description is available in [4].
References
[1]. Badie, C., Kabacik, S., Balagurunathan, Y., Bernard,
N., Brengues, M., Faggioni, G., Greither, R., Lista, F.,
Peinnequin, A., Poyot, T., Herodin, F., Missel, A., Terbrueggen, B., Zenhausern, F., Rothkamm, K., Meineke,
V., Braselmann, H., Beinke, C., & Abend, M. (2013).
Laboratory intercomparison of gene expression assays.
Radiat. Res., 180, 2, 138-148.
[2]. Tucker, J.D., Divine, G.W., Grever, W.E., Thomas, R.A.,
Joiner, M.C., Smolinski, J.M., & Auner G.W. (2013).
Gene expression-based dosimetry by dose and time in
mice following acute radiation exposure. PLoS One,
8(12), e83390.
[3]. Tucker, J.D., Joiner, M.C., Thomas, R.A., Grever, W.E.,
Bakhmutsky, M.V., Chinkhota, C.N., Smolinski, J.M.,
Divine, G.W., & Auner, G.W.J. (2014). Accurate gene
expression-based biodosimetry using a minima set of
human gene transcripts. Int. J. Radiat. Oncol. Biol.
Phys., 88, 933-939.
[4]. Brzoska, K., & Kruszewski, M. (2015). Toward the
development of transcriptional biodosimetry for the
identification of irradiated individuals and assessment
of absorbed radiation dose. Radiat. Environ. Biophys.,
54, 3, 353-363.
GENOTOXICITY OF SILVER NANOPARTICLES
IN LEUKOCYTES AND ERYTHROCYTE PRECURSORS
AFTER ORAL OR INTRAVENOUS ADMINISTRATION TO RATS
Iwona Grądzka, Iwona Wasyk, Teresa Iwaneńko, Sylwester Sommer, Iwona Buraczewska,
Katarzyna Sikorska, Teresa Bartłomiejczyk, Katarzyna Dziendzikowska1/,
Joanna Gromadzka-Ostrowska1/, Marcin Kruszewski
1/
Warsaw University of Life Sciences, Faculty of Human Nutrition and Consumer Sciences, Warszawa,
Poland
Nowadays the use of nanoparticles (NPs) is very
widespread, both in everyday life (e.g. food additives, cosmetics, packaging systems) and in medicine (e.g. drug delivery, bioimaging, tissue engineering, detection of proteins, cancer treatment)
[1]. NPs can easily reach different parts of the body
and accumulate; thus, it is reasonable to consider
the health consequences of their use. Silver nanoparticles (AgNPs) belong to the most commonly
used, characterized by antimicrobial properties
arising from free radical formation and oxidative
stress induction [2]. AgNPs present in consumer
goods are released into the environment, where
they could be bioaccumulated or enter the food
chain or drinking water supplies, potentially resulting in adverse and unpredictable effects. Hence,
estimation of their genotoxicity in vivo may bring
important information on their impact on human
health.
We investigated the genotoxic effects of AgNPs
(20 nm) in leukocytes and erythrocyte precursors
of rats (male Wistar, 14-week old). AgNPs were administered to the animals (10 mg/kg body weight/
day) intravenously, through the tail vein, or orally,
per os. After different time periods (from 24 h to
28 days), the rats were sacrificed, blood was taken
by heart puncture and bone marrow was flushed
from the femora. The positive control were rats,
24 h and 48 h after X-irradiation with the 3 Gy
dose. The percentage of micronuclei in reticulocytes – a measure of DNA damage in erythroid precursors – was evaluated both in the bone marrow
and blood. The bone marrow was prepared and
stained with acridine orange, according to the modified method of Hayashi et al. [3], then examined
under fluorescence microscope (Nikon, Japan). For
micronucleus test in blood, a cytometric method
of Harada et al. [4] was applied, with additional
56
staining of platelets; a flow cytometer BD LSR
Fortessa (USA) was used and the results were
analysed by a BD FACS Diva software. Direct
DNA damage (single and double strand breaks)
in peripheral blood lymphocytes was assessed by
the comet (single cell gel electrophoresis) assay
as described by Kruszewski et al. [5]. DNA base
damage (oxidative damage) was assessed after additional incubation of the cells with formamido-pyrimidine glycosylase (FPG) according to Kruszewski et al. [6]. Image analysis of the data was
performed by the Comet Assay IV Image Analysis
System (Perceptive Instruments, UK); the percentage of DNA in the comet’s tail was used as a
measure of DNA damage.
A
B
A
B
Fig.2. Alkaline comet assay: direct and oxidative DNA damage in rat peripheral blood leukocytes after intravenous
injection (24 h or 28 days) or oral (per os, 7 days or 28
days) administration of AgNPs. Bars show means (N  6)
+ 95% confidence intervals. Stars indicate values that are
significanly different from adequate controls (P < 0.05 by
t-test).
tration. Yet it was lowered 24 h after intravenous
administration (Fig.2B). These data support our
earlier results obtained for cell cultures treated
with AgNPs in vitro, where oxidative DNA damage was the main adverse effect [7].
Such type of damage may be considered as pre-mutagenic, leading to genetic instability [8]; thus,
in spite of the apparently minor damage estimated, the adverse effect of AgNPs for human health
cannot be excluded.
References
Fig.1. Percentage of micronucleated reticulocytes (% MN
in RET) in bone marrow and in blood after intravenous
injection (24 h or 28 days) or oral (per os, 7 days or 28
days) administration of AgNPs. Bars show means (N  6)
+ 95% confidence intervals. In rats X-irradiated with a
dose of 3 Gy, the level of micronuclei in bone marrow increased to 23.3% and 44.6% after 24 h and 48 h, respectively, while in blood the corresponding values were 1.4%
and 6.4% (not shown).
In spite of a very thorough analysis by several
methods both of cells present in the bone marrow
and blood no significant damage was found. No
differences were found in micronuclei frequency
in reticulocytes independently of the way of nanoparticle administration or of the time of estimation (Fig.1). The same applied to the directly estimated DNA damage by the comet assay in peripheral blood lymphocytes (Fig.2A). In contrast,
the oxidative DNA damage in these cells was significantly increased 7 days after per os adminis-
[1]. Yang, F., Jin, C., Subedi, S., Lee, C.L., Wang, Q., Jiang,
Y., Li, J., Di, Y., & Fu, D. (2012). Emerging inorganic
nanomaterials for pancreatic cancer diagnosis and treatment. Cancer Treat. Rev., 38, 6, 566-579.
[2]. Gaillet, S., & Rouanet, J.M. (2015). Silver nanoparticles: their potential toxic effects after oral exposure
and underlying mechanisms – a review. Food Chem.
Toxicol., 77, 58-63.
[3]. Hayashi, M., Morita, T., Kodama, Y., Sofuni, T., & Ishidata, M. (1990). The micronucleus assay with mouse
peripheral blood reticulocytes using acridine orange-coated slides. Mutat. Res., 245, 245-249.
[4]. Harada, A., Matsuzaki, K., Takeiri, A., Tanaka, K., &
Mishima, M. (2013). Fluorescent dye-based simple
staining for in vivo micronucleus test with flow cytometer. Mutat. Res., 751, 85-90.
[5]. Kruszewski, M., Green, M.H., Lowe, J.E., & Szumiel,
I. (1995). Comparison of effects of iron and calcium
chelators on the response of L5178Y sublines to X rays
and H2O2. Mutat. Res., 326, 155-163.
[6]. Kruszewski, M., Wojewódzka, M., Iwaneńko, T., Collins, A.R., & Szumiel, I. (1998). Application of the
comet assay for monitoring DNA damage in workers
57
exposed to chronic low dose irradiation. II. Base damage. Mutat. Res., 416, 37-57.
[7]. Kruszewski, M., Grądzka, I., Bartłomiejczyk, T., Chwastowska, J., Sommer, S., Grzelak, A., Zuberek, M., Lankoff, A., Dusinska, M., & Wojewódzka, M. (2013).
Oxidative DNA damage corresponds to the long term
survival of human cells treated with silver nanoparticles. Toxicol Lett., 219, 2, 151-159.
[8]. Hudecová, A., Kusznierewicz, B., Rundén-Pran, E.,
Magdolenová, Z., Hasplová, K., Rinna, A., Fjellsbø,
L.M., Kruszewski, M., Lankoff, A., Sandberg, W.J.,
Refsnes, M., Skuland, T., Schwarze, P., Brunborg, G.,
Bjøras, M., Collins, A., Miadoková, E., Gálová, E., &
Dušinská, M. (2012). Silver nanoparticles induce premutagenic DNA oxidation that can be prevented by
phytochemicals from Gentiana asclepiadea. Mutagenesis, 27, 6, 759-769.
WEAK EFFECT OF HALLOYSITE
ON HUMAN LUNG CARCINOMA A549 CELLS
AND THEIR NORMAL COUNTERPART – BEAS-2B CELLS
Sylwia Męczyńska-Wielgosz, Iwona Grądzka, Maria Wojewódzka, Iwona Wasyk, Teresa Bartłomiejczyk,
Lidia Zapór1/
1/
Central Institute for Labour Protection – National Research Institute (CIOP-PIB), Warszawa, Poland
Halloysite clay nanotubes have been developed for
a controlled release of anticorrosion agents [1] sustained release of drugs and proteins has also been
obtained. The latter property was the reason of increased interest in halloysite application for drug
delivery. Modified halloysite was used in in vitro
experiments for drug delivery (e.g. [1, 2]). Yet the
effects of its presence in culture medium on mammalian cells are not recognized. Here, unmodified
halloysite preparation (nanotubes,  100 nm of
length, Sigma-Aldrich) was used to check its effect
under cell culture conditions and compare it to
other nanomaterials: cerium oxide (CeO2) and zirconium oxide (ZrO2) nanoparticles (NPs). The
cerium oxide NPs exhibit a considerable ability to
induce oxidative stress in mammalian cells [3]. In
contrast, zirconium oxide NPs have vast technical
applications, whereas they rarely exert pronounced
cytotoxic effects. However, they are known to inhibit cell proliferation, induce DNA damage and
apoptosis by reducing the cell defense mechanism
against oxidative stress [4].
To characterize the halloysite nanotubes (HNs)
applied here we measured their hydrodynamic diameter, zeta potential and aggregation (polydispersity index) and compared the results with those
obtained for the other two nanoparticles. We used
the DLS (dynamic light scattering) method and
the Zetasizer Nano ZS (Malvern) at various intervals after sonication in water and transfer into
culture media used for the cell lines investigated.
HNs and CeO2 tend to aggregate in cell culture
media supplemented with fetal calf serum; this
tendency is particularly strong in HNs, whereas
ZrO2 show the highest stability under similar
conditions. In result of incubation in the LHC-9
medium the size of HNs increases to > 1 m.
To characterize the in vitro effect of HNs
and compare it with that of CeO2 and ZrO2 we
used adenocarcinomic human alveolar basal epithelial cells, A549, and their normal counterpart,
BEAS-2B. The cell cultures seeded 24 h earlier
were then incubated for 24 h or 72 h in cell culture medium containing the studied nanoparticles
at various concentrations. To estimate the metabolic activity/viability of nanoparticle-treated cells
the Alamar Blue test was applied, where resazurin,
a non-fluorescent indicator dye, is converted to
bright red-fluorescent resorufin via the reduction
reactions of metabolically active cells i.e. able to
maintain a reducing environment within the cytosol. The fluorescence measured is proportional to
the number of living cells and corresponds to the
metabolic activity/viability.
Under the conditions applied none of the examined nanoparticles exerted a significant cytotoxic
effect, as shown in Table 1. The measure of the
NPs effect was IC90 or IC50, that is, NPs concentration that reduced the metabolic activity by 10%
or 50% as compared to the control. There was a
similar weak response of BEAS-2B cells to all
three NPs. The largest difference was between IC50
values for 72 h incubation of A549 cells between
CeO2 and HNs. Since both NPs tend to aggregate
in serum-supplemented cell culture medium, aggregation is not the causal factor. Rather, the difference may be due to NP-specific interactions
with biologically important ligands present in cell
Table 1. IC90 and/or IC50 values determined in cancer (A549) cells and their normal counterpart, BEAS-2B for three
nanoparticles.
Cell line
A549
BEAS-2B
Cerium oxide
Zirconium oxide
Halloysite
IC90 24 h: 76.31 ±8.23
IC50 24 h: 106.18 ±1.61
IC90 24 h: 107.30 ±2.37
IC50 72 h: 230.87 ±1.25
IC50 72 h: 99.89 ±1.16
IC50 72 h: 96.83 ±2.61
IC90 24 h: 97.44 ±2.18
IC90 24 h: 100.78 ±0.48
IC90 24 h: 101.34 ±2.95
IC90 72 h: 91.83 ±2.63
IC90 72 h: 97.70 ±2.15
IC90 72 h: 95.62 ±1.87
58
culture media or on cell surface. In that case, the
adverse effect may be observed in the absence of
NPs internalization. In summary, in tests in vitro,
HNs seem not to be a harmful nanomaterial.
Nevertheless, further studies with the use of different experimental models are needed to clarify
this point.
References
[1]. Lvov, Y., Aerov, A., & Fakhrullin, R. (2014). Clay nanotube encapsulation for functional biocomposites. Adv.
Colloid Interface Sci., 207, 189-198.
[2]. Lee, Y., Jung, G.E., Cho, S.J., Geckeler, K.E,. & Fuchs,
H. (2013). Cellular interactions of doxorubicin-loaded DNA-modified halloysite nanotubes. Nanoscale, 5
(18), 8577-8585.
[3]. Park, E.J., Choi, J., Park, Y.K., & Park, K. (2008). Oxidative stress induced by cerium oxide nanoparticles in
cultured BEAS-2B cells. Toxicology, 245 (1-2), 90-100.
[4]. Asadpour, E., Sadeghnia, H.R., Ghorbani, A., & Boroushaki, M.T. (2014). Effect of zirconium dioxide nanoparticles on glutathione peroxidase enzyme in PC12 and
n2a cell lines. Iran. J. Pharm. Res., 13 (4), 1141-1148.
IMPACT OF SELECTED TYPES OF CARBON NANOMATERIALS
ON DNA REPAIR AND CLONOGENIC SURVIVAL IN VITRO
Magdalena Kowalska1/, Aneta Węgierek-Ciuk1/ Marcin Kruszewski2/, Halina Lisowska1/,
Sylwia Męczyńska-Wielgosz2/, Teresa Iwaneńko2/, Maria Wojewódzka2/, Anna Lankoff1,2/
1/
Jan Kochanowski University, Department of Radiobiology and Immunology, Kielce, Poland
2/
Institute of Nuclear Chemistry and Technology, Warszawa, Poland
Carbon nanomaterials are becoming increasingly common in everyday life. Among them, single
walled carbon nanotubes (SWCNTs) are attracting significant attention as a novel material in the
field of medicine for molecular imaging, biodetection of disease markers, tissue engineering, devices
for drug delivery and nanotargeted radionuclides
for tumour nuclear imaging and internal radiotherapy [1]. Such common applications in medical field raise concerns regarding the interaction
of SWCNTs with biological molecules in the human body. Moreover, apart from medical exposure,
SWCNTs can be absorbed into the body by inhalation of engine emissions containing diesel exhaust particles (DEPs) during the combustion of
diesel and biodiesel fuels in the urban environ-
(adenocarcinomic human alveolar basal epithelial
cells) were treated with a range of doses of SWCNTs
and DEPs. The alkaline comet assay with the formamido-pyrimidine glycosylase (FPG) was carried
out to estimate the extent of oxidative DNA damage. Percent of DNA in comet’s tail was chosen
as a measure of DNA breakage. Cytotoxicity of
SWCNTs and DEPs was determined with the
sulphorhodamine B assay (not shown) and clonogenic survival assay.
Figure 1 shows that the extent of X-ray (2 Gy)
induced SSB (single strand breaks) is not modified
by SWCNTs or DEPs treatment. In contrast, the
treatment considerably decreases the rate of repair of the oxidative DNA damage induced by 2
Gy X-rays. Figure 2 presents the clonogenic sur-
A
B
Fig.1. Ionizing radiation-induced DNA damage and repair in A549 cells treated with 50 g/mL of (A) SWCNTs or (B)
DEPs for 24 h. SSB – single strand breaks, FPG – oxidative DNA damage.
ment. It is therefore obvious that evaluation of
possible adverse effects of SWCNTs and DEPs is
very imperative and urgent.
Taking this into consideration the aim of our
study was to determine the impact of SWCNTs
and DEPs on DNA repair and cell survival in
A549 cells. The exponentially growing A549 cells
vival data and shows that the difference between
SWCNTs and DEPs cytotoxicity is not significant.
However, the obtained data indicate that the exposure to SWCNTs and DEPs decreases the colony
forming ability of A549 cells and also the colony
forming ability of A549 cells irradiated with 2 Gy
of X-rays.
A
59
B
Fig.2. Clonogenic survival of A549 cells treated with (A) SWCNTs or (B) DEPs (1-100 g/mL) and irradiated with
ionizing radiation (1-5 Gy).
The review of experimental data on SWCNTs
and DEPs in various biological models shows a
complicated pattern of damaging effects depending both on particle characteristics, cellular models
and end-points analysed [2-4].
This project is funded from Norway grants in
the Polish-Norwegian Research Programme operated by the National Centre for Research and Development: Pol-Nor/201040/72/2013 (FuelHealth).
References
[1]. De Volder, M.F.L., Tawfick, S.H., Baughman, R.H. &
Hart, A.J. (2013). Carbon nanotubes: present and future
commercial applications. Science, 339, 6119, 535-539.
[2]. Wang, J., Sun, P., Bao, Y., Liu, J., & An, L. (2011).
Cytotoxicity of single-walled carbon nanotubes on
PC12 cells. Toxicol. In Vitro, 25, 1, 242-250.
[3]. Kumarathasan, P., Breznan, D., Das, D., Salam, M.A.,
Siddiqui, Y., MacKinnon-Roy, C., Guan, J., de Silva,
N., Simard, B., & Vincent, R. (2015). Cytotoxicity of
carbon nanotube variants: A comparative in vitro exposure study with A549 epithelial and J774 macrophage cells. Nanotoxicology, 9, 2, 148-161.
[4]. Durga, M., Nathiya, S., Rajasekar, A., & Devasena, T.
(2014). Effects of ultrafine petrol exhaust particles on
cytotoxicity, oxidative stress generation, DNA damage
and inflammation in human A549 lung cells and murine
RAW 264.7 macrophages. Environ. Toxicol. Pharmacol.,
38, 2, 518-530.
FORMATION OF GLUTATHIONYL DINITROSYL IRON COMPLEXES
PROTECTS AGAINST IRON GENOTOXICITY
Hanna Lewandowska, Jarosław Sadło, Sylwia Męczyńska-Wielgosz, Tomasz M. Stępkowski,
Irena Szumiel, Grzegorz Wójciuk, Marcin Kruszewski
Dinitrosyl iron complexes (DNICs), intracellular
NO donors, are important factors in nitric oxide-dependent regulation of cellular metabolism and
signal transduction (reviewed in [1]). Despite the
fact that the interactions of low molecular weight
DNIC with proteins have been widely characterized, little is known about their direct interactions
with other important biological macromolecules,
such as DNA. The toxicity of DNICs components
seems to be mutually dependent on each other. It
has been shown that NO diminishes the toxicity
of iron ions and vice versa. To gain insight into
the possible role of DNIC in this phenomenon, we
examined the effect of GS-DNIC (a dinitrosyl iron
complex with glutathione, GSH) formation on the
ability of iron ions to mediate DNA damage, by
treatment of the pUC19 plasmid with physiologically relevant concentrations of GS-DNIC.
In order to estimate the extent of DNA damage
caused by the glutathionyl dinitrosyl iron complex
vs. the aquated or GSH-complexed Fe2+, a plasmid cleavage test was carried out. In this test, the
abundance of DNA bands, corresponding to the
supercoiled (CCC), open circular (OC) and linear
(L) forms of the plasmid, visualized after electrophoresis is directly related to DNA damage. Thus,
it was possible to estimate whether the binding of
iron in the form of DNIC can protect DNA from
oxidative stress-induced lesions.
Figure 1 presents the results of this test. Indeed,
in comparison with the control, free iron ion containing samples, we observed a significant reduction of DNA breakage in DNIC containing samples. We believe that this effect might have been
caused by iron binding in the form of GS-DNIC.
The substantial protective effect presented in Fig.1
did not occur for the DNA treated with Fe2+ in the
presence of GSH alone; thus the observed protection cannot be ascribed to the radical-scavenging
effect of GSH. As observed by the plasmid DNA
cleavage assay, a significant reduction of DNA
breakage was observed for GS-DNIC-bound iron,
as compared to the DNA-cleaving effect of free
iron ions (not shown). The results are in line with
the observations of other authors [2, 3] who have
shown that iron incorporation into nitrosyl complexes attenuates iron activity in the Fenton reaction. In addition, GS-DNIC was shown by electron
paramagnetic resonance to be stable in the presence of DNA. The presented data (see [4] for full
information) show that GS-DNIC formation protects against the genotoxic effect of iron ions alone
60
OC
L
CCC
A
1
2
3
4
5
#
6
7
8
9
#
OC
B
L
CCC
1
2
3
4
5
6
7
8
9
Fig.1. Nicking of the plasmid DNA by GS-DNIC vs. the effect of iron. Panel A: pH 6.2, panel B: pH 7.2. Gel images –
pUC19 plasmid (400 ng) was treated with the following solutions: Fe(aq) + 1000 M H2O2 (line 1), Fe(aq) + 100 M H2O2
(line 2), DNIC + 1000 M H2O2 (line 3), DNIC + 100 M H2O2 (line 4), (Fe)GSH + 1000 M H2O2 (line 5), (Fe)GSH
+ 100 M H2O2 (line 6), GSNO (line 7), non-treated (line 8). The mobility of the plasmid cleaved with Sma1 endonuclease (linear form) is shown in Line 9. Intensities of bands 1-8 correspond to the intensity graphs. Filled box – open
circular nicked form (OC), empty box – covalently closed circular-supercoiled form (CCC). Hash denotes statistically
significant difference vs. DNIC at 1000 M H2O2. The p-values are: 0.00187 for Fe(aq) vs. DNIC, and 0.0275 for Fe(GSH)
vs. DNIC.
and iron ions in the presence of a naturally abundant antioxidant, GSH. This sheds new light on
the iron-related protective effect of NO under the
circumstances of oxidative stress.
References
[1]. Lewandowska, H., Kalinowska, M., Brzóska, K., Wójciuk, K., Wójciuk, G., & Kruszewski, M. (2011). Nitrosyl iron complexes – synthesis, structure and biology.
Dalton Trans., 40, 33, 8273-8289.
[2]. Lu, C., & Koppenol, W.H. (2005). Inhibition of the
Fenton reaction by nitrogen monoxide. J. Biol. Inorg.
Chem., 7, 732-738.
[3]. Gorbunov, N.V., Yalowich, J.C., Gaddam, A., Thampatty, P., Ritov, V.B., Kisin, E.R., Elsayed, N.M., & Kagan, V.E. (1997). Nitric oxide prevents oxidative damage produced by tert-butyl hydroperoxide in erythroleukemia cells via nitrosylation of heme and non-heme
iron. Electron paramagnetic resonance evidence. J.
Biol. Chem., 272, 19, 12328-12341.
[4]. Lewandowska, H., Sadło, J., Męczyńska, S., Stępkowski, T.M., Wójciuk, G., & Kruszewski, M. (2015).
Formation of glutathionyl dinitrosyl iron complexes
protects against iron genotoxicity. Dalton Trans., 44,
28, 12640-12652.
LABORATORY OF NUCLEAR
ANALYTICAL METHODS
The Laboratory of Nuclear Analytical Methods was created in 2009 on the basis of the former
Department of Analytical Chemistry. 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 the outside institutions. The Laboratory is a producer of certified reference materials (CRMs) for the purpose of inorganic trace analysis and 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-ray counting.
In 2015, the research projects carried out in the Laboratory were concerned with chemical
aspects of nuclear power, and nuclear and related analytical techniques for environment protection.
In 2015, the Laboratory participated in the strategic research project from the National
Centre for Research and Development (NCBR), Poland “New technologies supporting development of safe nuclear energy”. The Laboratory participated also in the MODAS project from
the NCBR being a member of the consortium of eight leading Polish universities and scientific institutes. Within the scope of the MODAS project, the Laboratory was involved in preparation and certification of four new environmental CRMs certified for the contents of a
possibly great number of trace elements. The produced CRMs have been: Bottom Sediment
(M-2 BotSed), Herring Tissue (M-3 HerTis), Cormorant Tissue (M-4 CormTis) and Cod Tissue
(M-5 CodTis).
In 2015, the Laboratory of Nuclear Analytical Methods conducted a proficiency test (PT)
on the determination of H-3, Am-241, Ra-226 and Pu-239 in waters and food samples. PT
was provided on the request of the National Atomic Energy Agency (PAA), Poland. Eight
laboratories took part in the PT, five laboratories forming radiation monitoring network in
Poland (on the request of the PAA) and three other laboratories. The proficiency test was
provided following requirements of ISO/IEC 17043:2010 and IUPAC International Harmonized Protocol (2006).
62
CHROMATOGRAPHIC DETERMINATION
OF SELECTED PERFLUORINATED ORGANIC COMPOUNDS
AND TOTAL ORGANIC FLUORINE IN NATURAL WATERS
AND MILK SAMPLES
Marek Trojanowicz, Mariusz Koc1/, Katarzyna Chorąży1/
1/
University of Warsaw, Department of Chemistry, Warszawa, Poland
The widespread occurrence and environmental
persistence of perfluorinated organic compounds
(PFCs) received worldwide attention in recent
two decades [1, 2]. They are widely produced for
various applications in recent decades as stable
and efficient surfactants, are utilized in syntheses
of fluorinated polymers and are applied in household products and cosmetics [3]. Their unusual stability in the environment and resistance to chemical and biochemical degradation result in a wide
global proliferation, including remote regions without and anthropogenic activity. They are present
commonly in groundwater and drinking waters [4]
and in human organisms [5, 6]. It is commonly
known of their accumulation in particular organs
and incorporation into a lipid cell wall. The two
most commonly detected species such as perfluorooctanoic acid (PFOA) and perfluorooctane sulphonic acids (PFOS) globally occur in human
bloods and serum samples at g/L level, hence
wide investigations concerning the toxicity of those
compounds for humans [7, 8]. The suspected effects include hepatotoxicity, carcinogenicity, immunotoxicity and developmental toxicity. Recent
studies show concern about hepatotoxicity of
PFOA for the occupationally exposed humans and
immunotoxicity by PFOS [9]. Some effects of
PFCs on reproductive hormones in humans were
also discovered [10]. The presence of PFCs is investigated also in indoor and outdoor air; however, exposure via inhalation appears a minor
pathway [11]. An increasing attention is also focused in recent decade on the monitoring of their
content in foods, which, besides water, is the most
significant exposure route for humans [12].
Monitoring PFCs’ concentration in trace level
in complex matrices is a serious analytical challenge. Reliable methods of extraction, separation
and identification in complex matrixes are necessary. The difficulty in determining PFCs is very low
concentration in the samples (ng-pg/L or ng-pg/g)
and complexity of matrices [13, 14]. Numerous
analytical methods have been developed to determine PFCs and most of them are chromatographic
methods [15, 16]. For the determination of perfluorinated carboxylic acids (PFCAs), one of the
most frequently occurring and determined group
of PFCs, in analytical procedures without derivatization, liquid chromatography with mass spectrometry detection (LC/MS) and electrospray ionization are most commonly used in the analysis of
environmental and biological samples. Also instrumentally simpler methods such as, e.g. ion
chromatography with conductivity detection for
the separation of PFCAs having C3-8 alkyl chains
have also been proposed [17] with limit of detec-
tion (LOD) in the range 0.12-0.66 mg/L, while
with additional solid-phase extraction step, the determination of 50 g/L was possible. A reversed-phase HPLC method was developed based on
derivatization of the PFCAs with 3-bromoacetyl
coumarin [18]. With a 100-fold SPE preconcentration, the LOD values in the range 43-75 ng/L
were reported. Different approaches using solid-phase extraction methodology for preconcentration of PFCAs have been developed. For the determination with LC/MS, the methodology using
C18 sorbents has been mainly used by various
authors, which is limited for long-chain acids [19].
Also the application of polymeric sorbents Oasis
HLB and Oasis WAX mixed-mode weak anion-exchange reversed phase for PFCAs’ preconcentration has been presented [20].
A large number and diversity of PFCs occurring in environment, as well as the complexity of
their identification and determinations, create increasing interest in the evaluation of the valuable
and informative general parameter known as total
organic fluorine (TOF) [21]. The determination of
TOF with sufficient selectivity and low detection
limit is necessary to obtain a mass balance of TOF
in environmental and biological samples, as well
as, e.g. for monitoring of degradation processes of
fluorinated organic compounds. Such determinations can be carried out directly, e.g. by using 19F
NMR [22], but most commonly, they are carried
out by the release of fluorine from organic compounds and analytical determination of fluoride
ion. The release of fluorine can be achieved with
different methods, including combustion with oxygen in the furnace at 900-1000ºC [23] or by the
reaction with sodium biphenyl (SBP), which was
reported in our earlier work [24]. In the latter
case, the hydrolysis of the reaction mixture leads
to the formation of inorganic fluoride, which can
be then determined with various methods, for instance, by potentiometry with ion-selective electrode or ion chromatography. In our earlier works,
we have found a method originally used for the
determination of fluoride by gas chromatography
to be especially convenient in terms of detectability and selectivity [25]. It is based on reaction of
fluoride with trimethylhydroxysilane to form trimethylfluorosilane, and following this principle,
we used triphenylhydroxysilane (TPSiOH) for
fluoride derivatization (R – phenyl):
R3SiOH + H+ + F–  R3SiF + H2O
The obtained triphenylfluorosilane (TPSiF)
can be determined by gas chromatography (GC)
with MS or flame ionization (FID) detections [26],
as well as with reversed-phase HPLC with UV detection [27].
63
phase was taken for GC/FID analysis. Parallel prepared preconcentrated samples were taken for
LC/MS analysis for the determination of PFACs
from C3 to C12 and PFOS.
Chromatograms are shown in Fig.1, which were
recorded for GC/FID determinations of TOF using gas chromatograph HP 5890 Series II (Agilent). Figure 1A shows chromatograms for reaction mixture after derivatization with TPSiOH for
water as blank and for 10 M standard fluoride
solution, which indicated a very satisfactory selectivity and chromatographic efficiency of fluoride determination with developed method. Figure
1B shows chromatograms recorded for 50 ng/L
standard PFOA solution, cow milk and cow milk
sample spiked with 50 ng/L PFOA, as well as blank
of deionized water with signal below LOD for developed method.
A
B
Deionized water
10 ng/L PFOA standard
Milk
Milk spiked with 10 ng/L PFOA
Detector response
Detector resposne
The aim of the conducted investigations was
the comparison of results of the determination of
TOF by GC/FID with defluorination using SBP
and derivatization with TPSiOH in natural waters
and milk samples with results of the determination of selected PFOAs and PFOS using LC/MS.
The efficiency of TOF determination was also examined for selected fluorinated pharmaceuticals
and pesticides using HPLC with UV detection.
The samples of natural waters were filtered with
0.45 m filters and preconcentrated from 400 mL
using Sep-Pak Vac C18 (Waters) columns with
500 mg sorbent bed, then retained analytes were
eluted with methanol and acetonitrile (ACN) and
evaporated almost to dryness in argon atmosphere.
Samples of milk (5 mL of human milk samples and
100 mL of cow milk Łaciate 0%) were diluted
with 0.1 mM formic acid solution and analytes
TPSiF
10 PM NaF standard
Deionized water
Time,
Ti min
Time, min
Fig.1. Recorded gas chromatograms with FID for 10 M standard fluoride solution derivatized with TPSiOH (A) and for
TOF determination in cow milk sample after sodium biphenyl defluorination and derivatization with TPSiOH (B). Sample
volume – 2 L, carrier gas – He, column – HP1, 30 m  0.32 mm I.D., 1 m film.
were extracted using Supel™ Select™ HLB (Waters)
columns with 60 mg bed and then eluted with 1 mL
of 1% NH3 in ACN [28]. Using LC/MS, individual
PFCs were determined, while after evaporation
almost to dryness, defluorination with SBP was
carried out. To the sample evaporated for defluorination, 300 L SBP solution was added, and after
10-min reaction, 700 L of water was added. After
hydrolysis was processed, to the aqueous phase
the solution of TPSiOH in ACN was added and
HClO4, and after 10 min reaction, the organic
As natural samples were taken tap waters and
river waters collected in Warsaw, and also in Tarnów, in vicinity of large chemical plant producing
fluorinated compounds, including Polish polytetrafluoroethylene. The examined milk samples included commercial cow milk Łaciate 0% and two samples of human milk obtained from the Regional
Women Milk Bank in Holy Trinity Hospital in
Warsaw. The LC/MS determinations of individual
PFCs were carried out using HPLC system equipped with Agilent 6220 ESI-TOF mass spectrometer
Table 1. Results of LC/MS determination of selected perfluorinated organic compounds [ng/L] in natural waters and
milk samples and TOF determination [ng/L] using GC/FID, using defluorination with sodium diphenyl and fluoride derivatization with TPSiOH. C7-PFCA – perfluoroheptanoic acid, C9-PFCA – perfluorononoic acid, C10-PFCA – perfluorodecanoic acid, PFOA – perfluorooctanoic acid, PFOS – perfluoroctanosulfonic acid, F – sum of fluorine content
of individually determined PFCs, TOF – total organic fluorine, n.d. – not determined (below limit of detection).
PFOA C9-PFCA C10-PFCA PFOS
F
Sample
C7-PFCA
TOF Unknown PFCs [%]
River Vistula, Warsaw
2.5
3.3
4.9
2.0
5.6
12.4 14.2
13
Tap water, Warsaw
0.62
1.23
0.01
n.d.
n.d.
1.27 7.10
82
River Biała, Tarnów
0.78
0.56
0.14
n.d.
6.3
5.08 13.5
62
Tap water, Tarnów
0.06
2.5
n.d.
n.d.
4.3
4.54 7.77
42
Human milk I
0.08
29.6
n.d.
n.d.
1.1
30.8 35.1
12
Human milk II
0.10
24.1
n.d.
n.d.
3.3
27.5 37.7
23
Cow milk
0.07
18.4
n.d.
n.d.
10.2
28.9 35.2
41
64
and reversed-phase C18 Eclipse XDB column (5
m, 250 mm, 4.6 mm I.D.) from Agilent, with gradient elution using 10 mM formic acid solution
and increasing content of ACN.
of commonly occurring PFOA and PFOS was observed (except PFOS in tap water from Warsaw).
From examined PFCAs, in river water samples,
different levels of C7-PFCA and C9-PFCA were
Fig.2. Determination of fluorinated and perfluorinated
organic compounds using HPLC and LC/MS and TOF using GC/FID in natural water samples after solid-phase
preconcentration using Waters Sep-Pak Vac C18 columns,
defluorination with sodium biphenyl and derivatization
with TPSiOH.
Fig.3. Determination of fluorinated and perfluorinated
organic compounds using HPLC and LC/MS and TOF using GC/FID in human and cow milk samples after solid-phase preconcentration using Waters Sep-Pak Vac C18
columns, defluorination with sodium biphenyl and derivatization with TPSiOH.
The obtained results are presented in Table 1,
and Figs.2 and 3 show the results on histograms.
As it can be expected from the vast literature, in
all examined water and milk samples, the presence
found, while in milk samples, mostly C7-PFCA
was detected. In all examined samples, the content of other non-identified perfluorinated compounds range from 12-13% up to 60-80% in case
Table 2. Characteristics and applications of selected fluorinated pharmaceuticals and pesticides examined for their recovery in the procedure for TOF determination used for perfluorinated organic compounds.
Compound
Bifenthrin
Structure
Application
Example detected levels
in environmental samples
Pyrethroid insecticide 2.7-3.0 ng/L in sediment-pore waters [29]
Dexamethasone
Anti-inflammatory
steroid
Up to 22.6 ng/L in wastes [30]
5-Fluorouracil
Anticancer drug
5-27 ng/L in hospital wastes [31]
Hexaflumuron
Termiticide
No data found
Lufenuron
Insecticide
No data found
Tolylfluanid
Fugicide
No data found
of water samples. These results convincingly confirm the importance of the determination of TOF
as the most informative parameter indicating the
content for that class of compounds in examined
samples.
As a supplementary investigation for these
studies, the efficiency of the developed method
for TOF determination was examined for selected
fluorinated pharmaceuticals and pesticides, which
are widely used nowadays, and some of them were
already examined in environmental samples (Table
2). As it is shown in histogram in Fig.4, except
5-fluorouracil, for the investigated level of 20 M,
a satisfactory recovery in TOF determination 79%
to 104% was obtained for all examined compounds,
similarly to included in the same histogram PFCAs
and PFOS. The determination of fluorinated pharmaceuticals and pesticides was carried out using
reversed-phase HPLC with UV detection at 254
nm, with the use C18 column type Grace™ Gracesmart™ (5 m, 150 mm, 4.6 mm I.D.) from Fisher
Scientific, with gradient elution using mixture of
methanol with acetic acid solution and increasing
content of ACN. In examined natural samples,
only in case of commercial cow milk sample, a
65
[4].
[5].
[6].
[7].
[8].
[9].
[10].
[11].
[12].
Fig.4. Recovery of the determination of fluorinated and
perfluorinated organic compounds (20 M each) as TOF
using defluorination reaction with SBP, derivatization
with TPSiOH and final determination in GC/FID.
trace content of pesticides such as hexaflumuron
(0.37 ng/L) and lufenuron (0.28 ng/L) was detected, which jointly formed 0.5% of the determined TOF value for this particular sample. This
allows to conclude that the TOF value determined
with the developed method gives a reliable information about total content of PFCs in examined
water and milk samples.
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OPTIMIZATION OF SAMPLE PROCESSING
IN AUTOMATED FLOW PROCEDURE FOR ICP-MS DETERMINATION
OF 90Sr AND 99Tc
Kamila Kołacińska, Ewelina Chajduk, Jakub Dudek, Zbigniew Samczyński,
Anna Bojanowska-Czajka, Marek Trojanowicz
Radioisotopes 90Sr and 99Tc belong to the most
commonly determined radionuclides for environmental, industrial, medical and food control purposes [1, 2]. Usually, their determination with radiometric methods or mass spectrometry (MS) in
complex matrix detection requires a laborious and
time-consuming sample processing, hence performing such a processing in mechanized or automated flow systems is especially attractive, offering
shortened analyses time, enhancing safety of operations and improving the precision and accuracy
of numerous operations [3, 4]. Operations carried
out in flow systems may include both preconcentration of the analyte and separation from other
sample components, which may interfere in the
detection. In the case of traditional manual techniques, the whole analysis may take even several
days, while the automated flow methods may
shorten analysis time to several minutes. The laboratory flow instrumentation, such as, for instance,
a multisyringe system using the advanced lab-on-valve (MSFIA-LOV) for sorbent bed renewal,
which is used in this study, offers the possibility of
conducting mechanized operations of active sample
processing with small volumes of reagents and generated radioactive wastes. What is the most impor-
tant, however in the automated radionuclides determination, the analyst is not exposed to emitted
radiation due to remote computerized control of
whole system. Thus, flow systems became promising tools to apply for continuous monitoring of
radionuclides for industrial or environmental purposes. These studies were focused on optimization
of the active sample processing in MSFIA-LOV
system for 99Tc determination and on some additional aspects of the procedure reported in Ref.
[5] for the flow-injection determination of 90Sr
with inductively coupled plasma mass spectrometry
(ICP-MS) detection.
The essential feature of the MSFIA-LOV system (Crison Instruments, Spain) used in this work
is the use of so-called lab-on-valve (LOV), a rotary, computer-controlled multiposition valve incorporating a sorbent mini-column (microcolumn)
(1.6 mm I.D./16 mm long) for conducting a preconcentration and separation processes. The microcolumn can be automatically filled with renewable beads of 40 mg of Sr-resin or 50 mg of
TEVA resin, which were contained in a 1 mL
plastic syringe mounted on the outlet of one of
microchannels of the LOV. A glass fibre prefilter
(Millipore) is used at the end of the column to pre-
vent sorbent leaking. This unit is connected with
a syringe burette with a PTFE (polytetrafluoroethylene) holding coil (1.5 mm I.D./7 m long).
The rest of the flow network was constructed with
0.8 mm I.D. PTFE tubes connected to the microchannels of LOV, and they were used for direct
aspiration of eluents from reservoirs. The flow
procedure was programmed and operated by the
software AutoAnalysis 5.0 (Sciware, Spain). The
used ICP-MS instrument was Elan DRC II provided by Perkin Elmer (USA), equipped with a cross-flow nebulizer, Scott double-pass spray chamber
and nickel cones. In order to achieve more sensitive measurements, ICP-MS detector was equipped
with additional dynamic reaction cell (DRC) system working with methane and argon as a carrier
gas. The solutions of stable isotopes of examined
elements (strontium, rhenium, molybdenum, ruthenium) were obtained by appropriate dilutions of
the standards (Peak Performance, USA) with distilled water solutions and nitric acid (65% HNO3,
purified by sub-boiling point distillation). The active standard solution of 90Sr (40.68 kBq/g) was
obtained from Amersham (UK) and purified prior
to the use by separation from its daughter product 90Y on stationary column filled with Sr-resin.
In 90Sr determination, two different types of sorbents were used: (1) extraction resins – commercial
Sr-resin™ of particle size of 20-50 m, and 50-100
m (Triskem Industries, France), (2) the ion-exchange resin – Dowex 50WX8 100-200 mesh
(Serva, Germany). For 99Tc determination, the extraction resin TEVA 50-100 m (Triskem Industries,
France) was applied.
The methodology of 90Sr determination in flow
conditions was based on the mechanized processing of active sample in MSFIA-LOV system and
then off-line ICP-MS detection. The mechanized
sample processing procedure included a series of
operations including the loading extraction sorbent into the microcolumn built in LOV valve, its
conditioning, loading the sample onto the resin
bed and then a separation of sample components.
The detailed description of the studies on potential interferences in 90Sr determination was included in Ref. [5]. This year, studies were focused
on the examination the possibility of 90Sr preconcentration from a large sample volumes, which is
needed due to the low level of the analyte activity
reported in the reactor coolant, e.g. 666 Bq/L
value reported by Dyer and Bechtold [6]. We have
found earlier that this cannot be performed with
the use of extraction Sr-resin. Hence, for this purpose, a cation-exchange resin Dowex 50WX8
was used and packed in an outer microcolumn of
0.5 mL volume, which was incorporated into the
manifold of flow system. The 100 mL of 6 g/L
strontium solution in 0.1 M HNO3 was introduced into the cation-exchange column and then
retained analyte was eluted using 8 M nitric acid
(Fig.1). The conducted optimization of the concentration process began from the 100 mL of the
sample; however, further experiments also indicate the possibility of the effective strontium preconcentration even from 1000 mL of the sample.
67
Fig.1. Preconcentration and elution of strontium on cation-exchange resin Dowex 50WX8 (200 mesh) packed in 0.5
mL column. Plot shows the strontium concentration determined in an eluate during loading column with 100 mL
sample containing 6 g/L of strontium with a flow rate of
2 mL/min and elution of retained strontium with consecutive portions of 1 mL of 8 M HNO3 solution.
The elution of retained analyte requires the use of
2 mL of 8 M HNO3, and the obtained eluate can
be directly loaded onto Sr-resin microcolumn to
separate interfering species.
In further optimization, in the system and the
same conditions, the Sr-resin with smaller particle
size 20-50 m was examined. The microcolumn
of LOV was filled with 1 mL acidic suspension of
40 mg Sr-resin (20-50 m) and 1 mL sample of
strontium standard (250 g/L) was loaded, which
was followed by washing with 1 mL of 8 M HNO3
to remove interferences, and finally the retained
analyte was eluted with 10 mL of water. The collected fractions were measured by ICP-MS (88Sr).
The change of Sr-resin bed to smaller particles
resulted in the improvement of the total analyte
recovery which increased to 80%, but above all, it
allowed to use the same bed of the sorbent bed at
least for 30 analyses (Fig.2), while a resin of larger
particle size allowed to perform only three up to
five retention/elution cycles. This can probably
be attributed to the larger active surface of the
resin with smaller particle size, and hence slower
washing out of the layer of octanol film containing dissolved crown ether ligand, used for the
chelation of the analyte.
The final step of the development of the analytical procedure for 90Sr determination was a
more detailed optimization of the ICP-MS detection conditions involving the use of DRC module
Fig.2. Recovery of strontium in repeated cycles of retention/elution on 40 mg bed of Sr-resin of 20-50 m particle
size, evaluated by the determination of strontium in each
stage of the procedure: () injection of 1 mL sample containing 250 g/L of strontium into the column, () removal of interferences with 1 mL of 8 M HNO3, () final
elution of strontium with 10 mL of water.
68
as integrated module of commercial instrument.
In our initial measurements, nitrogen was used as
the carrier gas in an ICP-DRC-MS; however, it
was found in the literature that the use of nitrogen can be a source of some polyatomic interferences. Similar to the reported species such as
56
Fe16O(H2O)+, 58FeO2+, 58NiO(H2O)+ and 58NiO2+
[7], species such as 58Fe14N(H2O)+, 56Fe14(NH3)2+
and 57Fe16O(NH3)+ of a mass 90 can also be expected with iron isotopes, and thereby they can
interfere with measurements of 90Sr. In fact, we
have found that their effect was observed during
calibration of ICP-MS instrument for 57Fe isotope,
where increasing presence of species with mass
90 was observed. We have proved that this interference can be eliminated by replacing nitrogen to
methane as a reaction gas. Based on calibration
curve recorded in optimized measuring conditions
(Fig.3), both for stable and radioactive isomers of
strontium, the LOD values were evaluated as 20
pg/mL and 0.1 Bq/mL, respectively. The obtained detectability is sufficient to apply developed
ICP-DRC-MS method in determination of 90Sr,
which can present in reactor coolant. The first attempt carried out was based on the application of
developed procedure for ICP-MS determination
of 90Sr in simulated reactor water, which was prepared according to the IAEA (International Atomic
Energy Agency) description of model reactor coolant [8]. The activity level of 90Sr in the sample
was adjusted following the result of radiometric
The flow-injection determination of 99Tc can
be carried out in similar system with ICP-MS detection; however, it was confirmed that in this case,
the separation and preconcentration processes
can be carried out simultaneously with the use of
a commercially available TEVA resin dedicated
for the determination of tetravalent actinides and
technetium. The optimization process of analytical procedure was conducted with surrogate rhenium, as an analogue of technetium. The procedure
of 99Tc determination consists of several steps,
including loading the LOV microcolumn with the
TEVA resin and then conditioning it prior to introducing the sample. Because of organic contamination of the sorbent, the resin has to be first
washed with 1 M NaOH, water and 1 M HNO3.
The second stage of the analytical procedure is the
removal of 99Tc interferences by additional injection of portion of acidic eluent. Finally, the analyte
retained on the column is eluted with 8 M HNO3.
Fig.4. Scheme of a flow-injection sample processing procedure for 99Tc determination in reactor coolant with
MSFIA-LOV measuring system, which includes preconcentration and separation processes with the use of extraction type TEVA resin (50 mg) packed in microcolumn
incorporated in LOV.
Fig.3. A calibration curve for the determination of 90Sr in
the activity range up to 1000 Bq/mL with ICP-DRC-MS
detection using methane as a reaction gas.
detection of reactor coolant in real sample obtained from research nuclear reactor in Świerk
(Poland). The 1 L sample of simulated reactor
water containing 130 Bq/L of 90Sr was analysed
in developed MSFIA-LOV system with programmed preconcentration and separation processes.
First, whole sample in 10 mL portions (determined
by a volume of a syringe of the MSFIA unit) was
loaded at a flow rate 10 mL/min to outer column
filled with cation-exchange resin to preconcentrate
90
Sr. The retained analyte was eluted with 3 mL
of 8 M HNO3 and directly introduced to Sr-resin
microcolumn in LOV, where the separation process
took place. Finally, strontium was eluted with 10
mL of water and measured by ICP-DRC-MS. The
total recovery of 90Sr was 69% and the whole procedure took 6 h; however, some further attempts
will be focused on shortening the analysis time.
The processed samples are off-line measured by
ICP-MS. The scheme of developed procedure is
shown in Fig.4, while their details are as follows:
• The TEVA resin is loaded into a microcolumn:
1 mL of sorbent suspension (50 mg in 0.1 M
HNO3) is aspirated at a flow rate of 1 mL/min
first to the holding coil and then to the microcolumn built in the LOV.
• Conditioning of TEVA resin: the sorbent bed
is conditioned with 3 mL of 0.1 M HNO3 aspirated by port 3 of LOV to the holding coil
and then to the microcolumn at flow rate of 2
mL/min.
• Sample loading: 1 mL of 250 g/L rhenium solution, which was prepared in 0.1 M HNO3
from 10 mg/L sodium perrhenate solution, is
aspirated by port 4 in LOV to the holding coil
at a flow rate of 5 mL/min and then injected to
TEVA resin bed packed in the microcolumn at
a flow rate of 0.6 mL/min.
• Removal of interferences: The potential interferences are removed from TEVA bed by inject-
ing 1 mL of 0.1 M HNO3 from port 3 at a flow
rate of 5 mL/min to the holding coil and then
aspirated through the microcolumn at a flow
rate of 2 mL/min.
69
are shown in Fig.5. They demonstrate that all isobaric interferences have weak affinity to TEVA
resin, and hence they can be almost completely
removed in first two stages of the procedure, and
Fig.5. Efficiency of the removal of potential spectral interferences in ICP-MS determination of rhenium using a microcolumn packed with 50 mg TEVA resin, expressed by the recovery of each interfering element in sample flown through the
TEVA-resin column (first group of signals in histogram), in three portions of 1 mL of 2 M HNO3 solution used for elution
of interfering elements and in 1 mL of 8 M HNO3 solution used for elution of retained rhenium (last group of signals).
In each case, 1 mL 250 g/L rhenium solution containing 250 g/L of interfering elements (molybdenum, ruthenium)
was processed.
• Elution of rhenium: The analyte retained on
the resin is eluted with 1 mL of 8 M HNO3 at a
flow rate of 2 mL/min.
• ICP-MS detection: The solutions of rhenium
eluted from the column are collected and diluted 20 times with 2% HNO3 containing 5 g/L
of indium as an internal standard prior to the
measurement.
In the optimization of the flow procedure for
99
Tc determination, the first studied aspect was
the elimination of potential interferences that
may disturb the used ICP-MS detection. 99Ru and
98
Mo1H are considered as the main isobaric interferences. In the literature, one can find two different methods applied in purpose to separate technetium from molybdenum and ruthenium on TEVA
resin. First one assumes the elimination of the
mentioned interferences by use diluted HNO3 solution [9, 10], while the second one uses much
more concentrated HNO3 solution, e.g. 2 M HNO3
[11, 12]. Both of them were tested in our studies;
however, only the first one gave satisfactory results in application in flow procedure. In the conducted experiment, the potential isobaric interferences molybdenum and ruthenium were added
to the rhenium sample in equal concentration of
250 g/L. After loading and conditioning the TEVA
resin bed in the microcolumn, 1 mL of analysed
solution was introduced into the sorbent bed and
then the interferences were removed with three
successive 1 mL portions of 0.1 M HNO3 solution. Finally, the retained analyte was eluted with
1 mL of 8 M HNO3. The collected fractions were
measured with ICP-MS, and the obtained results
only up to 10% of their initial content can be present in the final eluate with the analyte.
The conducted optimization also included the
examination of the TEVA resin bed durability in repeated retention/elution cycles. The portion of the
sorbent (50 mg) loaded into the microcolumn allowed to carry out at least 30 successive analyses.
The analysis included injection of 1 mL sample of
rhenium solution (250 g/L), elimination of interferences by washing the column with 2 mL of 0.1
M HNO3 solution, and elution of the analyte with
1 mL of 8 M HNO3. The collected fractions were
analysed with ICP-MS. The results of the experiment are presented in Fig.6. In further research,
Fig.6. Recovery of rhenium in repeated cycles of retention/
elution on 50 mg bed of TEVA resin of 50-100 m particle
size, evaluated by the determination of strontium in each
stage of the procedure: () injection of 1 mL sample containing 250 g/L of rhenium into the column, () removal
of interferences with 2 mL of 2 M HNO3, () final elution
of rhenium with 1 mL of 8 M HNO3.
an attempt will be made to replace the same purpose of extracting TEVA resin with conventional
polymeric anionite.
70
References
[1]. Vajda, N., & Kim, C.K. (2010). Determination of radiostrontium isotopes: A review of analytical methodology. Appl. Radiat. Isot., 68, 12, 2306-2326.
[2]. Shi, K., Hou, X., Roos, P., & Wu, W. (2012). Determination of technetium-99 in environmental samples:
A review. Anal. Chim. Acta, 709, 1-20.
[3]. Grate, J.W., & Egorov, O.B. (2003). Automated radiochemical separation, analysis and sensing. In M. L’Annunziata (Ed.), Handbook of radioactivity analysis
(pp. 1129-1164). 2nd ed. USA: Academic Press.
[4]. Kołacińska, K., & Trojanowicz, M. (2014). Application of flow analysis in determination of selected
radionuclides. Talanta, 125, 131-145.
[5]. Kołacińska K., Bojanowska-Czajka A., & Trojanowicz
M. (2015). Study on interferences in flow-injection
determination of 90Sr with ICP-MS detection. In INCT
Annual Report 2014 (pp. 70-74). Warszawa: Institute of Nuclear Chemistry and Technology.
[6]. Dyer, N.C., & Bechtold, T.E. (1994). Radionuclides
in Unites States commercial nuclear power reactors.
Westinghouse Idaho Nuclear Company, Inc. (Report
WINCO-1191).
[7]. Taylor ,V.F., Evans, R.D., & Cornett, R.J. (2007). Determination of 90Sr in contaminated environmental
[8].
[9].
[10].
[11].
[12].
samples by tuneable bandpass dynamic reaction cell
ICP-MS. Anal. Bioanal. Chem., 387, 1, 343-350.
IAEA. (2011). Good practices for water quality
management in research reactors and spent fuel storage facilities. Vienna: IAEA, IAEA Nuclear Energy
Series No. NP.-T-5.2, p. 70.
Uchida, S., & Tagami, K. (1997). Separation and
concentration of technetium using a Tc-selective extraction chromatographic resin. J. Radioanal. Nucl.
Chem., 221, 1, 35-39.
Tagami, K., & Uchida, S. (2000). Separation of rhenium by an extraction chromatographic resin for determination by inductively coupled plasma-mass spectrometry. Anal. Chim. Acta, 405, 1, 227-229.
Mas, J.L., Garcia-León, M., & Bolivar, J.P. (2006).
Overcoming ICP-QMS instrumental limitations for
99
Tc determination in environmental solid samples using radiochemistry. Appl. Radiat. Isot., 64, 502-507.
Rodriguez, R., Leal, L., Miranda, S., Ferrer, L., Avivar,
J., Garcia, A., & Cerdà, V. (2015). Automation of 99Tc
extraction by LOV prior ICP-MS detection: Application to environmental samples. Talanta, 133, 88-93.
STABILITY TESTING OF NEW POLISH CERTIFIED REFERENCE MATERIALS
FOR INORGANIC TRACE ANALYSIS
BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY
Iga Kużelewska, Halina Polkowska-Motrenko, Zbigniew Samczyński
Certified reference materials (CRMs) are reference materials accompanied by documentation
issued by authority institutions giving one or more
specified property values with associated uncertainties and consistencies using the procedures of
proven regularity. These materials play an important role in the chemical measurements in analytical laboratories [1-3]. They are used to validate
analytical methods, quality assurance and quality
control, check skills of laboratories and analysts
[4-6]. The process of preparation and certification
of a candidate for reference material is a complex
task. The general strategy of the production of new
CRMs is based on the procedures from the Laboratory of Nuclear Analytical Methods INCT [3-5],
which follow the requirements of ISO Guides [7].
The manufacture of CRMs consists of the following steps: (a) choice of the type of material, (b)
collection of the suitable amount of material, (c)
preparation of the material (comminution, grinding, sieving, homogenization), (d) preliminary homogeneity and stability tests, (e) distribution of
the material into containers and radiation sterilization, (f) procedure of the determination of dry
mass, (g) final check of homogeneity and stability
tests, (h) organization of the certification interlaboratory comparison, (i) evaluation of results,
(j) printing of the certificate and finally (k) CRM
ready – starting distribution and sale [5, 7-9]. The
important thing is to prepare the materials as homogeneous and stable as possible [10-12]. Stability testing is one of the ISO guides requirements.
CRMs for the purpose of inorganic trace analysis
should be characterized with stability of the con-
tent of elements to be certified in time. There are
various causes of instability of this type of CRMs
such as decomposition of the analyte or matrix,
autocatalysis and the activity of the microorganisms. In order to test the stability of CRM, the
samples of the candidate CRM were stored at various temperatures and analysed after the chosen
time intervals [13]. The obtained results were subjected to the statistical analysis.
In this work, we have studied the stability of
the new Polish reference materials of biological
origin: MODAS-3 Herring Tissue (M-3 HerTis),
MODAS-4 Cormorant Tissue (M-4 CormTis) and
MODAS-5 Cod Tissue (M-5 CodTis).
Long-term stability of the CRMs was examined by comparing analytical results of their elemental composition obtained at 0, 2, 4, 6, 10, 12 and
15 months of storage. The samples were taken
from CRMs stored under controlled conditions
(temperature – 20oC). Isochronous testing was applied, then the samples were frozen at -20oC and
analysed together at the end of the study. Then,
the samples were mineralized in a high-pressure
microwave system using concentrated mineral
acids. Samples of mass ca. 250 mg were digested
with 6 mL of HNO3 and 2 mL of H2O2. After digestion, all obtained solutions were diluted using
2% HNO3 and selected element content was determined by inductively coupled plasma mass spectrometry (ICP-MS). The elements to be determined
were Ag, As, Ba, Cd, Co, Cr, Cu, Fe, Mn, Mo, Pb,
Sr, U, V and Zn. To study the short-time stability
(associated with transport), the CRMs were stored
in the CO2 incubator (ASAB) at 37oC, 100% hu-
71
Table 1. The results of the analysis of the Polish reference materials: Herring Tissue (M-3 HerTis), Cormorant Tissue
(M-4 CormTis) and Cod Tissue (M-5 CodTis).
Elements
January 2014 March 2014
[g/g]
[g/g]
May 2014
[g/g]
July 2014
[g/g]
November
2014
[g/g]
February
2015
[g/g]
March 2015
[g/g]
HerTis
5.74 ±0.28
5.71 ±0.14
6.06 ±0.13
5.81 ±0.13
6.05 ±0.17
6.72 ±3.02
6.61 ±0.37
CodTis
1.29 ±0.04
1.47 ±0.23
1.27 ±0.06
1.26 ±0.03
1.23 ±0.05
1.36 ±0.19
1.21 ±0.05
CormTis 20.22 ±3.28
18.17 ±0.16
18.46 ±0.16
18.46 ±0.07
18.46 ±0.06
18.50 ±1.38
18.58 ±0.05
Cu
HerTis
90.92 ±3.45
90.45 ±2.22
95.99 ±4.88
92.86 ±3.24 92.89 ±0.002 98.42 ±3.02
98.54 ±1.96
CodTis
16.08 ±0.34
16.92 ±0.67
15.33 ±0.40
15.22 ±0.11
14.86 ±0.53
15.19 ±0.19
15.28 ±0.08
CormTis 52.65 ±2.34
50.87 ±0.16
51.36 ±0.16
51.54 ±0.12
51.55 ±0.28
52.06 ±3.59
52.66 ±2.16
Zn
Se
HerTis
-
-
-
-
-
-
-
CodTis
1.06 ±0.06
1.11 ±0.06
1.21 ±0.16
0.95 ±0.05
0.98 ±0.07
1.01 ±0.02
0.93 ±0.001
CormTis
1.06 ±0.11
1.03 ±0.04
1.01 ±0.08
0.95 ±0.03
0.94 ±0.09
0.94 ±0.08
0.94 ±0.06
HerTis
13.48 ±0.63
13.39 ±1.68
13.96 ±0.29
15.54 ±4.11
13.84 ±0.36
14.15 ±0.27
13.91 ±0.57
Mn CodTis
0.96 ±0.04
0.83 ±0.02
0.83 ±0.02
0.82 ±0.02
0.81 ±0.01
0.73 ±0.02
0.82 ±0.06
2.09 ±0.12
2.00 ±0.06
1.95 ±0.004
1.97 ±0.05
2.07 ±0.07
1.99 ±0.16
1.96 ±0.03
CormTis
HerTis 257.22 ±8.04 248.48 ±2.57 255.58 ±26 248.30 ±2.84 259.77 ±4.45 260.69 ±1.99 248.26 ±1.33
Sr
CodTis
4.03 ±0.07
3.82 ±0.03
3.96 ±0.02
3.89 ±0.12
CormTis 0.260 ±0.07
0.206 ±0.02
0.240 ±0.01
Cd
3.67 ±0.07
3.47 ±0.02
3.80 ±0.11
0.270 ±0.04 0.238 ±0.004
0.257 ±1.7
0.319 ±0.231
HerTis
0.36 ±0.002
0.35 ±0.008
0.36 ±0.019
0.36 ±0.005
0.36 ±0.006
0.36 ±0.01
0.36 ±0.019
CodTis
-
-
-
-
-
-
-
CormTis 0.013 ±0.004 0.011 ±0.001 0.008 ±0.001 0.011 ±0.002 0.008 ±0.001 0.009 ±0.002 0.014 ±0.003
HerTis
9.06 ±0.30
9.23 ±0.12
9.63 ±0.16
9.29 ±0.28
9.21 ±0.15
9.64 ±0.01
9.69 ±0.23
CodTis
1.63 ±0.04
1.62 ±0.04
1.61 ±0.01
1.58 ±0.05
1.54 ±0.02
1.56 ±0.02
1.63 ±0.01
CormTis 0.100 ±0.004 0.102 ±0.003 0.101 ±0.002 0.097 ±0.001 0.094 ±0.01
0.097 ±0.01
0.112 ±0.01
As
midity and 5% CO2 for two months. Then, the
samples were taken and analysed by ICP-MS.
To check the stability, we have applied the
ICP-MS method for the determination of selected
elements in new CRMs: Herring, Cod, Cormorant
Tissue. The obtained results are shown in Table 1.
The results were evaluated using the regression
analysis. It was assumed that the relation c = f(t),
where: c – element concentration, t – time, could
be described as a straight line, i.e. the changes if
occurring were small. The least square method
Concentration, mg kg-1
1.0
M-3 HerTis
Cd
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
0
5
10
15
20
Time, months
Fig.1. Concentration of cadmium in MODAS-3 Herring
Tissue during storage.
was applied. Functions c = a t + b were calculated for the following elements: MODAS-3
Herring Tissue – U, Ba, Zn, Mn, Co, Cd, Th, Cu,
Pb, Sr, Cr, Al, V, Mg, Ni, Fe, Mo, Li, Be, As, Ag,
Tl, Sb; MODAS-4 Cormorant Tissue – U, Ba, Zn,
Mn, Co, Cd, Th, Cu, Pb, Sr, Cr, Al, V, Mg, Ni, Mo,
Li, Be, As, Ag, Tl, Sb, Se and MODAS-5 Cod
Tissue – Ba, Zn, Mn, Co, Cu, Sr, Cr, Al, V, Mg, Fe,
Li, As, Se. An example of the regression line is
shown in Fig.1.
For all the determined elements in the studied
CRMs, no evidence of any trend (value of a did
not differ in a statistically significant way from 0)
was revealed. The contribution of uncertainty associated with long-time stability to standard uncertainty of CRM was evaluated. The uncertainty
of stability was calculated as the standard deviation of the slope of the regression line. The uncertainty of short-time stability was found to be insignificant. The obtained results allowed to conclude that the prepared materials M-3 HerTis,
M-4 CormTis and M-5 CodTis meet the requirements for CRMs and are sufficiently stable.
This project is financed in the framework of
grant entitled “Production and attestation of new
types of reference materials crucial for achieving
European accreditation for Polish industrial laboratories” attributed by the National Centre for
Research and Development.
72
References
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[6]. Polkowska-Motrenko, H., Dybczyński, R.S., Chajduk,
E., Dano, B. Kulisa, K., Samczyński, Z., Sypuła, M.,
& Szopa, Z. (2006). Polish reference material: Corn
Flour (INCT-CF-3) for inorganic trace analysis preparation and certification. Warszawa: Institute of Nuclear Chemistry and Technology. (Raporty IChTJ. Seria A no. 3/2006).
[7]. ISO/IEC. (2006). ISO/IEC Guide 35 : Reference materials – general and statistical principles for certification.
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& Szopa, Z. (2002). Preparation and certification of
the Polish reference material: Mixed Polish Herbs
(INCT-MPH-2) for inorganic trace analysis. Warszawa: Institute of Nuclear Chemistry and Technology.
(Raporty IChTJ. Seria A no. 3/2002).
[9]. Dybczyński, R.S, Polkowska-Moternko, H., Samczyński, Z., & Szopa, Z. (1993). New Polish certified
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97-104.
[11]. Linsingier, P.J., Pauweles, J., Lamberty, A., Schimmel,
G.H., Van der Veen, A.M.H., & Siekman, L. (2001).
Estimating the uncertainty of stability for matrix
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Schimmel, H., & Lamberty, A. (2001). Homogeneity
and stability of reference materials. Accred. Qual.
Assur., 6, 1, 20-23.
[13]. Linsinger, P.J., Van der Veen, A.M.H., Gawlik, B.M.,
Pauwels, J., & Lamberty, A. (2004). Planning and
combining of isochronous stability studies of CRMs.
Accred. Qual. Assur., 9, 8, 464-472.
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 (nanoMOF) materials,
• synthesis of functional materials – silver-modified cotton and cellulose fibres using radiation beam techniques,
• improvement of usable surface properties of special materials applied in nuclear energy
technologies (zirconium alloys, steels) using high-intensity pulsed plasma beams (HIPPB),
• characterization of art objects.
The design and construction of coordination polymers have been studied intensively for
many years as evidenced by the very rapid growth of publications. Our interests are focused
on light s block metals, coordination polymers with carboxylate ligands showing carboxylic
group and/or heterocyclic ring nitrogen functionality. In the last year, the new crystal complex
of lithium catena-poly[[[aqualithium(I)]--pyrimidine-2-carboxylato-4N1,O2:N3,O2’] hemihydrate] has been synthesized and its structure solved and published.
Porous coordination polymers also called metal organic framework materials are the topical subject in the recent years. They exhibit unique pore architecture and a broad range of
potential applications. The latter include greenhouse gas removal, storage of gases and selective separation of components of gaseous mixtures that are interesting for the development
of modern energy technologies. The pores’ structure and host-guest molecule interaction in
the case of MOFs can be tailored relatively easily for a potential application by carefully combining the ligand and type of metallic ion. At present, many potential applications of MOFs
require to obtain them at the nanometre length scale. Nanoscopic dimensions are essential in
providing MOFs with high surface areas, as e.g. for tuning their properties (catalytic, separation, sensing and sorption), mixed matrix membrane synthesis where MOFs’ particles are
used as fillers in a polymer matrix. The others include MOFs with size-dependent properties
(optical, electrical and magnetic) and biocompatible materials for biomedical applications,
e.g. encapsulation and transport of drugs. The integration of nanoscale MOFs on porous support will be advantageous for creating thin layer membranes. The studies performed recently
in the Laboratory of Material Research concerning synthesis of nanoscale MOFs are reported. The applied methods include template synthesis in the pores of track-etched membranes
with well-defined cylindrical pores, synthesis in microfluidic flow reactor and synthesis of
MOFs on the surface of porous alumina substrate.
Zirconium, due to their good water corrosion and radiation resistance at normal working
conditions of nuclear reactors, is commonly used as cladding material for fuel elements. However, in the case of LOCA (loss-of-coolant accident) conditions, the fastest possible oxidation
of zirconium at steam atmosphere or and air/steam mixture at temperatures above 800oC
results in intense hydrogen generation and possible hydrogen-oxide mixture explosion. These
events, however very rare, negatively influence the public acceptance for nuclear energy and
result in the high restoration costs of accompanying damages. The development of the methods
to minimize the risk in the case of design-based and beyond design-based accidents is urgently needed. The materials with enhanced tolerance to the high temperature oxidation have
already been proposed for this purpose, such as silicon carbide, Mo-Zr, FeCrAl claddings,
MAX phases and multilayer zirconium silicide coatings.
The zirconium silicide or zirconium silicate coatings are known for good resistance in
high-temperature conditions and for that reason are considered for application as environmental barrier coatings for high-temperature gas-turbine components. Up to now, they are
less explored for application as corrosion protective coatings for nuclear fuel pellets. However,
a review of existing literature and analysis of thermodynamic data indicates that silicon-based
coatings may offer excellent prospects in this field. Particularly, they may provide a more
protective barrier than the native ZrO2 films formed on alloy cladding during routine nuclear
reactor exploitation. Our works in last year have focused on the development of silicon-based
coatings on zirconium alloy claddings and evaluation of their properties at accident scenario
as well as under regular operation of the reactor. Two processes are considered for coating
preparation. The first one is based on deposition of layers containing zirconium oxide and
silicon oxide on zirconium alloy tubes (and on flat samples also) followed by densification of
deposited layers. The second one is based on the deposition of gradient layers of zirconium
and silicon (and possible of their oxides) by physical vapour deposition (PVD) method.
For the deposition of coating precursors, three methods are proposed: dip coating method using the mixed zirconium oxide and silicon oxide sols prepared by the sol-gel method, plasma
electrolytic oxidation in silicate containing solutions, electrophoretic deposition from zirconium oxide and silicon oxide containing suspensions or directly ZrSiO4 suspension.
For the densification of prepared porous layers, the unique technique of high-intensity pulsed
plasma beams will be applied or alternatively, electron beam operating in scanning mode.
For the examination, characterization and analysis of cultural heritage artefacts or art objects and their component materials, a conservation scientist 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 give a basis for their restoration
and conservation. Among various methods used for the examination of art objects, nuclear
techniques are crucial due to their high sensitivity and reproducibility. Mediaeval Central
Europe coins: the Saxon coins, so-called the Otto and Adelheid denarii as well as the Polish
ones, the Władysław Herman and Bolesław Śmiały coins, were examined to determine their
provenance and dating. Non-destructive traditional surface analysis of silver-copper ancient
coins by X-ray fluorescence (XRF), electron probe microanalysis (EPMA) or particle-induced
X-ray emission spectroscopy (PIXE) may not result in reliable bulk composition data due to
silver enrichment of the near-surface layers. In our work, the prompt gamma activation analysis
(PGAA) method was chosen as the analytical method largely on the basis of ready application
as a non-destructive method which can be used to study a large number of samples and which,
in comparison with XRF, will give a bulk silver content free from errors due to surface leaching
or enrichment. At this stage, a selection of 55 silver denarii, minted during the period AD 960
to 1100, has been examined by means of PGAA method to determine their silver and copper
content. The Cu/Ag mass ratios were determined for the detection of debasement and ancient counterfeiting of coins. Consequently, PGAA seemed to be an ideal method for the determination of the bulk composition and can be considered as a non-destructive method,
which is the above all requirement for the investigation of valuable archaeological objects.
The investigation into the chemical composition and manufacturing technology of historical glass was continued in 2015. The main efforts were focused on the seventeenth-century colourless glass from Amsterdam in Holland. The project was carried out together with
bureau Monumenten en Archeologie (MenA), Amsterdam. Over 100 archaeological fragments
have been analysed using scanning electron microscopy-energy dispersive spectrometry
(SEM-EDS). The objects were collected from two glasshouse sites and the selected cesspits.
The obtained results allowed us to conclude that the seventeenth-century glass produced in
Amsterdam was of sodium type. It is worthy to underline that most of the glasses melted in
northern Europe during this time was of potassium rather than of sodium type, and from this
point of view, Amsterdam’s glass constitutes a unique production in the continent.
75
METAL ORGANIC FRAMEWORK COMPOSITE MATERIALS
WITH POLYMER OR CERAMIC BASE
Bożena Sartowska, Wojciech Starosta, Oleg Orelovitch1/, Pavel Apel1/, Marek Buczkowski
1/
Joint Institute for Nuclear Research, Flerov Laboratory of Nuclear Reactions, Dubna, Russia
Introduction
Metal organic framework (MOF) materials are
porous coordination polymers built from metal
(metal cluster) connected by multifunctional organic ligands. Their structure, particularly pore dimensions and geometry as well as physicochemical properties of pore walls, depends on the combination of metal ion and ligand. Tailoring of MOF
for specific applications is possible. MOF materials
are considered as novel, emerging class of sorbents for gas molecule storage and for separation of
gaseous mixtures. The number of new discovered
structures grew continuously. At present, a few
MOF compounds are produced commercially by
chemical company BASF. One of them is used for
testing in innovative fuel systems for natural gas
vehicles [1]. The detailed information concerned
MOF synthesis and applications can be found in
many review articles, conference materials and
regular papers, such as, e.g. in Ref. [2]. New field
of applications concerns removal of volatile radioactive species associated with nuclear fuel reprocessing, in particular, containing 124I, 85Kr, 14C
and tritium isotopes [3]. MOF-oriented research
work carrying out in the Laboratory of Material
Research at the Institute of Nuclear Chemistry and
Technology (INCT) is focused on (i) synthesis of
MOF crystals inside the pores of polymeric track-etched membranes (it would give the thin membrane which can be applied for gas mixture separation and for gas sensor preparation); (ii) synthesis
of MOF membrane on porous support like alumina
porous ceramics; (iii) synthesis of MOFs morphologically uniform crystallites, which can be applied
as fillers in polymers.
Template synthesis
Polymeric track-etched membranes are porous
systems comprising a polymer film with thin
channel-pores from surface to surface [4, 5]. Polymeric film is irradiated with accelerated heavy
ions and then etched in etching solution. Their
pore size, shape and density can be varied in a
controllable manner so that a membrane with the
required transport and retention characteristics
can be produced. The interfacial synthesis at the
room temperature in the system shown in Fig.1A
has been found effective for deposition of HKUST-1
crystallites inside the pores of track-etched membrane. The crystallization solutions were prepared
from copper nitrate trihydrate salt and 1,3,5-benzenetricarobxylate acid taken in stoichiometric
ratio and dissolved in water/ethanol/DMF solvent
[6]. The general view of the membrane side contacting crystallization solution with clearly seen
small crystallites filling the pores is presented in
Fig.1B. A deeper understanding of chemical reactions and molecular transport processes in confined space of pores will be necessary for reliable
composite membrane preparation.
A
B
Fig.1. (A) Scheme of synthesis set-up, (B) polymeric track-etched membrane surface with small HKUST-1 crystallites filling the pores (pore diameter – 0.45 m).
Synthesis on the surface of porous alumina
membrane
Synthesis of ZIF-8 crystallites on porous alumina membrane has been performed in two steps.
In the first step, the surface of membrane has been
activated by refluxing in the 2-methylimidazole
solution. Then, the sample has been transferred
to the PTFE lined autoclave for the synthesis
(120oC, 36 h). The crystallization solution has
been prepared from 0.018 M zinc chloride and
0.063 M 2-methylimidazole dissolved in 80 mL of
methanol. The 0.042 M of formic acid has been
added to this mixture, in order to support crystallization on the surface of alumina sample. Results
of this experiment are shown in Fig.2. Both composite components – alumina base and ZIF-8 –
were identified in the obtained product by X-ray
diffraction.
Microfluidic synthesis
The main advantages of this method are the
possibility to create particles with a narrow range
of sizes and the possibility of fine control of the
shape and composition of nanomaterials [7]. Used
instrument consist of syringe pumps for metal salt
and ligand solution stainless steel tube reactor
with the inside diameter of 0.85 mm and length of
1 m placed in the thermostat (Fig.3A). Uniform
76
A
A
B
B
Fig.2. (A) Porous alumina base, (B) porous alumina surface covered with ZIF-8 crystallites.
rod-shaped crystallites were formed (Fig.3B) using
0.06 M solution of copper nitrate hexahydrate and
0.135 M solution of 1,3,5-benzenetricarboxylic
acid solution in water/ethanol mixture at flow
speed of 1-2 mL/h and temperature of 80oC. The
presence of HKUST-1 phase has been confirmed
by X-ray powder diffraction.
Conclusions
MOF deposition inside the pores of polymeric
track-etched membranes and on the surface of porous alumina has been demonstrated. Microfluidic
synthesis method seems to be promising for the
fabrication of morphologically uniform nanoscale
MOFs.
The work has been performed in cooperation
with the Joint Institute for Nuclear Research
(JINR), Dubna, Russia, under contracts 04-5-10762009/2016 and 04-4-1121-2015/2017. The financial support by the Polish Ministry of Science and
Higher Education grants: 3090/ZIBJ Dubna/2014,
3176/ZIBJ Dubna/2014 and 3420/ZIBJ Dubna/
2015/0 is gratefully acknowledged.
References
[1]. Arnold, L., Averlant, G., Marx, S., Weickert, M., Müller, U., Mertel, J., Horch, C., Peksa, M., & Stallmach, F.
Fig.3. (A) The general view of microfluidic synthesis system, (B) HKUST-1 crystallites synthesized in microfluidic
flow system.
[2].
[3].
[4].
[5].
[6].
[7].
(2013). Metal organic framework for natural gas storage. Chem. Ing. Tech., 85 (11), 1726-1733. DOI:
10.1002/cite.201300093.
[Themed issue on MOFs]. (2014). Chem. Soc. Rev.,
43, 16, 5403-6176,
Chen, L., Reiss, P., Chong, S., Holden, D., Jelfs, K.,
Hasell, T., Little, M., Kewley, A., Briggs, M., Stephenson, A., Thomas, K., Armstrong, J., Bell, J., Busto, J.,
Noel, R., Liu, J., Strachan, D., Thallapally, P., & Cooper,
A. (2014). Separation of rare gases and chiral molecules by selective binding in porous organic cages. Nat.
Mater., 13, 954-960. DOI: 10.1038/nmat4035.
Apel, P. (2013). Track-etching. In Encyclopedia of
membrane science and technology (pp. 1-25). John
Wiley and Sons. DOI: 10.1002/9781118522318.
Apel, P., Blonskaya, I., Orelovich, O., & Sartowska,
B. (2012). Asymmetric track-etch membranes for microand nanofluidics. Procedia Eng.. 44, 649-652. DOI:
10.1016/j.proeng.2012.08.518.
Majano, G., & Pérez-Ramirez, J. (2012). Room temperature synthesis and size control of HKUST-1. Helv. Chim.
Acta, 95, 2278-2286. DOI: 10.1002/hlca.201200466.
Brown, A., Brunelli, N., Eum, K., Rashidi, F., Johnson, J., Koros, W., Jones, C., & Nair, S. (2014). Interfacial microfluidic processing of metal-organic framework hollow fiber membranes. Science, 345, 72-76.
DOI: 10.1126/science.1251181.
77
ARCHAEOMETRICAL STUDY OF MEDIAEVAL SILVER COINS
FROM POLAND AND CENTRAL EUROPE
BY PROMPT-GAMMA ACITIVATION ANALYSIS
Ewa Pańczyk, Lech Waliś, Zsolt Kasztovszky1/, Boglarka Maróti1/, Maciej Widawski2/,
Władysław Weker2/
1/
Centre for Energy Research, Hungarian Academy of Sciences, Budapest, Hungary
2/
National Archaeological Museum, Warszawa, Poland
The study of the composition and the content of
the trace elements of ancient coins provides valuable information about the metallurgy and economy
of the time of minting the coins. A material research on the historical artefact constitutes an
important additional factor that helps us to choose
the proper conservation methods. The goal of the
research project was to characterize a few groups
Saxon coin type I – obverse, reverse
Saxon coin type I – obverse, reverse
Saxon coin type II – obverse, reverse
Saxon coin type V – obverse, reverse
of the early mediaeval Central Europe coins. The
Sachsenpfenning struck from the mid-tenth century till the end of the eleventh century were selected for the examination. For comparison, the
Otto and Adelheid denarii (AD 991-995), Arabic
dirhams, Hungarian and Czech denarii as well as
the Polish ones, the Bolesław Chrobry, Bolesław
Śmiały, Władysław Herman and the Paltine Sieciech coins were also examined [1]. Examples of
investigated coins are presented in Fig.1.
Non-destructive traditional surface analysis of
silver-copper ancient coins by X-ray fluorescence
(XRF), electron probe microanalysis (EPMA) or
particle-induced X-ray emission spectroscopy
(PIXE) may not result in reliable bulk composition data due to silver enrichment of the near surface layers. In our work, the prompt-gamma activation analysis (PGAA) method was chosen as the
analytical method largely on the basis of ready application as a non-destructive method which can
be used to study a large number of samples and
which, in comparison with X-ray fluorescence, will
give a bulk silver content free from errors due to
surface leaching or enrichment.
At this stage, the selection of 55 silver denarii,
minted during the period AD 960 to 1100, has
been examined by means of PGAA method to determine their silver and copper content. Indeed,
the PIXE measurements of the test samples taken
from different surface points of one particular coin
show very inhomogeneous composition. Consequently, PGAA seemed to be an ideal method for
the determination of the bulk composition and can
be considered as a non-destructive method, which
is the above all requirement for the investigation
of valuable archaeological objects.
PGAA is a multicomponent analytical method,
i.e. all the chemical elements can be detected with
different sensitivities. In principle, it is possible to
determine both the major and the trace elements
Saxon coin type VI – obverse, reverse
Otto and Adelheid denarius – obverse, reverse
Fig.1. Examples of investigated coins.
Fig.2. Neutron-induced prompt-gamma spectroscopy system at the Budapest Neutron Centre.
78
100
prompt
decay
background
Intensity (cps)
10
1
0.1
0.01
0.001
0.0001
10
1000
2000
3000
E (keV)
4000
Decay-lines:
108Ag
2.39 min 618.8 keV; 633.0 keV
110Ag
24.6 s
5000
Intensity (cps)
0
108
Ag
110
6000
Ag
1
0.1
prompt
decay
0.01
0.001
657.8 keV
600
620
640
660
680
700
E (keV)
Fig.3. Typical PGAA spectrum of silver coin – prompt and decay spectrum of Ag.
simultaneously, although the detection limits are
matrix-dependent. The measurements do not require sample preparation; they give prompt results. Moreover, usually after some days of cooling (i.e. decay of radioactive products), the same
identical sample can be returned to the user. However, one has to be careful with irradiation of Ag
because (n,) the reaction on silver produces a
long-life radioactive daughter (see below). Because
of the limited irradiation time and the complexity
Change Cu/Ag ratio in investigated denarii
PGAA_2_np.sta 6v*55c
4,5
OAP type II
OAP type IV
4,0
Bolesław Chrobry denarius
3,5
3,0
dirhams type A
hungarian denarius
dirhams type B
Bolesław Śmiały denarius
denarii type II
Czech denaius of Bolesław II
denarii type II
Czech denarius of Spitygniew
denarii type V
denarus of Palatine Sieciech_1
denarii type VI-B
2,5
Cu/Ag
denarii type VI-C
denarii type VI-D
2,0
denary krzyżówe typ VI-E
denarii type VI-F
1,5
denarii type VII
1,0
denarii type VIII
0,5
0,0
-0,5
d2
d9
d16
d20
d212 d124
d33
d69
d152 d136 d169 d184 d219 d227
Fig.4. Change in composition of investigated denarii.
79
Table 1. Cu/Ag ratios of investigated denarii determined by PGAA method.
Sample
code
d2
d4
d5
d7
d9
d11
d14
d15
d16
d17
d18
d19
d20
d21
d22
d213
d212
d214
d215
d23
d124
d28
d29
d30
d33
d42
d43
d47
d59
d72
d80
d50
d152
d153
d146
d147
d136
d92
d107
d168
d169
d174
d182
d229
d184
d186
d201
d202
d219
d221
d223
d227
d231
d222
d211
Ag unc
Cu
unc
unc
Cu/Ag
abs unc
[wt%] [%] [wt%] [%]
[%]
Description
Subgroup
Dzierząźnia 203R, OAP
Grójec-35R, OAP
Grójec-36R, OAP
Grójec-37R, OAP
PMA/V/5386, Brzozowo Nowe 60R, OAP
Zakrzew 40R, PMA/V/5382, OAP
MN 293R, PMA/V/5296, OAP
MN 382R, PMA/V/5296, OAP
Obra Nowa 323R, dirham
Brzozowo-128R, type I
Brzozowo-129R, type I
Brzozowo-146R, type II
Brzozowo-152R, type II
Dzierząźnia 275R, type II
Dzierząźnia 278R, type II
Zbiersk-23R, type V
Zbiersk-24R, type V
Zbiersk-31R, type V
Zbiersk-kn 36R, type V
Zbiersk-28R, type V
Słuszków, type VI, MOZK11201
Śląsk [21], type VI
Górki-30R, type VI
Wodzierady-10R, type VI_Zn
Denarius of Palatine Sieciech, MOZK12659
Górki-33R, type VII
Górki-39R, type VII
Cieszyków 2009, type VII, C-J09[15]
Cieszyków 2009, type VII, C-T09[17]
Jastrzębniki 873[5], type VIII
Hungarian denarius (~1/2), Jastrzębniki, 891[7]
Czech denarius of Bolesław II (~1/2), Kalisz,
KSM25/2006[11]
Czech denarius of Spitygniew (~2/5), Cieszyków 2009,
C32009[19]
Denarius of Palatine Sieciech, MOZK12658
Denarius of Bolesław Śmiały, Kalisz - Stare Miasto [10]
Obra Nowa 130R, denarius of Bolesław Chrobry
IV
IV
IV
IV
IV
IV
IV
IV
IV
III
III
III
III
III
III
Ad
Bd
Bd
Bd
I
I
II
II
II
II
V
V
V
V
V
V
V
B
B
B
B
B
C
D
D
D
D
E
F
VII
VII
VII
VII
VIII
W
91.9
90.9
84.3
93.9
85.7
89.4
93.5
89.8
87.1
93.4
94.7
96.8
93.1
90.3
93.6
90.0
90.1
90.3
93.7
86.4
88.1
88.1
82.1
89.7
91.5
77.3
74.7
75.1
75.8
26.6
73.4
41.0
50.0
45.0
41.2
42.0
25.5
76.7
32.4
50.4
56.6
56.5
57.6
42.0
42.3
78.6
78.9
41.1
58.1
78.5
0.5
0.5
1.0
0.4
0.7
0.6
0.4
0.6
0.8
0.5
0.3
0.3
0.5
0.5
0.5
0.7
0.6
0.5
0.6
0.7
0.8
0.9
1.0
0.7
0.5
1.0
1.4
0.8
1.1
2.4
3.7
2.2
2.2
2.8
1.8
2.1
3.3
1.3
3.0
2.7
1.9
1.7
1.7
2.1
3.1
1.2
1.1
1.7
1.5
1.3
8.1
9.1
15.7
6.1
14.3
10.6
6.5
10.2
12.9
6.6
5.3
3.2
6.9
9.7
6.4
10.0
9.9
9.7
6.3
13.6
11.9
11.9
17.9
10.3
8.5
22.7
25.3
24.9
24.2
73.4
26.6
59.0
50.0
55.0
58.8
58.0
74.5
23.3
67.6
49.6
43.4
43.5
42.4
58.0
57.7
21.4
20.3
58.9
41.9
21.5
6.0
5.0
5.0
7.0
4.0
5.0
6.0
5.0
5.0
7.0
6.0
8.0
6.0
5.0
7.0
6.0
5.0
5.0
8.0
4.0
6.0
7.0
4.0
6.0
5.0
3.5
4.0
2.4
3.4
0.9
10.0
1.5
2.2
2.3
1.3
1.6
1.1
4.0
1.4
2.7
2.5
2.2
2.3
1.6
2.3
5.0
4.0
1.2
2.1
5.0
0.09
0.10
0.19
0.06
0.17
0.12
0.07
0.11
0.15
0.07
0.06
0.03
0.07
0.11
0.07
0.11
0.11
0.11
0.07
0.16
0.13
0.14
0.22
0.11
0.09
0.29
0.34
0.33
0.32
2.77
0.36
1.44
1.00
1.22
1.42
1.38
2.93
0.30
2.09
0.98
0.77
0.77
0.74
1.38
1.37
0.27
0.26
1.43
0.72
0.27
6.2
5.0
5.5
6.9
4.1
4.8
5.6
5.1
5.4
6.9
6.2
7.8
6.1
5.0
6.8
6.0
5.4
4.8
8.3
4.5
5.9
6.7
4.6
6.5
5.5
3.6
4.3
2.5
3.5
2.6
10.8
2.7
3.1
3.7
2.2
2.7
3.5
4.4
3.3
3.8
3.2
2.8
2.8
2.7
3.8
4.7
4.3
2.1
2.6
4.8
0.005
0.005
0.010
0.004
0.007
0.006
0.004
0.006
0.008
0.005
0.003
0.003
0.005
0.005
0.005
0.007
0.006
0.005
0.006
0.007
0.008
0.009
0.010
0.007
0.005
0.011
0.015
0.008
0.011
0.072
0.039
0.039
0.032
0.045
0.031
0.037
0.10
0.013
0.069
0.038
0.024
0.021
0.021
0.037
0.053
0.013
0.011
0.03
0.019
0.013
CB
93.1
0.5
6.9
6.0
0.07
6.1
0.005
CS
92.5
0.5
6.7
6.0
0.07
6.1
0.004
S
BŚ
BC
50.5
19.0
90.9
2.1
3.0
0.6
49.5
80.6
9.1
2.2
0.7
6.0
0.98
4.24
0.10
3.1
3.0
6.4
0.030
0.13
0.006
80
of elemental silver’s spectrum, we decided to determine the Cu/Ag ratios, instead of trace elements’ identification.
PGAA is based on the detection of gamma-ray
photons, which are emitted after the capture of
thermal or subthermal neutrons into the atomic
nuclei, i.e. the (n,) reaction. The photon energies
range between 50 keV and 11 MeV and are characteristic for a given element. The element identification is based on the precise determination of
gamma photon energies and intensities. The detected gamma-ray intensity is directly proportional to the mass of a given element, the analytical
sensitivity and the measurement time.
Instead of direct determination of every individual component’s mass, we apply the comparator method, or k0-method, which is widely used in
instrumental neutron activation analysis (INAA).
The k0 factors have been previously determined
from standardization measurement at the Budapest PGAA laboratory. A much more detailed
standardization procedure is described by Révay
and Molnár [2].
The PGAA measurements were performed at
neutron-induced prompt-gamma spectroscopy facility (Fig.2) at the Budapest Neutron Centre
(BNC). A guided cold neutron beam, obtained
from the 10 MW Budapest Research Reactor, is
used for the purpose of PGAA analysis. The thermal neutrons, which exit the reactor core, are
cooled by a liquid hydrogen cell down to 16 K.
Consequently, the achieved thermal equivalent
neutron flux is 5 107 cm–2s–1 [3]. The size of the
neutron beam was restricted to 1  1 cm2 area.
The investigated coins were packed in thin teflon
(FEP) films and were placed in a well-defined position of the sample holder chamber. In fact, because of the unacceptably high long-lived radioactivity of 64Cu and 110Ag isotopes, which were
produced during (n,) reaction, we had to reduce
the beam intensity. For this purpose, a perforated
plastic sheet, containing 6Li, was introduced.
According to a relative flux monitored by a thin
Cd-sheet, the estimated actual neutron flux was
as low as 1.7  106 cm–2s–1. The emitted gamma
photons were detected with a complex HPGe-BGO
detector system in Compton-suppression mode;
the signals were processed with a multichannel
analyser. The spectra were evaluated with Hypermet-PC software; the element identification was
performed on the basis of BNC prompt-gamma
element library.
During the investigation of silver coins, we have
focused on the determination of Cu/Ag ratio. The
peaks of interest were fitted by Hypermet-PC and
mass ratios were calculated. The combined standard uncertainties of the mass ratios depend on
the uncertainty of the counting statistics, the uncertainty of efficiency function and the uncertainty
of k0 factors. The most dominating of them is the
uncertainty of counting statistics.
The method was previously checked on a set
of copper-silver standard alloys, obtained from the
Institute of Standards for Noble Metals, Hungary,
and a good agreement was found [4]. The meas-
urement time for one individual coin varied between 460 s and 3700 s.
Although in most of the practical applications
in archaeometry [4, 5], PGAA is suitable for the
determination of both major and trace components, and in the case of silver objects it is almost
impossible to detect significant trace elements.
First, the limited irradiation time was not sufficient to reach the detection limits of most traces;
second, the complexity of the elemental silver spectrum and the high spectral density of prompt-gamma peaks cause numerous peak overlaps,
which makes the element identification much more
difficult than in the case of most other matrixes.
In order to determine the Cu/Ag mass ratios, the
practically interference-free 277.993 keV prompt-gamma peak of Cu and the 198.522 keV prompt-gamma peak of Ag were chosen (Fig.3). The possible peak overlapping was investigated, based on
BNC PGAA data library [5]. The theoretically
overlapping peaks for Cu – 277.993 keV (viz. Co
– 277.199 keV, Ir – 278.328 keV) and for Ag –
198.522 keV (viz. Ga – 198.002 keV, Cs – 198.111
keV, Er – 198.267 keV, As – 198.701 keV, Gd –
199.421 keV, Re – 199.439 keV and Ho – 199.659
keV) were excluded based on practical considerations.
Obtained results for all the 55 coins are shown
in Table 1. The bulk analysis of the coins has revealed an increasing Cu/Ag ratio as a function of
time. The mass ratio varies from about 0.03 to
about 4.24. The significant increase of Cu content, which is impossible to state by visual observation, can be discovered in Fig.4. This tendency
probably indicates the course of inflation at that
historical period.
Prompt-gamma activation analysis is a useful
non-destructive tool to investigate the bulk composition of valuable archaeological objects. In comparison with X-ray fluorescence analysis, it provides bulk silver content, which is free from errors
due to surface leaching and diffusion of copper
during the corrosion process.
This work has been performed at the Budapest
Neutron Centre, Hungary, within the contract
CHARISMA of the EU.
References
[1]. Pańczyk, E., Sartowska, B., Waliś, L., Dudek, J., Weker,
W., & Widawski, M. (2015). The origin and chronology of medieval silver coins based on the analysis of
chemical composition. Nukleonika, 60, 3, 657-663.
[2]. Révay, Zs., & Molnár, G.L. (2003). Standardisation
of the prompt gamma activation analysis method.
Radiochim Acta, 91, 361-369.
[3]. Révay, Zs., Belgya, T., Kasztovszky, Zs., Weil, J.L., &
Molnár, G.L. (2004). Cold neutron PGAA facility at
Budapest. Nucl. Instrum. Meth. B, 213, 385.
[4]. Szakmány, Gy., & Kasztovszky, Zs. (2004). Prompt
Gamma Activation Analysis: a new method in the
archaeological study of polished stone tools and
their raw materials. Eur. J. Mineral., 16(2), 285.
[5]. Révay, Zs., Molnár, G.L., Belgya, T., Kasztovszky, Zs.,
& Firestone, R.B. (2000). A new gamma-ray spectrum
catalog for PGAA. J. Radioanal. Nucl. Chem., 244(2),
383.
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 electron accelerators 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,
• support of industrial implementation of EBFGT process,
• 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;
• UV pulsed fluorescent SO2 analysers Model 40 and chemiluminescent NO/NOx analysers
with molybdenum converter Model 10 A/R, manufactured by Thermo Electron Corporation
(USA);
• gas chromatograph GC-17A with a mass spectrometer GCMS-QP5050 manufactured by
Shimadzu Corporation (Japan);
• portable gas analyser type Lancom II, manufactured by Land Combustion (UK) (NOx,
SO2, CO, O2, etc.).
The Laboratory is open for any form of cooperation. Especially we offer such activities as:
• laboratory research on environmental application of electron accelerators,
• theoretical modelling of chemical processes under electron beam irradiation,
• concept design of electron beam technology implementation,
• process equipment design with use of CFD methods.
In recent years, the Laboratory cooperated with such institutions as:
• Faculty of Chemical and Process Engineering, Warsaw University of Technology (Poland);
• International Atomic Energy Agency;
• Saudi ARAMCO (Saudi Arabia);
• EB Tech Co., Ltd. (Republic of 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 Pedagogics Academy (Ukraine);
•
•
•
•
•
•
•
•
Tsinghua University (China);
Alstom (Switzerland);
University of Palermo (Italy);
Institute for Polymers, Composites and Biomaterials (IPCB), National Research Council
(CNR) (Italy);
Hacettepe University (Turkey);
Institute of Macromolecular Chemistry “Petru Poni” Iasi (Romania);
University of Reims Champagne-Ardenne (France);
University Politehnica of Bucharest (Romania).
83
INVESTIGATION ON THE HIGH INLET CONCENTRATION
OF NOx REMOVAL UNDER ELECTRON BEAM IRRADIATION
Janusz Licki1/, Ewa Zwolińska, Sylwester Bułka, Andrzej G. Chmielewski, Yongxia Sun
1/
National Centre for Nuclear Research, Otwock-Świerk, Poland
NOx and SO2 are air pollutants harmful for humans, animals and nature. These pollutants can be
emitted from different sources such as burning of
fossil fuels, chemical industry or car engines. The
amounts of NOx and SO2 in exhaust gases can differ depending on the combustion process and type
of fuel used. Diesel oils, which are used among
others in cargo ship engines, contain very high
concentrations of both pollutants. This creates the
urgent need of finding the effective method for
cleaning off-gases that contain high concentrations of NOx and SO2, which would be possible to
apply in marine industry.
Electron beam flue gas treatment (EBFGT) is a
promising process for cleaning exhaust gases from
SO2 and NOx, which has been already applied in
Poland and China in power generation sector. The
technology principle is oxidation of the pollutants caused by irradiation of the gases with electrons from accelerator. This process was investigated with major focus on treatment off-gases
with low concentrations of SO2 and NOx. In this
study, we broadened the investigation to a wide
range of concentrations of both pollutants and
studied the influence of irradiation dose, inlet concentrations of SO2 and NOx as well as temperature on efficiency of the process. Furthermore, we
combined the EBFGT with wet scrubbing technology, which is widely used all over the world for
abatement of these pollutants. Using the hybrid
technology could significantly lower the energy
consumption, which would lead to a more cost
efficient process.
Experiments were carried out at an installation
for flue gas treatment in the Institute of Nuclear
Chemistry and Technology (INCT) equipped with
electron accelerator ILU-6. We obtained the simulated exhaust gas by adding appropriate amount
of NO and SO2 from gas cylinder to off-gases from
burning the light oil. The composition of the gas
before the reaction vessel was as follows: 70.6%
N2, 8.6% CO2, 8.2% H2O, 5.6% O2, 200-1700
ppmv NO and 500-2000 ppmv SO2. Two values of
temperature (70oC and 90oC) were studied to in-
Fig.1. Influence of the initial concentration of NO on NOx
removal efficiency under different irradiation dose.
vestigate the influence of this parameter on the
process. During other experiments, the temperature was 90oC. The irradiation dose varied between 4.4 kGy and 32.7 kGy. When the hybrid
technology was applied, gas after irradiation passed
through the following two wet scrubbers (500 mL
each) containing two types of oxidizing liquids:
simulated sea water (3.5% NaCl solution in deionized water) or simulated sea water with addition
of NaClO2 in KH2PO4 and Na2HPO4 buffer.
First, we investigated the influence of the initial concentration of NO on NOx removal efficiency; the results are presented in Fig.1.
NOx removal efficiency significantly drops with
increasing initial concentration of NO, especially
in the range between 200 ppmv and 1000 ppmv. Irradiation dose is the major parameter influencing
the removal efficiency of NO. The removal efficiency of NO increases with the increase in applied
dose. Nevertheless, when the initial concentration
of NO is high even when high dose is applied, the
efficiency is low.
Fig.2. Influence of the initial concentration of SO2 on NOx
removal efficiency, when the initial concentration of NO is
low (200 ppmv).
We also studied the influence of initial concentration of SO2 on NOx removal efficiency in the
following two cases: when the initial concentration of NO is low – 200 ppmv (Fig.2), when it is
high – 1000 ppmv (Fig.3).
In both cases, the initial concentration of SO2
has a positive effect on NOx removal efficiency. This
effect has been explained by the following chain
of reactions (1-4) [1]:
SO2 + OH + M = HSO3 + M
(1)
(M is a third body in a reaction system)
HSO3 + O2 = SO3 + HO2
(2)
NO + HO2 = NO2 + OH
(3)
NO2 + OH + M = HNO3 + M
(4)
Similarly, we investigated the influence of temperature in the reaction vessel on NOx removal ef-
84
electron beam (5.5%). The addition of NaClO2
buffered in KH2PO4 and Na2HPO4 induced even
higher NOx removal efficiency, up to 97%. This
effect can be explained by the following reaction
occurring in the scrubber (5) [2]:
4NO + 3NaClO2 + 2H2O = 4HNO3 + 3NaCl (5)
Fig.3. Influence of the initial concentration of SO2 on NOx
removal efficiency, when the initial concentration of NO is
high (1000 ppmv).
ficiency in two cases as follows: when the initial
concentration of NO is low – 200 ppmv (Fig.4),
when it is high – 1000 ppmv (Fig.5). In both cases,
the higher temperature causes higher NOx removal efficiency.
Fig.4. Influence of temperature in process vessel on NOx
removal efficiency at initial concentration of NO being
200 ppmv.
We also studied hybrid technology, which combines electron beam method with wet scrubber
with initial concentration of NO and SO2 being
1500 ppmv and 700 ppmv, respectively. First, simulated sea water was used as wet scrubber. We obtained significantly higher removal efficiency of
NOx (up to 50%) in comparison with using only
Fig.5. Influence of temperature in process vessel on NOx
removal efficiency at initial concentration of NO being
1000 ppmv.
Based on our experimental results, we draw
the following conclusions: NOx removal efficiency
mostly depends on irradiation dose and initial concentration of NO. The biggest differences in the
level of efficiency can be observed when the initial concentration of NO changes from 200 ppmv
to 1000 ppmv. Irradiation dose has no significant
impact on NOx removal efficiency when the initial concentration of NO is very high (above 1000
ppmv). When SO2 is present in exhaust gas, synergistic effect occurs and NOx removal significantly
improves. Higher temperature is beneficial to obtain higher removal efficiency of NOx irrespective
of initial NO concentration. The process can be
significantly improved by combining wet scrubber
with the presence of an oxidant, which enables to
obtain up to 97% removal efficiency of NOx, even
when the initial concentration of NO is as high as
1500 ppmv.
References
[1]. Chmielewski, A.G., Sun, Y., Licki, J., Pawelec, A., Witman, S., & Zimek, Z. (2012). Electron-beam treatment
of high NOx concentration off-gases. Radiat. Phys.
Chem., 81 (8), 1036-1039. DOI: 10.1016/j.radphyschem.2011.12.012.
[2]. Adewuyi, Y.G., He, X., Shaw, H., & Lolertpihop, W.
(1999). Simultaneous absorption and oxidation of NO
and SO2 by aqueous solutions of sodium chlorite.
Chem. Eng. Commun., 174, 1, 21-51. DOI: 10.1080/
00986449908912788.
85
OPTIMIZATION OF PROCESS PARAMETERS INFLUENCING
THE REMOVAL OF SO2 AND NOx
DURING ELECTRON BEAM FLUE GAS TREATMENT PROCESS
BY MATHEMETICAL MODELLING IN MATLAB
Ewa Zwolińska, Valentina Gogulancea1/, Vasile Lavric1/, Yongxia Sun, Andrzej G. Chmielewski
1/
University Politehnica of Bucharest, Bucharest, Romania
One of the most dangerous pollutants in the air is
sulphur dioxide (SO2) and nitrogen oxides (NOx),
especially NO and NO2. All of them are components of acid rain, which leads to the damage of
historical buildings and monuments as well as nature. Nitrogen oxides also cause eutrophication of
lakes, which results in lower content of oxygen in
water. SO2 and NOx are produced in many industrial processes, burning of fossil fuels or chemical
processes. To avoid releasing these oxides into the
atmosphere, there are many methods that are used
for the removal of these pollutants from exhausted gases. One of the most promising methods is
electron beam flue gas treatment (EBFGT), which
uses electron beam from accelerator to oxidize and
remove SO2 and NOx from gases. As it is a novel
approach, the intensified work is implemented to
optimize the technology as well as to find out the
mechanisms of reactions, which are occurring during the process.
Previously, the mathematical model based on
the system of first-order differential equations was
developed in programming environment MATLAB,
which finally contained 1034 reactions, where 115
species were involved. As a result, we obtained the
dependencies between the concentrations of main
species and time of irradiation, changes in removal efficiencies of both pollutants within the time
of irradiation and the influence of absorbed dose
on the concentration of SO2 and NOx [1].
This year, we validated the model by comparing the results obtained by mathematical computation with the experimental results [2]. Conditions of experiments and modelling are as shown
in Tables 1 and 2 giving the comparisons between
the results.
The average relative deviations for SO2 and
NOx are 9.5% and 11.5%, respectively. It shows
that the model is in a good agreement with results
obtained experimentally.
In order to provide a more thorough study of
the influence of conditions on results, we decided
to implement the factorial experiment and check
the response of the model in three cases: the worst,
base and the best conditions for removal of NOx
and SO2. We decided to study five parameters as
follows: irradiation dose, humidity content, NO
initial concentration, temperature and ammonia
stoichiometry. Conditions of experiment no. 3 were
chosen as the base case because of the lowest
Table 1. Experimental and modelling conditions.
No.
T [oC]
H [vol%]
D [kGy]
 [s]
CNOx [ppm]
CSO2 [ppm]
NH3
1
58.6
12.0
10.0
14.43
127
383
0.92
2
59.2
10.7
10.0
14.36
171
364
0.89
3
60.4
8.6
10.2
4.11
161
673
0.89
4
54.9
8.2
10.0
13.4
129
359
0.88
5
60.3
7.7
10.1
4.05
196
467
0.88
6
78.8
6.9
10.1
6.02
216
430
0.90
7
55.1
7.9
12.5
3.56
157
465
0.91
8
55.8
8.0
12.7
3.63
159
484
0.88
9
78.8
6.7
10.1
5.99
216
421
0.91
10
61.2
8.1
7.1
4.37
181
427
0.87
11
62.3
7.8
5.1
4.41
186
515
0.91
12
59.8
7.8
2.8
4.22
182
510
0.87
13
59.1
9.0
8.0
4.03
146
462
0.93
14
59.3
8.0
10.4
4.13
158
624
0.91
15
60.9
8.2
10.2
4.11
194
443
0.89
16
60.8
9.8
10.1
11.94
175
314
0.91
17
59.0
12.4
11.4
13.78
181
358
0.90
18
60.6
10.7
12.1
14.36
168
377
0.87
19
59.8
7.7
12.1
4.08
190
386
0.90
20
61.8
7.7
10.2
4.13
185
398
0.90
86
Table 2. Comparisons between the removal efficiencies of SO2 and NOx obtained from experiments and modelling.
No.
Experimental
Modelling
Relative deviation
removal NOx [%]
removal SO2 [%]
removal NOx [%]
removal SO2 [%]
NOx [%]
SO2 [%]
1
77.9
93.2
88.6
99.4
-13.7
-6.7
2
72.5
99.2
89.6
98.4
-23.6
0.8
3
82.1
81.0
81.3
85.5
1.0
-5.6
4
81.0
98.6
88.1
99.4
-8.8
-0.8
5
74.0
74.1
83.0
83.7
-12.2
-13.0
6
74.1
67.7
84.5
87.3
-14.0
-29.0
7
73.9
89.2
83.5
90.8
-13.0
-1.8
8
77.3
81.0
83.5
90.5
-8.0
-11.7
9
74.1
74.3
84.6
87.4
-14.2
-17.6
10
74.6
84.8
74.9
77.1
-0.4
9.1
11
65.6
85.4
59.3
75.3
9.6
11.8
12
47.3
89.0
37.4
68.2
20.9
23.4
13
63.7
77.9
80.1
81.2
-25.7
-4.2
14
75.1
84.6
82.3
86.8
-9.6
-2.6
15
79.4
74.3
83.8
84.5
-5.5
-13.7
16
80.8
93.3
89.2
97.8
-10.4
-4.8
17
74.6
97.4
89.8
99.1
-20.4
-1.7
18
76.7
99.3
89.4
99.6
-16.6
-0.3
19
86.8
73.6
85.6
90.4
1.4
-22.8
20
83.2
78.6
84.6
85.3
−1.7
-8.5
relative deviation between modelling and experimental results for both pollutants. The best conditions for NOx removal were as follows: high dose
and humidity, low NO initial concentration, high
temperature and concentration of ammonia. For
SO2 removal, the best conditions were almost the
same, with the difference in temperature (low temperature for the best case). The worst conditions
were reverse to the best case. Values are presented in Table 3.
That can be explained by the fact that at this high
irradiation dose and high temperature, the rates
of reactions, which lead to the generation of NOx,
are increased. In the case of SO2, trends are more
straightforward leading to the conclusion that the
removal efficiency increases with higher doses.
The other parameter, which significantly influences the removal efficiency, is humidity. With increase in content of water, the removal efficiency
increases for both pollutants. The decrease of tem-
Table 3. Parameter values used in factorial experiment.
Conditions
Irradiation dose
[kGy]
Humidity content
[%]
NO initial concentration
[ppmv]
Temperature
[oC]
Ammonia
stoichiometry
NOx worst
8.2
6.9
193
48.5
0.71
NOx base
10.2
8.6
161
60.6
0.89
NOx best
12.2
10.3
129
72.5
1.0
SO2 worst
8.2
6.9
193
72.5
0.71
SO2 base
10.2
8.6
161
60.6
0.89
SO2 best
12.2
10.3
129
48.5
1.0
The influence of the dose on the NOx and SO2
removal efficiencies in three different cases are
shown in Figs.1 and 2, respectively. Irradiation
dose has a major effect on the removal of both
pollutants, especially when the dose is lower than
10.2 kGy, the removal efficiencies drop significantly. It can be noticed that when the best conditions are applied, rising the dose over 10.2 kGy
does not improve NOx removal efficiency, and it
decreased in comparison to base condition case.
perature can slightly improve SO2 removal efficiency; however, the influence on NOx removal efficiency is not linear. During the worst conditions,
the higher temperature is beneficial, on the contrary to the best conditions when the lower temperature is preferable. When the base case scenario
is applied, the temperature effect is negligible. The
effect of inlet concentration of NO shows a similar
trend to temperature when considering the NOx removal efficiency. High inlet concentration is pref-
87
Fig.1. Influence of the dose on NOx removal efficiency in
the worst, base and best case.
Fig.2. Influence of the dose on SO2 removal efficiency in
the worst, base and best case.
erable only in the best condition scenario. Furthermore, the SO2 removal efficiency decreases with
increase of NO inlet concentration. The growth of
ammonia ratio significantly improves the removal
efficiency of SO2 as well as NOx. Only in the best
condition scenario, the content of ammonia does
not improve the removal of NOx.
The conclusions are as follows:
• The developed model was in a good agreement
with experimental results. With a good level of
accuracy, it can predict the behaviour of species
involved in a process of electron beam flue gas
treatment.
• The removal efficiency of NOx strongly depends
on a dose, humidity and ammonia ratio. The influence of temperature and inlet concentration
of NO is dependent on other parameters. Modelling shows that when very high dose is applied,
the removal efficiency in best case scenario is
lower than that with moderate conditions. This
can be explained by accelerating reaction rates
responsible for NO2 generation, which is caused
by high dose and high temperature in the best
case scenario.
• The removal efficiency of SO2 depends on dose,
humidity, temperature, inlet concentration of
NO and ammonia stoichiometry. The dependencies in the case of SO2 removal efficiency are
more straightforward than those related to NOx
removal efficiency.
References
[1]. Zwolińska, E., Gogulancea, V., Lavric, V., & Sun, Y.
(2014). Modelling study of the abatement of SO2 and
NOx from the accelerated electron beam by using
MATLAB. In INCT Annual Report 2014 (pp. 95-96).
Warszawa: Institute of Nuclear Chemistry and Technology.
[2]. Chmielewski, A.G., Tymiński, B., Dobrowolski, A., Iller, E., Zimek, Z., & Licki, J. (2000). Empirical models
for NOx and SO2 removal in a double stage flue gas
irradiation process. Rad. Phys. Chem., 57, 527-530.
DOI: 10.1016/S0969-806X(99)00419-3.
Basic activity of the Stable Isotope Laboratory concern the techniques and methods of stable
isotope measurements (H, C, N, O, S) 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 1112NC (ThermoFinnigan, Italy);
• GasBench II (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);
• freeze dryer Alpha 1-2 LD plus (Christ, Germany).
Research staff of the Laboratory is involved in the following projects:
• “The study of the influence of the environmental factors on the isotopic compositions of
dairy products”,
• accreditation process (isotopic method for food authenticity control),
• interlaboratory proficiency test FIT-PTS (food analysis using isotopic techniques – proficiency testing scheme).
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:
• Agricultural and Food Quality Inspection,
• Polish Association of Juice Producers,
• customs inspections,
• food export-import company,
• food control laboratories,
• private customers
and foreign partners:
• Eurofins Scientific Analytics (France),
• International Atomic Energy Agency (IAEA),
• Joint Research Centre (Ispra, Italy).
90
STUDY OF ISOTOPIC COMPOSITION OF CO2 IN SPARKLING DRINKS
Ryszard Wierzchnicki
Stable isotope analyses have been useful tool for
food authenticity control. An important limitation
of the application isotopic method for food authenticity control is a lack of database of stable isotope
composition for different origin food. Stable Isotope Laboratory of the Institute of Nuclear Chemistry and Technology (INCT) from many years
carries out a study on isotopic composition of food
for the elaboration and implementation of new isotope ratio mass spectrometry (IRMS) methods and
database for some food from Polish market.
Some of the most popular European sparkling
wines are as follows: French Champagne, Italian
Spumante, Portuguese Espumante, Spanish Cava,
German Sekt and Russian Sovietskoye Shampanskoye. Other alcoholic sparkling drinks are cider
and beer. Sparkling wines can be in every type:
extra brut, brut, sec, demi-sec, asti, doux. Non-alcoholic sparkling beverages are natural and artificial carbonated mineral waters and a lot of carbonated soft drinks.
For sparkling wine is allowed only natural
methods of bubbles CO2 production by addition
of sugar to fermentation. The addition of sugar to
produce CO2 bubbles in wine is allowed during
the first fermentation or second fermentation. The
addition of beet sugar (C3 plants – Calvin cycle) or
cane sugar and corn syrup (C4 plans – Hatch-Slack
pathway) results in different isotopic composition of CO2. Artificial carbonated drinks typically
using CO2 from industrial source results in other
13C value (Table 1).
Subject of the study is to investigate the stable
carbon isotope composition of the CO2 bubbles of
sparkling drinks for the control of authenticity of
the drinks. The basic aim was to identify the
source of CO2 in these drinks. Our method is to
look for the range of the 13C values for authentic
sparkling drinks. Basic problem is: Is the CO2 gas
Table 1. Carbon isotopic composition 13C for CO2 of different origin [1-4].
Origin of CO2
Fermentation:
– C3 sugar
– C4 sugar
13C – CO2 [‰]
-26 ÷ -20
-12 ÷ -9
Air
Fossil fuels combustion:
– coal
– petroleum
– natural gas
-8 ÷ -7
-33 ÷ -22
-31 ÷ -25
-75 ÷ -15
Carbonate sediments
-14 ÷ 1
Natural mineral water
-7 ÷ -4
Carbonated mineral waters
-45 ÷ -28
in sparkling drink from natural source (natural
fermentation or from spring) or by artificial carbonation of those drinks? In the study, the stable
isotope method for the control (natural or exogenous carbonation) of CO2 bubbles will be elaborated to control the quality of sparkling drink and
their compliance with labelling.
The GasBench vials were initially filled by
flushing with helium 5.0 for 1 min. After that,
100 l of CO2 gas was taken from the headspace
of the bottle with the sparkling drinks with the
use of the gastight syringe. CO2 was transferred to
the GasBench vials with septum cap. The bottles
with sparkling drinks were stabilized at room temperature. The GasBench vials were put to the
GasBench tray for the normal procedure of CO2
gas measurements.
The isotopic composition was determined using GasBench II (ThermoQuest) connected in continuous flow mode to DELTAplus (FinniganMat)
mass spectrometer. Every sample was measured
B1
B2
B3
c1g
c2g
c3g
c4g
c5g
c6g
c7g
c8g
MW1
MW2
MW3
MW4
MW7
MW9
MW13
MW14
MW5
MW6
MW8
MW10
MW11
MW12
SW1
SW2
SW3
SW4
SW5
SW6
SW7
CO2 in sparkling drinks
0
-5
δ13C - CO2 [‰]
-10
-15
-20
-25
-30
-35
-40
-45
-50
Fig.1. The measured 13C values for CO2 for different groups of sparkling drinks: B – beer, C – cider, MW – mineral water,
SW – sparkling wine.
six times for carbon isotopic composition. The
standard deviation of the values obtained from
measurements for 13C was 0.2‰.
The isotopic composition of 13C in CO2 is finally expressed by the following equation:
13C vsPDB
 13 C 
 13 C 
  12 
 12 C 

 SAMPLE  C  STANDARD

 1000 0 00
 13 C 
 12 C 

 STANDARD
The measured values of 13C of sparkling drinks
are presented in Fig.1.
We can see a big difference in carbon isotopic
composition 13C in CO2 in every group of products. This is connected with different origin of the
CO2. Biggest difference we can see between mineral waters which contained a natural gas from
spring and carbonated by industrial gas. This is
agreeable with the foreseen of these gases’ origin
(Table 1).
Conclusions are the following:
• The final product of the study is a new simplified
method for origin control of CO2 in sparkling
drinks. It is necessary to test the sensitivity of
the method for big population samples with
good origin confirmed.
91
• The study will be continued for different commercial sparkling drinks and the database for
Polish mineral waters, ciders and beers will be
constructed. The correlation between a carbon
isotopic composition 13C in CO2 and C2H5OH
for different authentic, alcoholic drinks will be
tested.
References
[1]. Gonzalez-Martin, I., Gonzalez-Perez, C., & Marques-Macias, E. (1997). Contribution to the study of the
origin of CO2 in Spanish sparkling wines by determination of the 13C/12C isotope ratio. J. Agric. Food Chem.,
45, 1149-1151.
[2]. Gaillard, L., Guyon, F., Salagoity, M.-H., & Medina, B.
(2013). Authenticity of carbon bubbles in French ciders
through multiflow-isotope ratio mass spectrometry
measurements. Food Chem., 141, 2103-2107.
[3]. Martinelli, L.A., Moreira, M.Z., Ometto, J.P.H.B., Alcarde, A.R., Rizzon, L.A., Stange, E., & Ehleringer, J.R.
(2003). Stable carbon isotopic composition of the wine
and CO2 bubbles of sparkling wines: detecting C4
sugar additions. J. Agric. Food Chem., 51, 2625-2631.
[4]. Cabañero, A.I., San-Hipólito, T., & Rupérez, M. (2007).
GasBench/isotope ratio mass spectrometry: a carbon
isotope approach to detect exogenous CO2 in sparkling drinks. Rapid Commun. Mass Spectrom., 21(20),
3323-3328.
LABORATORY
FOR MEASUREMENTS
OF TECHNOLOGICAL DOSES
The 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
(1.5-40 kGy),
• 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” and a Gamma Chamber 5000. The sources were calibrated in April 2009 and in March
2012, respectively, according to NPL (National Physical Laboratory, Teddington, UK) primary
standard. The uncertainty of the dose rate was estimated to be 2.9% and 3.1% (U, k = 2).
94
VALIDATION OF METHODS FOR MEASURING THE DOSE
USING CALORIMETERS
Anna Korzeniowska-Sobczuk, Magdalena Karlińska
A plan for the validation of methods for measuring the dose using calorimeters was prepared.
It included the following:
• three groups of calorimeters manufactured by
the High Dose Laboratory, Risø: polystyrene –
old (nos. 829, 830, 904), polystyrene – new (nos.
1167, 1168, 1169), graphite (nos. 1191, 1192,
1193);
• determination of calibration curves for doses
of electron radiation in the range 5-40 kGy;
• creating a balance of uncertainty for calorimetric
method;
• criterion for acceptance of calorimeter method
– expanded uncertainty U (k = 2)  8%.
45
Absorbed dose - alanine NPL [kGy]
In accordance with the recommendations of the
standard PN-EN ISO/IAC 17025:2005 [1], validation is the confirmation by examination and the
provision of objective evidence that the particular
requirements for a specific intended use are fulfilled. Validation of methods of measurement is
documented course of action that repeatedly gets
results that match the given criteria of acceptance.
Calibration of all types of calorimeters applied in
dosimetry system and used as routine dosimeters
should be checked by comparison with reference
standard or transfer standard dosimeter. A detailed guidance on the experiment is shown in the
standard ISO/ASTM 51631:2013(E) [2].
The Laboratory for Measurements of Technological Doses (LMTD) has nine calorimeters manufactured by the High Dose Laboratory, Risø, Denmark. Manufacturer’s recommendations were to
calibrate the calorimeters by the user in real operating conditions and each time after receiving a
dose of total 2000 kGy. The calorimeters were
irradiated with 10-MeV electron beams from an
industrial 10-kW linear accelerator radiation (accelerator Elektronika 10/10). For control of applied doses, the alanine reference dosimeters having the traceable to a primary standard maintained
by the National Physical Laboratory – NPL (Teddington, UK) were used. The mean electron energy
measured by the wedge method was in the range
9.6-9.8 MeV. Approved doses range 5-40 kGy, corresponding to routine sterilization process in the
(INCT). Dose measurements were performed using software Caldose, Risø.
40
35
30
25
20
15
Calorimetr 829
10
Calorimetr 830
5
Calorimetr 904
0
0
5
10
15
20
25
30
35
40
45
Absorbed dose - polistyrene calorimeters - old [kGy]
Fig.1. Examples of calibation curves DNPL = f(Dcal).
For all three groups of calorimeters, calibration curves were determined as a function of
DNPL = f(Dcal). Examples of calibration curves are
shown in Fig.1. Results for alanine and calorimeter dose measurements are given in Table 1 (in
example only dose 20 kGy). The results show the
Table 1. Results for alanine NPL and calorimeter dose measurements (~20 kGy).
Reference dosimeter
alanine NPL no.
Calorimeter
no.
Average dose
of alanine NPL
[kGy]
Dose
of the calorimeter
[kGy]
Error absolute
Difference
in the dose
[%]
66/2460
66/2461
829
18.40
18.76
0.36
1.96
66/2460
66/2461
830
18.40
20.22
1.82
9.89
66/2461
66/2462
904
18.56
18.98
0.43
2.29
66/2460
66/2461
1167
18.40
18.65
0.25
1.36
66/2460
66/2461
1168
18.40
17.81
-0.59
3.21
66/2460
66/2461
1169
18.40
18.17
-0.23
1.25
66/2461
66/2462
1191
18.56
18.08
-0.48
2.56
66/2461
66/2462
1192
18.56
18.31
-0.25
1.32
66/2461
66/2462
1193
18.56
18.13
-0.43
2.29
95
Table 2. Summary of the results of calibration for all calorimeters.
Type of calorimeters
Calorimeter no.
Regression equation
DNPL= f(Dcal)
Correlation coefficient R2
Uncertainty determine
calibration curve [%]
829
y = 0.9792x + 0.123
0.9996
1.78
830
y = 0.9737x – 0.1191
0.9980
3.17
904
y = 0.9908x – 0.0585
0.9992
2.40
1167
y = 1.0092x + 0.2542
0.9983
1.74
1168
y = 0.9998x + 0.6217
0.9993
2.58
1169
y = 0.9712x + 0.878
0.9983
3.35
1191
y = 1.0465x + 0.0743
0.9999
0.72
1192
y = 1.0608x – 0.2419
0.9982
2.72
1193
y = 1.0439x – 0.0472
0.9999
1.02
Polystyrene – old
Polystyrene – new
Graphite
agreement between doses measured with alanine
reference dosimeters and the calorimeters with a
rimeters and irradiation in accelerator Electronics
10/10 did not exceed 8%.
Table 3. Measurement uncertainties of routine calorimetric dosimetry systems.
Sources of uncertainty [%]
Calibration curve
Polystyrene calorimeters (old) Polystyrene calorimeters (new) Graphite calorimeters
nos. 829, 839, 904
nos. 1167, 1168, 1169
nos. 1191, 1192, 1193
3.17
3.35
2.72
Instability of the beam current
of the accelerator
1
1
1
Instantaneous change speed
conveyor
0.1
0.1
0.1
Standard uncertainty uc
3.32
3.50
2.90
Expanded uncertainty U
(k = 2)
6.64
7.00
5.80
maximum difference of 4%. The result of calibration verification is accepted and meets the requirements of ASTM. The results are shown in Table 2.
Single doses exceeding the maximum difference
indicates a lack of stability of the accelerator beam
current. Developed balance takes into account the
uncertainty of such cases as mentioned above.
Sources of uncertainty and the values are shown
in Table 3. The assumed acceptance criteria in the
validation plan have been met, and the expanded
uncertainty of the dosimetric system using calo-
References
[1]. Polski Komitet Normalizacyjny. (2005). Ogólne wymagania dotyczące kompetencji laboratoriów badawczych i wzorcujących (General requirements for the
competence of testing and calibration laboratories).
PN-EN ISO/IAC 17025:2005.
[2]. ASTM International. (2013). Practice for use of calorimetric dosimetry systems for electron beam dose
measurements and routine dosimetry system calibration. ISO/ASTM 51631:2013(E).
LABORATORY FOR DETECTION
OF IRRADIATED FOOD
The Laboratory for Detection of Irradiated Food was created at the Institute of Nuclear
Chemistry and Technology in 1994. The adoption of the quality assurance system resulted in
the accreditation of this unit in 1999. The Laboratory received its first accreditation certificate from the Polish Centre of Accreditation (PCA). From that time, the Laboratory for
Detection of Irradiated Food possess constantly the status of accredited R&D unit and is
authorized to proceed the examination of food samples and to classify them whether irradiated
or non-irradiated. Every four years, the Laboratory accreditation certificate has to be renewed
after passing positively the PCA expert audit. The current, already the 5th accreditation certificate, was received on 30th September 2014 and is valid until 24th October 2018.
Professional and well-experienced staff is engaged in the improvement of irradiation detection methods adapted in the Laboratory to make them more sensitive and reliable for the
identification of radiation treatment in the extended group of food articles. The Laboratory
offers analytical service in this field to domestic and foreign customers an extended assortment of food articles with the use of five appropriate and normalized analytical methods. The
Scope of Accreditation – an integral part of accreditation certificate, offers to the customers
five methods suitable for the detection of radiation treatment in almost all food assortments
available in the open market. During the last 16 years of analytical activity, nearly 3000 food
samples were successfully examined and classified.
Nowadays, a lot of many component food assortments like herbal pharmaceuticals, diet supplement, food extracts are delivered from our domestic and foreign customers for examination whether irradiated.
The Laboratory implemented and validated the following detection methods:
• method for the detection of irradiated food containing bone with the use of electron paramagnetic spectroscopy (EPR/ESR) based on an analytical procedure offered by the CEN
European standard EN-1786;
• method for the detection of irradiated food containing cellulose with the use of EPR spectroscopy based on an analytical procedure given by the CEN European standard EN-1787;
• method for the detection of irradiated food containing crystalline sugars with EPR spectroscopy based on analytical procedures given by the CEN European standard EN-13708;
• method for the detection of irradiated food from which silicate minerals can be isolated
using a thermoluminescence (TL) reader and based on analytical procedures recommended by the CEN European standard EN-1788;
• method for the detection of irradiated food using a photostimulated luminescence (PSL)
reader and based on analytical procedures recommended by the CEN European standard
EN-13751.
The application of the above five standardized detection methods addressed to specified
groups of foods and validated in the Laboratory guarantees accurate analysis and reliable
classification of food samples delivered to the Laboratory for testing.
The Laboratory is currently active in effective implementation of improved analytical and
measuring procedures suitable for the detection of irradiation in complex food articles containing low or very low concentration of irradiated ingredients. These are typically aromatic
herbs and spices admixed to the product.
It has been proven experimentally that modification of mineral isolation procedure, the determination of mineral content isolated and the effectiveness of mineral thermoluminescence
are the important factors which influence the detection ability of analytical method in use.
In 2015, the samples for irradiation control were delivered from domestic and foreign
firms. The latter from Germany, Italy, Denmark, Switzerland, Great Britain, China, Latvia,
Hungary. The assortment of samples comprised spices, fermented rice, mushrooms, herbal
pharmaceuticals, diet supplements, food extracts. In total, 316 samples were examined. 306
samples were examined by the TL method, while the PSL based analytical procedures were
applied only four times and EPR – six times.
From 19th June 2012, the Laboratory has the status of the reference laboratory in the field
of the detection of irradiated food in Poland under the nomination of the Ministry of Health
(National Reference Laboratory No. 5). As such, the Laboratory is responsible for the organization of the control and monitoring of irradiated food around the country.
In May 2015, the Laboratory was invited to join the “Intercomparative exercise for quality assurance on TL, PSL and EPR irradiated food detection method” organized by the Food
Technology Department of the Spanish Agency for Food Safety and Nutrition with the participation of specialized analytical laboratories from many countries.
99
INVESTIGATION WITH THERMOLUMINESCENCE
AND PHOTOLUMINESCENCE METHODS
OF IRRADIATED DIET SUPPLEMENTS AND THEIR VEGETAL
COMPONENTS
Magdalena W. Sadowska, Grzegorz P. Guzik, Wacław Stachowicz, Grażyna Liśkiewicz
Introduction
Worldwide spread diet supplements contain
typically dried vegetal components such as herbs,
spices, roots, vegetables, fruits and fruit extracts
which, as believed from the ancient times, influence positively on human condition and health.
These components, which are harvested usually in
very traditional manner, contain lot of impurities
and microbial contaminants including dangerous
pests. For this reason, these products undergo disinfection including microbial decontamination.
One of effective methods of microbial decontamination of vegetal components is irradiation. As recommended by FAO/WHO, the safe dose of ionizing is 5-10 kGy [1]. However, recently for the decontamination of these products, thermal and high
pressure methods are applied in combination with
irradiation. It is known that in the combined disinfection processes, markedly lower doses of ionizing radiation are applied.
The aim of the present study was the determination of the possibility and reliability of the detection of irradiation in diet supplements and their
vegetal components irradiated with low doses of
ionizing radiation. The analytical procedures applied are based on the following two CEN European standards: EN-1788 on the detection of
irradiated food from which silicate minerals can
be isolated based on thermoluminescence (TL)
method [2] and EN-13751 on the detection of irradiated food giving rise to photostimulated luminescence (PSL) based on pulsed photostimulated
luminescence (PPSL) method [3]. The subjects of
the investigation were three diet supplements available in the pharmacies and six components of these
products. The samples were irradiated with the
dose 5 kGy (the lowest recommended technological dose) and with the considerably lower dose
0.5 kGy comparable with doses applied in combined processes mentioned above. For comparison, non-irradiated samples of all tested products
have been investigated.
The following diet supplements were studied:
• Humavit – for the improvement of the state of
hair and nails,
• Extra Spasmina – the calmative,
• PilexTM – assist for blood circulation system
and
their components such as dried horsetail, dried
leaves of nettle, dried leaves of lemon balm, dried
root of valerian and also two oriental herbs such
as neem-tree (niem) and powdered amalaki fruit.
Examination of samples with the TL method
The tablets of diet supplements or the content
of capsules were diluted (spread) in water and subsequently subjected to the action of ultrasounds
for at least 30 min. The following density separa-
tion was carried out in compliance with the procedure given in EN-1788 standard. All samples
were sieved on 250 m nylon sieves. Silicate minerals isolated from the samples were placed in
stainless steel TL measuring cups and heated at
50oC. Thermoluminescence measurements were
carried out with RISOE TL/OSL DA 20 reader.
The instrument adjustments are the following: initial temperature – 50oC, final temperature – 450oC,
speed of the heating – 6oC/s.
Two subsequent TL measurements have been
conducted with each of samples. These were as follows: preliminary measure (glow 1) and calibrated
measure (glow 2) which has been done after calibrated irradiation of TL measuring cups containing minerals radiating with the dose 1 kGy of the
60
Co gamma rays.
Table 1 in the following comprises the results
obtained with diet supplements and with their
vegetal components. The TL intensities attributed to glow 1 and glow 2 represent the integrated
area under the TL time-dependent curve within
the range 150-250oC.
The recorded TL glow 1 curves of all investigated samples show the maxima of the TL intensity in the range of temperatures between 170oC
and 190oC (Table 1), which is typical for irradiated silicate minerals isolated from the food. On
the contrary, glow 1/glow 2 ratio calculated for all
samples was higher than 0.1 which is proved based
on EN-1788 the irradiation of samples. The weights
of minerals isolated from all samples were found
high enough to proceed with the reliable TL
measurement. According to EN-1788, the mass of
separated mineral should exceed 0.1 mg (Table 1).
It has been surprisingly found that TL intensity obtained with minerals isolated from the
samples irradiated with the dose 0.5 kGy was only
slightly lower than those obtained with samples
irradiated with 5 kGy. In both cases, the thermoluminescence measurements delivered the results
of comparably high reliability allowing to classify
the samples as irradiated. Unexpectedly, one of
diet supplements purchased (DermoSkrzyp Forte)
comprising horsetail and nettle extract has been
irradiated, and the appropriate information did
not appear in the etiquette of this product. It is an
example of negligence by the food producer in
necessitating with labelling the irradiated food despite of the requirements of EU directives [4, 5].
It is a strong argument for the necessity and extent of the area of inspecting the irradiated food
products.
Examination of samples with the PPSL method
The tablets of diet supplements or the content
of capsules were crumbled to the uniform powder
and placed in Petri dishes to cover the bottom of
100
Table 1. Dose applied, weight of samples, weight of isolated mineral, temperature and glow ratios of minerals isolated
from diet supplements and their vegetal components.
Designation
and name of product
Radiation
Mass
Mass
Intensity
dose
of sample of minerals
glow 1
[kGy]
[g]
[mg]
150-250oC
Intensity
glow 2
150-250oC
glow 1/glow 2
150-50oC
TL max. TL max.
glow 1 glow 2
[oC]
[oC]
T1A – Humavita)
diet supplement
powdered
0
50
0.57
54 888
23 907 979
0.0023
295
182
0.5
31
2.92
1 481 778
1 511 538
0.9803
184
176
5
31
2.84
4 967 586
1 150 237
4.3187
176
182
T2A – Extra
Spasminab)
diet supplement
powdered
0
15
3.20
314
284 669
0.0011
−
185
0.5
15
2.86
400 933
731 637
0.5480
176
176
5
15
1.13
3 314 158
1 118 965
2.9618
170
166
T3A – PilexTMc)
diet supplement
powdered
0
32
4.97
228 189
279 934 130
0.0008
340
178
0.5
32
4.49
60 330 166 209 192 892
0.2884
185
185
5
32
2.79
208 168 678 183 591 921
1.1339
182
182
0
50
0.23
0.5
50
5
50
0
50
2.32
573 484
0.5
50
1.51
5
50
0.37
0
50
0.5
T1B – horsetail
T1C – nettle leaves
T2B – lemon balm
T2C – valerian root
T3B – neem
(Melia azadirachta)
236 693
101 917 246
0.0023
350
176
0.86
50 993 243
66 184 360
0.7705
182
176
0.60
240 132 789 102 446 530
2.3440
174
176
82 800 736
0.0069
280
186
20 476 481
33 773 052
0.6063
193
187
62 319 140
17 901 040
3.4813
187
185
2.66
480 800
99 887 036
0.0048
286
172
50
1.83
57 820 359
76 573 427
0.7551
180
172
5
50
0.91
170 608 158 58 591 759
2.9118
174
172
0
50
0.47
78 106
50 660 372
0.0009
346
168
0.5
50
2.23
54 644 822
76 941 967
0.7102
178
170
512 066
0
90
4.94
347 694 255
0.0015
343
160
0.5
90
3.34
68 002 813 285 927 499
0.2378
189
187
5
90
2.56
202 202 507 228 604 764
0.8845
185
185
287 577 625
0.0003
358
174
T3C – amalaki
(Emblica offcinalis)
0
90
2.21
0.5
90
1.88
25 850 854 204 516 726
0.1264
174
168
5
90
2.20
197 747 585 237 177 645
0.8338
166
167
DermoSkrzyp Forte
diet supplement
0
31
0.45
0.2960
214
163
d)
86 173
793 634
2 680 860
a)
One tablet contains: 1.1 g of barm, 50 mg of the extract from the herb of the horsetail and 30 mg of the extract from
the nettle.
b)
One capsule contains: 250 mg of the dry root and valerian extracts, 50 mg of lemon balm extract from dry leaves, 80 mg
of magnesium oxide, 5 mg of the vitamin B6.
c)
One capsule contains: 260 mg Balsamodendron mukul, 32 mg Shilajeet, 14 mg Melia azadirachta (the neem tree),
64 mg Berberis aristata, 32 mg Emblica officinalis (amalaka), 32 mg Terminalia the onion, 32 mg Terminalia belerica,
32 mg Cassia fistula, 32 mg Bauhinia variegata, 6 mg Mesua ferrea, the microcrystalline cellulose, the stearate of the
magnesium.
d)
One tablet contains: 103.5 mg of the extract from horsetail, 43.5 mg of the extract from nettle, 10 mg of the extract of
evening primrose, 70 mg of zinc gluconate, 50 mg of biotin, the microcrystalline cellulose, soda-salt of carboxymethyl
cellulose, starch of corn, the silica.
the dish with thin layer of the sample. The weight
of samples equalled to 3.0 ±0.2 g. Petri dishes
with sample powder were stored in dark before
the measurement, in order to avoid accidental exposition to bright light. The PPSL measurements
were carried out with the reader produced by the
Scottish University Research Reactor Centre
(SURRC), actually an only producer of PPSL instruments known. The analytical procedure of
PPSL measurements and the instrument adjustments were based on European standard EN-13751.
The samples were examined as purchased and
then for the second time after calibrated irradiation of samples with 60Co gamma rays from Gamma
Chamber 5000 with the dose 5 kGy (dose rate –
3.262 kGy/h). The obtained results (multiplier
flash counts) express correspond to the intensity of
PPSL of the sample. The obtained results are referred to critical threshold values. If the number of
counts is less than 700 counts, the sample is classified non-irradiated, and if the number of counts
exceeds 5000, the sample is classified irradiated.
101
Table 2. Dose applied, weights of samples and the number of counts obtained by the PPSL method with untreated and
calibrated (irradiation 5 kGy) samples of diet supplements and their vegetal components.
Designation and name Radiation dose Weight of samples
of products investigated
[kGy]
[g]
Number of counts sample
irradiated with 5 kGya)
0
3.0674
374
1 245
0.5
3.1298
1 183
2 881
5
3.0912
2 393
3 891
0
3.4826
148
4 692
0.5
3.3127
1 283
3 934
5
3.4652
1 884
1 905
0
3.0612
339
74 892
0.5
3.0162
160 389
194 899
5
3.0116
320 201
520 260
0
3.0467
423
36 304
0.5
3.0706
17 993
18 324
5
3.0707
10 417
13 631
T2A – nettle leaves
powdered
0
3.0917
277
27 728
0.5
3.0689
155 875
12 113
5
3.0587
23 613
26 022
T2B – lemon balsam
leaves
0
3.0877
360
29 812
0.5
3.0857
20 692
28 229
5
3.0578
56 766
62 470
0
3.0697
495
857 032
T2C – valerian roots
0.5
3.1771
258 108
826 981
5
3.0995
521 181
924 779
0
3.0157
445
70 241
0.5
3.0371
36 817
59 308
5
3.0142
54 341
61 329
0
3.0269
297
2 410
0.5
3.0753
3 253
4 225
T1A – Humavit
diet supplement
T2B – Extra Spasmina
diet supplement
T3A – PilexTM
diet supplement
T1B – horsetail
powdered
T3C – neem
(Melia azadirachta)
T3C – amalaki
(Emblica offcinalis)
DermoSkrzyp Forte
diet supplement
a)
Number of counts
untreated samplea)
5
3.1417
3 227
11 448
0
3.1032
439
918
0.5
3.0120
608
1 241
5
3.0624
1 060
2 194
Number of counts represents mean value of two measurements (deviation ±15%).
Table 2 comprehends the results obtained with diet
supplements and their vegetal components obtained with the use of PPSL method.
The PPSL measurements on samples designated T3C, T1B, T1C, T2B, T2C, T3B and T3C delivered positive result. It means that both non-irradiated and irradiated samples were classified properly
(Table 2). The obtained numbers of counts were
lower than 700 counts (non-irradiated samples) or
were higher than 5000 counts (samples irradiated). These results have been confirmed after calibrating irradiation of enumerated samples with 5
kGy.
The measurements of samples designated T1A
and T2A (diet supplements – Humavit and Extra
Spasmina), which were done before and after calibrating irradiation, did not deliver satisfactory
results. The number of counts obtained with non-
-irradiated samples was extremely low, while for
samples irradiated with both 0.5 kGy and 5 kGy
was found too low to be classified as samples irradiated (intermediate result between 700 counts
and 5000 counts). Similar results were obtained
after the examination of DermoSkrzyp Forte, a
diet supplement which was found irradiated by
the producer. The described measurements conclusively show that three of the five investigated
diet supplements did not deliver satisfactory results as examined by the PPSL method.
Conclusions
The investigation on three diet supplements
and six vegetal components of the latter showed
that both groups of products can be investigated
effectively whether irradiated by the TL method.
It is not the case, however, with the PPSL method
which was studied in parallel to the latter. The
102
PPSL examination of these samples was effective
in the studies on diet supplement vegetal components but was not satisfactory by the examination
of diet supplements, the complex products. The
limited range of the usage of the PPSL method to
prove radiation treatment of diet supplements is
due to the small release of stimulated photoluminescence from investigated diet supplements in
contrast to their vegetal components. Diet supplement processing destroys probably in some degree the structure of rigid parts of dried vegetal
components suitable to trap irradiation energy giving rise to luminescence. The PPSL method for
the detection of irradiation in food is relatively
simple contrast to more complex and time consuming but more universal thermoluminescence
method. It remains very useful and reliable by the
examination of irradiation of less complex products such as spices, herbs, seasoning, etc.
The important achievement of the present study
was that it was ascertained that both methods of
the detection of irradiated food, TL an PPSL, are
suitable for the identification of food irradiated
with low doses of ionizing radiation (0.5 kGy and
lower). Thus, both methods are suitable and effective for the control of food articles irradiated
with low doses. These kinds of food products are
quite probably present in food market as the consequence of the development and implementation
of combined microbial decontamination methods
such as thermal/radiation treatment.
References
[1]. FAO/WHO. General Standard for Irradiated Foods.
Codex Stan 106-1983, Rev.1-2003.
[2]. European Committee for Standardization. Foodstuffs –
Thermoluminescence detection of irradiated food from
which silicate minerals can be isolated. EN-1788:2001.
[3]. European Committee for Standardization. Foodstuffs
– Detection of irradiated food using photostimulated
luminescence. EN-13751:2009.
[4]. Directive 1999/2/EC of the European Parliament and
of the Council on the approximation of the laws of the
Member States concerning foods and food ingredients
treated with ionizing radiation.
[5]. Directive 1999/3/EC of the European Parliament and
of the Council on the establishment of a Community
list of foods and food ingredients treated with ionizing radiation.
LABORATORY
OF NUCLEAR CONTROL SYSTEMS
AND METHODS
The main subject of the Laboratory activity in 2015 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;
• construction and industrial testing of a gamma scanner for diagnostics of industrial installations;
• development of measuring equipments for other Institute laboratories and centres;
• 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;
• elaboration of biotechnology for uranium recovery from former uranium mines waste materials;
• elaboration of new technology for treatment of municipal sediments obtained during the
wastewater clarification.
In the field of elaboration and construction of new nuclear instrumentation the works
were directed towards radioactive contamination detection, measurements of concentration
of radon daughters and wireless data transmission.
The system for attached and unattached radon 222Rn decay products in air or water was
tested in laboratory conditions. In the frame of realized R&D project, development of a new
generation of mining radiometers was undertaken.
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.
104
HYBRID NUCLEAR TECHNIQUES
IN THE MULTIPHASE FLOW INVESTIGATIONS
Jacek Palige, Otton Roubinek, Andrzej Dobrowolski, Wiesław Ołdak, Wojciech Sołtyk
In exploiting big multiphase installations, a very
important task is to maintain their proper technical
conditions.
During the process run, some emergency states
can be observed, and it is important to identify their
reasons and the places of their location. The application of nuclear techniques such as tracer method
and scanning technique or computational fluid dynamics (CFD) method is very profitable in solving
these kinds of problems. The application of these
techniques is presented in the example of big laboratory fermentation installation for biogas production.
emission of soft beta radiation – 0.018 MeV. Total
applied activity was 6000 Bq. The tracer was injected instantaneously in the input of fermenter
while charging the mixture from hydrolyser to fermenter. The samples of materials were taken on
output of fermenter during the periodic discharge.
The activity of samples was measured with liquid
scintillator Wallac-Guardian application. Taking
into account the requirement of clarity of measuring samples, all taking from fermenter samples
were distillated before measuring procedure. The
mean flow, Q, during the experiment was 3.8
dm3/day. The results of measurement with back-
Fig.1. Scheme of the process: 1 – biomass tank, 2 – hydrolyser, 3 – fermenter, 4 – tank for liquid digestate.
The steel fermentation installation comprising
cylindrical hydrolyser of volume V1 = 57 dm3 and
fermenter with volume V2 = 531 dm3 was constructed. From the process engineering point of
view, it was important to investigate the biogas
ground cutting and with data extrapolation are
presented in Fig.4.
The experimental RTD curve is exhibited with
the measured curve, tracer concentration vs. time
of experiment.
Fig.2. Scheme of the material flow in installation.
production process (gas composition and gas
quantity per 1 kg of dry mass) and also optimize
of mixing efficiency and check the liquid-phase
residence time distribution (RTD) function inside
the fermenter.
The system is working quasi continuously with
partial 50% – recirculation of liquid phase from
fermenter to hydrolyser. For each two to three days,
about 20 dm3 of liquid is removed from fermenter
(10 dm3 is recirculated).
Figures 1 and 2 present the scheme of flow. The
general view of installation is presented in Fig.3.
The volume of liquid phase (suspension of solid
particles in water) in fermenter and hydrolyser
was 274 dm3 and 20 dm3, respectively, so the total
volume of system was 294 dm3.
Taking into account the consistency of liquid
phase in fermenter, only radioactive tracer can be
used for RTD function determination. The hydrogen isotope tritium in the form of tritium water was
used. Half-time of tritium is T1/2 = 4510 days,
Taking into account the construction of fermenter, the scheme of flow was simulated by the
simple model comprising plug flow and two units
of perfect mixing. The result of fitting the experi-
Fig.3. General view of installation.
105
mixing, was done. The volume of cylindrical fermenter and liquid phase was 531 dm3 and 274
dm3, respectively. The scheme of input and output valves for charging and discharging of liquid
suspension is presented in Fig.6. The diameter of
valves is 21.5 mm.
Fig.4. Experimental curve activity of samples vs. time of
experiment.
mental data with theoretical RTD curve is presented in Fig.5.
The model parameters are the following:
• plug flow unit – T1 = 0.6 days;
• perfect mixers – T2 = 84 days, T3 = 1.5 days.
The theoretical mean residence time (MRT) of the
system was 294 dm3 : 3.8 dm3/day = 77.4 days.
The experimental value of MRT was 76.1 days.
Obtained results indicate that dead volume
does not exist in fermenter, and the system can be
described practically as a perfect mixer with small
plug flow T3 = 1.5 days.
Fig.6. Scheme of input and output valves for charging and
discharging of fermenter.
Modelling of flow was realized using the CFD
method and specialized software FLUENT.
The calculations were done for feeding of liquid
by valves 1.2 and 4 and discharging by valves 3.5.
The liquid flow rates were changing in interval
30-60 dm3/min.
As an example, the scheme of liquid flow inside
the fermenter for input of liquid by valves 1 and 2
and discharge by valve 5 for flow rate Q = 30
dm3/min is presented in Fig.7.
Fig.7. Structure of flow for input of water by valves 1 and
2 discharge by valve 5. Flow rate Q = 30 dm3/min.
Fig.5. Comparison of experiential and model RTD function.
During the tracer experiment, the level of liquid
phase, i.e. the volume of suspension inside fermenter, was controlled using the gamma scanner
technique with application of Co-60 and Cs-137
sealed radioactive sources with activity 10 mCi.
The modelling of the liquid phase flow inside
the fermenter, during the charging and periodical
The obtained results indicate that the used
system of fermenter feeding and periodical mixing ensure the good mixing of suspension inside
all fermenter volume and is in accordance with
results of radiotracer experiment.
The presented results indicate the effectiveness of nuclear technique applications for investigations of complex flow systems.
106
ARTICLES
Journals from Thomson Reuters database JCR
1.
Abramowska A., Cieśla K.A., Buczkowski M.J., Nowicki A., Głuszewski W.
The influence of ionizing radiation on the properties of starch-PVA films.
Nukleonika, 60, 3, 669-677 (2015).
2.
Apel P.Yu., Blonskaya I.V., Dmitriev S.N., Orelovich O.L., Sartowska B.A.
Ion track symmetric and asymmetric nanopores in polyethylene terephthalate foils for versatile applications.
Nuclear Instruments and Methods in Physics Research B, 365, 409-413 (2015).
3.
Baranowska I., Kowalski B., Polkowska-Motrenko H., Samczyński Z.
Trace metal determinations using voltammetric (DPV-HMDE) and atomic absorption spectrometry
(F-AAS and ET-AAS) in bottom sediment, cod, herring, and cormorant tissue samples.
Polish Journal of Environmental Studies, 24, 5, 1911-1917 (2015), DOI: 10.15244/pjoes/39526.
4.
Barnard S., Ainsbury E.A., Al-hafidh J., Hadjidekova V., Hristova R., Lindholm C., Monteiro Gil O.,
Moquet J., Moreno M., Rößler U., Thierens H., Vandevoorde C., Vral A., Wojewódzka M., Rothkamm K.
The first gamma-H2AX biodosimetry intercomparison exercise of the developing European Biodosimetry Network RENEB.
Radiation Protection Dosimetry, 164, 265-270 (2015), DOI: 10.1093/rpd/ncu259.
5.
Bartosiewicz I., Chwastowska J., Polkowska-Motrenko H.
Fractionation studies of trace elements in Polish uranium-bearing geological materials: potential environmental impact.
International Journal of Environmental Analytical Chemistry, 95, 2, 121-134 (2015), http://dx.doi.org/
10.1080.03067319.2014.994613.
6.
Bator G., Rok M., Sawka-Dobrowolska W., Sobczyk L., Zamponi M., Pawlukojć A.
p-N,N’-tetraacetylodiaminodurene. The structure and vibrational spectra.
Chemical Physics, 459, 148-154 (2015).
7.
Bojanowska-Czajka A., Kciuk G., Gumiela M., Borowiecka S., Nałęcz-Jawecki G., Koc A., Garcia-Reyes J.F., Solpan Ozbay D., Trojanowicz M.
Analytical, toxicological and kinetic investigation of decomposition of the drug diclofenac in waters and
wastes using gamma radiation.
Environmental Science and Pollution Research, 22, 20255-20270 (2015).
8.
Bourg S., Geist A., Narbutt J.
SACSESS – the EURATOM FP7 project on actinide separation from spent nuclear fuels.
Nukleonika, 60, 4, 809-814 (2015).
9.
Bourg S., Narbutt J.
Towards safe and optimized separation processes, a challenge for nuclear scientists. [Editorial].
Nukleonika, 60, 4, 807 (2015).
10. Brykała M., Deptuła A., Rogowski M., Łada W.
Modification of IChTJ sol gel process for preparation of medium sized ceramic spheres (Ø < 100 m).
Ceramics International, 41, 13025-13033 (2015).
11. Brykała M., Rogowski M., Olczak T.
Carbonization of solid uranyl-ascorbate gel as an indirect step of uranium carbide synthesis.
Nukleonika, 60, 4, 921-925 (2015).
107
12. Brzóska K., Kruszewski M.
Toward the development of transcriptional biodosimetry for the identification of irradiated individuals
and assessment of absorbed radiation dose.
Radiation and Environmental Biophysics, 54, 353-363 (2015), DOI: 10.1007/s00411-015-0603-8.
13. Brzóska K., Męczyńska-Wielgosz S., Stępkowski T.M., Kruszewski M.
Adaptation of HepG2 cells to silver nanoparticles-induced stress is based on the pro-proliferative and
anti-apoptotic changes in gene expression.
Mutagenesis, 431-439 (2015), DOI: 10.1093/mutage/gev001.
14. Cheng L., Lisowska H., Sollazzo A., Węgierek-Ciuk A., Stępień K., Kuszewski T., Lankoff A., Haghdoost S., Wójcik A.
Modulation of radiation-induced cytogenetic damage in human peripheral blood lymphocytes by hypothermia.
Mutation Research/Genetic Toxicology and Environmental Mutagenesis, 793, 96-100 (2015).
15. Cieśla K., Sartowska B., Królak E.
SEM studies of the structure of the gels prepared from untreated and radiation modified potato starch.
Radiation Physics and Chemistry, 106, 289-302 (2015).
16. Czajka M., Sawicki K., Sikorska K., Popek S., Kruszewski M., Kapka-Skrzypczak L.
Toxicity of titanium dioxide nanoparticles in central nervous system.
Toxicology in Vitro, 29, 1042-1052 (2015).
17. Dhruv D.K., Nowicki A., Patel B.H., Dhamecha V.D.
Memory switching characteristics in amorphous ZnIn2Se4 thin films.
Surface Engineering, 31, 7, 556-562 (2015), DOI: 10.1179/1743294415Y.0000000001.
18. Dobrowolski J.Cz.
The chiral graph theory.
MATCH Communications in Mathematical and in Computer Chemistry, 73, 347-374 (2015).
19. Dobrowolski J.Cz., Ostrowski S.
On the HOMA index of some acyclic and conducting systems.
RSC Advances, 5, 9467-9471 (2015).
20. Dybczyński R.
50 Years of adventures with neutron activation analysis with the special emphasis on radiochemical
separations.
Journal of Radioanalytical and Nuclear Chemistry, 303, 1067-1090 (2015), DOI: 10.1007/s10967-014-3822-6.
21. Dybczyński R., Kulisa K., Pyszynska M., Bojanowska-Czajka A.
New reversed phase-high performance liquid chromatographic method for selective separation of
yttrium from all rare earth elements employing nitrilotriacetate complexes in anion exchange mode.
Journal of Chromatography A, 1386, 74-80 (2015).
22. Fuks L., Oszczak A., Gniazdowska E., Sternik D.
Calcium alginate and chitosan as potential sorbents for strontium radionuclide.
Journal of Radioanalytical and Nuclear Chemistry, 304, 15-20 (2015).
23. Gajda D., Kiegiel K., Zakrzewska-Kołtuniewicz G., Chajduk E., Bartosiewicz I., Wołkowicz S.
Mineralogy and uranium leaching of ores from Triassic Peribaltic sandstones.
24. Gałczyńska K., Kurdziel K., Adamus-Białek W., Wąsik S., Szary K., Drabik M., Węgierek-Ciuk A.,
Lankoff A., Arabski M.
The effects of nickel(II) complexes with imidazole derivatives on pyocyanin and pyoverdine production by Pseudomomas aeuginosa strains isolated from cystic fibrosis.
Acta Biochimica Polonica, 62, 4, 739-745 (2015).
25. Głuszewski W., Boruc B., Kubera H., Abbasowa D.
The use of DRS and GC to study the effects of ionizing radiation on paper artifacts.
Nukleonika, 60, 3, 665-668 (2015).
26. Głuszewski W., Zagórski Z.P., Rajkiewicz M.
The comparison of radiation and a peroxide crosslinking of elastomers.
KGK – Kautschuk Gummi Kunststoffe, 11-12, 46-49 (2015).
108
27. Guzik G.P., Stachowicz W., Michalik J.
Identification of irradiated dried fruits using EPR spectroscopy.
Nukleonika, 60, 3, 627-631 (2015).
28.
Houée-Lévin C., Bobrowski K., Horakova L., Karademir B., Schöneich C., Davies M.J., Spickett C.M.
Exploring oxidative modifications of tyrosine: an update on mechanisms of formation, advances in
analysis and biological consequences.
Free Radical Research, 49, 4, 347-373 (2015).
29. Ignasiak M.T., Houée-Levin Ch., Kciuk G., Marciniak B., Pędziński T.
A reevaluation of the photolytic properties of 2-hydroxybenzophenone-based UV sunscreens: are chemical sunscreens inoffensive?
ChemPhysChem, 16, 628-633 (2015).
30. Jakowiuk A., Modzelewski Ł., Pieńkos J., Kowalska E.
Industrial diagnostics system using gamma radiation.
Nukleonika, 60, 3, 633-636 (2015).
31. Jamróz M.H., Ostrowski S., Dobrowolski J.Cz.
Facilitation of the PED analysis of large molecules by using global coordinates.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 149, 463-467 (2015).
32. Jastrzębska I., Morawiak M., Rode J.E., Seroka B., Siergiejczyk L., Morzycki J.W.
Oxidation of olefins with benzeneselenic andryhide in the presence of TMSOTf.
Journal of Organic Chemistry, 80, 6052-6061 (2015), DOI: 10.1021/acs.joc.5b00410.
33. Jednoróg S., Polkowska-Motrenko H., Szewczak K., Bieńkowska B., Paduch M., Prokopowicz R.,
Ciupek K., Chajduk E., Samczyński Z., Krajewski P., Laszyńska E.
Neutron activation of PF-100 device parts during long-term fusion research.
34. Karpińska G., Dobrowolski J.Cz.
On tautomerism of 1,2,4-triazol-3-ones.
Computational and Theoretical Chemistry, 1052, 58-67 (2015).
35. Karpińska G., Dobrowolski J.Cz.
On the 6- and 7-substituted chromosome system. A computational study.
Computational and Theoretical Chemistry, 1067, 158-163 (2015).
36.
Kaźmierczak U., Banaś D., Braziewicz J., Czub J., Jaskóła M., Korman A., Kruszewski M., Lankoff A.,
Lisowska H., Malinowska A., Stępkowski T., Szefliński Z., Wojewódzka M.
Dosimetry in radiobiological studies with the heavy ion beam of the Warsaw cyclotron.
Nuclear Instruments and Methods in Physics Research B, 365, 404-408 (2015).
37.
Kaźmierczak U., Bantsar A., Banaś D., Braziewicz J., Czub J., Jaskóła M., Korman A., Kruszewski M.,
Lankoff A., Lisowska H., Pietrzak M., Pszona S., Stępkowski T., Szefliński Z., Wojewódzka M.
Heavy ion beams for radiobiology: dosimetry and nanodosimetry at HIL.
Acta Physica Polonica A, 127, 5, 1516-1519 (2015).
38. Kiegiel K., Zakrzewska-Kołtuniewicz G., Gajda D., Miśkiewicz A., Abramowska A., Biełuszka P.,
Danko B., Chajduk E., Wołkowicz S.
Dictyonema black shale and Triassic sandstones as potential sources of uranium.
Nukleonika, 60, 3, 515-523 (2015).
39. Kocia R., Grodkowski J., Mirkowski J.
Pulse radiolysis studies of p-terphenyl in the ionic liquid methyltributylammonium bis[(trifluoromethyl)
sulfonyyl]imide, [MeBu3N][NTf2].
Research on Chemical Intermediates, 41, 5079-5093 (2015).
40. Kowczyk-Sadowy M., Świsłocka R., Lewandowska H., Piekut J., Lewandowski W.
Spectroscopic (FT-IT, FT-Raman, 1H- and 13C-NMR), theoretical and microbiological study of trans
o-coumaric acid and alkali metal o-coumarates.
Molecules, 20, 3146-3169 (2015).
41. Koźmiński P., Gniazdowska E.
Synthesis and in vitro/in vivo evaluation of novel mono- and trivalent technetium-99m labeled gherin
peptide complexes as potential diagnostic radiopharmaceuticals.
Nuclear Medicine and Biology, 42, 28-37 (2015).
109
42. Krawczyńska A., Dziendzikowska K., Gromadzka-Ostrowska J., Lankoff A., Herman A.P., Oczkowski M., Królikowski T., Wilczak J., Wojewódzka M., Kruszewski M.
Silver and titanium oxide nanoparticles alter oxidative/inflammatory response and renin-angiotensin
system in brain.
Food and Chemical Toxicology, 85, 96-105 (2015).
43. Kulka U., Ainsbury E., Atkinson M., Barnard S., Smith R., Barquinero J.F., Barrios L., Bassinet C.,
Beinke C., Cucu A., Darroudi F., Fattibene P., Bortolin E., Della Monacca S., Gil O., Gregoire E.,
Hadjidekova V., Haghdoost S., Hatzi V., Hempel W., Herranz R., Jaworska A., Lindholm C., Lumniczky K., M’kacher R.M., Mörtl S., Montoro A., Moquet J., Moreno M., Noditi M., Ogbazghi A.,
Oestreicher U., Palitti F., Pantelias G., Popescu I., Prieto M.J., Roch-Lefevre S., Roessler U., Romm
H., Rothkamm K., Sabatier L., Sebastia N., Sommer S., Terzoudi G., Testa A., Thierens H., Trompier
F., Turai I., Vandevoorde C., Vaz P., Voisin P., Vral A., Ugletveit F., Wieser A., Woda C., Wójcik A.
Realising the European Network of Biodosimetry: RENEB – status quo.
Radiation Protection Dosimetry, 164, 1-2, 42-45 (2015).
44. Leszek P., Sochanowicz B., Brzóska K., Danko B., Kraj L., Kuśmierczyk M., Piotrowski W., Sobieszczańska-Małek M., Rywik T.M., Polkowska-Motrenko H., Kruszewski M.
Does myocardial iron load determine the severity of heart insufficiency?
International Journal of Cardiology, 182, 191-193 (2015).
45. Lewandowska H., Sadło J., Męczyńska S., Stępkowski T.M., Wójciuk G., Kruszewski M.
Formation of glutathionyl dinitrosyl iron complexes protects against iron genotoxicity.
Dalton Transactions, 44, 12640-12652 (2015).
46. Licki J., Pawelec A., Zimek Z., Witman-Zając S.
Electron beam treatment of simulated marine diesel exhaust gases.
Nukleonika, 60, 3, 689-695 (2015).
47. Łuczyńska K., Drużbicki K., Łyczko K., Dobrowolski J.Cz.
Experimental (X-ray, 13C CP/MAS NMR, IR, RS, INS, THz) and solid-state DFT study on (1:1) co-crystal of bromanilic acid and 2,6-dimethylpyrazine.
The Journal of Physical Chemistry B, 119, 6852-6872 (2015), DOI: 10.1021/acs.jpcb.5b03279.
48. Łyczko K., Łyczko M., Miecznikowski J.
A series of tricarbonylrhenium(I) complexes with the N-methyl-2-pyridinecarboxyamide ligand: Synthesis, structure, spectroscopic characterization and computational studies.
Polyhedron, 87, 122-134 (2015).
49. Łyczko K., Łyczko M., Woźniak K., Stachowicz M., Ozimiński W.P., Kubo K.
Influence of pH and type of counterion on the formation of bismuth(III) complexes with tropolonato and
5-methyltropolonato ligands: Synthesis, structure, spectroscopic characterization and calculation studies.
Inorganica Chimica Acta, 436, 57-68 (2015).
50. Łyczko K., Ostrowski S.
Crystal structures and conformers of CyMe4-BTBP.
Nukleonika, 60, 4, 853-857 (2015).
51. Marzec K.M., Kochan K., Fedorowicz A., Jasztal A., Chruszcz-Lipska K., Dobrowolski J.Cz., Chłopicki S., Barańska M.
Raman microimaging of murine lungs: insight into the vitamin A content.
Analyst, 140, 2171-2177 (2015).
52. Mazurek A., Dobrowolski J.Cz.
On the incorporation effect of the ring-junction heteroatom. The sEDA(III) and pEDA(III) descriptors.
Journal of Physical Organic Chemistry, 28, 290-297 (2015).
53. Mroczyński R., Szymańska M., Głuszewski W.
Reactive magnetron sputtered hafnium oxide layers for nonvolatile semiconductor memory devices.
Journal of Vacuum Science & Technology B, 33, 1, 01A113-1–01A113-5 (2015), DOI: 10.1116/1.4906090.
54. Narbutt J., Wodzyński A., Pecul M.
The selectivity of diglycolamide (TODGA) and bis-triazine-bipyridine (BTBP) ligands in actinide/lanthanide complexation and solvent extraction separation – a theoretical approach.
Dalton Transactions, 44, 2657-2666 (2015).
110
55. Olszewska W., Miśkiewicz A., Zakrzewska-Kołtuniewicz G., Lankof L., Pająk L.
Multibarrier system preventing migration of radionuclides from radioactive waste repository.
Nukleonika, 60, 3, 557-563 (2015).
56. Oszczak A., Fuks L.
Sorption of Sr-85 and Am-241 from liquid radioactive wastes by alginate beads.
Nukleonika, 60, 4, 927-931 (2015).
57. Pańczyk E., Sartowska B., Waliś L., Dudek J., Weker W., Widawski M.
The origin and chronology of medieval silver coins based on the analysis of chemical composition.
Nukleonika, 60, 3, 657-663 (2015).
58. Polkowska-Motrenko H., Fuks L., Kalbarczyk P., Dudek J., Kulisa K., Oszczak A., Zuba M.
Preparation of water samples for proficiency testing on radionuclides.
Applied Radiation and Isotopes, 103, 61-64 (2015).
59. Pruszyński M., Łyczko M., Bilewicz A., Zalutsky M.R.
Stability and in vivo behavior of Rh[16aneS4-diol]211At complex: A potential precursor for astatine
radiopharmaceuticals.
Nuclear Medicine and Biology, 42, 439-445 (2015).
60. Przybytniak G., Boguski J., Placek V., Verardi L., Fabiani D., Linde E., Gedde U.W.
Inverse effect in simultaneous thermal and radiation aging of EVA insulation.
eXPRESS Polymer Letters, 9, 4, 384-393 (2015).
61. Ptaszek M., Orlikowski L.B., Migdał W., Gryczka U.
E-beam irradiation for the control of Phytophthora nicotianae var. nicotianae in stonewool cubes
Nukleonika, 60, 3, 679-682 (2015).
62. Rydlová E., Kopecká I., Kunicki-Goldfinger J.J.
Two Stangelgläser from the collection of the Museum of Decorative Arts in Prague: Decorative techniques, material analyses, and conservation.
Studies in Conservation, 60, 3, 185-193 (2015).
63. Sadło J., Bugaj A., Strzelczak G., Sterniczuk M., Jaegermann Z.
Multifrequency EPR study on radiation induced centers in calcium carbonates labeled with 13C.
Nukleonika, 60, 3, 429-434 (2015).
64. Sartowska B., Barlak M., Waliś L., Starosta W., Senatorski J., Kosińska A.
Tribological properties of AISI 316L steel surface layer implanted with rare earth element.
65. Skotnicki K., Bobrowski K.
Molecular hydrogen formation during water radiolysis in the presence of zirconium dioxide.
66. Sommer S., Buraczewska I., Sikorska K., Bartłomiejczyk T., Szumiel I., Kruszewski M.
The rapid interphase chromosome assay (RICA) implementation: comparison with other PCC methods.
Nukleonika, 60, 4, 933-941 (2015).
67. Steczek Ł., Narbutt J., Charbonnel M.-Ch., Moisy Ph.
Determination of formation constants of uranyl(VI) complexes with a hydrophililc SO3-Ph-BTP ligand,
using liquid-liquid extraction.
Nukleonika, 60, 4, 821-827 (2015).
68. Stępkowski T.M., Wasyk I., Grzelak A., Kruszewski M.
6-OHDA-induced changes in Parkinson’s disease-related gene expression are not affected by the overexpression of PGAM5 in in vitro differentiated embryonic mesencephalic cells.
Cellular and Molecular Neurobiology, 35, 1137-1147 (2015).
69. Szkliniarz K., Jastrzębski J., Bilewicz A., Chajduk E., Choiński J., Jakubowski A., Janiszewska Ł.,
Leszczuk E., Łyczko M., Sitarz M., Stolarz A., Trzcińska A., Wąs B., Zipper W.
Medical radioisotopes produced using the alpha particle beam from the Warsaw Heavy Ion Cyclotron.
111
70. Szreder T., Kocia R.
Electron beam irradiation of r-SANEX and i-SANEX solvent extraction systems: analysis of gaseous
products.
Nukleonika, 60, 4, 899-905 (2015).
71. Szumiel I.
From radioresistance to radiosensitivity: In vitro evolution of L5178Y lymphoma.
International Journal of Radiation Biology, 91, 6, 465-471 (2015).
72. Szumiel I.
Ionizing radiation-induced oxidative stress, epigenetic changes and genomic instability: The pivotal
role of mitochondria.
International Journal of Radiation Biology, 91, 1, 1-12 (2015).
73. Walo M., Przybytniak G., Męczyńska-Wielgosz S., Kruszewski M.
Improvement of poly(ester-urethane) surface properties by RAFT mediated grafting initiated by gamma
radiation.
European Polymer Journal, 68, 398-408 (2015).
74. Westphal K., Wiczk J., Miloch J., Kciuk G., Bobrowski K., Rak J.
Irreversible electron attachment – a key to DNA damage by solvated electrons in aqueous solution.
Organic & Biomolecular Chemistry, 13, 1036210369 (2015).
75.
Wojewódzka M., Sommer S., Kruszewski M., Sikorska K., Lewicki M., Lisowska H., Węgierek-Ciuk A.,
Kowalska M., Lankoff A.
Defining blood processing parameters for optimal detection of -H2AX foci: a small blood volume method.
Radiation Research, 184, 95-104 (2015).
76. Zając G., Kaczor A., Buda S., Młynarski J., Frelek J., Dobrowolski J.Cz., Barańska M.
Prediction of ROA and ECD related to conformational changes of astaxanthin enantiomers.
The Journal of Physical Chemistry B, 119, 12193-12201 (2015).
77. Zdrowowicz M., Chomicz L., Miloch J., Wiczk J., Rak J., Kciuk G., Bobrowski K.
Reactivity pattern of bromonucleosides induced by 2-hydroxypropyl radicals: photochemical, radiation
chemical, and computational studies.
The Journal of Physical Chemistry B, 119, 6545-6554 (2015).
78. Zgadzaj A., Skrzypczak A., Welenc I., Ługowska A., Parzonko A., Siedlecka E., Sommer S., Sikorska K., Nałęcz-Jawecki G.
Evaluation of photodegradation, phototoxicity and photogenotoxicity of ofloxacin in ointments with
sunscreens and in solutions.
Journal of Photochemistry and Photobiology B: Biology, 144, 76-84 (2015).
79.
Zuberek M., Wojciechowska D., Krzyżanowski D., Męczyńska-Wielgosz S., Kruszewski M., Grzelak A.
Glucose availability determines silver nanoparticles toxicity in HepG2.
Journal of Nanobiotechnology, 13, 72 [10] p. (2015), DOI: 10.1186/s12951-015-0132-2.
80. Zwolińska E., Sun Y., Chmielewski A.G., Nichipor H., Bułka S.
Modelling study of NOx removal in oil-fired waste off-gases under electron beam irradiation.
Radiation Physics and Chemistry, 113, 20-23 (2015).
Scientific journals (without IF) evaluated
by the Ministry of Science and Higher Education (List B)
81. Chmielewski A.G., Smoliński T.
Polityka energetyczna wybranych krajów Europy, rola energetyki jądrowej (Energy policy of selected
European countries, role of the nuclear energy).
Instal, 2, 12 (2015).
82. Czajka M., Rachubik P., Rzeszutek J., Matysiak M., Kruszewski M., Kapka-Skrzypczak L.
Polimorfizm genowy a dyslipidemie (Role of gene polymorphism in dislipidemia).
Pediatric Endocrinology Diabetes and Metabolism, 23, 1, 37-45 (2015).
83. Głuszewski W.
Unikatowe cechy radiacyjnej konserwacji dużych zbiorów obiektów o znaczeniu historycznym (Unique
features of radiation conservation of high collections of objects of historical interest).
Wiadomości Konserwatorskie (Journal of Heritage Conservation), 41, 84-91 (2015).
112
84. Jakowiuk A., Jarosz Z., Ptaszek S., Modzelewski Ł., Kowalska E., Wołoszczuk K.
Determiniantion of radon content in water respecting to Directive of Council 2013/51/EURATOM.
World Journal of Nuclear Science and Technology, 5, 192-199 (2015), DOI: 10.4236/winst.2015.53019.
85. Lazurik V.M., Lazurik V.T., Popov G., Zimek Z.
Energy characteristics in two-paramagnetic model of electron beam.
Visnyk Kherson National Technical University, 3, 397-403 (2015).
86. Lundberg D., Łyczko K.
Crystal structure of hexakis(dmpu)-di-2-hydroxidodialuminium tetraiodide dmpu tetrasolvate [dmpu
is 1,3-dimethyltetrahydropyrimidin-2(1H)-one]: a centrosymmetric dinuclear aluminium complex containing AlO5 polyhedra.
Acta Crystallographica Section E – Crystallographic Communications, 71, 895-898 (2015).
87. Sawicki Ł., Gołębiewski T., Fornalski K.W., Gajda D.
Nuclear Poland? The second approach after 20 years.
Nuclear Espana. Journal of Spanish Nuclear Professionals, 365, 14-16 (2015).
88. Starosta W., Leciejewicz J.
Crystal structure of catena-poly[[[aqualithium(I)]--pyridine-2-carboxylato-4N1,O2:N3,O2’]hemihydrate].
Acta Crystallographica Section E – Crystallographic Communications, 71, 76-78 (2015).
89. Walczak R., Krajewski S., Szkliniarz K., Sitarz M., Abbas K., Choiński J., Jakubowski A., Jastrzębski J., Majkowska A., Simonelli F., Stolarz A., Trzcińska A., Zipper W., Bilewicz A.
Cyclotron production of 43Sc for PET imaging.
EJMMI Physics, 2, 33 (10 p.) (2015), DOI: 10.1186/s40658-015-0136-x.
Other journals
90. Boguski J., Zwolińska E.
Program ERASMUS+ szansą dla młodych naukowców (The Erasmus+ programme the chance for the
young scientists).
Postępy Techniki Jądrowej, 58, 4, 9-12 (2015).
91. Brzóska K., Kowalska M., Kruszewski M., Lankoff A., Sommer S.
Strategiczny projekt badawczy Narodowego Centrum Badań i Rozwoju pt. „Technologie wspomagające
rozwój bezpiecznej energetyki jądrowej”. Zadanie nr 6 „Rozwój metod zapewnienia bezpieczeństwa
jądrowego i ochrony radiologicznej dla bieżących i przyszłych potrzeb energetyki jądrowej”. Cel 2:
Rozwój metod dozymetrii biologicznej oraz biofizycznych markerów i indykatorów wpływu promieniowania na organizmy żywe (The National Centre for Research and Development strategic research
project “Technologies supporting development of safe nuclear power engineering”. Task no. 6 “Development of nuclear safety and radiological protection methods for the nuclear power engineering’s current
and future needs”. Objective 2: Development of the biodosimetry and biophysics markers of ionizing
radiation in living beings).
92. Ciupek K., Krajewski P., Kozak K., Śliwka I., Pliszczyński T., Polkowska-Motrenko H.
jądrowego i ochrony radiologicznej dla bieżących i przyszłych potrzeb energetyki jądrowej”. Cel 1:
Opracowanie ogólnej koncepcji i metod badań środowiskowych (w tym zdrowotności) dla przewidywanej lokalizacji EJ (The National Centre for Research and Development strategic research project
“Technologies supporting development of safe nuclear power engineering”. Task no. 6 “Development
of nuclear safety and radiological protection methods for the nuclear power engineering’s current and
future needs”. Objective 1: General concept and methodology for baseline environmental research and
public health investigation in the foreseen location of NPP).
93. Fuks L., Oszczak A.
Strategiczny projekt badawczy Narodowego Centrum Badań i Rozwoju „Technologie wspomagające
rozwój bezpiecznej energetyki jądrowej. Zadanie nr 4 „Rozwój technik i technologii wspomagających
gospodarkę wypalonym paliwem i odpadami promieniotwórczymi” (The National Centre for Research
and Development strategic research project “Technologies supporting development of safe nuclear
power engineering”. Task no. 4 “Development of spent nuclear fuel and radioactive waste management
techniques and technologies”).
113
94. Głuszewski W.
Innowacje w przemyśle tworzyw polimerowych (Innovation in the plastics industry).
95. Głuszewski W.
Radiacyjna sterylizacja opakowań. Niewidoczne, ale pracowite (Radiation sterilization packaging. Invisible but busy).
Packing Polska, 5, 24-25 (2015).
96. Głuszewski W.
features of radiation conservation of large object collections of historical importance).
97. Głuszewski W., Przybytniak G.
Radiacyjna modyfikacja kompozytów polimerowych (Radiation modification of polimer composites).
Tworzywa Sztuczne w Przemyśle, 2, 38-40 (2015).
98. Głuszewski W., Rajkiewicz M., Turliński Z.
Radiacyjne sieciowanie polimerów na przykładzie elastomeru ENGAGE 8200 (Radiation crosslinking
of polymers on the example of elastomer ENGAGE 8200).
Tworzywa Sztuczne w Przemyśle, 1, 32-34 (2015).
99. Guzik G.P.
Oszacowanie metodami EPR, TL i PPSL odpowiedzi próbek przy wykrywaniu potencjonalnego napromieniowania żywności (Evaluation of detection of potential radiation treatment of foodstuff samples
using EPR, TL and PPSL methods).
100. Łada W., Wawszczak D.
Nowe cząsteczki w postaci mikrosfer 89Y2O3 otrzymywanych w IChTJ zmodyfikowaną metodą zol-żel
do zwalczania nowotworów wątroby (The new molecules in the form of microspheres 89Y2O3 obtained
by the modified INCT sol-gel method for liver cancer treatment).
101. Michalik J.
Chemiczne aspekty energetyki jądrowej w projekcie Narodowego Centrum Badań i Rozwoju „Technologie wspomagające rozwój bezpiecznej energetyki jądrowej” (Chemical aspects of nuclear power in
the National Centre for Research and Development project “Technologies supporting development of
safe nuclear power engineering”).
102. Michalik J., Kocia R.
rozwój bezpiecznej energetyki jądrowej”. Zadanie nr 7 „Analiza procesów generacji wodoru w reaktorze
jądrowym w trakcie normalnej eksploatacji i w sytuacjach awaryjnych z propozycjami działań na rzecz
podniesienia poziomu bezpieczeństwa jądrowego” (The National Centre for Research and Development strategic research project “Technologies supporting development of safe nuclear power engineering”. Task no. 7 “Study of hydrogen generation processes in nuclear reactors under regular operation
conditions and in emergency cases, with suggested actions aimed at upgrade of nuclear safety”).
103. Rajkiewicz M., Głuszewski W.
Polimerowe kompozyty: Czy można zastąpić ołów w ochronie radiologicznej? (Polymer composites: Is
it possible to replace lead in radiological protection?).
104. Sommer S.
RENEB (Realizing the European Network in Biodosimetry) w stronę Europejskiej Sieci Biodozymetrycznej (RENEB (Realizing the European Network in Biodosimetry) towards the European Biodosimetry Network).
Ekoatom, 17, 28-34 (2015).
105. Sommer S.
Ryzyko niskich dawek promieniowania a ochrona radiologiczna (Risk of low doses of radiation in radiological protection).
Bezpieczeństwo Jądrowe i Ochrona Radiologiczna, 4, 33-38 (2015).
114
106. Stachowicz W.
Początki i rozwój badań radiacyjnych w IBJ na Żeraniu (Beginnings and the development of radiation
research at the Institute of Nuclear Research, Żerań).
107. Usidus J., Chmielewski A.G., Palige J., Kryłowicz A.
Zintegrowane wysokoefektywne sposoby wykorzystania biomasy do celów energetycznych (Integrated
high effective methods of biomass utilization for energy production purposes).
Energia Elektryczna – Klient, Dystrybucja, Przesył, 11, 16-19 (2015).
108. Zimek Z.
Strategie i urządzenia przeznaczone do usuwania z obszaru obudowy bezpieczeństwa wodoru emitowanego w trakcie poważnej awarii reaktora jądrowego (Strategy and equipment suitable for hydrogen
removal from containment during severe accidents of nuclear reactor).
Ekoatom, 17, 4-19 (2015).
109. Zimek Z., Głuszewski W.
Bezpieczeństwo przemysłowych zastosowań technik radiacyjnych (Safety industrial application of
radiation techniques).
Bezpieczeństwo Jądrowe i Ochrona Radiologiczna, 4, 39-43.
110. Zimek Z., Przybytniak G., Głuszewski W.
Radiacyjna modyfikacja polimerów (Radiation modification of polymers).
Magazyn Polska Chemia, 1, 26-27 (2015).
BOOKS
1. Analiza procesów generacji wodoru w reaktorze jądrowym w trakcie normalnej eksploatacji i w sytuacjach awaryjnych z propozycjami działań na rzecz podniesienia poziomu bezpieczeństwa jądrowego.
Zadanie wykonane w ramach projektu strategicznego NCBR Technologie wspomagające rozwój bezpiecznej energetyki jądrowej (Study of hydrogen generation processes in nuclear reactors under regular
operation conditions and in emergency cases, with suggested actions aimed at upgrade of nuclear safety.
Task realized in the frame of the NCBR strategic project Technologies supporting development of safe
nuclear power engineering).
Red. nauk. J. Michalik, R. Kocia. Instytut Chemii i Techniki Jądrowej, Warszawa 2015, 163 p.
2. Analiza procesów zachodzących przy normalnej eksploatacji obiegów wodnych w elektrowniach jądrowych z propozycjami działań na rzecz podniesienia poziomu bezpieczeństwa jądrowego. Zadanie wykonane w ramach projektu strategicznego NCBR Technologie wspomagające rozwój bezpiecznej energetyki
jądrowej (Study of processes occurring under regular operation of water circulation systems in nuclear
power plants with suggested actions aimed at upgrade of nuclear safety. Task realized in the frame of
the NCBR strategic project Technologies supporting development of safe nuclear power engineering).
Red. nauk. A. Bojanowska-Czajka. Instytut Chemii i Techniki Jądrowej, Warszawa 2015, 168 p.
3. Od Instytutu Badań Jądrowych do Instytutu Chemii i Techniki Jądrowej. Kronika i wspomnienia
1955-2015 (From the Institute of Nuclear Research to the Institute of Nuclear Chemistry and Technology. Chronicle and the memories 1955-2015).
Pod red. dra inż. L. Walisia. Instytut Chemii i Techniki Jądrowej, Warszawa 2015, 316 p.
4. The industrial and environmental applications of electron beams.
Ed. D. Chmielewska-Śmietanko. Institute of Nuclear Chemistry and Technology, Warszawa 2015, 108 p.
CHAPTERS IN BOOKS
1.
Bilewicz A.
Międzynarodowe Studia Doktoranckie (International Ph.D. Studies).
In: Od Instytutu Badań Jądrowych do Instytutu Chemii i Techniki Jądrowej. Kronika i wspomnienia
1955-2015. Pod red. dra inż. L. Walisia. Instytut Chemii i Techniki Jądrowej, Warszawa 2015, pp. 281-282.
2.
Borowik K.
Opracowanie wydzielania 137-Cs z dużych objętości roztworów wody o dużym stopniu zasolenia (New
procedures for Cs-137 sorption from simulated high salinity waters).
115
In: Analiza procesów zachodzących przy normalnej eksploatacji obiegów wodnych w elektrowniach
jądrowych z propozycjami działań na rzecz podniesienia poziomu bezpieczeństwa jądrowego. Zadanie
wykonane w ramach projektu strategicznego NCBR Technologie wspomagające rozwój bezpiecznej
energetyki jądrowej. Red. nauk. A. Bojanowska-Czajka. Instytut Chemii i Techniki Jądrowej, Warszawa
2015, pp. 135-153.
3.
Bugaj A., Sadło J., Strzelczak G., Sterniczuk M.
Badanie mechanizmów sorpcji radionuklidów pochodzących z korozji materiałów obiegu pierwotnego
na wybranych wymieniaczach jonowych (Mechanisms of radionuclide sorption of corrosion products
in pimary cooling water on selected ionic exchangers).
2015, pp. 155-168.
4.
Bursa B.
Dział Informacji Naukowo-Ekonomicznej (Department of Scientific Information).
W: Od Instytutu Badań Jądrowych do Instytutu Chemii i Techniki Jądrowej. Kronika i wspomnienia
5.
Chajduk E., Chwastowska J., Kulisa K., Samczyński Z., Skwara W.
Ocena stopnia zaawansowania procesu korozji na podstawie oznaczeń wybranych produktów korozji
(Assessment of the degree of the corrosion process based on the determination of chosen radionuclides-corrosion products).
2015, pp. 45-57.
6.
Chajduk E., Kulisa K., Samczyński Z.
Weryfikacja szczelności prętów paliwowych na podstawie oznaczania produktów wybranych radioizotopów w wieloskładnikowych roztworach wodnych (Verification of the assessing fuel integrity based on
the determination of chosen radionuclides in water solutions).
2015, pp. 9-21.
7.
Chmielewska-Śmietanko D., Liang Zhao, Stachurska L.
Synteza selektywnych wymieniaczy do usuwania Cs i innych produktów rozszczepienia ze zbiorników
do przechowywania wypalonego paliwa i wody obiegu pierwotnego (Synthesis of selective ion exchangers for Cs and other fission products removal from the spent fuel storage basins and the nuclear
reactor primary water circuit).
2015, pp. 117-133.
8.
Chmielewski A.G.
Okruchy wspomnień – moja praca w IChTJ (Scraps of memories – my work in the INCT).
9.
Chmielewski A.G.
IChTJ – nowe rozdanie (The INCT – new deal).
10. Chmielewski A.G., Iller E., Palige J.
Inżynieria chemiczna i procesowa (Chemical and process engineering).
11. Chmielewski A.G., Sun Y.
Electron accelerators application in air pollution control.
116
In: The industrial and environmental applications of electron beams. Ed. D. Chmielewska-Śmietanko.
Institute of Nuclear Chemistry and Technology, Warszawa 2015, pp. 59-70.
12. Dancewicz A.M., Szumiel I.
Zakład Radiobiologii i Ochrony Zdrowia (Department of Radiobiology and Health Protection).
13. Deptuła A.
Wspomnienia obecnie najstarszego (stażem) pracownika (Memories today oldest (internships) employee).
14. Dybczyński R.S., Polkowska-Motrenko H.
Zakład Chemii Analitycznej (Department of Analytical Chemistry).
15. Gryczka U., Migdał W., Chmielewska-Śmietanko D.
Application of electron beam accelerators for food irradiation.
16. Kołacińska K., Trojanowicz M., Bojanowska-Czajka A.
Monitoring stężenia wybranych radionuklidów z wykorzystaniem metod przepływowych (Application
of flow injection analysis in determination of selected radionuclides).
2015, pp. 23-37.
17. Łyczko M., Filipowicz B., Łyczko K., Bilewicz A.
Opracowanie ulepszonych technologii wydzielania radionuklidów będących produktami korozji z płynów dekontaminacyjnych (Elaboration of the separation methods for isolation corrosion product radionuclides from decontamination solutions).
2015, pp. 106-115.
18. Migdał W.
Samodzielna Pracownia Radiacyjnego Utrwalania Płodów Rolnych (Pilot Plant for Food Irradiation).
19. Ostyk-Narbutt J.
60 lat radiochemii na Żeraniu (Sixty years of radiochemistry at Żerań).
20. Pałyska W.
Zakład IIA Chemicznej Inżynierii Jądrowej (Department of Chemical Nuclear Engineering IIA).
21. Parus J.L.
Zakład Chemicznej Inżynierii Jądrowej (Department of Chemical Nuclear Engineering).
22. Pieńkos J.P.
Zakład Aparatury i Metod Jądrowych (XVA) (Department of Radioisotope Instruments and Methods
– XVA).
117
23. Pieńkos J.P.
Zakład Doświadczalny Aparatury Elektronicznej (Experimental Establishment of Electronic Equipment).
24. Przybytniak G., Cieśla K., Kornacka E., Sadło J., Buczkowski M., Nowicki A.
Radiation synthesis and curing of nanocomposites suitable for practical applications. Chapter 10.
In: Radiation curing of composites for enhancing their features and utility in health care and industry.
IAEA-TECDOC-1764. IAEA, Vienna 2015, pp. 148-166.
25. Przybytniak G., Zimek Z.
Application of electron accelerators in cable industry.
26. Rafalski A., Rzepna M.
Electron beam sterilization.
27. Skotnicki K., Celuch M., Masłowska A., Kisała J., Pogocki D., Bobrowski K.
Badanie wpływu obecności tlenku cyrkonu oraz tlenków metali wchodzących w skład stopu cyrkonowego na wydajność wodoru cząsteczkowego w obecności typowych zanieczyszczeń w chłodziwie (wodzie)
reaktora (The effect of zirconium dioxide and other metals dioxides present in zircaloy for radiation
yield of molecular hydrogen in reactor water cooling system).
In: Analiza procesów generacji wodoru w reaktorze jądrowym w trakcie normalnej eksploatacji i w sytuacjach awaryjnych z propozycjami działań na rzecz podniesienia poziomu bezpieczeństwa jądrowego.
Zadanie wykonane w ramach projektu strategicznego NCBR Technologie wspomagające rozwój bezpiecznej energetyki jądrowej. Red. nauk. J. Michalik, R. Kocia. Instytut Chemii i Techniki Jądrowej,
Warszawa 2015, pp. 9-18.
28. Stachowicz W.
Samodzielne Laboratorium Identyfikacji Napromieniowania Żywności (Laboratory for Detection of
Irradiated Food).
29. Starosta W.
Zakład Badań Strukturalnych (Department of Structural Research).
30. Starosta W., Barlak M., Buczkowski M., Kosińska A., Sartowska B., Waliś L., Janiak T.
Analiza mechanizmów tworzenia się oraz właściwości warstw tlenkowych powstających w wyniku
rozkładu wody na powierzchni koszulek cyrkonowych oraz zbadanie wpływu modyfikacji struktury
warstwy wierzchniej koszulek na procesy generacji wodoru (Studies on properties and formation mechanisms of oxide layer growing in the process of water decomposition on zirconium claddings and on
influence of cladding’s surface layer structural modifications on hydrogen generation).
31. Strzelczak G., Sadło J., Sterniczuk M.
Badanie oddziaływania dodatków w chłodziwie reaktora (wodzie) i ich wpływu na zmianę wydajności
wodoru w reakcjach radiolizy wody (The study of interaction of additives in reactor coolant water and
its influence on the efficiency of hydrogen during water radiolysis reactions).
32. Szreder T., Warchoł S.
Chemia radiacyjna chłodziwa reaktorów jądrowych LWR. Oddziaływanie promieniowania jonizującego
na wodę oraz układy wodne w warunkach awaryjnych (Radiation chemistry of LWR reactors’ coolant.
The impact of ionizing radiation on water and aqueous systems in emergency conditions).
118
33. Waliś L.
Kronika [zawiera: Uchwała powołująca Instytut Badań Jądrowych, Dyrektorzy IBJ, Rada Naukowa IBJ,
Habilitacje i profesury Ośrodka Żerań IBJ, Czasy Instytutu Badań Jądrowych, Zarządzenie powołujące
Instytut Chemii i Techniki Jądrowej, Dyrektorzy IChTJ, Rada Naukowa IChTJ, Habilitacje i profesury
w IChTJ, Czasy Instytutu Chemii i Techniki Jądrowej] (Chronicle [contains: The resolution on IBJ;
List of IBJ directors, Information on IBJ Scientific Council, Habilitations and professorships, At time of
IBJ, Decree on the INCT establishment, List of the INCT directors, Information on the INCT Scientific
Council, Habilitations and professorships in the INCT, At time of the INCT]).
34. Waliś L.
Od „Dwudziestki” do „Jedynki” (From Department XX to Department I).
35. Wiśniewski A.
NSZZ “Solidarność”.
36. Zakrzewska-Kołtuniewicz G.
Advancement in membrane methods for liquid radioactive waste processing. Current opportunities,
challenges, and the global scenario.
In: Handbook of membrane separations. Chemical, pharmaceutical, food, and biotechnological applications. 2nd ed. Eds. A.K. Pabby, S.S.H. Rizvi, A.M. Sastre. CRC Press, 2015, pp. 665-707.
37. Zimek Z.
Chemia i technologia radiacyjna (Radiation chemistry and radiation processing).
38. Zimek Z.
Introduction to electron beam accelerators.
39. Zimek Z.
Układy mieszania, wentylacji i kontroli oraz aktywne i pasywne urządzenia przeznaczone do usuwania
wodoru w obszarze obudowy bezpieczeństwa, emitowanego w trakcie awarii reaktora jądrowego (Mixing, ventilation and control systems and active and passive equipment for hydrogen removal from containment during severe accidents of nuclear reactor).
Warszawa 2015, pp. 119-142.
THE INCT PUBLICATIONS
1. INCT Annual Report 2014.
Institute of Nuclear Chemistry and Technology, Warszawa 2015, 176 p.
2. Analiza procesów generacji wodoru w reaktorze jądrowym w trakcie normalnej eksploatacji i w sytuacjach awaryjnych z propozycjami działań na rzecz podniesienia poziomu bezpieczeństwa jądrowego.
Zadanie wykonane w ramach projektu strategicznego NCBR Technologie wspomagające rozwój bezpiecznej energetyki jądrowej (Study of hydrogen generation processes in nuclear reactors under regular
operation conditions and in emergency cases, with suggested actions aimed at upgrade of nuclear safety.
Task realized in the frame of the NCBR strategic project Technologies supporting development of safe
nuclear power engineering).
Red. nauk. J. Michalik, R. Kocia. Instytut Chemii i Techniki Jądrowej, Warszawa 2015, 163 p.
119
3. Analiza procesów zachodzących przy normalnej eksploatacji obiegów wodnych w elektrowniach jądrowych z propozycjami działań na rzecz podniesienia poziomu bezpieczeństwa jądrowego. Zadanie wykonane w ramach projektu strategicznego NCBR Technologie wspomagające rozwój bezpiecznej energetyki jądrowej (Study of processes occurring under regular operation of water circulation systems in
nuclear power plants with suggested actions aimed at upgrade of nuclear safety. Task realized in the
frame of the NCBR strategic project Technologies supporting development of safe nuclear power engineering).
Red. nauk. A. Bojanowska-Czajka. Instytut Chemii i Techniki Jądrowej, Warszawa 2015, 168 p.
4. Od Instytutu Badań Jądrowych do Instytutu Chemii i Techniki Jądrowej. Kronika i wspomnienia
1955-2015 (From the Institute of Nuclear Research to the Institute of Nuclear Chemistry and Technology. Chronicle and the memories 1955-2015).
Pod red. dra inż. L. Walisia. Instytut Chemii i Techniki Jądrowej, Warszawa 2015, 316 p.
5. The industrial and environmental applications of electron beams.
Ed. D. Chmielewska-Śmietanko. Institute of Nuclear Chemistry and Technology, Warszawa 2015, 108 p.
6. Tor mikrofalowy akceleratora elektronów LAE 10/15 Stacji Sterylizacji Radiacyjnej (Microwave route
of electron accelerator LAE 10/15 at the Radiation Sterilization Facility).
Instytut Chemii i Techniki Jądrowej, Warszawa 2015. Raporty IChTJ. Seria B nr 1/2015, 32 p.
CONFERENCE PROCEEDINGS
1.
Boguski J., Rzepna M.
Wyznaczanie dawki sterylizacyjnej (Determination of the sterilization dose).
XIII Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 22-23.10.2015,
[4] p.
2.
Brzóska K.
Biologiczne działanie i ryzyko promieniowania jonizującego (The biological effects and risk of ionizing
radiation).
[4] p.
3.
Bułka S.
Analiza ryzyka procesu sterylizacji radiacyjnej (The risk analysis of radiation sterilization process).
[3] p.
4.
Chmielewski A.G.
Stacje sterylizacji radiacyjnej wyposażone w izotopowe źródła promieniowania gamma (Irradiation facility equipped with isotope gamma sources).
[9] p.
5.
Głuszewski W.
Oddziaływanie promieniowania jonizującego na materię (The impact of ionizing radiation on the matter).
[5] p.
6.
Konarska E.M.
Rola opakowań w sterylizacji radiacyjnej (The role of packaging in the radiation sterilization).
[6] p.
7.
Korzeniowska-Sobczuk A.
Akredytowane Laboratorium Pomiarów Dawek Technologicznych (Accredited Laboratory for Measurements of Technological Doses).
[2] p.
8.
Przybytniak G.
Modyfikacja materiałów polimerowych pod wpływem promieniowania jonizującego (Modification of
polymeric materials by ionizing radiation).
[6] p.
120
9.
Rafalski A.
Kontrola dozymetryczna radiacyjnej sterylizacji wyrobów medycznych (Dosimetry of radiation sterilization of medical devices).
[6] p.
10. Rafalski A.
Sterylizacja radiacyjna na tle innych metod wyjaławiania (Radiation sterilization compared to other
sterilization methods).
[3] p.
11. Rafalski A.
Wiadomości niezbędne dla klientów Stacji Sterylizacji Radiacyjnej (Information for Radiation Sterilization Plant clients).
[2] p.
12. Sadowska M.W.
Samodzielne Laboratorium Identyfikacji Napromieniowania Żywności. Identyfikacja napromieniowanej żywności w IChTJ (Laboratory for Detection of Irradiated Food. Identification of irradiated food in
the INCT).
[6] p.
13. Schreinemachers C., Middendorp R., Bukaemskiy A.A., Modolo G., Brykała M., Rogowski M., Deptuła A., Čuba V., Pavelková T., Šebesta F., John J.
Conversion of actinides into oxide pre-cursors for innovative fuel fabrication.
In: Fuel Top Reactor Fuel Performance 2015: Conference Proceedings Zurich, Switzerland 13-17 September 2015. Part II. European Nuclear Society, 2015, pp. 471-480.
14. Trojanowicz M., Bojanowska-Czajka A., Łyczko M., Kulisa K., Kciuk G., Moskal J.
Radiolytic decomposition of environmentally persistent perfluorinated surfactants with the use of ionizing radiation.
Proceedings of the Third International Conference on Radiation and Applications in Various Fields of
Research, Budva, Montenegro, 8-12.06.2015. Ed. G. Ristić. RAD Association, Niš 2015, pp. 11-15.
15. Walo M.
Nowe materiały polimerowe modyfikowane radiacyjnie (New radiation-modified polymeric materials).
[5] p.
16. Zimek Z.
Akceleratory elektronów dla potrzeb sterylizacji radiacyjnej (Electron accelerators for radiation sterilization).
[6] p.
CONFERENCE ABSTRACTS
1.
Abramowska A., Gajda D., Miśkiewicz A., Zakrzewska-Kołtuniewicz G.
Purification of backflow fluids after hydraulic fracturing of Polish gas shales.
XXXII European Membrane Society Summer School 2015 “Integrated and Electromembrane Processes”,
Stráž pod Ralskem, Czech Republic, 21-26.06.2015. Book of abstracts, p. 30.
2.
Bilewicz A., Janiszewska Ł., Koźmiński P., Łyczko M., Pruszyński M., Jastrzębski J., Choiński J., Stolarz A., Trzcińska A., Szkliniarz K., Zipper W.
Gold nanoparticle-substance P(5-11) conjugate as a carrier for 211At in alpha particle therapy.
EANM’15 – Annual Congress of the European Association of Nuclear Medicine, Hamburg, Germany,
10-14.10.2015. European Journal of Nuclear Medicine and Molecular Imaging, 42, Suppl. 1, S245 (2015).
3.
Bilewicz A., Walczak R., Szkliniarz K., Sitarz M., Krajewski S., Abbas K., Choiński J., Cydzik I.,
Jakubowski A., Jastrzębski J., Stolarz A., Trzcińska A., Zipper W.
Cyclotron production of 43Sc – new radionuclide for PET technique.
121
4.
Bobrowski K., Filipiak P., Hug G.L., Pogocki D., Marciniak B.
Stabilization of monomeric sulfur cations in methionine-containing peptides with oligoprolines backbones.
3. Annual Scientific Meeting of the COST Action CM 1201: Biomimetic Radical Chemistry, Athenes,
Greece, 11-13.05.2015, p. 21.
5.
Boguski J., Przybytniak G., Mirkowski K., Głuszewski W.
Ocena wpływu promieniowania gamma na degradację kabli elektrycznych zainstalowanych w elektrowniach jądrowych metodami termicznymi (Assessment of gamma irradiation influence of electrical
cable degradation installed in nuclear power plants by thermal methods).
Mądralin-2015: Wybrane aspekty bezpieczeństwa elektrowni jądrowej w Polsce. Wspólna konferencja
naukowo-techniczna PTN i SFEN, Mądralin, Poland, 24-25.11.2015, p. 13.
6.
Bojanowska-Czajka A., Trojanowicz M., Łyczko M., Moskal J., Kulisa K., Kciuk G.
Monitoring rozkładu związków perfluorowanych pod wpływem promieniowania jonizującego z wykorzystaniem metod chromatograficznych (The monitoring of radiolytic decomposition of perfluorinated
surfactants with the use of ionizing radiation and chromatography).
IX Polska Konferencja Chemii Analitycznej „Chemia analityczna to ciągłe wyzwania”, Poznań, Poland,
6-10.07.2015, p. 249.
7.
Chajduk E., Danko B., Polkowska-Motrenko H.
Komplementarne zastosowanie technik INAA i ICP-MS w analizie składu metalowych obiektów historycznych (The complementary use of INAA and ICP-MS in the analysis of metallic historical objects).
6-10.07.2015, p. 39.
8.
Chajduk E., Pyszynska M., Polkowska-Motrenko H.
Comparison of performance of INAA, RNAA and ICP-MS for the determination of essential and toxic
elements in infant formulas.
14th International Conference on Nuclear Analytical Methods in the Life Sciences NAMLS, Delft, The
Netherlands, 23-28.08.2015, p. 146.
9.
Chmielewska D., Marek A.
Electron beam-tool for silver nanoparticles synthesis in different matrixes.
NAARI International Conference on State of the Art Radiation Processing, Mubai, India, 4-6.03.2015,
p. 27.
10. Chmielewska D., Stachurska L., Pańczyk E.
Silica based ion exchangers for different radionuclides removal from the spent fuel storage basins and
the nuclear reactor primary water circuit.
The Energy & Materials Research Conference – EMR2015, Madrid, Spain, 25-27.02.2015. Book of
abstracts, p. 197.
11. Cieśla K., Abramowska A., Buczkowski M.
The effects of some compositional factors and ionizing radiation on the properties of starch-PVA films.
BIOPOL 2015 – 5th International Conference on Biobased and Biodegradable Polymers, San Sebastian, Spain, 6-9.10.2015, [2] p.
12. Cieśla K., Abramowska A., Mathew A., Buczkowski M., Boguski J., Głuszewski W., Bielecki S.
The effect of ionising radiation on the films formed in the starch-PVA-nanocellulose system.
Advances in cellulose processing and application – research goes to industry. COST Action FT1205.
Joint Working Groups & Management Committee Meetings, Iasi, Romania, 10-11.03.2015, pp. 67-69.
13. Depuydt J., Vral A., Beinke C., Gil O., Popova L., Lumniczky K., Mkacher R., Moquet J., Obreja D.,
Oestreicher U., Sommer S., Testa A., Thierens H., Wójcik A.
Inter-laboratory comparison for the micronucleous assay in the frame of the European Network of
Biodosimetry – RENEB.
ICRR 2015 – 15th International Congress of Radiation Research, Kyoto, Japan, 25-29.05.2015, [1] p.
14. Diaconu D., Constantin M., Pavel G., Kralj M., Daris I., Istenič R., Zakrzewska G.
Public perception on education and information about the ionizing radiation across the EU.
International Conference: RICOMET 2015: Risk perception, communication and ethics of exposures to
ionizing radiation, Brdo, Slovenia, 15-17.06.2015, [1] p.
15. Drewnik J., Cieśla K., Buczkowski M., Boguski J.
The influence of ionizing radiation on properties of Cornstarch-PVA-nanocellulose films.
122
4th EPNOE International Polysaccharide Conference “Polysaccharides and polysaccharide-based advanced materials: from science to industry”, Warsaw, Poland, 19-22.10.2015, p. 303.
16. Dybczyński R.S.
Neutronowa analiza aktywacyjna i jej rola w metrologii chemicznej (Neutron activation analysis and
its role in chemical metrology).
58. Zjazd Naukowy Polskiego Towarzystwa Chemicznego w Gdańsku „Polska chemia w mieście wolności”, Gdańsk, Poland, 21-25.09.2015, [1] p., S12.
Niektóre trudne problemy oznaczania małych ilości itru ze szczególnym uwzględnieniem metod chromatograficznych (Some difficult problems in the determination of small amounts of yttrium with the
special emphasis on chromatographic methods).
4. Konferencja Naukowa „Monitoring i analiza wody. Chromatograficzne metody oznaczania substancji
o charakterze jonowym”, Toruń, Poland, 15-17.03.2015, p. 19.
18. Dybczyński R.
Słowo wstępne – materiały odniesienia (CRM) i związane z nimi problemy z perspektywy 40-u lat
doświadczeń (Introductory word – reference materials and associated problem from the perspective of
40 years experience).
Ogólnopolska Konferencja Naukowa „Jakość w chemii analitycznej”, Mory k/Warszawy, Poland,
25-27.11.2015, p. 7.
19. Dybczyński R., Kulisa K., Pyszynska M., Bojanowska-Czajka A.
Powinowactwo kompleksów pierwiastków ziem rzadkich (REE) z kwasem nitrylotrioctowym do fazy
stacjonarnej RP-HPLC modyfikowanej surfaktantem kationowym (Affinity of rare earth element (REE)
complexes with nitrilotriacetic acid to the RP-HPLC stationary phase modified with cationic surfactant).
XXIV Poznańskie Konwersatorium Analityczne „Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków”, Poznań, Poland, 9-10.04.2015, pp. 100-101.
20. Georgantzopoulou A., Gutleb A., Cambier S., Serchi T., Lankoff A., Kruszewski M., Balachandran Y.,
Grysan P., Audinot J.N., Ziebel J., Guignard C., Murk A.J.
Inhibition of multixenobiotic resonance (MXR) transporters by silver nanoparticles and -ions in vitro
and in vivo.
EUROTOX-51 Congress of the European Societies of Toxicology, Porto, Portugal, 13-16.09.2015. Toxicology Letters, 238, 2S, S210 (2015).
21. Głuszewski W., Rosen M.
Wykorzystanie DRS i GC do badania odporności radiacyjnej starodruków (The use of DRS and GC to
study the radiation resistance of old prints).
Konferencja „Analiza śladowa w ochronie zabytków XV”, Warszawa, Poland, 3-4.12.2015, pp. 15-16.
22. Głuszewski W., Zimek Z., Mirkowski K.
Radioliza tworzyw polimerowych w składowiskach odpadów promieniotwórczych (Radiolysis of polimer
materials in the radioactive waste stockpiles).
23. Gregoire E., Kulka U., Ainsbury E., Barrios L., Beinke C., Cucu A., Fattibene P., Gil O., Hadjidekova V.,
Jaworska A., Lindholm C., Lumniczky K., Mörtl S., Montoro A., Moreno M., Oestreicher U., Palitti F.,
Pantelias G., Rothkamm K., Roy L., Terzoudi G., Trompier F., Sabatier L., Sommer S., Testa A., Vaz P.,
Vral P., Woda C., Wójcik A., Voisin P.
WP3 Education, training and quality of the dosimetry network.
ConRad 2015 – Global Conference on Radiation Topics – Preparedness, Response, Protection and Research – 21st Nuclear Medical Defence Conference, Munich, Germany, 4-7.05.2015, [1] p.
24. Gryczka U., Migdał W., Chmielewska D., Walo M.
Application of electron beam irradiation in modification of thermal stability of lignocellulose.
p. 32.
25. Gumiela M., Gniazdowska E., Bilewicz A.
Radiofarmaceutyki znakowane akceleratorowo otrzymanym technetem-99m (Radiopharmaceuticals labelled with accelerator produced technetium-99m).
ChemSession’15 – XII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 8.05.2015,
p. 89.
123
Znakowanie radiofarmaceutyków technetem-99m otrzymanym w cyklotronie (Labelling of radiopharmaceuticals with cyclotron produced technetium-99m).
58. Zjazd Naukowy Polskiego Towarzystwa Chemicznego w Gdańsku „Polska chemia w mieście
wolności”, Gdańsk, Poland, 21-25.09.2015, [1] p.
Znakowanie radiofarmaceutyków technetem-99m otrzymanym w cyklotronie (Labelling of radiopharmaceuticals with cyclotron produced technetium-99m).
III Międzynarodowa Konferencja Radiofarmaceutyczna, Łódź, Poland, 28-29.05.2015, p. 59.
28. Herdzik-Koniecko I., Zakrzewska-Kołtuniewicz G., Cojocaru C., Chajduk E.
Experimental design and optimization of leaching process for recovery of valuable metals from low-grade
uranium ore.
29. Iwińska K., Miśkiewicz A.
Budowa platformy dla wzmocnienia badań społecznych związanych z energetyką jądrową w Europie
środkowo-wschodniej (Building a platform for enhanced societal research related to nuclear energy in
Central and Eastern Europe).
30. Kalbarczyk P., Miśta E.A., Rzeszotarska-Nowakiewicz A., Nowakiewicz T., Trela K.
Research on the corrosion character and ornamentation of the metal artifacts from archaeological site
Czaszkowo, Poland.
XXIV Poznańskie Konwersatorium Analityczne „Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków”, Poznań, Poland, 9-10.04.2015, p. 103.
31. Kiegiel K., Gajda D., Abramowska A., Miśkiewicz A., Oszczak A., Zakrzewska-Kołtuniewicz G.
Uran z łupków gazonośnych? (Uranium from gas-bearing shales?)
32. Kiegiel K., Gajda D., Abramowska A., Miśkiewicz A., Zakrzewska-Kołtuniewicz G.
The recovery of valuable metals from flowback fluids after hydraulic fracturing of Polish gas-bearing
shales.
3rd Annual International Conference on Chemistry and Physics, Athens, Greece, 20-23.05.2015, p. 42.
33. Kiegiel K., Gajda D., Zakrzewska-Kołtuniewicz G.
Odzysk uranu i metali towarzyszących z odpadów przemysłowych różnego pochodzenia (Recovery of
uranium and accompanying metals from various types of industrial wastes).
34. Kiegiel K., Zakrzewska-Kołtuniewicz G., Wołoszczuk K., Krajewski P.
Analiza krajowych i regionalnych struktur wspierających rozwój programów badań jądrowych poprzez
zastosowanie zintegrowanego podejścia (Assessment of regional capabilities for new reactors development through an integrated approach).
35. Kołacińska K., Bojanowska-Czajka A., Chajduk E., Samczyński Z., Dudek J., Trojanowicz M.
Zastosowanie systemów przepływowych do automatyzacji analizy próbek radioaktywnych – przykład
optymalizacji procedury oznaczeń 90Sr (Application of flow systems for automation of radioanalysis –
example of flow-procedure for 90Sr determination).
36. Kowalska M., Biedrzycki J., Węgierek-Ciuk A., Czarnocka J., Kruszewski M., Lisowska H., Mruk R.,
Oczkowski M., Oddvar M., Gromadzka-Ostrowska J., Øvrevik J., Męczyńska-Wielgosz S., Wojewódzka M., Lankoff A.
Wpływ cząstek pochodzących ze spalania paliw 1 i 2 generacji biodiesla na cytotoksyczność i genotoksyczność w komórkach A549 (Cyto- and genotoxicity of 1st and 2nd generation biodiesel exhausts
particles on A549 cells).
VIII Międzydyscyplinarna Konferencja Doktorantów Uniwersytetu Szczecińskiego, Szczecin, Poland,
16.10.2015, p. 23.
124
37. Kowalska M., Węgierek-Ciuk A., Kruszewski M., Lisowska H., Męczyńska-Wielgosz S., Iwaneńko T.,
Wojewódzka M., Lankoff A.
Evaluating the toxicity of selected types of carbon nanomaterials in vitro.
EUROTOX-51 Congress of the European Societies of Toxicology, Porto, Portugal, 13-16.09.2015. Toxicology Letters, 238, 2S, S202 (2015).
38. Krajewski P., Kruszewski M., Olko P., Golnik N.
Review of major results of the “SPREY” network supporting prospective requirements of nuclear power
development in Poland.
39. Kralj M., Daris I., Železnik N., Marega M., Istenič R., Diaconu D., Zakrzewska G.
What do institutions which take advantage of ionizing radiation want to tell the public.
International Conference RICOMET 2015: Risk perception, communication and ethics of exposures to
40. Kulka U., Ainsbury E., Barrios L., Beinke C., Cucu A., Fattibene P., Gil O., Gregoire E., Hadjidekova V.,
Jaworska A., Lindholm C., Lumniczky K., Mörtl S., Montoro A., Moreno M., Oestreicher U., Palitti F.,
Pantelias G., Rothkamm K., Terzoudi G., Trompier F., Sabatier L., Sommer S., Testa A., Vaz P., Voisin P.,
Vral P., Woda C., Wójcik A.
RENEB – biological dosimetry for large scale radiological incidents.
ConRad 2015, Global Conference on Radiation Topics – Preparedness, Response, Protection and Research – 21st Nuclear Medical Defence Conference, Munich, Germany, 4-7.05.2015, [2] p.
41. Kulka U., Ainsbury E., Barrios L., Beinke C., Cucu A., Fattibene P., Gil O., Hadjidekova V., Jaworska A.,
Lindholm C., Lumniczky K., Mörtl S., Montoro A., Moreno M., Oestreicher U., Palitti F., Pantelias G.,
Rothkamm K., Terzoudi G., Trompier F., Sabatier L., Sommer S., Testa A., Vaz P., Voisin P., Vral A.,
Woda C., Wójcik A.
RENEB – biological dose estimation following a large scale radiological incident.
International Conference on Individual Monitoring of Ionising Radiation, Bruges, Belgium, 20-24.04.2015,
[2] p.
42. Kulka U., Oestreicher U., Ainsbury E.A., Moquet J., Gregoire E., Roch-Lefevre S., Barquinero J.F.,
Barrios L., Beinke C., Cucu A., Popescu I., Noditi M., Montoro A., Palitti F., Gil O. M., Vaz P., Hadjidekova V., Hatzi V., Pantelias G., Terzoudi G., Lindholm C., Sabatier L., Moreno M., Prieto M., Buraczewska I., Sommer S., Testa A., Wojcik A., Fattibene P., Mörtl A.S., Jaworska A., Thierens H., Vral A.,
Lumniczky K., Safrany G.
RENEB – Biodosimetry Network – Solution to enhance positive perception in the European Society.
43. Kużelewska I., Chajduk E., Polkowska-Motrenko H.
Zastosowanie neutronowej analizy aktywacyjnej i spektrometrii mas ze wzbudzeniem w plazmie indukcyjnie sprzężonej do badania trwałości certyfikowanych materiałów odniesienia o matrycy biologicznej
(Application of neutron activation analysis and inductively coupled plasma mass spectrometry to stability testing of certified reference materials with biological origin).
6-10.07.2015, p. 50.
44. Kużelewska I., Polkowska-Motrenko H., Danko B.
Opracowanie procedury oznaczania chromu w próbkach środowiskowych z zastosowaniem neutronowej analizy aktywacyjnej (NAA) (Procedure of chromium determination in enviromental materials by
neutron activation analysis (NAA)).
XXIV Poznańskie Konwersatorium Analityczne „Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków”, Poznań, Poland, 9-10.04.2015, pp. 104-105.
45. Lankoff A., Węgierek-Ciuk A., Kowalska M., Kruszewski M., Lisowska H., Męczyńska-Wielgosz S.,
Wójciuk G., Wojewódzka M.
Effects of single walled carbon nanotubes and diesel engine nanoparticles on ionizing radiation-induced DNA damage and repair in A549 cells.
15. International Congress of Radiation Research – ICRP 2015, Kyoto, Japan, 25-29.05.2015, [1] p.
(2-PS3D-07).
46. Latek S.
Media about Polish Nuclear Power Programme.
125
47. Lazurik V.M., Lazurik V.T., Popov G., Zimek Z.
Two-parametric model of electron beam computational dosimetry for radiation processing.
13th Tihany Symposium on Radiation Chemistry, Balatonalmadi, Hungary, 29.08.-3.09.2015, O.53.
48. Lisowska H., Czub J., Banas D., Braziewicz J., Kubala A., Wudarczyk J., Szumiel I., Wójcik A.
Analysis of elements secreted by CHO-K1 cells exposed to gamma radiation under different conditions.
(4-PS3F-05).
49. Lisowska H., Eland N., Stępień K., Węgierek-Ciuk A., Lankoff A., Haghdoost S., Sollazzo A., Wójcik A.
The application of PCC to study the mechanisms of the radioprotective effect of hypothermia in human
peripheral blood lymphocytes.
(3-PS3B-06).
50. Łyczko M., Pruszyński M., Łyczko K., Wąs B., Męczyńska S., Kruszewski M., Bilewicz A., Jastrzębski J., Choiński J., Sitarz M., Stolarz A., Trzcińska A., Szkliniarz K., Zipper W.
Nowy potencjalny radiofarmaceutyk terapeutyczny oparty na At-211 (Novel potential therapeutic radiopharmaceutical based on At-211).
III Międzynarodowa Konferencja Radiofarmaceutyczna, Łódź, Poland, 28-29.05.2015, p. 60.
51. Majkowska-Pilip A., Koźmiński P., Piotrowska A., Bruchertseifer F., Morgenstern A., Bonelli M.,
Laurenza M., Bilewicz A.
223
Na-NaA-PEG-SP(5-11) radiobioconjugate as a new potential radiopharmaceutical for targeted 
therapy of glioblastoma multiforme.
52. Matysiak M., Czajka M., Pankiewicz P., Kruszewski M., Kapka-Skrzypczak L.
Udział pestycydów fosforoorganicznych w stymulacji proliferacji komórek tłuszczowych (Contribution
of organophosphate pesticides in stimulation of proliferation in apidocytes).
Kongres Medycyny i Zdrowia Wsi, Lublin, 24-26.05.2015. Streszczenia, p. 75.
53. Matysiak M., Czajka M., Pankiewicz P., Kruszewski M., Kapka-Skrzypczak L.
Contribution of organophosphate pesticides in stimulation of proliferation in apidocytes.
Kongres Medycyny i Zdrowia Wsi, Lublin, 24-26.05.2015. Streszczenia, pp. 75-76.
54. Mays C., Valuch J., Zakrzewska G., Daris I., Diaconu D.
Results of discussions with journalists form Poland, Slovenia, Romania and France reporting about
ionizing radiation.
55. Migdał W., Gryczka U., Chmielewska D., Ptaszek M., Orlikowski L.B.
The innovative of electron beam in disinfection process.
p. 32.
56. Miśkiewicz A., Zakrzewska-Kołtuniewicz G.
Membrany w oczyszczaniu ciekłych odpadów promieniotwórczych – ograniczenia w stosowaniu oraz
metody badania niekorzystnych zjawisk (Membranes in radioactive wastes treatment – limitation on
the use and method of study the unfavorable phenomena).
57. Miśkiewicz A., Zakrzewska-Kołtuniewicz G., Wójtowicz K.
Studying the socio-economic effects of implementation of the Polish Nuclear Power Programme.
SENIX Conference – The Role of Social Sciences in a Low-Carbon Energy Mix, Stockholm, Sweden,
25-27.05.2015. Book of abstracts, p. 29.
58. Nieścior-Browińska P., Zakrzewska-Kołtuniewicz G.
Public perception of ionising radiation / studies on metal models of radiation in Poland.
Third International Conference on Radiation and Applications in Various Fields of Research, Budva,
Montenegro, 8-12.06.2015. Book of abstracts. Ed. G. Ristić. RAD Association, Niš 2015, p. 403.
59. Nieścior-Browińska P., Zakrzewska-Kołtuniewicz G.
The recovery of boron by using membrane technologies – the review.
126
60. Oestreicher U., Ainsbury E., Baeyens A., Barrios L., Beinke C., Cucu A., De Amicis A., De Sanctis A.,
Di Giorgio M., Dominquez I., Duy P.N., Espinoza M., Monteiro Gil O., Gregoire E., Guerrero-Carvajal
C., Hadjidekova V., Kulka U., Lamadrid A. I., Lindholm C., Lumniczky K., Martinez-Lopez W.,
M’kacher R., Moquet J., Montoro A., Moreno M., Noditi M., Palitti F., Pajic J., Samaga D., Slabbert J.,
Sommer S., Stuck Oliveira M., Suto Y., Testa A., Valdivia P., Vral P., Zafiropopoulos D., Wilkins R.,
Yanti L., Wójcik A.
Inter-laboratory comparison on the dicentric chromosomes assay in the frame of the European Network of Biodosimetry – RENEB.
61. Oestreicher U., Ainsbury E., Baeyens A., Barrios L., Beinke C., Cucu A., De Amicis A., De Sanctis A.,
Di Giorgio M., Dominquez I., Duy P. N., Espinoza M., Monteiro Gil O., Gregoire E., Guerrero-Carvajal
C., Hadjidekova V., Kulka U., Lamadrid A.I., Lindholm C., Lumniczky K., Martinez-Lopez W.,
M’kacher R., Moquet J., Montoro A., Moreno M., Noditi M., Palitti F., Pajic J., Samaga D., Slabbert J.,
Sommer S., Stuck Oliveira M., Suto Y., Testa A., Valdivia P., Vral P., Zafiropopoulos D., Wilkins R.,
Yanti L., Wójcik A.
Results of a global inter-laboratory comparison on the dicentric chromosomes assay in the frame of the
European Network of Biodosimetry – RENEB.
EPR BIODOSE 2015, Hanover, New Hampshire, USA, 4-8.10.2015, [2] p.
62. Olszewska W., Zakrzewska-Kołtuniewicz G., Miśkiewicz A.
Communication and information on ionizing radiation as a tool for social consensus around the construction of new repositories for radioactive waste in Poland.
63. Oszczak A., Fuks L.
Sorption of selected radionuclides from liquid radioactive wastes by alginate beads.
64. Oszczak A., Fuks L., Herdzik-Koniecko I.
Polisacharydy jako sorbenty w procesie zatężania ciekłych odpadów promieniotwórczych (Polysaccharides as a sorbents of liquid radioactive waste in the concentrating process).
65. Perko T., Diaconu D., Železnik N., Mays C., Kralj M., Zakrzewska G., Daris I., Marega M., Istenič R.,
Valuch J., Nagy A., Lammers P., Condi C., Koron B., Turcanu C., Constantin M., El Jamal M.H.,
Rollinger F., Pavel G., Schneider N., Meskens G., Van Roey E.
Eagle findings related to communication and stakeholder involvement in nuclear and radiological emergencies.
66. Przybytniak G., Boguski J.
Thermally and radiation-induced aging of electrical cables operating in NPP.
13th Tihany Symposium on Radiation Chemistry, Balatonalmádi, Hungary, 29.08.-3.09.2015, [1] p.
O63.
67. Ptaszek M., Gryczka U., Migdał W., Orlikowski L.
Wykorzystanie metody radiacyjnej do odkażania podłoży (Application of radiation methods for disinfection of horticultural substrates).
Konferencja „Innowacyjne technologie dla polskiego ogrodnictwa – Nauka – Praktyce”, Warszawa,
Poland, 23.04.2015, p. 107.
68. Rogowski M., Olczak T., Wawszczak D., Łada W., Smoliński T., Brykała M., Wojtowicz P.
Otrzymywanie sferycznych tlenkowych i węglikowych paliw uranowych zawierających neodym, jako
surogat ameryku(III) (Preparation of spherical oxide and carbide uranium fuel containing neodymium
as a surrogate of americium(III)).
naukowo-techniczna PTN i SFEN, Mądralin, Poland, 24-25.11.2015, [1] p.
69. Romm H., Ainsbury E., Barquinero J. F., Barrios L., Beinke C., Cucu A., Fabregat N.S., Filipi S., Monteiro Gil O., Gregoire E., Hadjidekova V., Hatzi V., Lindholm C., M’kacher R., Kulka U., Montoro A.,
127
Moquet J., Moreno Domene M., Noditi M., Oestreicher U., Palitti F., Pantelias G., Prieto M.J., Popescu I., Roch-Lefevre S., Rothkamm K., Sommer S., Terzoudi G., Testa A., Vaz P., Voisin P., Wójcik A.
Use of a web based scoring method for an intercomparison of the dicentric chromosome assay within
seventeen European biodosimetry laboratories.
70. Roubinek O., Palige J., Szołucha M., Kalbarczyk P.
Odzysk uranu z pokopalnianych hałd rud uranowych (Uranium recovery from postmining heap of
uranium ores).
71. Rzepna M., Przybytniak G.
Ocena oddziaływania promieniowania jonizującego na poliestry biodegradowalne (Assessment of the
impact of ionizing radiation on biodegradable polyesters).
p. 181.
72. Samczyński Z., Dybczyński R.S., Pyszynska M., Kulisa K., Polkowska-Motrenko H., Kużelewska I.,
Bartosiewicz I.
Nowa metoda wydzielania śladowych ilości pierwiastków ziem rzadkich z materiałów biologicznych
i środowiskowych (New method of isolation of trace amounts of rare earth elements from biological
and environmental materials).
6-10.07.2015, p. 37.
73. Samczyński Z., Polkowska-Motrenko H., Dybczyński R.S.
Nowe materiały odniesienia dla nieorganicznej analizy śladowej: MODAS-2 BotSed, MODAS 3 HerTris,
MODAS 4 CormTis, MODAS 5 CodTis – przygotowanie i certyfikacja (New reference materials for inorganic trace analysis: MODAS-2 BotSed, MODAS 3 HerTis, MODAS 4 CormTis, MODAS 5 CodTis
– preparation and certification).
Ogólnopolska Konferencja Naukowa „Jakość w chemii analitycznej”, Mory k/Warszawy, Poland,
25-27.11.2015, p. 24.
74. Sartowska B., Starosta W., Orelovitch O.L., Apel P.Yu., Buczkowski M.
Metal organic frameworks (MOFs) composite materials with polymer or ceramic base.
European Association for Chemical and Molecular Sciences (EuCheMS) 21st Conference on Organometallic Chemistry (EuCOMC XXI), Bratislava, Slovak Republic, 5-9.07.2015. Book of abstracts, [1] p.
75. Sartowska B., Starosta W., Waliś L., Barlak M.
Modification of the surface layer of zirconium alloys using high intense pulsed plasma beams (HIPPB).
21. International Quench Workshop, Karlsruhe, Germany, 27-29.10.2015, [1] p.
76. Skotnicki K., Bobrowski K., de la Fuente J., Cañete A.
Radiation-induced radical processes involving amino acids and quinoxalin-2-one derivatives.
29. Miller Conference on Radiation Chemistry, Bowness-on-Windermere, United Kingdom, 14-19.03.2015,
p. 37.
77. Skotnicki K., Bobrowski K., de la Fuente J., Cañete A.
Radiation induced radical processes involving amino acids and quinoxalin-2-one derivatives relevant to
their pharmacological application.
13th Tihany Symposium on Radiation Chemistry, Balatonalmádi, Hungary, 29.08.-3.09.2015, [1] p.
O13.
78. Skotnicki K., Celuch M., Masłowska A., Kisała J., Pogocki D., Bobrowski K.
Molecular hydrogen yields in radiolysis of heterogeneous water/ceramic oxides systems.
29. Miller Conference on Radiation Chemistry, Bowness-on-Windermere, United Kingdom, 14-19.03.2015,
p. 52.
79. Smoliński T., Deptuła A., Wawszczak D., Łada W., Wojtowicz P., Olczak T., Brykała M., Rogowski M.,
Miłkowska M., Chmielewski A.G., Zaza F.
Synteza metodą zol-żel ceramicznych matryc (Ti) opartych na hollyandycie, przenaczonych do zestalania odpadów promieniotwórczych (Synthesis of ceramic (Ti) matrixes based on hollandite, intended
for solidifying radioactive waste by sol-gel method).
128
80. Sommer S., Ainsbury E.A., Barquinero J.F., Beinke C., Buraczewska I., Cucu A., Fattibene P., Gil O.M.,
Gregoire E., Hadjidekova V., Hatzi V., Jaworska A., Lindholm C., Lumniczky K., Kulka U., Montoro A.,
Moquet J., Mörtl S., Moreno M., Noditi M., Palitti F., Prieto M., Oestreicher U., Pantelias G., Popescu I., Roch-Lefevre S., Sabatier L., Safrany G., Terzoudi G., Testa A., Thierens H., Vaz P., Vral A.,
Wojcik A.
RENEB – europejska sieć laboratoriów dozymetrii biologicznej (RENEB – Running the European network of biological dosimetry and physical retrospective dosimetry).
XVIII Konferencja Inspektorów Ochrony Radiologicznej „Ochrona radiologiczna teraz i w przyszłości”,
Skorzęcin, Poland, 17-20.06.2015, [2] p.
81. Sommer S., Szumiel I., Bartłomiejczyk T., Buraczewska I.
Low doses of radiation – hot spot in dose perception and radiological protection.
82. Starosta W., Barlak M., Tomassi P., Sartowska B., Waliś L., Miłkowska M.
Pokrycia ochronne koszulek cyrkonowych dla zwiększenia ich odporności na utlenianie w warunkach
awarii typu LOCA (Protective covers of circonium claddings for enchancing oxidation resistance in
LOCA conditions).
83. Szkliniarz K., Bilewicz A., Choiński J., Jakubowski A., Jastrzębski J., Leszczuk E., Łyczko M., Stolarz A., Trzcińska A., Was B., Zipper W.
New results on the radioisotope 211At produced using the alpha particle beam.
84. Trojanowicz M., Bojanowska-Czajka A., Łyczko M., Kulisa K., Kciuk G., Moskal J.
Radiolytic decomposition of environmentally persistent perfluorinated surfactants with the use of ionizing radiation.
85. Vaidyanathan G., McDougald D., Choi J., Koumarianou E., Pruszyński M., Osada T., Lyerly H., Lahoutte T., Zalutsky M.R.
An anti-HER2 nanobody labeled with 18F using a residualizing label for assessing HER2 status.
86. Węgierek-Ciuk A., Lisowska H., Kowalska M., Wolszczak M., Wójcik A., Lankoff A.
Radiation induced gamma H2AX foci and their modulation by selected protoberberines.
15. International Congress of Radiation Research, ICRP 2015, Kyoto, Japan, 25-29.05.2015, [1] p.
(3-PS2E-33).
87. Wojtowicz P., Deptuła A., Wawszczak D., Łada W., Smoliński T., Olczak T., Brykała M., Rogowski M.,
Miłkowska M., Chmielewski A.G.
Synteza metodą zol-żel szkieł krzemionkowych stosowanych w zestalaniu odpadów promieniotwórczych (Synthesis of silica glasses used for solidification of radioactive waste by sol-gel).
88. Wołkowicz S., Galica D., Dunst N., Zakrzewska G., Olszewska W.
Ocena kosztów pozyskania uranu z dolnoordowickich łupków dictyonemowych Obniżenia Podlaskiego
(Assessment of the costs of uranium extraction from ordovician dictyonema shale of Podlasie Depression).
4. Ogólnopolska Konferencja Naukowa „Złoża kopalin, aktualne problemy prac poszukiwawczych,
badawczych i dokumentacyjnych”, Warszawa, Poland, 15-17.04.2015, pp.70-71.
89. Wójcik A., Ainsbury E., Barrios L., Beinke C., Cucu A., Fattibene P., Gil O., Gregoire E., Hadjidekova
V., Jaworska A., Kulka U., Lindholm C., Lumniczky K., Mörtl S., Montoro A., Moreno M., Oestreicher
U., Palitti F., Pantelias G., Rothkamm K, Terzoudi G., Trompier F., Sabatier L., Sommer S., Testa A.,
Vaz P., Voisin P., Vral A., Woda C.
European networking in biological dosimetry: results of two performance intercomparisons carried out
within the RENEB project.
ConRad 2015, Global Conference on Radiation Topics – Preparedness, Response, Protection and Research, 21st Nuclear Medical Defence Conference, Munich, Germany, 4-7.05.2015, [1] p.
129
90. Zakrzewska-Kołtuniewicz G., Miśkiewicz A.
Public perception and acceptance – the experience of stakeholds’ involvement in the implementation of
the Program of Polish Nuclear Energy.
SENIX Conference – The Role of Social Sciences in a Low-Carbon Energy Mix, Stockholm, Sweden,
25-27.05.2015. Book of abstracts, pp. 40-41.
91. Železnik N., Constantin M., Schneider N., Mays C., Zakrzewska G., Diaconu D.
Presentation of mental model research in Slovenia, Poland, France and Romania.
92. Zimek Z., Przybyła M., Roman K.
Laboratory EB facility for studying industrial wastewater effluents treatment by radiation.
13th Tihany Symposium on Radiation Chemistry, Balatonalmadi, Hungary, 29.08.-3.09.2015, P.38.
93. Zimek Z., Roman K., Długoń S.
Możliwości i ograniczenia urządzeń i strategii stosowanych przy usuwaniu wodoru uwalnianego w trakcie
awarii reaktora (Opportunities and limitations of equipment and strategies of hydrogen removal during
severe accidents of nuclear reactor).
94. Zwolińska E., Gogulancea V., Lavric V., Sun Y.
Modelowanie procesu oczyszczania gazów z dwutlenku siarki (SO2) i tlenków azotu (NOx) za pomocą
wiązki elektronów (Mathematical modelling of sulphur dioxide (SO2) and nitrogen oxides (NOx) removal using electron beam technology).
p. 221.
SUPPLEMENT LIST OF THE PUBLICATIONS IN 2014
1.
Bandzierz K., Bieliński D.M., Korycki A., Przybytniak G.
Radiation crosslinking of acrylonitrile-butadiene rubber – the influence of sulfur and dibenzothiazole
disulfide on the process. (Chapter 11).
In: High performance elastomer materials. An engineering approach. Eds. D.M. Bieliński, R. Kozłowski,
G.E. Zaikov. CRC Press, Toronto 2014, pp. 129-141.
2.
Brykała M., Rogowski M.
Wykorzystanie pierwiastków wyodrębnionych z wypalonego paliwa do wytwarzania prekursorów paliwa do reaktorów nowej generacji (The usage of elements separated from spent nuclear fuel for the production of fuel precursors for new generation of reactors).
In: Rozwój technik i technologii wspomagających gospodarkę wypalonym paliwem i odpadami promieniotwórczymi. Red. nauk. L. Fuks. Instytut Chemii i Techniki Jądrowej, Warszawa 2014, pp. 235-251.
3.
Brykała M., Walczak R., Rejnis M.
Otrzymywanie ZrO2 za pomocą kompleksowej metody zol-żel (CSGP) (Preparation of ZrO2 by a complex sol-gel method (CSGP)).
4.
Celuch M., Bobrowski K.
Badania stabilności radiacyjnej wybranych układów ekstrakcyjnych ważnych z punktu widzenia procesu GANEX (Radiation stability of chosen extractant systems important for GANEX process).
5.
Chmielewski A.G., Palige J., Urbaniak A., Wawryniuk K., Szołucha M.
Wzbogacanie biogazu w metan z wykorzystaniem membrany poliimidowej (Methane enrichment of
biogas with the aid of a polyamide membrane).
In: Konwersja odpadów przemysłu rolno-spożywczego do biogazu – podejście systemowe. Pod red.
I. Wojnowskiej-Baryły, J. Gołaszewskiego. Wydawnictwo UWM, Olsztyn 2014, pp. 183-197.
6.
Ciezkowska M., Poszytek K., Roubinek O., Palige J., Skłodowska A., Drewniak Ł.
A novel lab-scale two-stage reactor for biogas production through the use of efficient and stable microbial consortia.
New Biotechnology, 315, S125 (2014), http://dx.doi.org/10.1016/j.nbt.2014.05.1918.
130
7.
Filipowicz B., Blicharska M., Bartoś B., Łyczko M., Koźmiński P., Pruszyński M., Bilewicz A.
Rozwój technik i technologii w zakresie zmniejszania radiotoksyczności odpadów promieniotwórczych,
w tym metodami radiochemicznymi (The development of techniques and technologies for reducing
radiotoxicity of nuclear waste, including radiochemical methods).
8.
Grabias E., Solecki J., Gładysz-Płaska A., Fuks L., Oszczak A., Majdan M.
Local minerals for engineering barriers for the national radioactive waste repository (NRWR): sorption
of U(VI), Am(III), Sr(II) and Cs(I) ions on red clay.
9.
Jamróz M.H.
On the internal coordinates in the potential energy distribution (PED) analysis: bending or torsion?
Enliven: Bioinformatics, 1, 4, 1-3 (2014).
10. Kaźmierczak U., Banaś D., Braziewicz D., Buraczewska I., Czub J., Jaskóła M., Kaźmierczak Ł., Korman A., Kruszewski M., Lankoff A., Lisowska H., Nesteruk M., Szefliński Z., Wojewódzka M.
Investigation of the bystander effect in CHO-K1 cells.
Reports of Practical Oncology and Radiotherapy, 19, S37-S41 (2014).
11. Kunicki-Goldfinger J.J., Freestone I.C., Gilderdale-Scott H., Ayers T., McDonald I.
Problematyka badań witraży średniowiecznych (Issues in medieval stained glass research).
Archeologia Polski, LIX, 1-2, 47-78 (2014).
12. Lipiński P.F.J., Dobrowolski J.Cz.
Local chirality measures in QSPR : IR and VCD spectroscopy.
RSC Advances, 4, 47047-47055 (2014).
13. Lipiński P.F.J., Dobrowolski J.Cz.
Substituent effect in theoretical VCD spectra.
RSC Advances, 4, 27062-27066 (2014).
14. Migdał W., Gryczka U.
Radiacyjna inaktywacja czynników bioterrorystycznych (Rozdział 15) (Radiation inactivation of bioterrorism agents (Chapert 15)).
In: Analiza i symulacja epidemii chorób przenoszonych drogą pokarmową. Red. nauk. J. Bertrandt, T.
Nowicki, R. Pytlak. Wojskowa Akademia Techniczna, Warszawa 2014, pp. 231-238.
15. Narbutt J., Rejnis M., Herdzik-Koniecko I., Steczek Ł., Wodyński A.
Zbadanie wpływu wybranych ligandów hydrofilowych na proces grupowej ekstrakcji aktynowców –
GANEX (The effect of some hydrophilic ligands on the process of group extraction of actinides – GANEX).
In: Rozwój technik i technologii wspomagających gospodarkę wypalonym paliwem i odpadami promieniotwórczymi. Red. L. Fuks. Instytut Chemii i Techniki Jądrowej, Warszawa 2014, pp. 9-26.
16. Ostrowski S., Dobrowolski J.Cz.
What does the HOMA index really measure?
RSC Advances, 4, 44158-44161 (2014).
17. Oszczak A., Fuks L., Majdan M.
Modyfikowane związki naturalne jako sorbenty w procesach składowania nisko- i średnioaktywnych
odpadów promieniotwórczych (Modification of compounds of the biological origin, potential sorbents
for low and intermediate radioactive wastes).
18. Palige J., Chmielewski A.G., Zalewski M., Roubinek O., Usidus J.
Układ bioreaktorów do wytwarzania biogazu (A system of bioreactors for biogas production).
In: Konwersja odpadów przemysłu rolno-spożywczego do biogazu – podejście systemowe. Pod red.
I. Wojnowskiej-Baryły, J. Gołaszewskiego. Wydawnictwo UWM, Olsztyn 2014, pp. 165-181.
19. Pawlukojć A., Hetmańczyk Ł.
INS, DFT and temperature dependent IR investigations of dynamical properties of low temperature
phase of choline chloride.
Chemical Physics, 445, 31-37 (2014).
20. Rozwój technik i technologii wspomagających gospodarkę wypalonym paliwem i odpadami promieniotwórczymi. Zadanie wykonane w ramach projektu strategicznego NCBR Technologie wspomagające
131
rozwój bezpiecznej energetyki jądrowej (Development of spent nuclear fuel and radioactive waste management techniques and technologies. Task realized in the frame of the NCBR strategic project Technologies supporting development of safe nuclear power engineering).
Red. nauk. L. Fuks. Instytut Chemii i Techniki Jądrowej, Warszawa 2014, 251 p.
21. Starosta W.
Inteligentne nanosorbenty do zastosowań w bezpiecznej energetyce jądrowej (Intelligent nanosorbents
for application in safe nuclear technologies).
22. Szreder T., Strzelczak G., Skrzypczak A.
Badania stabilności radiacyjnej cieczy jonowych stosowanych w ekstrakcji plutonu i aktynowców
mniejszościowych (Radiation stability of ionic liquids used in plutonium and minor actinides extraction).
23. Trojanowicz M.
Applications of gold nanoparticles in electroanalysis. (Chapter 11).
In: Gold nanoparticles in analytical chemistry. Comprehensive analytical chemistry. Vol. 66. Eds. M. Valcárcel, Á.I. López-Lorente. Elsevier, Amsterdam 2014, pp. 429-476, http://dx.doi.org/10.1016/B978-0-444-63285-2.00011-0.
24. Trojanowicz M.
Enantioselective electrochemical sensors and biosensors: a mini-review.
Electrochemistry Communications, 38, 47-52 (2014).
25. Wojtowicz P., Smoliński T., Deptuła A.
Otrzymywanie szkieł krzemionkowych oraz materiałów typu Synroc (Preparation of silica glass and Synroc materials).
26. Zając G., Kaczor A., Chruszcz-Lipska K., Dobrowolski J.Cz., Barańska M.
Bisignate resonance Raman optical activity: a pseudo breakdown of the single electronic state model
of RROA?
Journal of Raman Spectroscopy, 45, 859-862 (2014).
27. Zakrzewska-Kołtuniewicz G., Miśkiewicz A., Olszewska W., Harasimowicz M., Jaworska-Sobczak A.,
Cojocaru C.
Rozwój technik i technologii w zakresie przerobu i postępowania z nisko- i średnioaktywnymi odpadami promieniotwórczymi – procesy membranowe (Development of techniques and technologies for
the processing and handling of low and intermediate level radioactive waste – membrane processes).
132
NUKLEONIKA
NUKLEONIKA
THE INTERNATIONAL JOURNAL OF NUCLEAR RESEARCH
EDITORIAL BOARD
Andrzej G. Chmielewski (Editor-in-Chief, Poland), Krzysztof Andrzejewski (Poland), Henryk Anglart
(Sweden), 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), Robert H. Schuler (USA), Christian Streffer (Germany),
Irena Szumiel (Poland), Alexander Van Hook (USA), Bożena Bursa (secretary)
CONTENTS OF NO. 1/2015
Proceedings of the 10th All-Polish Seminar on Mössbauer Spectroscopy OSSM 2014, 15-18 June
2014, Wrocław, Poland
1.
Mössbauer study of treated Nd2Fe14B
M. Budzyński, V.C. Constantin, A.-M.J. Popescu, Z. Surowiec, T.M. Tkachenka, K.I. Yanushkevich
2.
The study of crystal and magnetic properties of MnNi0.85Fe0.15Ge
M. Budzyński, V.I. Valkov, A.V. Golovchan, V.I. Mitsiuk, A.P. Sivachenko, Z. Surowiec, T.M. Tkachenka
3.
The microstructure and magnetic properties of Nd8.5Tb1.5Fe83Zr1B6 ribbons obtained at various cooling
rates
M. Dośpiał, J. Olszewski, M. Nabiałek, P. Pietrusiewicz, T. Kaczmarzyk
4.
Mobility of interacting inorganic nanoparticles
K. Dziedzic-Kocurek, P. Fornal, J. Stanek
5.
Effect of heat treatment on the shape of the hyperfine field induction distributions and magnetic properties of amorphous soft magnetic Fe62Co10Y8B20 alloy
K.M. Gruszka, M. Nabiałek, K. Błoch, J. Olszewski
6.
Microstructure and magnetic properties of Nd-Fe-B-(Re, Ti) alloys
M. Hasiak
7.
Temperature dependence of the short-range order parameter for Fe0.90Cr0.10 and Fe0.88Cr0.12 alloys
R. Idczak, R. Konieczny
8.
Mean hyperfine fields at 57Fe in dilute iron-based alloys studied by Mössbauer spectroscopy
R. Idczak, R. Konieczny, J. Chojcan
9.
X-ray diffraction and Mössbauer spectroscopy studies of a mechanosynthesized Fe75B25 alloy
E. Jartych, L.M. Kubalova, V.I. Fadeeva
10. Crystal structure and Mössbauer study of FeAl2O4
I. Jastrzębska, J. Szczerba, P. Stoch, A. Błachowski, K. Ruebenbauer, R. Prorok, E. Śnieżek
11. Mössbauer spectroscopy of reduced forms of a Fe-tetraphenylporphyrine complex
T. Kaczmarzyk, I. Rutkowska, K. Dziliński
12. Mössbauer study of a tetrakis (pentafluorophenyl) porphyrin iron (III) chloride in comparison with the
fluorine unsubstituted analogue
T. Kaczmarzyk, K. Dziedzic-Kocurek, I. Rutkowska, K. Dziliński
13. Magnetic nanowires (Fe, Fe-Co, Fe-Ni) – magnetic moment reorientation in respect of wires composition
B. Kalska-Szostko, U. Wykowska, D. Satuła
14. Atomic short-range order in mechanically synthesized iron based Fe-Zn alloys studied by
bauer spectroscopy
R. Konieczny, R. Idczak
Fe Möss-
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133
15. Interactions between osmium atoms dissolved in iron observed by the 57Fe Mössbauer spectroscopy
R. Konieczny, R. Idczak, J. Chojcan
16. Structure and some magnetic properties of (BiFeO3)x-(BaTiO3)1−x solid solutions prepared by solid-state
sintering
K. Kowal, M. Kowalczyk, D. Czekaj, E. Jartych
17. The influence of thermal annealing on structure and oxidation of iron nanowires
M. Krajewski, K. Brzózka, B. Górka, W.-S. Lin, H.-M. Lin, T. Szumiata, M. Gawroński, D. Wasik
18. Search for canted spin arrangement in Er2−xTbxFe14B with Mössbauer spectroscopy
P.M. Kurzydło, B.F. Bogacz, A.T. Pędziwiatr, D. Oleszak, J. Przewoźnik
19. Analysis of heat capacity and Mössbauer data for LuZnSn2 compound
K. Łątka, J. Przewoźnik, J. Żukrowski, Yu. Verbovytskyy, A.P. Gonçalves
20. Effects of Co, Ni, and Cr addition on microstructure and magnetic properties of amorphous and nanocrystalline Fe86−xMxZr7Nb2Cu1B4 (M = Co, Ni, CoCr, and Cr, x = 0 or 6) alloys
A. Łukiewska, J. Świerczek, M. Hasiak, J. Olszewski, J. Zbroszczyk, P. Gębara, W. Ciurzyńska
21. Structure and Mössbauer spectroscopy studies of mechanically activated (BiFeO3)1–x-(BaTiO3)x solid
solutions
B. Malesa, A. Antolak-Dudka, D. Oleszak, T. Pikula
22. Subsurface structure and magnetic parameters of Fe-Mo-Cu-B metallic glass
M. Miglierini, M. Hasiak, M. Bujdoš
23. Hyperfine interaction and some thermomagnetic properties of amorphous and partially crystallized
Fe70−xMxMo5Cr4Nb6B15 (M = Co or Ni, x = 0 or 10) alloys
J. Rzącki, J. Świerczek, M. Hasiak, J. Olszewski, J. Zbroszczyk, W. Ciurzyńska
24. Determination of hyperfine fields and atomic ordering in NiMnFeGe exhibiting martensitic transformation
D. Satuła, K. Szymański, K. Rećko, W. Olszewski, B. Kalska-Szostko
25. Mössbauer spectroscopy study of 60P2O5-40Fe2O3 glass crystallization
P. Stoch, A. Stoch
26. Influence of annealing temperature on structural and magnetic properties of MnFe2O4 nanoparticles
Z. Surowiec, M. Wiertel, W. Gac, M. Budzyński
27. Position of Fe ions in MgO crystalline structure
J. Szczerba, R. Prorok, P. Stoch, E. Śnieżek, I. Jastrzębska
28. The role and position of iron in 0.8CaZrO3-0.2CaFe2O4
J. Szczerba, E. Śnieżek, P. Stoch, R. Prorok, I. Jastrzębska
29. Iron-containing phases in fly ashes from different combustion systems
T. Szumiata, M. Gzik-Szumiata, K. Brzózka, B. Górka, M. Gawroński, R. Świetlik, M. Trojanowska
30. Magnetic and structural properties of Sc(Fe1−xSix)2 Laves phases studied by Mössbauer spectroscopy and
neutron diffraction
M. Wiertel, Z. Surowiec, M. Budzyński, J. Sarzyński, A.I. Beskrovnyi
Regular papers
31. Modelling of a passive autocatalytic hydrogen recombiner – a parametric study
A. Rożeń
32. Minor actinides impact on basic safety parameters of medium-sized sodium-cooled fast reactor
P. Darnowski, N. Uzunow
33. Validation of the method for determination of plutonium isotopes in urine samples and its application
in a nuclear facility at Otwock
K. Rzemek, A. Czerwiński, M. Dymecka, J. Ośko, T. Pliszczyński, Z. Haratym
Proceedings of the 12th Kudowa Summer School “Towards Fusion Energy”, 9-13 June 2014, Kudowa
Zdrój, Poland
1.
Generation of shock waves in dense plasmas by high-intensity laser pulses
134
NUKLEONIKA
J. Pasley, I.A. Bush, A.P.L. Robinson, P.P. Rajeev, S. Mondal, A.D. Lad, S. Ahmed, V. Narayanan, G. Ravindra Kumar, R.J. Kingham
2.
Selected methods of electron- and ion-diagnostics in tokamak scrape-off-layer
M.J. Sadowski
3.
Ion acceleration from intense laser-generated plasma: methods, diagnostics and possible applications
L. Torrisi
4.
Shock dynamics induced by double-spot laser irradiation of layered targets
A.A. Aliverdiev, D. Batani, A.A. Amirova, R. Benocci, R. Dezulian, E. Krouský, M. Pfeifer, J. Skala,
R. Dudzak, K. Jakubowska
5.
The source of X-rays and high-charged ions based on moderate power vacuum discharge with laser
triggering
M.A. Alkhimova, E.D. Vovchenko, A.P. Melekhov, R.S. Ramakoti, A.S. Savelov, P.S. Krapiva, I.N. Moskalenko
6.
Numerical simulations of generation of high-energy ion beams driven by a petawatt femtosecond laser
J. Domański, J. Badziak, S. Jabłoński
7.
Hot electron refluxing in the short intense laser pulse interactions with solid targets and its influence
on K- radiation
V. Horný, O. Klimo
8.
Electromagnetic pulses produced by expanding laser-produced Au plasma
M. De Marco, J. Cikhardt, J. Krása, A. Velyhan, M. Pfeifer, E. Krouský, D. Klír, K. Řezáč, J. Limpouch,
D. Margarone, J. Ullschmied
9.
High Power Laser Laboratory at the Institute of Plasma Physics and Laser Microfusion: equipment and
preliminary research
A. Zaraś-Szydłowska, J. Badziak, M. Rosiński, J. Makowski, P. Parys, M. Piotrowski, L. Ryć, J. Wołowski
10. First dedicated observations of runaway electrons in the COMPASS tokamak
M. Vlainić, J. Mlynář, V. Weinzettl, R. Papřok, M. Imríšek, O. Ficker, P. Vondráček, J. Havlíček
11. Liquid micro pulsed plasma thruster
A. Szelecka, J. Kurzyna, D. Daniłko, S. Barral
12. Second order reflection from crystals used in soft X-ray spectroscopy
I. Książek
13. Overview of processing technologies for tungsten-steel composites and FGMs for fusion applications
J. Matějíček, B. Nevrlá, M. Vilémová, H. Boldyryeva
14. Heat load and deuterium plasma effects on SPS and WSP tungsten
M. Vilémová, J. Matějíček, B. Nevrlá, M. Chernyshova, P. Gasior, E. Kowalska-Strzeciwilk, A. Jäger
15. R&D on divertor plasma facing components at the Institute for Plasma Research
Y. Patil, S. Khirwadkar, S.M. Belsare, R. Swamy, M.S. Khan, S. Tripathi, K. Bhope
16. Change of silica luminescence due to fast hydrogen ion bombardment
V.P. Zhurenko, O.V. Kalantaryan, S.I. Kononenko
17. Study of tungsten surface interaction with plasma streams at DPF-1000U
M.S. Ladygina, E. Skladnik-Sadowska, D.R. Zaloga, K. Malinowski, M.J. Sadowski, M. Kubkowska,
E. Kowalska-Strzeciwilk, M. Paduch, E. Zielinska, R. Miklaszewski, I.E. Garkusha, V.A. Gribkov
18. Recent ion measurements within the modified DPF-1000U facility
R. Kwiatkowski, K. Czaus, E. Skladnik-Sadowska, M.J. Sadowski, D.R. Zaloga, M. Paduch, E. Zielinska
19. Recent measurements of soft X-ray emission from the DPF-1000U facility
W. Surała, M.J. Sadowski, M. Paduch, E. Zielinska, K. Tomaszewski
20. Comparison of optical spectra recorded during DPF-1000U plasma experiments with gas-puffing
D.R. Zaloga, E. Skladnik-Sadowska, M. Kubkowska, M.S. Ladygina, K. Malinowski, R. Kwiatkowski,
M.J. Sadowski, M. Paduch, E. Zielinska, V.A. Makhlaj
21. Temporal distribution of linear densities of the plasma column in a plasma focus discharge
B. Cikhardtova, P. Kubeš, J. Cikhardt, M. Paduch, E. Zielinska, J. Kravárik, K. Řezáč, J. Kortanek, O. Šíla
22. Determination of the emission rate for the 14 MeV neutron generator with the use of radio-yttrium
E. Laszynska, S. Jednorog, A. Ziolkowski, M. Gierlik, J. Rzadkiewicz
NUKLEONIKA
135
23. MCNP calculations of neutron emission anisotropy caused by the GIT-12 hardware
O. Šíla, D. Klír, K. Řezáč, B. Cikhardtova, J. Cikhardt
24. Operation modes of the FALCON ion source as a part of the AMS cluster tool
O. Girka, A. Bizyukov, I. Bizyukov, M. Gutkin, S. Mishin
Regular papers
25. Important problems of future thermonuclear reactors
M.J. Sadowski
26. Evaluation of passive autocatalytic recombiners operation efficiency by means of the lumped parameter
approach
T. Bury
27. CFD modeling of passive autocatalytic recombiners
M. Orszulik, A. Fic, T. Bury
28. Enhanced resonant second harmonic generation in plasma based on density transition
N. Kant, V. Thakur
29. Monte Carlo study of medium-energy electron penetration in aluminium and silver
A. Aydın, A. Peker
30. Neutronic analysis for core conversion (HEU–LEU) of the low power research reactor using the MCNP4C
code
S. Aldawahra, K. Khattab, G. Saba
31. Erratum to “Subsurface structure and magnetic parameters of Fe–Mo–Cu–B metallic glass” [Nukleonika
2015;60(1):115–119]
M. Miglierini, M. Hasiak, M. Bujdoš
CONTENTS OF NO. 3/2015 (PART I)
Proceedings of the III Electron Magnetic Resonance Forum EMR-PL, Kraków, Poland, 23–25 May
2014
1.
Editorial
C. Rudowicz, Z. Sojka, J. Jezierska, P. Pietrzyk
2.
EMR-related problems at the interface between the crystal field Hamiltonians and the zero-field splitting Hamiltonians
C. Rudowicz, M. Karbowiak
3.
Dyson line and modified Dyson line in the EPR measurements
V. Popovych, M. Bester, I. Stefaniuk, M. Kuzma
4.
Determination of the fraction of paramagnetic centers not-fulfilling the Curie law in coal macerals by
the two-temperature EPR measurement method
G.P. Słowik, A.B. Więckowski
5.
The dynamics of the surface layer of lipid membranes doped by vanadium complex: computer modeling
and EPR studies
R. Olchawa, D. Man, B. Pytel
6.
EMR study and superposition model analysis of Cr3+ and Fe3+ impurity ions in mullite powders used in
aerospace industry
I. Stefaniuk, I. Rogalska
7.
Growth and EPR properties of ErVO4 single crystals
G. Leniec, S.M. Kaczmarek, M. Berkowski, M. Głowacki, T. Skibiński, B. Bojanowski
8.
Magnetic resonance study of co-modified (Co,N)-TiO2 nanocomposites
N. Guskos, G. Zolnierkiewicz, A. Guskos, J. Typek, P. Berczynski, D. Dolat, S. Mozia, C. Aidinis, A.W.
Morawski
9.
The MAS NMR study of solid solutions based on the YAG crystal
B.V. Padlyak, N.A. Sergeev, M. Olszewski, P. Stępień
10. Copper-manganese-zinc spinels in zeolites: study of EMR spectra
P. Decyk, A.B. Więckowski, L. Najder-Kozdrowska, I. Bilkova
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NUKLEONIKA
11. Multifrequency EPR study on radiation induced centers in calcium carbonates labeled with 13C
J. Sadło, A. Bugaj, G. Strzelczak, M. Sterniczuk, Z. Jaegermann
12. Magnetic transformation in Ni-Mn-In Heusler alloy
M. Kuzma, W. Maziarz, I. Stefaniuk
13. Effect of microwave power on EPR spectra of thermally sterilized eucerinum anhydricum
P. Ramos, P. Pepliński, B. Pilawa
14. EPR examination of free radicals thermally formed in vaselinum flavum
P. Ramos, B. Pilawa
15. Effect of microwave power on EPR spectra of natural and synthetic dental biocompatible materials
J. Adamczyk, P. Ramos, B. Pilawa
16. Impact of humic acids on EYL liposome membranes: ESR method
B. Pytel, A. Filipiak, I. Pisarek, R. Olchawa, D. Man
17. Spin trapping studies of essential oils in lipid systems
K. Makarova, K. Drązikowska, B. Suska, K. Zawada, I. Wawer
18. Oxidative stability of the lipid fraction in cookies – the EPR study
K. Zawada, M. Kozłowska, A. Żbikowska
19. The acid-catalyzed interaction of melanin with nitrite ions. An EPR investigation
Z. Matuszak, C.F. Chignell, K.J. Reszka
20. Effect of UV irradiation on free radicals in synthetic melanin and melanin biopolymer from Sepia officinalis – EPR examination
M. Zdybel, B. Pilawa
Regular papers
21. A Monte Carlo study on dose enhancement and photon contamination production by various nanoparticles in electron mode of a medical linac
M.T. Bahreyni Toossi, M. Ghorbani, L. Sobhkhiz Sabet, F. Akbari, M. Mehrpouyan
22. Synthesis and evaluation of radiolabeled, folic acid-PEG conjugated, amino silane coated magnetic nanoparticles in tumor bearing Balb/C mice
J. Razjouyan, H. Zolata, O. Khayat, F. Nowshiravan, N. Shadanpour, M. Mohammadnia
23. Levels of natural radioactivity in mineral and thermal waters of Bosnia and Herzegovina
A. Kasić, F. Adrović, A. Kasumović, E. Hankić
CONTENTS OF NO. 3/2015 (PART II)
Proceedings of the International Conference on Development and Applications of Nuclear Technologies NUTECH 2014, Warsaw, Poland, 21-24 September 2014
1.
Dictyonema black shale and Triassic sandstones as potential sources of uranium
K. Kiegiel, G. Zakrzewska-Kołtuniewicz, D. Gajda, A. Miśkiewicz, A. Abramowska, P. Biełuszka, B. Danko, E. Chajduk, S. Wołkowicz
2.
Assesment of advanced step models for steady state Monte Carlo burnup calculations in application to
prismatic HTGR
G. Kępisty, J. Cetnar
3.
Neutronic and thermal-hydraulic coupling for 3D reactor core modeling combining MCB and fluent
I.P. Królikowski, J. Cetnar
4.
Thermal-hydraulic calculations for a fuel assembly in a European Pressurized Reactor using the RELAP5
code
M. Skrzypek, R. Laskowski
5.
Measurement of anthropogenic radionuclides in post-Fukushima Pacific seawater samples
G. Lutter, F. Tzika, M. Hult, M. Aoyama, Y. Hamajima, G. Marissens, H. Stroh
6.
On release of radionuclides from a near-surface radioactive waste repository to the environment
A. Gudelis, I. Gorina
7.
Multibarrier system preventing migration of radionuclides from radioactive waste repository
W. Olszewska, A. Miśkiewicz, G. Zakrzewska-Kołtuniewicz, L. Lankof, L. Pająk
NUKLEONIKA
137
8.
Fabrication and performance of fly ash granule filter for trapping gaseous cesium
J.J. Park, J.M. Shin, J.H. Yang, Y.H. Baek, G.I. Park
9.
Comparative analysis between measured and calculated concentrations of major actinides using destructive assay data from Ohi-2 PWR
M. Oettingen, J. Cetnar
10. Modeling minor actinide multiple recycling in a lead-cooled fast reactor to demonstrate a fuel cycle
without long-lived nuclear waste
P. Stanisz, J. Cetnar, G. Domańska
11. Charged projectile spectrometry using solid-state nuclear track detector of the PM-355 type
A. Malinowska, M. Jaskóła, A. Korman, A. Szydłowski, K. Malinowski, M. Kuk
12. Review of international normatives for natural radioactivity determination in building materials
E. Mossini, E. Macerata, M. Giola, M. Mariani
13. Effects of the pre-irradiation storage procedure on the dose response of a Fricke xylenol orange gel
dosimeter
G.M. Liosi, F. Giacobbo, E. Pignoli, M. Carrara, G. Gambarini, M. Mariani
14. Application of alanine dosimetry in dose assessment for ocular melanoma patients undergoing proton
radiotherapy – preliminary results
G. Mierzwińska, M. Kłodowska, B. Michalec, A. Pędracka, M. Rydygier, J. Swakoń, M.P.R. Waligórski
15.
U isotopic characterization of natural and enriched uranium materials by using multigroup analysis
(MGA) method at a defined geometry using different absorbers and collimators
H. Yücel, E. Yeltepe, A.Ö. Yüksel, H. Dikmen
235
16. Application of X-ray fluorescence method for elemental analysis of PM2.5 fraction
L. Samek, L. Furman, T. Kawik, K. Welnogorska
17. Identification of irradiated dried fruits using EPR spectroscopy
G.P. Guzik, W. Stachowicz, J. Michalik
18. Industrial diagnostics system using gamma radiation
A. Jakowiuk, Ł. Modzelewski, J. Pieńkos, E. Kowalska
19. An application of LSC method for the measurement of gross alpha and beta activities in spiked water
and drinking water samples
G.Ö. Çakal, R. Güven, H. Yücel
20. Application of the micronucleus assay performed by different scorers in case of large-scale radiation
accidents
K. Rawojć, D.M. Tarnawska, J.U. Miszczyk, J. Swakoń, L. Stolarczyk, M. Rydygier
21. Application of the new Monte Carlo code AlfaMC to the calibration of alpha-particle sources
M. Jurado Vargas, A. Fernández Timón, C. García Orellana
22. The origin and chronology of medieval silver coins based on the analysis of chemical composition
E. Pańczyk, B. Sartowska, L. Waliś, J. Dudek, W. Weker, M. Widawski
23. The use of DRS and GC to study the effects of ionizing radiation on paper artifacts
W. Głuszewski, B. Boruc, H. Kubera, D. Abbasowa
24. The influence of ionizing radiation on the properties of starch-PVA films
A. Abramowska, K.A. Cieśla, M.J. Buczkowski, A. Nowicki, W. Głuszewski
25. E-beam irradiation for the control of Phytophthora nicotianae var. nicotianae in stonewool cubes
M. Ptaszek, L.B. Orlikowski, W. Migdał, U. Gryczka
26. Studies of scintillator response to 60 MeV protons in a proton beam imaging system
M. Rydygier, G. Mierzwińska, A. Czaderna, J. Swakoń, M.P.R. Waligórski
27. Electron beam treatment of simulated marine diesel exhaust gases
J. Licki, A. Pawelec, Z. Zimek, S. Witman-Zając
CONTENTS OF NO. 4/2015 (PART I)
Proceedings of the 42nd Polish Seminar on Positron Annihilation, Lublin, Poland, 29 June-1 July
2015
138
NUKLEONIKA
1.
Preface
B. Zgardzińska
2.
Positron annihilation in liquid crystals
E. Dryzek, E. Juszyńska-Gałązka
3.
Positron annihilation studies of high-manganese steel deformed by rolling
E. Dryzek, M. Sarnek, M. Wróbel
4.
The detection of reverse accumulation effect in the positron annihilation profile of stack of aluminum
and silver foils
J. Dryzek, K. Siemek
5.
PALS investigations of matrix Vycor glass doped with molecules of luminescent dye and silver nanoparticles. Discrepancies from the ETE model
M. Gorgol, B. Jasińska, R. Reisfeld
6.
Studies of stainless steel exposed to sandblasting
P. Horodek, M.K. Eseev, A.G. Kobets
7.
Slow positron beam at the JINR, Dubna
P. Horodek, A.G. Kobets, I.N. Meshkov, A.A. Sidorin, O.S. Orlov
8.
Searches for discrete symmetries violation in ortho-positronium decay using the J-PET detector
D. Kamińska, A. Gajos, E. Czerwiński, T. Bednarski, P. Białas, M. Gorgol, B. Jasińska, Ł. Kapłon, G. Korcyl, P. Kowalski, T. Kozik, W. Krzemień, E. Kubicz, Sz. Niedźwiecki, M. Pałka, L. Raczyński, Z. Rudy,
O. Rundel, N.G. Sharma, M. Silarski, A. Słomski, A. Strzelecki, A. Wieczorek, W. Wiślicki, M. Zieliński,
B. Zgardzińska, P. Moskal
9.
Toward a European Network of Positron Laboratories
G.P. Karwasz, R.S. Brusa, W. Egger, O.V. Ogorodnikova
10. Isotropic distributions in hcp crystals
G. Kontrym-Sznajd
11. Processing optimization with parallel computing for the J-PET scanner
W. Krzemień, M. Bała, T. Bednarski, P. Białas, E. Czerwiński, A. Gajos, M. Gorgol, B. Jasińska, D. Kamińska, Ł. Kapłon, G. Korcyl, P. Kowalski, T. Kozik, E. Kubicz, Sz. Niedźwiecki, M. Pałka, L. Raczyński,
Z. Rudy, O. Rundel, N.G. Sharma, M. Silarski, A. Słomski, K. Stola, A. Strzelecki, D. Trybek, A. Wieczorek, W. Wiślicki, M. Zieliński, B. Zgardzińska, P. Moskal
12. Studies of unicellular microorganisms Saccharomyces cerevisiae by means of positron annihilation lifetime spectroscopy
E. Kubicz, B. Jasińska, B. Zgardzińska, T. Bednarski, P. Białas, E. Czerwiński, A. Gajos, M. Gorgol,
D. Kamińska, Ł. Kapłon, A. Kochanowski, G. Korcyl, P. Kowalski, T. Kozik, W. Krzemień, Sz. Niedźwiecki, M. Pałka, L. Raczyński, Z. Rajfur, Z. Rudy, O. Rundel, N.G. Sharma, M. Silarski, A. Słomski,
A. Strzelecki, A. Wieczorek, W. Wiślicki, M. Zieliński, P. Moskal
13. Investigation of corrosion defects in titanium by positron annihilation
R. Pietrzak, R. Szatanik
14. Understanding electron-positron momentum densities in solids: effect of the positron distribution
A. Rubaszek
15. Reconstruction of hit time and hit position of annihilation quanta in the J-PET detector using the Mahalanobis distance
N.G. Sharma, M. Silarski, T. Bednarski, P. Białas, E. Czerwiński, A. Gajos, M. Gorgol, B. Jasińska, D. Kamińska, Ł. Kapłon, G. Korcyl, P. Kowalski, T. Kozik, W. Krzemień, E. Kubicz, Sz. Niedźwiecki, M. Pałka,
L. Raczyński, Z. Rudy, O. Rundel, A. Słomski, A. Strzelecki, A. Wieczorek, W. Wiślicki, M. Zieliński,
B. Zgardzińska, P. Moskal
16. Comparison of the free volume sizes and shapes determined from crystallographic and PALS data
M. Tydda, B. Jasińska
17. PALS investigations of free volumes thermal expansion of J-PET plastic scintillator synthesized in polystyrene matrix
A. Wieczorek, B. Zgardzińska, B. Jasińska, M. Gorgol, T. Bednarski, P. Białas, E. Czerwiński, A. Gajos,
D. Kamińska, Ł. Kapłon, A. Kochanowski, G. Korcyl, P. Kowalski, T. Kozik, W. Krzemień, E. Kubicz,
Sz. Niedźwiecki, M. Pałka, L. Raczyński, Z. Rudy, O. Rundel, N.G. Sharma, M. Silarski, A. Słomski,
A. Strzelecki, W. Wiślicki, M. Zieliński, P. Moskal
NUKLEONIKA
139
18. Study on the effect of atmospheric gases adsorbed in MnFe2O4/MCM-41 nanocomposite on ortho-positronium annihilation
M. Wiertel, Z. Surowiec, M. Budzyński, W. Gac
19. Positron annihilation lifetime spectroscopy study of roller burnished magnesium alloy
R. Zaleski, K. Zaleski, M. Gorgol
20. Principles of positron porosimetry
R. Zaleski
21. Ortho-para spin conversion of Ps by paramagnetic O2 dissolved in organic compounds
B. Zgardzińska, W. Białko, B. Jasińska
CONTENTS OF NO. 4/2015 (PART II)
Proceedings of the International Workshop “Towards safe and optimized separation processes, a challenge for nuclear scientists” (FP7 European Collaborative Project SACSESS), Warsaw, Poland, 22-24
April 2015
1.
Towards safe and optimized separation processes, a challenge for nuclear scientists
S. Bourg, J. Narbutt
2.
SACSESS – the EURATOM FP7 project on actinide separation from spent nuclear fuels
S. Bourg, A. Geist, J. Narbutt
3.
TS-BTPhen as a promising hydrophilic complexing agent for selective Am(III) separation by solvent
extraction
P. Kaufholz, F. Sadowski, A. Wilden, G. Modolo, F.W. Lewis, A.W. Smith, L.M. Harwood
4.
Determination of formation constants of uranyl(VI) complexes with a hydrophilic SO3-Ph-BTP ligand,
using liquid-liquid extraction
L. Steczek, J. Narbutt, M.-Ch. Charbonnel, Ph. Moisy
5.
Development of the Chalmers Grouped Actinide Extraction Process
J. Halleröd, C. Ekberg, E. Löfström-Engdahl, E. Aneheim
6.
A calculation model for liquid-liquid extraction of protactinium by 2,6-dimethyl-4-heptanol
A.W. Knight, E.S. Eitrheim, A.W. Nelson, M.K. Schultz
7.
Structure and separation quality of various N- and O-donor ligands from quantum-chemical calculations
M. Trumm, B. Schimmelpfennig, A. Geist
8.
Crystal structures and conformers of CyMe4-BTBP
K. Lyczko, S. Ostrowski
9.
A study of cerium extraction by TBP and TODGA using a rotating diffusion cell
M.A. Bromley, C. Boxall
10. The effect of SO3-Ph-BTBP on stainless steel corrosion in nitric acid
R.J. Wilbraham, C. Boxall
11. Reprocessability of molybdenum and magnesia based inert matrix fuels
E.L. Ebert, A. Bukaemskiy, F. Sadowski, S. Lange, A. Wilden, G. Modolo
12. Gamma radiolytic stability of CyMe4BTBP and the effect of nitric acid
H. Schmidt, A. Wilden, G. Modolo, J. Švehla, B. Grüner, C. Ekberg
13. Characterization of solvents containing CyMe4-BTPhen in selected cyclohexanone-based diluents after
irradiation by accelerated electrons
P. Distler, J. Kondé, J. John, Z. Hájková, J. Švehla, B. Grüner
14. Physico chemical properties of irradiated i-SANEX diluents
E. Mossini, E. Macerata, M. Giola, L. Brambilla, C. Castiglioni, M. Mariani
15. Electron beam irradiation of r-SANEX and i-SANEX solvent extraction systems: analysis of gaseous
products
T. Szreder, R. Kocia
16. Pyrochemical reprocessing of molten salt fast reactor fuel: focus on the reductive extraction step
D. Rodrigues, G. Durán-Klie, S. Delpech
140
NUKLEONIKA
17. Uranium and neodymium partitioning in alkali chloride melts using low-melting gallium based alloys
S.Yu. Melchakov, D.S. Maltsev, V.A. Volkovich, L.F. Yamshchikov, D.G. Lisienko, A.G. Osipenko, M.A.
Rusakov
18. Carbonization of solid uranyl-ascorbate gel as an indirect step of uranium carbide synthesis
M. Brykala, M. Rogowski, T. Olczak
19. Sorption of Sr-85 and Am-241 from liquid radioactive wastes by alginate beads
A. Oszczak, L. Fuks
Regular papers
20. The rapid interphase chromosome assay (RICA) implementation: comparison with other PCC methods
S. Sommer, I. Buraczewska, K. Sikorska, T. Bartłomiejczyk, I. Szumiel, M. Kruszewski
21. Estimation of radiation doses for transition from emergency to existing exposure situation
A.A. Hamed, E.F. Salem, A.K. Abdien
22. The dose of gamma radiation from building materials and soil
G. Manić, V. Manić, D. Nikezić, D. Krstić
23. In memoriam – Dr. Sueo Machi (1934-2015)
Information
NUKLEONIKA
Dorodna 16, 03-195 Warszawa, Poland
phone: +48 22 504 11 32, fax: +48 22 811 15 32, e-mail: [email protected]
Full texts are available on-line at http://www.nukleonika.pl
141
EDITORIAL BOARD
Stanisław Latek (Editor-in-Chief), Wojciech Głuszewski, Maria Kowalska, Łukasz Kuźniarski, Andrzej
Mikulski, Marek Rabiński, Edward Rurarz, Elżbieta Zalewska
1.
Energetyka jądrowa w 2014 roku (Nuclear power in the world in 2014)
A. Mikulski
2.
Reaktor EWA po wielu latach (EWA research reactor after many years)
A. Mikulski
3.
Historia pracy reaktora EWA (History of the research reactor EWA operation)
T. Matysiak
4.
Nie zapominajmy o personelu reaktora EWA (Do not forget about reactor EWA operators)
J. Kozieł
5.
Raport z eksploatacji reaktora badawczego MARIA w 2014 roku (Report on the MARIA research reactor operation in 2014)
J. Idzikowski
6.
Nowe cząsteczki w postaci mikrosfer 89Y2O3 otrzymywanych w IChTJ zmodyfikowaną metodą zol-żel
do zwalczania nowotworów wątroby (The new molecules in the form of microspheres 89Y2O3 obtained
by the modified INCT sol-gel method for liver cancer treatment)
W. Łada, D. Wawszczak
7.
features of radiation conservation of large object collections of historical importance)
W. Głuszewski
8.
Maria Skłodowska-Curie – znane i mało znane fakrty z życia Uczonej, ciąg dalszy (Maria Skłodowska-Curie – known and undiscovered facts of Scientist’s life, continued)
B. Gwiazdowska, W. Bulski, M. Sobieszczak-Marciniak
9.
Problemy oczyszczania wody jako element usuwania skutków awarii w elektrowni jądrowej Fukushima
(Water purification as part of Fukushima power plant breakdown associated nuclear waste removal process)
K. Rzymkowski
10. Reaktory jądrowe: przegląd procesu licencjonowania we Francji (Nuclear reactors: overview of the licensing process in France)
M. Varescon
1. Reaktor MARIA dziś – 2015 (The MARIA reactor today – 2015)
A. Mikulski
2. Reaktor MARIA widziany w 2004 roku z perspektywy trzydziestolecia jego eksploatacji (Reactor MARIA
as seen in 2004 after thirty years of operation)
W. Dąbek
3. Bitwa o reaktor MARIA po modernizacji (The fight for the research reactor MARIA after its refurbishment)
S. Chwaszczewski
4. Chemiczne aspekty energetyki jądrowej w projekcie Narodowego Centrum Badań i Rozwoju „Technologie
wspomagające rozwój bezpiecznej energetyki jądrowej” (Chemical aspects of nuclear power in the National Centre for Research and Development project “Technologies supporting development of safe nuclear power engineering”)
J. Michalik
142
5. Strategiczny projekt badawczy Narodowego Centrum Badań i Rozwoju pt. „Technologie wspomagające
rozwój bezpiecznej energetyki jądrowej”. Zadanie nr 4 „Rozwój technik i technologii wspomagających
gospodarkę wypalonym paliwem i odpadami promieniotwórczymi” (The National Centre for Research
and Development strategic research project “Technologies supporting development of safe nuclear power
engineering”. Task no. 4 “Development of spent nuclear fuel and radioactive waste management techniques and technologies”)
L. Fuks, A. Oszczak
jądrowego i ochrony radiologicznej dla bieżących i przyszłych potrzeb energetyki jądrowej” (The National Centre for Research and Development strategic research project “Technologies supporting development of safe nuclear power engineering”. Task no. 6 “Development of nuclear safety and radiological
protection methods for the nuclear power engineering’s current and future needs”)
P. Krajewski, G. Krajewska
rozwój bezpiecznej energetyki jądrowej”. Zadanie nr 6 „Rozwój metod zapewnienia bezpieczeństwa jądrowego i ochrony radiologicznej dla bieżących i przyszłych potrzeb energetyki jądrowej”. Cel 1: Opracowanie ogólnej koncepcji i metod badań środowiskowych (w tym zdrowotności) dla przewidywanej lokalizacji EJ (The National Centre for Research and Development strategic research project ‘Technologies
supporting development of safe nuclear power engineering”. Task no. 6 “Development of nuclear safety and
radiological protection methods for the nuclear power engineering’s current and future needs”. Objective 1: General concept and methodology for baseline environmental research and public health investigation in the foreseen location of NPP)
K. Ciupek, P. Krajewski, K. Kozak, I. Śliwka, T. Pliszczyński, H. Polkowska-Motrenko
rozwój bezpiecznej energetyki jądrowej”. Zadanie nr 6 „Rozwój metod zapewnienia bezpieczeństwa jądrowego i ochrony radiologicznej dla bieżących i przyszłych potrzeb energetyki jądrowej. Cel 2: Rozwój metod
dozymetrii biologicznej oraz biofizycznych markerów i indykatorów wpływu promieniowania na organizmy żywe (The National Centre for Research and Development strategic research project “Technologies
supporting development of safe nuclear power engineering”. Task no. 6 “Development of nuclear safety and
radiological protection methods for the nuclear power engineering’s current and future needs”. Objective 2. Development of the biodosimetry and biophysics markers of ionizing radiation in living beings)
K. Brzóska, M. Kowalska, M. Kruszewski, A. Lankoff, S. Sommer
1. Ponad 50 lat pracy akceleratora typu Van de Graaffa „Lech” w Instytucie Badań Jądrowych (Over 50 years
of operation of the “Lech” accelerator at the Institute of Nuclear Research)
M. Jaskóła, A. Korman
rozwój bezpiecznej energetyki jądrowej”. Zadanie nr 7 „Analiza procesów generacji wodoru w reaktorze
jądrowym w trakcie normalnej eksploatacji i w sytuacjach awaryjnych z propozycjami działań na rzecz
podniesienia poziomu bezpieczeństwa jądrowego” (The National Centre for Research and Development
strategic research project “Technologies supporting development of safe nuclear power engineering”. Task
no. 7 “Study of hydrogen generation processes in nuclear reactors under regular operation conditions
and in emergency cases, with suggested actions aimed at upgrade of nuclear safety”
J. Michalik, R. Kocia
3. Międzynarodowe podstawowe normy ochrony przed promieniowaniem i bezpieczeństwa źródeł promieniowania (Radiation protection and safety of radiation sources: international basic safety standards)
T. Musiałowicz
4. Probabilistyczna analiza bezpieczeństwa na poziomie 3 (Probabilistic safety assessment level 3)
E. Staroń
5. Początki i rozwój badań radiacyjnych w IBJ na Żeraniu (Beginnings and the development of radiation
research at the Institute of Nuclear Research, Żerań)
W. Stachowicz
6. Innowacje w przemyśle tworzyw polimerowych (Innovation in the plastics industry)
W. Głuszewski
7. 90. rocznica rozpoczęcia budowy Instytutu Radowego w Warszawie (Ninety anniversary of the commencement of Radium Institute in Warsaw construction)
M. Sobieszczak-Marciniak, W. Bulski
143
1. Zestawy krytyczne (reaktory mocy zerowej) w Instytucie Badań Jądrowych (Critical assemblies (zero
power reactors) at the Institute of Nuclear Research)
A. Mikulski
2. Program Erasmus+ szansą dla młodych naukowców (The Erasmus+ programme the chance for the
young scientists)
J. Boguski, E. Zwolińska
3. Oszacowanie metodami EPR, TL i PPSL odpowiedzi próbek przy wykrywaniu potencjalnego napromieniowania żywności (Evaluation of detection of potential radiation treatment of foodstuff samples using
EPR, TL and PPSL methods)
G.P. Guzik
4. Budujemy dom… – ocena promieniotwórczości naturalnej wybranych surowców i materiałów budowlanych (We are building a house... – evaluation of natural radioactivity of the selected raw and building
materials)
B. Piotrowska, K. Isajenko, M. Fujak, J. Szymczyk, M. Krajewska
5. Byłem w Czarnobylu, byłem w Fukuszimie, byłem w Hiroszimie… (I have visited Chernobyl, Fukushima
and Hiroshima…)
K.W. Fornalski
6. Wkład energetyki jądrowej w przeciwdziałanie zmianom klimatu (Nuclear power is part of the solution
for fighting climate change)
7. Remonty kapitalne w kanadyjskich elektrowniach jądrowych (Refurbishment of Canadian nuclear power
plants)
D.W. Kulczyński
8. Polimerowe kompozyty: Czy można zastąpić ołów w ochronie radiologicznej? (Polymer composites: Is
it possible to replace lead in radiological protection?)
M. Rajkiewicz, W. Głuszewski
Information
phone: +48 22 504 12 48, fax: +48 22 811 15 32, e-mail: [email protected]
www.ptj.waw.pl
144
INTERVIEWS IN 2015
INTERVIEWS IN 2015
1. Chmielewski A.G.
Truszczak D.: 60-lecie IBJ i działalność jego sukcesorów – Narodowego Centrum Badań Jądrowych (NCBJ)
oraz Instytutu Chemii i Techniki Jądrowej (IChTJ) (On 60th anniversary of the Institute of Nuclear Research – the research activity of its successors: National Centre for Nuclear Research (NCBJ) and Institute
of Nuclear Chemistry and Technology (INCT)). Program I Polskiego Radia, 28.07.2015.
2. Chmielewski A.G.
Haber M.: One gram of uranium is equivalent to 1.5-2 tonnes of coal. Polish Market, 9 (229), 32-33
(2015).
3. Chmielewski A.G., Sobolewski L.
Jawerth N.: Electron beams help Poland’s coal-driven power industry clean up its air. IAEA Bulletin,
September, 12-13 (2015), www.iaea.org/bulletin.
4. Łada W.
Polski patent na hydroksyapatyt (Polish patent on hydroxyapatite). Rynek Estetyczny, 4/X-XII, 38-40
(2015).
5. Łada W.
Telewizyjny Kurier Warszawski. TVP Warszawa, 12.10.2015.
145
PATENTS
1. Prekursor radiofarmaceutyku, sposób jego wytwarzania, radiofarmaceutyk oraz jego zastosowanie (Precursor of the radiopharmaceutical, the method for its production, radiopharmaceutical and its application)
G. Wójciuk, M. Kruszewski
Polish Patent
2. Sposób dezynfekcji podłoży ogrodniczych z wykorzystaniem wiązki wysokoenergetycznych elektronów
(Method for horticultural substrates disinfection with a high-energy electron beam)
W. Migdał, U. Gryczka, D. Chmielewska-Śmietanko
Polish Patent
3. Sposób i sorbent do otrzymywania radionuklidu arsenu-72 oraz sposób wytwarzania tego sorbentu
(Sorbent for receiving radionuclide arsenic-72, production of this sorbent)
E. Chajduk, H. Polkowska-Motrenko, A. Bilewicz, K. Doner
Polish Patent
4. Sposób jednorodnego sieciowania wykonanych z poliolefin izolacji i osłon przewodów i kabli elektrycznych przy wykorzystaniu wiązki elektronów (Application of electron beam for uniform cross-linking of
electrical cable insulations and jackets made of polyolefins)
Z. Zimek, G. Przybytniak, A. Nowicki, K. Roman
Polish Patent
5. Method of dissolution of thorium oxide
K. Łyczko, M. Łyczko, I. Herdzik, B. Zielińska
European Patent 11460009.1
6. Method of obtaining and separating valuable metallic elements, specifically from low-grade uranium ores
and radioactive liquid wastes
G. Zakrzewska-Trznadel, W. Łada
European Patent 12196071.0
7. Process for the preparation of uranium dioxide with spherical and irregular grains
A. Deptuła, M. Brykała, W. Łada, D. Wawszczak, T. Olczak, A.G. Chmielewski
Russian Patent 2538255
8. Method for the disposal of radioactive wastes in structures of silica glasses
A.G. Chmielewski, A. Deptuła, M. Miłkowska, W. Łada, T. Olczak
9. A selective extraction of uranium and protactinium from material containing thorium
P. Kalbarczyk, H. Polkowska-Motrenko, E. Chajduk
PATENT APPLICATIONS
1.
Sposób wytwarzania diuranianu amonu z roztworów o niskiej zawartości uranu (Method for preparing
ammonium diuranate from solutions with low uranium concentration)
G. Zakrzewska-Kołtuniewicz, K. Kiegiel, A. Abramowska, D.K. Gajda, W. Łada
Polish Patent Application P-410956
2.
Kompozytowy wymieniacz jonowy, zwłaszcza do sorbcji radioizotopów Sr-85, Co-60, Zn-65 i sposób
jego wytwarzania (Composite ion exchanger for adsorption of Sr-85, Co-60, Zn-65 and method for its
preparation)
B. Filipowicz, B. Bartoś, M. Łyczko, K. Łyczko, A. Bilewicz
146
3.
Sposób unieruchamiania radionuklidów metali z odpadowych roztworów wodnych z zastosowaniem
biosorbentu pochodzenia roślinnego (Immobilization of the metallic radionuclides present in aqueous
radioactive wastes using natural sorbent of the plant origin)
L. Fuks, A. Oszczak, W. Dalecka, W. Łada,
4.
Radiofarmaceutyk terapeutyczny oparty na znakowanych astatem-211 nanocząstkach złota oraz sposób
jego wytwarzania (Therapeutic radiopharmaceutical based on gold nanoparticles labelled with astatine-211 and a method for its preparation)
Ł. Janiszewska, P. Koźmiński, M. Pruszyński, A. Majkowska, A. Bilewicz
5.
Selektywny, nanokompozytowy wymieniacz jonowy na bazie krzemionki modyfikowanej oraz sposób
otrzymywania wymieniacza jonowego (Selective nanocomposite modified silica-based ion exchanger
and method for the ion exchanger obtaining)
D. Chmielewska-Śmietanko
6.
Nieorganiczny wymieniacz jonowy typu “core/shell” o właściwościach magnetycznych, metoda jednoetapowej syntezy nieorganicznego wymieniacza jonowego typu “core/shell” (Inorganic “core/shell” ion
exchanger with magnetic properties, method for the one-step synthesis of the inorganic “core/shell” ion
exchanger)
Liang Zhao, D. Chmielewska-Śmietanko
7.
Diagnostyczny lub terapeutyczny radiofarmaceutyk receptorowy posiadający powinowactwo do receptora Her-2, sposób jego wytwarzania oraz jego zastosowanie (Diagnostic or therapeutic receptor radiopharmaceutical having affinity for HER-2 receptor, method for its preparation and application)
E. Gniazdowska, P. Koźmiński
8.
Radiofarmaceutyk diagnostyczny do obrazowania infekcji, sposób jego wytwarzania oraz jego zastosowanie (Diagnostic radiopharmaceutical for infection imaging, method for its preparation and application)
P. Koźmiński, E. Gniazdowska, M. Chojnowski, A. Kopatys, L. Królicki
9.
Radiofarmaceutyk diagnostyczny do obrazowania infekcji bakteryjnych oraz sposób jego wytwarzania
(Diagnostic radiopharmaceutical for bacterial infection imaging and method for its preparation)
P. Koźmiński, E. Gniazdowska
10. Diagnostyczny i/lub terapeutyczny radiofarmaceutyk receptorowy posiadający powinowactwo do receptora NK-1, sposób jego wytwarzania oraz zastosowanie (Diagnostic and/or therapeutic receptor
radiopharmaceutical having affinity for NK-1 receptor, method for its preparation and application)
E. Gniazdowska, P. Koźmiński
11. Sposób wytwarzania węglika uranu o ziarnach sferycznych i nieregularnych jako prekursora paliwa do
reaktorów nowej, IV generacji (Method for producing of spherically- and irregularly-grained uranium
carbide as fuel precursor for novel 4th generation reactors)
M. Brykała, M. Rogowski
147
CONFERENCES ORGANIZED AND CO-ORGANIZED
BY THE INCT IN 2015
1.
2ND ANNUAL SACSESS (SAFETY OF ACTINIDE SEPARATION PROCESSES) MEETING,
19-21 APRIL 2015, WARSZAWA, POLAND
Organized by the Institute of Nuclear Chemistry and Technology, SACSESS Coordination Committee
Organizing Committee: Stéphane Bourg, Ph.D., Bastien Duplantier, M.Sc., Prof. Jerzy Narbutt, Ph.D., D.Sc.,
Tomasz Szreder, Ph.D., Dorota Gajda, M.Sc., Magdalena Rejnis, M.Sc.
2.
FIRST INTERNATIONAL WORKSHOP OF THE FP7 EUROPEAN COLLABORATIVE PROJECT SACSESS (SAFETY OF ACTINIDE SEPARATION PROCESSES) “TOWARDS SAFE
AND OPTIMIZED SEPARATION PROCESSES, A CHALLENGE FOR NUCLEAR SCIENTISTS”, 22-24 APRIL 2015, WARSZAWA, POLAND
Organized by the Institute of Nuclear Chemistry and Technology, SACSESS Coordination Committee
Organizing Committee: Prof. Jerzy Narbutt, Ph.D., D.Sc., Stéphane Bourg, Ph.D., Tomasz Szreder, Ph.D.,
Dorota Gajda, M.Sc., Magdalena Rejnis, M.Sc., Anna Abramowska, M.Sc.
3.
REGIONAL TRAINING COURSE “DOSIMETRY AT ELECTRON BEAM FACILITIES” IN
THE FRAME OF THE IAEA TECHNICAL COOPERATION REGIONAL PROJECT RER/1/014
“INTRODUCING AND HARMONIZING STANDARDIZED QUALITY CONTROL PROCEDURES FOR RADIATION TECHNOLOGIES”, 11-15 MAY 2015, WARSZAWA, POLAND
Organized by the Institute of Nuclear Chemistry and Technology, International Atomic Energy Agency
Organizing Committee: Zbigniew Zimek, Ph.D., Andrzej Rafalski, Ph.D., Magdalena Rzepna, M.Sc.
4.
WARSZTATY „PERSPEKTYWY ROZWOJU DIALOGU I REKOMENDACJE DLA INTERESARIUSZY INWESTYCJI” W RAMACH PROJEKTU PLATENSO (BUILDING A PLATFORM
FOR ENHANCED SOCIETAL RESEARCH RELATED TO NUCLEAR ENERGY IN CENTRAL
AND EASTERN EUROPE) (WORKSHOP “PROSPECTS FOR THE DEVELOPMENT OF
DIALOGUE AND RECOMMENDATIONS FOR STAKEHOLDERS OF INVESTMENT ” IN
THE FRAME OF THE PROJECT PLATENSO (BUILDING A PLATFORM FOR ENHANCED
SOCIETAL RESEARCH RELATED TO NUCLEAR ENERGY IN CENTRAL AND EASTERN
EUROPE), 20 MAY 2015, WARSZAWA, POLAND
Organized by the Collegium Civitas, Nicolaus Copernicus University in Toruń, Institute of Nuclear Chemistry and Technology
Organizing Committee: Katarzyna Iwińska, Ph.D., Piotr Stankiewicz, Ph.D., Agnieszka Miśkiewicz, Ph.D.
5.
SYMPOZJUM „CHEMIA I TECHNIKA RADIACYJNA WCZORAJ, DZIŚ I JUTRO” – WSPOMNIENIE O PROFESORZE ZBIGNIEWIE ZAGÓRSKIM I PROFESORZE JANIE GRODKOWSKIM (SYMPOSIUM “RADIATION CHEMISTRY AND RADIATION PROCESSING
YESTERDAY, TODAY AND TOMORROW – IN MEMORY OF PROFESSOR ZBIGNIEW ZAGÓRSKI AND PROFESSOR JAN GRODKOWSKI”), 28 MAY 2015, WARSZAWA, POLAND
Organized by the Institute of Nuclear Chemistry and Technology
Organizing Committee: Zbigniew Zimek, Ph.D., Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT,
Prof. Krzysztof Bobrowski, Ph.D., D.Sc., Wojciech Głuszewski, Ph.D.
6.
„MASS MEDIA A INFORMACJA W ASPEKCIE WDRAŻANIA POLSKIEGO PROGRAMU
ENERGETYKI JĄDROWEJ” SPOTKANIE W RAMACH PROJEKTU EAGLE (ENHANCING
148
EDUCATION, TRAINING AND COMMUNICATION PROCESSES FOR INFORMED BEHAVIORS AND DECISION-MAKING RELATED TO IONIZING RADIATION RISKS) (MEETING “MASS MEDIA AND THE INFORMATION REGARDING THE IMPLEMENTATION
OF THE POLISH NUCLEAR POWER PROGRAMME” IN THE FRAME OF THE PROJECT
EAGLE (ENHANCING EDUCATION, TRAINING AND COMMUNICATION PROCESSES
FOR INFORMED BEHAVIORS AND DECISION-MAKING RELATED TO IONIZING RADIATION RISKS), 2 JUNE 2015, WARSZAWA, POLAND
Organizing Committee: Prof. Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., Agnieszka Miśkiewicz,
Ph.D., Paulina Nieścior-Browińska, M.Sc., Wioleta Olszewska, M.Sc., Dorota Gajda, M.Sc., Katarzyna
Kiegiel, Ph.D., Anna Abramowska, M.Sc., Sylwester Sommer, Ph.D., Stanisław Latek, Ph.D.
7.
SYMPOZJUM „60-LECIE IBJ: FIZYKA I CHEMIA JĄDROWA W SŁUŻBIE MEDYCYNY”
(SYMPOSIUM “60th ANNIVERSARY OF IBJ: NUCLEAR PHYSICS AND CHEMISTRY FOR
MEDICINE), 10 JUNE 2015, ŚWIERK, POLAND
Organized by the National Centre for Nuclear Research, Institute of Nuclear Chemistry and Technology
8.
SEMINARIUM „ZASTOSOWANIE MODELI MATEMATYCZNYCH DO BADANIA SPOŁECZNO-EKONOMICZNYCH EFEKTÓW WDRAŻANIA POLSKIEGO PROGRAMU ENERGETYKI JĄDROWEJ” W RAMACH PROJEKTU “STUDYING THE SOCIAL AND SOCIO-ECONOMIC EFFECTS OF THE IMPLEMENTATION OF THE POLISH NUCLEAR POWER
PROGRAMME USING NEW METHODOLOGY” IAEA CRP 18541/RO (SEMINAR “THE
USE OF MATHEMATICAL MODELS TO STUDY THE SOCIO-ECONOMIC EFFECTS OF
THE IMPLEMENTATION OF THE POLISH NUCLEAR POWER PROGRAMME” IN THE
FRAME OF THE PROJECT “STUDYING THE SOCIAL AND SOCIO-ECONOMIC EFFECTS
OF THE IMPLEMENTATION OF THE POLISH NUCLEAR POWER PROGRAMME USING
NEW METHODOLOGY” IAEA CRP 18541/RO), 31 JULY 2015, WARSZAWA, POLAND
Organized by the Institute of Nuclear Chemistry and Technology, International Atomic Energy Agency
Organizing Committee: Prof. Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., Agnieszka Miśkiewicz,
Ph.D., Katarzyna Kiegiel, Ph.D., Dorota Gajda, M.Sc.
9.
2ND INTERNATIONAL CONFERENCE ON SCIENCE DIPLOMACY & DEVELOPMENTS
IN CHEMISTRY, 13-16 AUGUST 2015, WARSZAWA, POLAND
Organized by the Faculty of Mathematics and Natural Sciences, Cardinal Stefan Wyszyński University in
Warsaw; Institute of Nuclear Chemistry and Technology; Societas Scientiarum Varsaviensis
Organizing Committee: Prof. Stanisław Dziekoński, Ph.D., D.Sc., Prof. Janusz Lipkowski, Ph.D., D.Sc.,
Marian Turzański, Ph.D., D.Sc., professor UKSW, Prof. Stanisław Filipek, Ph.D., D.Sc., Prof. Kinga
Suwińska, Ph.D., D.Sc., Prof. Jerzy Pielaszek, Ph.D., D.Sc., Prof. Aleksander Bilewicz, Ph.D., D.Sc.,
Prof. Janusz Rachoń, Ph.D., D.Sc.
10. THE FIRST CYCLE OF THE INTENSIVE PROGRAMMES WITHIN THE FRAMEWORK OF
ERASMUS+ KA2 PROJECT ENTITLED “JOINT INNOVATIVE TRAINING AND TEACHING/
LEARNING PROGRAM IN ENHANCING DEVELOPMENT AND TRANSFER KNOWLEDGE
OF APPLICATION OF IONIZING RADIATION IN MATERIALS PROCESSING”, 7-17 SEPTEMBER 2015, WARSZAWA, POLAND
Organizing Committee: Yongxia Sun, Ph.D., D.Sc., professor in INCT, Grażyna Przybytniak, Ph.D., D.Sc.,
professor in INCT, Marta Walo, Ph.D., Urszula Gryczka, M.Sc.
11. 2nd ANNUAL ARCADIA MEETING, 29-30 SEPTEMBER 2015, WARSZAWA, POLAND
Organized by the Institute of Nuclear Chemistry and Technology, Central Laboratory for Radiological
Protection, National Centre for Nuclear Research
Organizing Committee: Katarzyna Kiegiel, Ph.D., Prof. Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc.,
Anna Abramowska, M.Sc., Bogusława Mysłek-Laurikainen, Ph.D., Katarzyna Wołoszczuk, M.Sc.
149
12. SEMINAR “SELECTED ASPECTS OF IMPLEMENTATION OF GEN III/IV IN NMS” IN THE
FRAME OF THE FP7 PROGRAMME “ASSESSMENT OF REGIONAL CAPABILITIES FOR NEW
REACTORS DEVELOPMENT THROUGH AN INTEGRATED APPROACH (ARCADIA)”, 1 OCTOBER 2015, WARSZAWA, POLAND
Organized by the Institute of Nuclear Chemistry and Technology, Central Laboratory for Radiological
Protection, National Centre for Nuclear Research
Organizing Committee: Katarzyna Kiegiel, Ph.D., Prof. Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc.,
Katarzyna Wołoszczuk, M.Sc., Bogusława Mysłek-Laurikainen, Ph.D., Dorota Gajda, M.Sc., Anna Abramowska, M.Sc., Agnieszka Miśkiewicz, Ph.D.
13. XIII SZKOŁA STERYLIZACJI I MIKROBIOLOGICZNEJ DEKONTAMINACJI RADIACYJNEJ (XIII TRAINING COURSE ON RADIATION STERILIZATION AND HYGIENIZATION),
22-23 OCTOBER 2015, WARSZAWA, POLAND
Organizing Committee: Zbigniew Zimek, Ph.D., Andrzej Rafalski, Ph.D., Wojciech Głuszewski, Ph.D.,
Jacek Boguski, M.Sc.
150
Ph.D. THESES
1. Katarzyna Anna Kosno, M.Sc.
Mechanizmy rodnikowe reakcji nikotyny i jej związków modelowych (Free radicals in reaction of nicotine and model compounds)
supervisor: Dariusz Pogocki, Ph.D., D.Sc., professor in INCT
Institute of Nuclear Chemistry and Technology, 10.04.2015
2. Agata Zofia Piotrowska, M.Sc.
Sfunkcjonalizowane nanozeolity jako nośniki radioizotopów 223Ra, 224Ra i 225Ra dla celowanej terapii
radionuklidowej (Functionalized nanozeolites as a carrier for 223Ra, 224Ra and 225Ra for targeted radionuclide therapy)
supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc.
3. Jacek Boguski, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Dobór krytyczny oceny degradacji radiacyjnej i termicznej kabli (Criteria for the evaluation of radiation
and thermal degradation of cables)
supervisor: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT
D.Sc. THESES
1. Ewa Gniazdowska, Ph.D. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Projektowanie nowych potencjalnych radiofarmaceutyków receptorowych opartych na analogach peptydów wazopresyny i greliny oraz leku lapatinib (Design of novel potential receptor radiopharmaceuticals
based on analogues of the peptides vasopressin and ghrelin and the drug lapatinib)
EDUCATION
151
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 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 defence of the dissertation thesis.
In 2015, the following lecture series and lectures were organized:
• Radiation chemistry with elements of chemistry of radicals – Prof. Krzysztof Bobrowski (Institute
of Nuclear Chemistry and Technology, Warszawa, Poland);
• Safe nuclear energy production vs. alternative prospects. Part II – Prof. Holger Tietze-Jaensch
(Forschungszentrum Jülich, Germany);
• An introduction to flow techniques of analysis – Prof. Victor Cerdà (Department of Chemistry,
University of the Balearic Islands);
• Backgrounds of the flow techniques – Prof. Victor Cerdà (Department of Chemistry, University of
the Balearic Islands);
• Separation and preconcentration methods in flow techniques – Prof. Victor Cerdà (Department of
Chemistry, University of the Balearic Islands);
• Some environmental applications of flow techniques and their hyphenation with complex instruments – Prof. Victor Cerdà (Department of Chemistry, University of the Balearic Islands);
• Nuclear research opportunities for students through the European project “Gentle” – Dr. Dario
Manara (Joint Research Centre – Institute For Transuranium Elements, Materials Research, Karlsruhe,
Germany);
• Nuclear chemistry – Prof. Aleksander Bilewicz (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: Ewa Gniazdowska, Ph.D., D.Sc., professor in INCT
(phone: +48 22 504 11 78, e-mail: [email protected]).
152
EDUCATION
TRAINING OF STUDENTS
Country
Number
of participants
Period
Cardinal Stefan Wyszyński University in Warsaw,
Faculty of Mathematics and Natural Sciences
Poland
2
1 month
Maria Curie-Skłodowska University
Poland
1
1.5 months
Medical University of Warsaw
Poland
1
1 month
3
2 months
National Graduate School of Chemistry, Montpellier
France
1
3 months
Nicolaus Copernicus Bilingual School in Warsaw
Poland
1
2 weeks
Pedagogical University of Cracow
Poland
25
one-day course
University of Białystok, Faculty of Chemistry
Poland
2
3 weeks
13
one-day course
1
3 weeks
3
1 month
3
3 months
1
1 month
2
1.5 months
34
one-day course
2
3 weeks
6
1 month
3
one-day course
24
one-day course
2
1 month
2
3 months
Institution
University of Warsaw, Faculty of Chemistry
Poland
University of Warsaw, Faculty of Physics
Poland
Warsaw University of Life Sciences – SGGW
Poland
Warsaw University of Technology, Faculty of Chemistry
Poland
Warsaw University of Technology,
Faculty of Environmental Engineering
Poland
Warsaw University of Technology, Faculty of Physics
Poland
Warsaw University of Technology,
Faculty of Power and Aeronautical Engineering
Poland
MASTER’S AND BACHELOR’S DISSERTATIONS
1. Maciej Wisłowski
Bachelor’s dissertation: Inżynieryjne aspekty oczyszczania wody chłodzącej z zastosowaniem technik
jonowymiennych (Engineering aspects of cooling water treatment using ion exchange methods)
supervisors: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc., Michał Lewak, Ph.D.
Warsaw University of Technology, Faculty of Chemical and Process Engineering
2. Andrzej Krześniak
Bachelor’s dissertation: Badanie adsorpcji Co-58 z symulowanych roztworów płynów dekontaminacyjnych stosowanych w procesie LOMI do dekontaminacji elementów konstrukcyjnych reaktorów jądrowych
(Study of adsorption of Co-58 from simulated decontamination liquid solutions used in the low oxidation
state metal ions process for decontamination of structural components of nuclear reactors)
supervisors: Michał Bystrzejewski, Ph.D., D.Sc., Monika Łyczko, Ph.D.
University of Warsaw, Faculty of Chemistry
153
RESEARCH PROJECTS GRANTED
BY THE NATIONAL SCIENCE CENTRE
IN 2015
1.
Physicochemical and biochemical studies of selected biological conveyers of nitrogen oxide. Relation
between the molecular structure and distribution of electric charge and the biological activity of nitrosyl complexes of iron.
supervisor: Hanna Lewandowska-Siwkiewicz, Ph.D.
2.
Chiral cores/monomers of drugs and conducting polymers: from calculations to experimental characteristics.
supervisor: Prof. Jan Cz. Dobrowolski, Ph.D., D.Sc.
3.
Nanobodies labelled with alpha emitters as potential radiopharmaceuticals in targeted radioimmunotheraphy.
supervisor: Marek Pruszyński, Ph.D.
4.
Nanoparticles of gold, gold-gold sulphide and titanium dioxide modified with tellurium as carriers for
At-211 for targeted alpha theraphy.
5.
Studies on the phenomena occurring in the membrane boundary layer during the filtration of aqueous
solutions and suspensions proceeding in membrane apparatuses with different configurations.
supervisor: Agnieszka Miśkiewicz, Ph.D.
6.
The influence of nanoparticles on beta-amyloid removal by microglia cells.
supervisor: Katarzyna Sikorska, M.Sc.
7.
Impact of nanoparticles on cellular signalling activated by tumour necrosis factor.
supervisor: Kamil Brzóska, Ph.D.
8.
Analytical, kinetic and toxicological study of degradation selected perfluorinated compounds using
ionizing radiation.
supervisor: Prof. Marek Trojanowicz, Ph.D., D.Sc.
9.
New analytical procedures based on neutron activation analysis for the determination of chosen Se,
As and Fe chemical formulae in infant alimentation.
supervisor: Halina Polkowska-Motrenko, Ph.D., D.Sc., professor in INCT
10. Radiation-induced radical processes involving amino acids and quinoxalin-2-one derivatives relevant
to their pharmacological applications.
supervisor: Konrad Skotnicki, M.Sc.
PROJECTS GRANTED
BY THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT
IN 2015
1. Elaboration and certification of new reference materials needed for obtaining European accreditation by
Polish laboratories involved in industrial analytics (programme INNOTECH, project MODAS).
supervisor: Halina Polkowska-Motrenko, Ph.D., D.Sc., professor in INCT
2. Conspan BlueGas – technology for treatment of flowback fluids from gas-bearing shales hydraulic fracturing with water recycling and reclamation of valuable metals (programme BlueGas).
Konsorcjum naukowe: Pyrocat Catalyse World (lider), Institute of Nuclear Chemistry and Technology,
Polish Geological Institute – National Research Institute
154
APPLIED RESEARCH PROGRAMME
OF THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT
IN 2015
1. Optimization of two stages bioreactor for biogas with high methane contents production – elaboration
of biostarters and biomarkers of methane fermentation. Task 2.1. Construction in laboratory scale of
two stages bioreactors for biogas production with high methane concentration (BioMeth).
supervisor: Jacek Palige, Ph.D.
2. Alternative methods for technetium-99m production. Task 8. Isolation of Tc-99m using zirconium
modified TiO2 nanotubes and by extraction method with HDEHP (ALTECH).
3. The integrated system of sewage treatment, biogas production and its enrichment in the methane.
4. Syntheses of radiopharmaceuticals based on scandium radionuclides for positron emission tomography
(Petscand).
INTERNATIONAL PROJECTS CO-FUNDED
BY THE MINISTRY OF SCIENCE AND HIGHER EDUCATION
IN 2015
1.
Radiation supporting synthesis and curing of nanocomposites suitable for practical applications.
supervisor: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT
2.
Advanced fuels for generation IV reactors: reprocessing and dissolution (ASGARD).
supervisor: Andrzej Deptuła, Ph.D.
3.
The industrial and environmental applications of electron beams.
supervisor: Dagmara Chmielewska-Śmietanko, M.Sc.
4.
Safety of actinide separation processes (SACSESS).
supervisor: Prof. Jerzy Narbutt, Ph.D., D.Sc.
5.
Transnational access to large infrastructure for a safe management of actinide (TALISMAN).
supervisor: Prof. Jan Cz. Dobrowolski, Ph.D., D.Sc.
6.
Advanced nanostructured porous materials formation and characterization (NONAMAPOR).
supervisor: Bożena Sartowska, Ph.D.
7.
Based on starch-PVA system and cellulose reinforced active packaging materials for food prepared
using of radiation modification (PackRad).
supervisor: Krystyna Cieśla, Ph.D., D.Sc., professor in INCT
8.
Application of advanced membrane systems in nuclear desalination (NUCDESAL).
supervisor: Prof. Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc.
9.
Coordination of actinides with hydrophilic ligands.
10. Development of dosimetry methods and safety of radiation and nuclear facilities.
supervisor: Roman Janusz, M.Sc.
11. Studying the social and socio-economic effects of the implementation of the Polish nuclear programme
using new methodology.
supervisor: Agnieszka Miśkiewicz, Ph.D.
12. Application of hybrid nuclear techniques in the multiphases flows investigations in wastewater treatment and biogas production plants.
13. Electron beam for preservation of biodeteriorated cultural heritage paper-based objects.
14. Laboratory and feasibility study for industrial wastewater effluents treatment by radiation.
supervisor: Zbigniew Zimek, Ph.D.
155
15. Introducing and harmonizing standardized quality control procedures for radiation technologies.
supervisor: Zbigniew Zimek, Ph.D.
16. The study of the influence of the environmental factors on the isotopic compositions of dairy products.
supervisor: Ryszard Wierzchnicki, Ph.D.
STRATEGIC PROJECT
“TECHNOLOGIES SUPPORTING DEVELOPMENT
1. Scientific problem no. 7: Study of hydrogen generation processes in nuclear reactors under regular operation conditions and in emergency cases, with suggested actions aimed at upgrade of nuclear safety.
supervisor: Prof. Jacek Michalik, Ph.D., D.Sc.
2. Scientific problem no. 8: Study of processes occurring under regular operation of water circulation
systems in nuclear power plants with suggested actions aimed at upgrade of nuclear safety.
supervisor: Anna Bojanowska-Czajka, Ph.D.
IAEA RESEARCH CONTRACTS IN 2015
1.
Radiation supporting synthesis and curing of nanocomposites suitable for practical applications
(NANO-RAD).
No. 16666
principal investigator: Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT
2.
Laboratory and feasibility study for industrial waste water effluent treatment by radiation.
No. 16454
principal investigator: Zbigniew Zimek, Ph.D.
3.
Application of hybrid nuclear techniques in the multiphases flows investigations in wastewater treatment and biogases production plants.
No. 17366
principal investigator: Jacek Palige, Ph.D.
4.
Based on starch-PVA system and cellulose reinforced active packaging materials for food prepared
using of radiation modification (PackRad).
No. 17493
principal investigator: Krystyna Cieśla, Ph.D., D.Sc., professor in INCT.
5.
The study of the influence of the environmental factors on the isotopic compositions of dairy products.
No. 18056
principal investigator: Ryszard Wierzchnicki, Ph.D.
6.
Application of advanced membrane systems in nuclear desalination.
No. 18539/RO
principal investigator: Prof. Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc.
7.
Studying the social and socio-economic effects of the iomplementation of the Polish nuclear programme
using new methodology.
No. 18541/RO
principal investigator: Agnieszka Miśkiewicz, Ph.D.
8.
Interlaboratory comparison in the range of high technological doses in the frame of project IAEA
RAS1015.
principal investigator: Andrzej Rafalski, Ph.D.
9.
Application of low energy electron beam for microbiological control of food and agricultural products.
No. RC-19000
principal investigator: Urszula Gryczka, M.Sc.
10. Radiometric methods applied in hydrometallurgical processes development and optimization.
No. 18945
principal investigator: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.
156
11. Silicide/silicate coatings on zirconium alloys for improving the high temperature corrosion resistance.
No. 19026
principal investigator: Bożena Sartowska, Ph.D.
12. Recovery of uranium and accompanying metals from various types of industrial wastes.
No. 18542
principal investigator: Katarzyna Kiegiel, Ph.D.
13. Electron beam for preservation of biodeteriorated cultural heritage paper-based objects.
No. 18493
IAEA TECHNICAL AND REGIONAL CONTRACTS IN 2015
1. Introducing and harmonizing standardized quality control procedures for radiation technologies.
RER 1014
PROJECTS WITHIN THE FRAME
OF EUROPEAN UNION FRAME PROGRAMMES
IN 2015
1. FP7 – EURATOM, Fission: Advanced fuels for generation IV reactors: reprocessing and dissolution
(ASGARD).
principal investigator: Andrzej Deptuła, Ph.D.
2. FP7 – EURATOM, Fission: Realizing the European Network in Biodosimetry (RENEB)
principal investigator: Sylwester Sommer, Ph.D.
3. FP7 – Transnational access to large infrastructure for a safe management of actinide (TALISMAN).
principal investigator: Prof. Jan Cz. Dobrowolski, Ph.D., D.Sc.
4. FP7 – Safety of actinide separation processes (SACSESS).
principal investigator: Prof. Jerzy Narbutt, Ph.D., D.Sc.
5. FP7 – Assessment of regional capabilities for new reactors development through an integrated approach (ARCADIA).
6. FP7 – Enhancing education, training and communication processes for informed behaviors and decision-making related to ionizing radiation risks (EAGLE).
7. FP7 – Building a platform for enhanced societal research related to nuclear energy in Central and
Eastern Europe (PLATENSO).
OTHER INTERNATIONAL RESEARCH PROGRAMMES IN 2015
1. Advanced nanostructured porous materials: formation and characterization (with Joint Institute for
Nuclear Research, Dubna, Russia).
supervisor: Bożena Sartowska, Ph.D.
2. Studies on nanoscale MOF synthesis methods.
No. 04-4-1121-2015/2017
supervisor: Wojciech Starosta, Ph.D.
3. Coordination of actinides with hydrophilic ligands (with the French Alternative Energies and Atomic
Energy Commission – CEA).
157
PROJECTS GRANTED
BY THE FOUNDATION FOR POLISH SCIENCE
IN 2015
1. New radiopharmaceuticals based on alpha emitters against glioblastoma stem cells.
supervisor: Agnieszka Majkowska-Pilip, Ph.D.
ERASMUS+ PROGRAMME
1. Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing.
No. 2014-1-PL01-KA203-003611
2. Mobility for learners and staff higher education student and staff mobility.
Key action 1
3. Inter-institutional agreement 2015-2017 between institutions from programme and partner countries
(China).
Key action 1
158
THE NCBR STRATEGIC RESEARCH PROJECT
“TECHNOLOGIES SUPPORTING DEVELOPMENT
Since 2011 till 2015 the Institute of Nuclear Chemistry and Technology (INCT) participated in the
strategic research project “Technologies supporting development of safe nuclear power engineering”
which was established by the National Centre for Research and Development (NCBR) in order to
reinforced the government programme of nuclear power implementation. Its main goal was to build
up the technical expertise related to different aspects of nuclear energy useful for investor (PGE) and
regulator (National Atomic Energy Agency, Poland – PAA) of first Polish nuclear plant. The project
comprised 10 research tasks among which 3 tasks concerning chemical aspects of nuclear power were
coordinated by the Institute of Nuclear Chemistry and Technology:
• Task 4: Development of spent nuclear fuel and radioactive waste management techniques and technologies.
• Task 7: Study of hydrogen generation processes in nuclear reactors under regular operation conditions and in emergency cases, with suggested actions aimed at upgrade of nuclear safety.
• Task 8: Study of processes occurring under regular operation of water circulation systems in nuclear
power plants with suggested actions aimed at upgrade of nuclear safety.
Task 4
Development of spent nuclear fuel and radioactive waste management techniques
and technologies
Coordinator: Leon Fuks, Ph.D.
Task 4 concerned management of spent fuel and radioactive waste, separation of long-lived actinides
from spent fuel and fabrication of fuel precursors for reactors of new generations. The task was carried
out by 8 research units: National Centre for Nuclear Research, POLATOM, Institute of Nuclear Chemistry and Technology, Institute of Nuclear Physics PAS, Institute of Electronic Materials Technology,
AGH University of Science and Technology, Maria Curie-Skłodowska University – Faculty of Chemistry and Radioactive Waste Management Plant. Significant part of research activity was dedicated to
decrease radiotoxicity of radioactive waste. New sorbents for removal of radioactive elements were
tested and it was shown that red clay, cheap domestic sorption material could be effectively used as a
barrier layer in low and medium radioactive waste disposals. The optimalization of hybrid processes for
radioactive waste treatment had been also accomplised. New methods of solidification of high radioactive waste in glasses and Synroc materials had been worked up. The new separation methods of some
radionuclides such as Ru-106, Sr-90, Co-60, Zn-65 from nuclear waste left after fuel processing had
been proposed. Those radionuclides can be applied in nuclear medicine and radiation technologies.
Task 7
Study of hydrogen generation processes in nuclear reactors
under regular operation conditions and in emergency cases, with suggested actions
aimed at upgrade of nuclear safety
Coordinator: Prof. Jacek Michalik, Ph.D., D.Sc.
In task 7 in which four outer research units were involved: Łódź University of Technology – Faculty of
Chemistry, Jerzy Haber Institute of Catalysis and Surface Chemistry PAS, Warsaw University of Technology – Faculty of Chemical and Process Engineering, and Silesian University of Technology – Institute of Thermal Technology, the complex processes of hydrogen formation in cooling water of primary
system and its removal from reactor containment had been studied. The decomposition of cooling
water in pressurized water reactors (PWR) initiated by ionizing radiation but also caused by thermocatalytic processes taking place on the surface of zircaloy claddings at temperatures above 1000oC was
159
investigated. The analysis of new technologies which can distinctly limit the hydrogen storage in reactor
containment during low-of-cooling accident (LOCA) was also carried out.
The radiation studies had been focused on the influence of temperature and metal oxides contamination in cooling water on radiation yield of molecular hydrogen. The experiments confirmed rapid
increase of water oxidation rate with temperature for reaction with hydrogen atoms. Under normal
operation of PWR reactor (~300oC) this reaction becomes a substantial source of hydrogen and hydroxyl radicals which are the most active corrosion agents.
The studies on hydrogen circulation in reactor containment after LOCA had been carried out using
CFD calculation – the Ansys Fluent and HEPCAL codes. CFD modelling of gas circulation and water
vapour condensation inside TOSQAN installation designed for the studies of processes proceeding
inside safety containments of LWR reactors shows good agreement between calculations and experimental results. HEPCAL code was also used for the simulations of LOCA accidents in EPR and ABWR
reactors. They showed that hydrogen concentration in reactor containment reached the limit of hydrogen ignition (4%) half an hour after fuel rod puncturing. The CFD calculation showed also the radical
decrease of hydrogen concentration in the containments where hydrogen passive autocatalytic recombiners (PAR) were installed.
The new types of catalysts for PAR recombiners had been investigated in the framework of task 7.
It was found out that the catalysts consist of bimetallic nanoparticles Pd-Pt and Pd-Au immobilized on
SiO2 and Al2O3 carriers are active already under low hydrogen concentration and their disactivation
degree is low in the presence of water vapour.
Task 8
Study of processes occurring under regular operation of water circulation systems
in nuclear power plants with suggested actions aimed at upgrade of nuclear safety
Coordinator: Anna Bojanowska-Czajka, Ph.D.
The adequate control of chemical composition of reactor cooling water is one of the most important factors decisive on safe reactor exploitation. Cooling water of primary system contains radionuclides formed by activation of diffusing trace elements from fuel claddings and corrosion products of
construction materials. In addition water gets decomposed by radiolysis producing many aggressive
chemical products such as hydroxyl radicals, hydrogen atoms and hydrogen peroxide. They affect the
corrosion rate of construction materials of primary cooling system in substantial degree.
Task 8 was carried out by research network consisting of the Institute of Nuclear Chemistry and
Technology, Institute of Physical Chemistry PAS, University of Warsaw – Faculty of Chemistry, and
Warsaw University of Technology – Department of Materials Engineering.
As the result of cooperative studies the new methods for control fuel claddings tightness were
found out. They are based on the measurements of Sr-90, Tc-99, Pu-241 and Am-241 radionuclides
using flow radiochemical methods. For monitoring of corrosion product concentration in primary
cooling circuit the mass spectrometry and ionic chromatography were applied. The major achievement
of task 8 was synthesis of novel selective sorbents for removal caesium and other radionuclides from
primary cooling system effectively working in LOCA conditions when sea water is used for reactor
cooling.
In the research works of strategic project many young scientific were participating who won a broad
knowledge and deep experience in nuclear sciences. In future they should play an important role of
experts involved in development of Polish nuclear energy programme.
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1.
Adliene Diana, Kaunas University of Technology, Lithuania, 08-09.10.15
2.
Augel Antonio, University of Bologna, Italy, 16-20.11.15
3.
Bondar Yulia, Institute of Environmental Geochemistry, National Academy of Sciences of Ukraine,
23-27.11.15
4.
Calinescu Ioan, University Politehnica of Bucharest, Romania, 03-07.11.15
5.
Cerdà Victor, Department of Chemistry, University of the Balearic Islands, 15-19.06.15
6.
Coqueret Xavier, Université de Reims Champagne-Ardenne, France, 08-09.10.15
7.
Cousines T. Ian, Department of Applied Environmental Science, Stockholm University, Sweden,
23.10.15
8.
D’angelantonio Mila, Institute of Polymers, Composites and Biomaterials (IPCB), National Research
Council (CNR), Italy, 16-20.11.15
9.
Dispenza Clelia, University of Palermo, Italy, 08-09.10.15
10. Gogulancea Valentina, University Politehnica of Bucharest, Romania, 01.03.-31.06.15
11. Grate W. Jay, Pacific Northwest National Laboratory, Richland, Washington, USA, 13.11.15
12. Guerard Bruno, Institut Laue-Langevin, Grenoble, France, 29.06.15
13. Jovarauskiene Donata, Kaunas University of Technology, Lithuania, 08-09.10.15
14. Kodaira Keiichi, Bonn Office, Japan Society for the Promotion of Science, Germany, 20.08.15
15. Lavric Vasile, University Politehnica of Bucharest, Romania, 03-07.11.15
16. Lazunik Walentin, N.V. Karazin Kharkov National University, Ukraine, 10-16.05.15
17. Lysychenko Georgii, Institute of Environmental Geochemistry, National Academy of Sciences of Ukraine,
23-27.11.15
18. Manara Dario, Joint Research Centre-Institute for Transuranium Elements, Materials Research, Karlsruhe,
Germany, 23.09.15
19. Marchini Mariana, University of Bologna, Italy, 18.04.15
20. Nyisztor Daniel, Hungarian Atomic Energy Authority, Hungary, 25.11.15
21. Olkhovyk Yuriy, Institute of Environmental Geochemistry, National Academy of Sciences of Ukraine,
23-27.11.15
22. Parparita Elena, Institute of Macromolecular Chemistry “Petru Poni” Iasi, Romania, 08-09.10.15
23. Popov Genadii, N.V. Karazin Kharkov National University, Ukraine, 10-16.05.15
24. Sheibani Shahab, Nuclear Science and Technology Research Institute, Teheran, Iran, 15-29.11.15
25. Silvestre Clara, Institute of Polymers, Composites and Biomaterials (IPCB), National Research Council
(CNR), Italy, 08-09.10.15
26. Solpan Ozbay Dilek, Hacettepe University, Turkey, 08-09.10.15
27. Szmidt Holger, Forschungszentrum Julich GmbH, Niemcy, 30.08.-05.09.15
28. Torun Murat, Hacettepe University, Turkey, 08-09.10.15
29. Venturi Margherita, University of Bologna, Italy, 18.04.15
161
1.
Prof. Victor Cerdà (Department of Chemistry, University of the Balearic Islands)
An introduction to flow techniques of analysis
2.
Backgrounds of the flow techniques
3.
Separation and preconcentration methods in flow techniques
4.
Some environmental applications of flow techniques and their hyphenation with complex instruments
5.
Edyta Cędrowska, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Biokoniugaty nanocząstek tlenków metali jako nośniki emiterów cząstek  w celowanej terapii radionuklidowej (Bioconjugates of metal-oxide nanoparticles as  emitters carriers for targeted radionuclide
therapy)
6.
Prof. Ian T. Cousins (Department of Applied Environmental Science, Stockholm University, Sweden)
Sources and fate of per- and polyfluoroalkyl substances
7.
Dorota Gajda, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Odzysk wybranych metali ciężkich z rud i surowców odpadowych (Recovery of selected heavy metals
from ores and raw materials)
8.
Jay W. Grate, Ph.D. (Pacific Northwest National Laboratory, Richland, Washington, USA)
Methodology and application of automation in radiochemical separations and analysis
9.
Bruno Guerard (Institut Laue-Langevin, Grenoble, France)
Recent development of the multi-grid detector for large area neutron scattering instruments
10. Prof. Keiichi Kodaira (Bonn Office, Japan Society for the Promotion of Science, Germany)
Introduction to the international programs of Japan Society for the Promotion of Science (JSPS)
11. Kamila Kołacińska, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Oznaczanie wybranych radionuklidów w chłodziwie reaktorowym z zastosowaniem metod analizy przepływowej (Determination of selected radionuclides in reactor coolant by using flow techniques)
12. Piotr F.J. Lipiński, M.Sc. (Mossakowski Medical Research Centre, Polish Academy of Sciences,
Warszawa, Poland)
Nowe aspekty chiralnej analizy QSPR (Novel aspects of chiral QSPR analysis)
13. Sueo Machi, Ph.D. (Fellow of Japan Atomic Energy Agency and Coordinator of Japan, Forum of
Nuclear Cooperation in Asia)
Prospects of nuclear power in Japan and Asian countries
14. Marcin Rogowski, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Otrzymywanie węglika uranu metodą zol-żel (Synthesis of uranium carbide by sol-gel method)
15. Konrad Skotnicki, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Reakcje rodnikowe chinoksalin-2-onów w aspekcie ich zastosowań farmakologicznych (Radical reactions
of quinoxalin-2-ones in the aspect of their pharmacological applications)
162
LECTURES AND SEMINARS DELIVERED OUT OF THE INCT
IN 2015
LECTURES
1.
Brzóska K.
Towards development of transcriptional biodosimetry for identification of irradiated individuals and
assessment of absorber radiation dose.
4th Annual RENEB Meeting, Rome, Italy, 04-06.03.2015.
2.
Chmielewski A.G.
Czterdzieści lat sterylizacji radiacyjnej materiałów medycznych w Polsce/Forty years of radiation sterilization of health care products in Poland.
60-lecie IBJ: Fizyka i chemia jądrowa w służbie medycyny/60th Anniversary of IBJ: Nuclear physics
and chemistry for medicine, Świerk, Poland, 10.06.2015.
3.
Chmielewski A.G.
Developments in the electron beam accelerators and e/X systems engineering. Industrial applications
of electron beams – materials processing, sterilization, food irradiation and environment.
APAE Kick-off Meeting “The applications of particle accelerators in Europe”, London, United Kingdom,
18-19.06.2015.
4.
Chmielewski A.G.
Energy mix in Poland with potential share of nuclear energy.
Polish-Japanese Conference “Greening the national energy system: Japanese and Polish perspectives”,
Olsztyn, Poland, 02.07.2015.
5.
Chmielewski A.G.
Nuclear chemistry – fear and hope.
2nd International Conference on Science Diplomacy and Developments in Chemistry, Warszawa, Poland,
13-16.08.2015.
6.
Chmielewski A.G., Szołucha M.
Radiation chemistry for modern nuclear energy.
13th Tihany Symposium on Radiation Chemistry, Balatonalmádi, Hungary, 29.08.-03.09.2015.
7.
Chmielewski A.G.
Accelerators for the future research, industry and environmental applications.
IAEA Technical Meeting on New Generation of EB Accelerators for Emerging Radiation Processing
Applications, Vienna, Austria, 07-11.09.2015.
8.
Chmielewski A.G.
Electron beam flue gas treatment.
International Atomic Energy Agency Scientific Forum “Atoms in industry: radiation technology for development”, Vienna, Austria, 15-16.09.2015.
9.
Chmielewski A.G.
Industrial application of electron beam.
International Nuclear Atlantic Conference INAC 2015, São Paulo, Brazil, 04-09.10.2015.
10. Chmielewski A.G.
Recent developments in electron accelerators applications for environmental protection.
12th International Topical Meeting on Nuclear Applications of Accelerators (AccApp’15), Washington
D.C., USA, 10-13.11.2015.
11. Chmielewski A.G.
Polish R&D activities in the field of fuel reprocessing and radioactive waste treatment.
Central & Eastern Europe Nuclear New Build Congress 2015, Warszawa, Poland, 24-25.11.2015.
163
12. Cieśla K.
Application of radiation modified polysaccharide hydrogels.
Erasmus+ TL-IRMP “Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing”, Palermo,
Italy, 28.09.-02.10.2015.
13. Cieśla K.
Biopolymer hydrogels. Application of radiation modification.
Italy, 28.09.-02.10.2015.
14. Cieśla K.
Characterization of natural polymers systems, their structural properties, related applications and desirable modification. Part I. Basic components and raw materials.
Italy, 28.09.-02.10.2015.
15. Cieśla K.
Characterization of natural polymers systems, their structural properties, related applications and desirable modification. Part II. Composites/nanocomposites and nanoparticles.
Italy, 28.09.-02.10.2015.
16. Cieśla K.
Chemical and physical modification of polysaccharide systems: specific features of electromagnetic
radiation.
Italy, 28.09.-02.10.2015.
17. Cieśla K.
Radiation degradation of polysaccharides and modification of activity of active polysaccharides.
Italy, 28.09.-02.10.2015.
18. Cieśla K.
Radiation modification of composites based on proteins the other non-polysaccharide biopolymers as
well as composites/nanocomposites based on those biopolymers. Part I. Edible and biodegradable films
and coatings.
Italy, 28.09.-02.10.2015.
19. Cieśla K.
Radiation modification of composites based on proteins the other non-polysaccharide biopolymers as
well as composites/nanocomposites based on those biopolymers. Part II. Silk, and rubber.
Italy, 28.09.-02.10.2015.
20. Cieśla K.
Radiation modification of polysaccharide composites for packaging.
Italy, 28.09.-02.10.2015.
21. Cieśla K.
Radiation modification of polysaccharide composites: potential for the other areas.
Italy, 28.09.-02.10.2015.
Neutronowa analiza aktywacyjna i jej rola w metrologii chemicznej (Neutron activation analysis and
its role in chemical metrology).
164
58 Zjazd Naukowy Polskiego Towarzystwa Chemicznego, Gdańsk, Poland, 21-25.09.2015.
23. Głuszewski W.
Opakowania napromieniowane czy promieniotwórcze (Packaging – irradiated or radioactive?).
LearnShops – Independent Seminars during the International Packaging Trade Show – Packaging Innovations 2015, Warszawa, Poland, 09-10.04.2015.
24. Gumiela M.
Nowa metoda wydzielania Tc-99m z napromienionej w cyklotronie tarczy molibdenowej (The new method
of isolation of Tc-99m from irradiated in the cyclotron molybdenum target).
25. Kiegiel K., Zakrzewska-Kołtuniewicz G., Gajda D., Polkowska-Motrenko H.
Recovery of uranium and accompying metals from various type of industrial waste.
First Research Coordination Meeting on Uranium/Thorium Fuelled High Temperature Gas Cooled Reactor Applications for Energy Neutral and Sustainable Comprehensive Extraction and Mineral Product
Development Processes, Vienna, Austria, 02-05.11.2015.
26. Koźmiński P.
Grelinowe kompleksy technetu-99m jako potencjalne radiofarmaceutyki diagnostyczne (Ghrelin peptide
labelled with technetium-99m complexes as potential diagnostic pharmaceuticals).
27. Leszczuk E.
Nanocząstki TiO2-Substancja P (5-11) jako nośniki dla 225Ac w celowanej terapii radionuklidowej
(TiO2-Substance P (5-11) nanoparticles as 225Ac carriers in targeted radionuclide therapy).
28. Zakrzewska-Kołtuniewicz G.
Application of advanced membrane systems in nuclear desalination.
2nd Research Coordination Meeting of the IAEA CRP “Application of advanced low temperature desalination systems to support nuclear power plants and non-electric applications”, Vienna, Austria, 01-03.12.2015.
29. Zimek Z.
Reliability and availability of high power electron accelerators for radiation processing.
IAEA Technical Meeting on New Generation of EB Accelerators for Emerging Radiation Processing
Applications, Vienna, Austria, 07-11.09.2015.
30. Zimek Z.
Electron accelerators application.
CERN Accelerator School – Advanced Accelerator Physics Course, Warszawa, Poland, 27.09.-09.10.2015.
31. Zyśk J., Niedzicki W., Latek S., Zakrzewska-Kołtuniewicz G.
Nuclear industry promotion vs citizen centered risk communication.
ionising radiation, Brdo, Slovenia, 15-17.06.2015.
SEMINARS
1.
Chmielewski Andrzej G.
Industrial applications of electron accelerators.
Oak Ridge National Laboratory, Oak Ridge, USA, 16.11.2015.
2.
Cieśla Krystyna
Characterization of natural polymers systems, their structural properties, related applications and desirable modification. Part I. Basic components and raw materials.
Hacettepe University, Department of Chemistry, Ankara, Turkey, 04.05.2015.
3.
Cieśla Krystyna
Characterization of natural polymers systems, their structural properties, related applications and desirable modification. Part II. Composites/nanocomposites and nanoparticles.
165
4.
Cieśla Krystyna
Adsorbents. Classics and the current directions in research.
5.
Cieśla Krystyna
Radiation processes in biopolymer system.
6.
Cieśla Krystyna
Biopolymer hydrogels. Application of radiation modification.
7.
Cieśla Krystyna
Edible and biodegradable films and coatings based on proteins and polysaccharides.
8.
Cieśla Krystyna
Radiation modification of composites. Part I. Modification of the properties of biodegradable plastics.
9.
Cieśla Krystyna
Radiation modification of composites. Part II. Radiation processes in nanotechnology, technical and
food industries, agriculture and the other areas.
10. Gajda Dorota
Czarnobyl wczoraj i dziś (Chernobyl yesterday and today).
The Maria Skłodowska-Curie Museum, Warszawa, Poland, 26.09.2015.
11. Głuszewski Wojciech
Maria Skłodowska-Curie prekursorką radiacyjnej konserwacji dzieł sztuki (Maria Skłodowska-Curie
forerunner of preservation of cultural heritage artefacts).
The Maria Skłodowska-Curie Museum, Warszawa, Poland, 19.09.2015.
12. Kołacińska Kamila
Energetyka jądrowa dla Polski (Nuclear energy for Poland).
Warsaw School of Economics, Warszawa, Poland, 06.03.2015.
13. Kołacińska Kamila
Energetyka jądrowa dla Polski (Nuclear energy for Poland).
Warsaw School of Economics, Warszawa, Poland, 23.10.2015.
14. Kruszewski Marcin
Naprawa uszkodzeń DNA – już chemia czy jeszcze biologia? Nagroda Nobla 2015 (DNA repair – chemistry or biology? Nobel Prize 2015).
Warsaw University of Technology, Warszawa, Poland, 17.12.2015.
15. Przybytniak Grażyna
Negatywne i pozytywne następstwa działania promieniowania jonizującego na polimery syntetyczne
(Positive and negative influence of ionizing radiation on synthetic polymers).
Polish Radiation Research Society, Łódź Branch, Łódź, Poland, 19.05.2015.
Postępowanie z odpadami promieniotwórczymi z elektrowni jądrowej (Disposal of radioactive waste from
the nuclear power plant).
XIII Fair of Renewable Sources of Energy ENEX – New Energy, Kielce, Poland, 05.03.2015.
Współczesne zastosowania technik jądrowych (Modern applications of nuclear techniques).
General Tadeusz Kościuszko Military Academy of Land Forces, Wrocław, Poland, 22.10.2015.
Odpady promieniotwórcze – nie takie straszne? (Radioactive waste – not that terrible?).
University of Gdańsk, Faculty of Law and Administration, Gdańsk, Poland, 28.10.2015.
Odpady promieniotwórcze – nie takie straszne? (Radioactive waste – not that terrible?).
Gdańsk University of Technology, Faculty of Electrical and Control Engineering, Gdańsk, Poland,
29.10.2015.
166
AWARDS IN 2015
AWARDS IN 2015
1.
Preparation of yttrium trioxide in the form of spherical grains
Platinum Medal at the International Warsaw Invention Show IWIS 2015, Warszawa, Poland, 12-14.10.2015
Andrzej Deptuła, Wiesława Łada, Danuta Wawszczak, Edward Iller, Leszek Królicki, Jerzy Ostyk-Narbutt
2.
Preparation of yttrium trioxide in the form of spherical grains
Grand Prix at the International Warsaw Invention Show IWIS 2015, Warszawa, Poland, 12-14.10.2015
Andrzej Deptuła, Wiesława Łada, Danuta Wawszczak, Edward Iller, Leszek Królicki, Jerzy Ostyk-Narbutt
3.
Therapeutic radiopharmaceutical labelled with radionuclides of radium and method for its obtaining
Silver Medal at the International Warsaw Invention Show IWIS 2015, Warszawa, Poland, 12-14.10.2015
Aleksander Bilewicz, Agata Kasperek, Tadeusz Olczak
4.
Therapeutic radiopharmaceutical labelled with radionuclides of radium and method for its obtaining
AGEPI (State Agency on Intellectual Property of the Republic of Moldova) Medal at the International
Warsaw Invention Show IWIS 2015, Warszawa, Poland, 12-14.10.2015
Aleksander Bilewicz, Agata Kasperek, Tadeusz Olczak
5.
National Order of Merit awarded by the President of the French Republic in recognition of her achievements in the field of nuclear chemistry and contribution to the French-Polish scientific cooperation
Grażyna Zakrzewska-Kołtuniewicz
6.
Professor Jan Obrąpalski medal awarded by the Main Board of the Association of Polish Electrical
Engineers SEP for achievements in teaching and research in the field of energy production
Andrzej G. Chmielewski
7.
Sposób unieszkodliwiania odpadów promieniotwórczych w szkłach krzemionkowych (Method for the
disposal of radioactive wastes in structures of silica glasses; authors: A.G. Chmielewski, A. Deptuła,
M. Miłkowska, W. Łada, T. Olczak)
Diploma of the Ministry of Science and Higher Education
8.
Alavi-Mandell Award of the Society of Nuclear Medicine and Molecular Imaging and the Education
and Research Foundation for Nuclear Medicine and Molecular Imaging for publication “Improved tumor
targeting of anti-HER2 nanobody through N-succinimidyl 4-guanidinomethyl-3-lodobenzoate radiolabeling” in “Journal of Nuclear Medicine”
Marek Pruszyński
9.
Maria Skłodowska-Curie scientific prize for Polish scientists for achievements in nuclear materials
science awarded by AREVA-EDF, French Embassy and French Institute in Poland
Marta Walo
10. Porównanie bioługowania i ługowania chemicznego uranu oraz metali towarzyszących z rud ubogich
w Polsce (A comparison of the uranium and accompanying metals recovery from Polish low-grade ore
by bioleaching and acid leaching; authors: M. Szołucha, A.G. Chmielewski)
Diploma for the best poster presented at the I Symposium of Young Scientists of the Faculty of Physics,
Warszawa, Poland, 20.05.2015
Monika Szołucha
11. Charakterystyki neutronowe rdzenia reaktora MARIA. Analiza modelem dyfuzyjnym (MARIA reactor
core characteristics of neutron. Diffusion calculations)
Third degree award of the Polish Nuclear Society for the best bachelor’s dissertation concerning nuclear sciences
Monika Szołucha
12. Officer’s Cross of the Order of the Rebirth of Poland
Andrzej G. Chmielewski
AWARDS IN 2015
167
13. Officer’s Cross of the Order of the Rebirth of Poland
Rajmund S. Dybczyński
14. Knight’s Cross of the Order of the Rebirth of Poland
Jacek Michalik
Jerzy Ostyk-Narbutt
Wacław Stachowicz
17. Silver Cross of Merit
Roman Janusz
Zbigniew Samczyński
Bożena Sartowska
Wojciech Starosta
21. Bronze Cross of Merit
Ewelina Chajduk
Krzysztof Łyczko
Agnieszka Miśkiewicz
Andrzej Nowicki
Andrzej Rafalski
Karol Roman
27. Gold Medal for Long-Time Service
Barbara Bartoś
Wanda Dalecka
Wiesława Wawrzyniak
30. Bronze Medal for Long-Time Service
Dorota Korniszewska
31. Bronze Medal for Long-Time Service
Natalia Pawlik
32. Pro Masovia commemorative medal awarded by the Marshal of the Mazowieckie Voivodeship for outstanding services and activity for Mazovia Voivodship
Aleksander Bilewicz
33. Pro Masovia commemorative medal awarded by the Marshal of the Mazowieckie Voivodeship for outstanding services and activity for the Mazovia Voivodship
Ewa Gniazdowska
Urszula Gryczka
Roman Janusz
168
AWARDS IN 2015
Marcin Kruszewski
Wiesława Łada
Wojciech Maciąg
Wojciech Migdał
Marta Walo
Tomasz Zawisza
Zbigniew Zimek
43. Honorary Medal of Merit for Economic Development in the Polish Republic
Rajmund S. Dybczyński
Jacek Michalik
Jerzy Ostyk-Narbutt
Wacław Stachowicz
47. First degree team award of Director of the Institute of Nuclear Chemistry and Technology in 2015 for a
series of three original and valuable publications concerning the investigations of radiopharmaceuticals
Ewa Gniazdowska, Przemysław Koźmiński, Leon Fuks
48. Second degree team award of Director of the Institute of Nuclear Chemistry and Technology in 2015
for a series of twelve publications dedicated to radiation chemistry
Jacek Boguski, Leon Fuks, Ewa M. Kornacka, Krzysztof Łyczko, Krzysztof Mirkowski, Andrzej Nowicki, Grażyna Przybytnik, Jarosław Sadło, Marta Walo, Zbigniew P. Zagórski, Zbigniew Zimek
49. Third degree team award of Director of the Institute of Nuclear Chemistry and Technology in 2015 for
a series of four publications dedicated to obtaining uranium ores for fabrication of nuclear fuel
Grażyna Zakrzewska-Kołtuniewicz, Katarzyna Kiegiel, Łukasz Steczek, Irena Herdzik-Koniecko,
Ewelina Chajduk, Jakub Dudek
50. Distinction of the first degree of Director of the Institute of Nuclear Chemistry and Technology in 2015
for the achieved progress in the preparation of Ph.D. thesis and professional activity, including published articles, participation in the actions organized and co-organized by the Institute and participation in the preparation and realization of research projects and contracts outside the Institute
Edyta Cędrowska
51. Distinction of the second degree of Director of the Institute of Nuclear Chemistry and Technology in
2015 for the achieved progress in the preparation of Ph.D. thesis and professional activity, including
published articles, participation in the actions organized and co-organized by the Institute and participation in the preparation and realization of research projects and contracts outside the Institute
Ewa Zwolińska
52. Distinction of the third degree of Director of the Institute of Nuclear Chemistry and Technology in 2015
for the achieved progress in the preparation of Ph.D. thesis and professional activity, including published articles, participation in the actions organized and co-organized by the Institute and participation in the preparation and realization of research projects and contracts outside the Institute
Rafał Walczak
AWARDS IN 2015
169
53. Award of Director of the Institute of Nuclear Chemistry and Technology in 2015 for management of
Erasmus+ programme
Yongxia Sun
54. Award of Director of the Institute of Nuclear Chemistry and Technology in 2015 for the activity in
gaining cooperative research projects with industrial partners
Zbigniew Zimek
55. Award of Director of the Institute of Nuclear Chemistry and Technology in 2015 for the chairing the
Doctoral Dissertation Committee of the INCT Scientific Council
Grażyna Przybytniak
56. Award of Director of the Institute of Nuclear Chemistry and Technology in 2015 for acting as the director proxy for student practices
Marta Pyszynska
170
A
Abramowska Anna 20, 50
Apel Pavel 75
B
Bartłomiejczyk Teresa 55, 57
Bojanowska-Czajka Anna 66
Brykała Marcin 36
Brzóska Kamil 54
Buczkowski Marek 20, 75
Bułka Sylwester 25, 83
Buraczewska Iwona 55
C
Chajduk Ewelina 66
Chmielewski Andrzej G. 83, 85
Chorąży Katarzyna 62
Cieśla Krystyna 20
D
Dalecka Wanda 32
Deptuła Andrzej 36
Dobrowolski Andrzej 104
Dobrowolski Jan Cz. 46
Drużbicki Kacper 46
Dudek Jakub 66
Dziendzikowska Katarzyna 55
Korzeniowska-Sobczuk Anna 94
Kowalska Magdalena 58
Kozera Klaudia 23
Koźmiński Przemysław 43
Kruszewski Marcin 54, 55, 58, 59
Kubera Hieronim 23
Kużelewska Iga 70
L
Lankof Leszek 40
Lankoff Anna 58
Lavric Vasile 85
Lewandowska Hanna 59
Licki Janusz 83
Lisowska Halina 58
Liśkiewicz Grażyna 99
Ł
Łada Wiesława 36
Łuczyńska Katarzyna 46
Łyczko Krzysztof 46
M
F
Maróti Boglarka 77
Masłowska Katarzyna 43
Męczyńska-Wielgosz Sylwia 57, 58, 59
Mikiciuk-Olasik Elżbieta 43
Mirkowski Krzysztof 17
Miśkiewicz Agnieszka 40, 50
Fuks Leon 32
N
G
Narbutt Jerzy 29
Nowicki Andrzej 17
Gajda Dorota 50
Głuszewski Wojciech 23
Gniazdowska Ewa 43
Gogulancea Valentina 85
Grądzka Iwona 54, 55, 57
Gromadzka-Ostrowska Joanna 55
Guzik Grzegorz P. 99
H
Herdzik-Koniecko Irena 29
I
Iwaneńko Teresa 55, 58
K
Karlińska Magdalena 94
Kasztovszky Zsolt 77
Kiegiel Katarzyna 50
Koc Mariusz 62
Kołacińska Kamila 66
O
Olczak Tadeusz 36
Olszewska Wioleta 40
Ołdak Wiesław 104
Orelovitch Oleg 75
Oszczak Agata 32
P
Pająk Leszek 40
Palige Jacek 104
Pańczyk Ewa 77
Polkowska-Motrenko Halina 70
Przybytniak Grażyna 17
R
Rejnis Magdalena 29
Rogowski Marcin 36
Roubinek Otton 104
171
S
W
Sadło Jarosław 59
Sadowska Magdalena W. 99
Samczyński Zbigniew 66, 70
Sartowska Bożena 75
Sikorska Katarzyna 55
Smoliński Tomasz 36
Sochanowicz Barbara 54
Sołtyk Wojciech 104
Sommer Sylwester 55
Stachowicz Wacław 99
Starosta Wojciech 75
Steczek Łukasz 29
Stępkowski Tomasz M. 59
Sun Yongxia 83, 85
Szumiel Irena 59
Szymański Paweł 43
Waliś Lech 77
Wasyk Iwona 55, 57
Wawszczak Danuta 36
Weker Władysław 77
Węgierek-Ciuk Aneta 58
Widawski Maciej 77
Wierzchnicki Ryszard 90
Wojewódzka Maria 57, 58
Wojtowicz Patryk 36
Wójciuk Grzegorz 59
T
Trojanowicz Marek 62, 66
Z
Zakrzewska-Kołtuniewicz Grażyna 40, 50
Zapór Lidia 57
Zimek Zbigniew 25
Zwolińska Ewa 83, 85
INSTITUTE OF NUCLEAR
CHEMISTRY AND TECHNOLOGY
phone: +48 22 504 12 05, fax: +48 22 811 15 32
e-mail: [email protected]
www.ichtj.waw.pl

annual report 2015 - Instytut Chemii i Techniki Jądrowej

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