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ANNUAL REPORT
2015
INSTITUTE
OF NUCLEAR CHEMISTRY
AND TECHNOLOGY
EDITORS
Prof. Jacek Michalik, Ph.D., D.Sc.
Ewa Godlewska-Para, M.Sc.
GENERAL INFORMATION 7
SCIENTIFIC STAFF 13
PROFESSORS 13
SENIOR SCIENTISTS (Ph.D.) 13
THE PROPERTIES AND IONIZING RADIATION EFFECTS IN THE STARCH-PVA FILMS PREPARED
BASED ON VARIOUS SUBSTRATES
K. Cieśla, A. Abramowska, M. Buczkowski 20
NOVEL PROCEDURE FOR THE REMOVAL OF THE RADIOACTIVE METALS FROM AQUEOUS WASTES
BY THE MAGNETIC CALCIUM ALGINATE
L. Fuks, A. Oszczak, W. Dalecka 32
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
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
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
NUKLEONIKA 132
EDUCATION 151
Ph.D. PROGRAMME IN CHEMISTRY 151
TRAINING OF STUDENTS 152
MASTER’S AND BACHELOR’S DISSERTATIONS 152
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 Chem-
istry 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 to-
gether 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, ra-
diation chemistry, nuclear chemical engineering and technology, application of nuclear
methods in material engineering and process engineering, radioanalytical techniques, de-
sign and production of instruments based on nuclear techniques, environmental research,
cellular radiobiology, etc. The results of work at the INCT have been implemented in vari-
ous 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 ap-
plication, 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 Eco-
nomic 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 de-
fended.
The Institute won one of the ten projects granted in the action 2 of Erasmus+ pro-
gramme. This project “Joint innovative training and teaching/learning program in enhancing
development and transfer of application of ionizing radiation in materials processing” is in-
tended 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 Collabo-
rating 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 nu-
clear energy related EU projects. Its expertise and infrastructure was the basis for partici-
pation 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 acti-
nide;
• UCARD-2 WP4: Applications of accelerators: The industrial and environemntal ap-
plications 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 publica-
tions 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, Łu-
kasz 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 scien-
tific meetings.
MANAGEMENT OF THE INSTITUTE 9
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.
• Centre for Radiation Research and Technology • Laboratory of Nuclear Analytical Methods
Zbigniew Zimek, Ph.D. Halina Polkowska-Motrenko, Ph.D., D.Sc.,
professor in INCT
• Centre for Radiochemistry and Nuclear
Chemistry • Stable Isotope Laboratory
Prof. Grażyna Zakrzewska-Kołtuniewicz, Ryszard Wierzchnicki, Ph.D.
Ph.D., D.Sc.
• Pollution Control Technologies Laboratory
• Centre for Radiobiology and Biological Andrzej Pawelec, Ph.D./Yongxia Sun, Ph.D.,
Dosimetry D.Sc., professor in INCT
Prof. Marcin Kruszewski, Ph.D., D.Sc.
• Laboratory for Detection of Irradiated Food
• Laboratory of Nuclear Control Systems Wacław Stachowicz, Ph.D./Grażyna Liśkiewicz
and Methods
• Laboratory for Measurements of Technological
Jacek Palige, Ph.D.
Doses
• Laboratory of Material Research Anna Korzeniowska-Sobczuk, M.Sc.
Wojciech Starosta, Ph.D.
12. Prof. Zbigniew Galus, Ph.D., D.Sc. 26. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc.
University of Warsaw Institute of Nuclear Chemistry and Technology
13. Prof. Henryk Górecki, Ph.D., D.Sc. 27. Andrzej Pawlukojć, Ph.D., D.Sc., professor
in INCT
Wrocław University of Technology
Institute of Nuclear Chemistry and Technology
14. Prof. Leon Gradoń, Ph.D., D.Sc.
28. Dariusz Pogocki, Ph.D., D.Sc., professor
Warsaw University of Technology
in INCT
15. † Jan Grodkowski, Ph.D., D.Sc., professor Institute of Nuclear Chemistry and Technology
in INCT
29. Halina Polkowska-Motrenko, Ph.D., D.Sc.,
Institute of Nuclear Chemistry and Technology
professor in INCT
16. Edward Iller, Ph.D., D.Sc., professor in NCBJ Institute of Nuclear Chemistry and Technology
National Centre for Nuclear Research
30. Grażyna Przybytniak, Ph.D., D.Sc., professor
17. Adrian Jakowiuk, M.Sc. in INCT
Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology
18. Prof. Marcin Kruszewski, Ph.D., D.Sc. 31. Prof. Janusz Rosiak, Ph.D., D.Sc.
(Vice-chairman) Technical University of Łódź
Institute of Nuclear Chemistry and Technology 32. Lech Waliś, Ph.D.
19. Prof. Anna Lankoff, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology
Institute of Nuclear Chemistry and Technology 33. Maria Wojewódzka, Ph.D.
20. Prof. Marek Wojciech Lankosz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology
AGH University of Science and Technology 34. Prof. Grażyna Zakrzewska-Kołtuniewicz, Ph.D.,
21. Prof. Janusz Lipkowski, Ph.D., D.Sc. D.Sc.
Institute of Physical Chemistry, Polish Academy (Vice-chairman)
of Sciences Institute of Nuclear Chemistry and Technology
22. Zygmunt Łuczyński, Ph.D. 35. Zbigniew Zimek, Ph.D.
Institute of Electronic Materials Technology Institute of Nuclear Chemistry and Technology
9. Prof. Zbigniew Florjańczyk, Ph.D., D.Sc. 23. Prof. Jarosław Mizera, Ph.D., D.Sc.
(Chairman) Warsaw University of Technology
Warsaw University of Technology 24. Prof. Jan Namieśnik, Ph.D., D.Sc.
10. Prof. Zbigniew Galus, Ph.D., D.Sc. Gdańsk University of Technology
University of Warsaw 25. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc.
11. Prof. Janusz Gołaszewski, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology
University of Warmia and Mazury 26. Andrzej Pawlukojć, Ph.D., D.Sc., professor
12. Prof. Henryk Górecki, Ph.D., D.Sc. in INCT
Wrocław University of Technology Institute of Nuclear Chemistry and Technology
13. Edward Iller, Ph.D., D.Sc., professor in NCBJ 27. Halina Polkowska-Motrenko, Ph.D., D.Sc.,
professor in INCT
National Centre for Nuclear Research
(Vice-chairman)
14. Michał Jamróz, Ph.D., D.Sc., professor in INCT Institute of Nuclear Chemistry and Technology
Institute of Nuclear Chemistry and Technology
28. Marek Pruszyński, Ph.D.
15. Prof. Marek Janiak, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology
Military Institute of Hygiene and Epidemiology
29. Grażyna Przybytniak, Ph.D., D.Sc., professor
16. Rafał Kocia, Ph.D. in INCT
Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology
17. Prof. Marcin Kruszewski, Ph.D., D.Sc. 30. Prof. Janusz Rosiak, Ph.D., D.Sc.
(Vice-chairman) Technical University of Łódź
Institute of Nuclear Chemistry and Technology
31. Yongxia Sun, Ph.D., D.Sc., professor in INCT
18. Krzysztof Kulisa, Eng. Institute of Nuclear Chemistry and Technology
Institute of Nuclear Chemistry and Technology
32. Prof. Marek Trojanowicz, Ph.D., D.Sc.
19. Prof. Anna Lankoff, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology
Institute of Nuclear Chemistry and Technology
33. Lech Waliś, Ph.D.
20. Prof. Marek Wojciech Lankosz, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology
AGH University of Science and Technology
34. Maria Wojewódzka, Ph.D.
21. Prof. Jacek Michalik, Ph.D., D.Sc. Institute of Nuclear Chemistry and Technology
Institute of Nuclear Chemistry and Technology
35. Prof. Grażyna Zakrzewska-Kołtuniewicz, Ph.D.,
22. Wojciech Migdał, Ph.D., D.Sc., professor D.Sc.
in INCT (Vice-chairman)
Institute of Nuclear Chemistry and Technology Institute of Nuclear Chemistry and Technology
ORGANIZATION SCHEME
Scientific
DIRECTOR
Council
Deputy Director
for Research and Development
Laboratory of Nuclear
Analytical Methods
Laboratory of Material
Research
SCIENTIFIC STAFF
PROFESSORS
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 tech-
nology 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 com-
plemented by steady-state radiolysis, stopped-flow absorption spectrofluorimetry and product
analysis using chromatographic methods. Studies on radiation-induced intermediates are dedi-
cated 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 reso-
nance (ENDOR), also focused on research problems in nanophase chemistry and radiation-in-
duced cross-linking of selected and/or modified polymers and copolymers.
This research has a wide range of potential applications, including creating more environ-
mentally friendly and sustainable packaging, improving product safety, and modifying ma-
terial properties. Electron accelerators provide streams of electrons to initiate chemical reac-
tions 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 manufac-
turing processes.
Advanced EB technology offered by the Centre provides a unique platform with the ap-
plication for: sterilization medical devices, pharmaceutical materials, food products shelf-life
extension, polymer advanced materials, air pollution removal technology and others. EB ac-
celerators replace frequently thermal and chemical processes for cleaner, more efficient,
lower-cost manufacturing. EB accelerators sterilize products and packaging, improve the per-
formance of plastics and other materials, and eliminate pollution for industries such as phar-
maceutical, 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 sup-
ported 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 function-
ing. That is the best example of capability and great potential of concentrated equipment,
methods and staff working towards application of innovative radiation technology.
CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 17
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 com-
pounds with n = 0 and n = 1.
18 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY
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.
Fig.4. SEM images of the particles constructed from urea-formaldehyde resin microcapsules containing epoxy resin.
20 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY
shells constructed from hydrophobic-hydrophilic composites. Radiat. Phys. Chem., 76 (8–9), 1308-1311.
hybrid structures, e.g. 2,6-dimethylphenol. DOI: 10.1016/j.radphyschem.2007.02.021.
The work reported was co-funded by the In- [4]. Coqueret, X., Krzeminski, M., Ponsaud, P., & De-
foort, B. (2009). Recent advances in electron-beam
ternational Atomic Energy Agency (CRP F22051,
curing of carbon fiber-reinforced composites. Radiat.
Research Contract no. 16666) and the Polish Min- Phys. Chem., 78 (7-8), 557-561. DOI: 10.1016/j.rad-
istry of Science and Higher Education (Contract physchem.2009.03.042.
no. 3141/IAEA/2014). [5]. Pitarresi, G., Alessi S., Tumino D., Nowicki, A., & Spa-
daro, G. (2014). Interlaminar fracture toughness be-
References havior of electron-beam cured carbon-fiber reinforced
[1]. Degrand, H., Cazaux, F., Coqueret, X,, Defoort, B., epoxy-resin composites. Polym. Composites, 35 (8),
Boursereau, F., & Larnac, G. (2003). Thermal effects 1529-1542. DOI: 10.1002/pc.22806.
on the network structure of diglycidylether of bisphe- [6]. Singh, A., Saunders, C.B., Barnard, J.W., Lopata, V.J.,
nol-A polymerized by electron-beam in the presence Kremers, W., McDougall, T.E., Chung, M., & Tateishi, M.
of an iodonium salt. Radiat. Phys. Chem., 68 (5), (1996). Electron processing of fibre-reinforced advanced
885-891. DOI: 1016/S0969-806X(03)00208-1. composites. Radiat. Phys. Chem., 48 (2), 153-170. DOI:
[2]. Alessi, S., Parlato, A., Dispenza, C., De Maria, M., & 10.1016/0969-806X(95)00424-V.
Spadaro, G. (2007). The influence of the processing [7]. White, S.R., Sottos, N.R., Geubelle, P.H., Moore, J.S.,
temperature on gamma curing of epoxy resins for the Kessler, M.R., Sriram, S.R., Brown, E.N., & Viswana-
production of advanced composites. Radiat. Phys. than, S., (2001). Autonomic healing of polymer com-
Chem., 76 (8-9), 1347-1350. DOI: 10.1016/j.radphy- posites. Nature, 409 (15 Feb), 794-797. DOI: 10.1038/
schem.2007.02.029. 35057232.
[3]. Alessi, S., Dispenza, C., Fuochi, P.G., Corda, U., Lav- [8]. Yuan, l., Gu, A., Nutt, S., Wu, J., Lin, Ch., Chen, F., &
alle, M., & Spadaro, G. (2007). E-beam curing of epoxy- Liang G. (2013). Polym. Adv. Technol., 24, 81-89. DOI:
-based blends in order to produce high-performance 10.1002/pat.3053.
Irradiation was carried out with Co-60 gamma films have revealed the highest tensile strength
rays in nitrogen at ambient temperature in the accompanied by a relatively high flexibility (Figs.1
Gamma Chamber GC 5000 applying a dose rate of and 2) and the highest wetting angle as compared
5.00 kGy/h. Irradiation of the films were carried to the other ones (Fig.3); although the films con-
out using doses of 25 kGy and 10 kGy. taining PVA3 were also characterized by the high
Mechanical tests were carried out using Ins- contact angle.
tröm testing machine [2]. The wetting (contact) 0 kGy 25 kGy
angle measurements (enabling to evaluate the hy-
100
drophilic/hydrophobic properties) were done us-
ing the instrument constructed in the Department
of Nuclear Methods of Materials Engineering, 80
18 0 kGy 25 kGy
20
16
Tensile strength [MPa]
14
0
12
PVA1 PVA2 PVA3 PVA4
10 Fig.3. Wetting angle of the starch:PVA (40:60) films con-
8 taining SC3 and various PVAs, non-irradiated and irradi-
ated with gamma rays applying a dose of 25 kGy.
6
4 No particular effect of irradiation with the ab-
sorbed dose of 25 kGy on tensile strength of the
2
films containing PVA1 was noticed, while decrease
0 in this parameter was observed in the cases of all
PVA1 PVA2 PVA3 PVA4 other films. Decreases in flexibility and in wetting
Fig.1. Tensile strength of the starch:PVA (40:60) films angle were detected after the irradiation in cases
containing SC3 and various PVAs, non-irradiated and ir- of all the compositions. However, only a slight de-
radiated with gamma rays applying a dose of 25 kGy. crease in wetting angle was noticed in the case of
the films based on PVA1, and these films have still
In the first step, studies of the effect of appli- revealed the best mechanical parameters (tensile
cation of the various PVAs on the properties of strength and elongation at break) and the higher
starch-PVA films, i.e. non-irradiated and irradi- contact angle. Moreover, these films revealed the
ated were carried out. Pre-irradiated cornstarch lowest swelling parameter, and this parameter has
SC3 (absorbed dose of 10 kGy) was selected as a decreased additionally after the radiation treat-
starch component. ment, contrary to all the other compositions (no
The results (Figs.1-4) have shown that appli- effect in the case of PVA2 and increase in swelling
cation of PVA1 (characterized by the highest mo- in the cases of PVA3 and PVA4), (Fig.4). Further-
lecular mass) enables to obtain the films with the more, it was found that the films containing PVA
best properties as compared to the application of with the low molecular mass contain more low
other PVAs. This was observed directly after syn- 450
0 kGy 25 kGy
thesis as well as after subsequent irradiation. These
400
200 0 kGy 25 kGy
180 350
Elongation at break [%]
160 300
swelling [%]
140 250
120
200
100
150
80
60 100
40 50
20 0
0 PVA1 PVA2 PVA3 PVA4
PVA1 PVA2 PVA3 PVA4 Fig.4. Swelling in water related to the dry mass of the
Fig.2. Elongation at break of the starch:PVA (40:60) films starch:PVA (40:60) films containing SC3 and various PVAs,
containing SC3 and various PVAs, non-irradiated and ir- non-irradiated and irradiated with gamma rays applying a
radiated with gamma rays applying a dose of 25 kGy. dose of 25 kGy.
22 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY
molecular fractions (probably moisture) already the native SC4 starch were characterized by rather
before swelling in water. In addition, phase separa- moderate properties, and their swelling capability
tion was observed in the starch-PVA films formed was very high. The next in sequence after the films
using PVA4 component. Therefore, it can be con- containing SC4 (10 kGy) were the films contain-
cluded that PVA1 constitutes the best substrate ing the pre-irradiated cornstarch SC3. The films
for the films’ preparation. 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.
Accordingly, PVA1 was used as the PVA com- characterized by worst properties as compared to
ponent in the next step of the studies dealing the films containing all the cornstarches. In par-
with the effect of application of various prepara- ticular, a strong swelling was observed in the case
tions of starch on the properties of the starch-PVA of these starches (similar to the case of the native
films, non-irradiated and irradiated. The results cornstarch SC4); due to the low stability in water,
are shown in Table 1 and in Figs.5 and 6. the swelling parameter was not determined for the
The films obtained using the starch subjected majority of these films, especially the irradiated
to pre-irradiation (10 kGy) were characterized by ones. Only in some cases, gamma irradiation with
the best properties. These films revealed the high- a dose of 25 kGy induces a very slight deteriora-
est mechanical resistance (Table 1), the highest tion of the mechanical properties of the films,
wetting angle (Fig.5) and not very high swelling while irradiation with a dose of 10 kGy has no
parameter. Simultaneously, the films containing impact on these properties. A small decrease in
wetting angle was noticed in the majority of the
100
0 kGy 10 kGy 25 kGy
90 600
0 kGy 10 kGy 25 kGy
80
500
70
Wetting angle [°]
60 400
Swelling [%]
50
300
40
30 200
20
100
10
0 0
SC2 SC3 SC4 S7 S8 SC4 SC2 (10kGy) SC3 (10kGy) SC4 (10kGy) S7 (10kGy) S8 (10kGy)
(10kGy) (10kGy) (10kGy) (10kGy) (10kGy) (0kGy)
Fig.6. Swelling in water related to the dry mass of the
Fig.5. Wetting angle of the starch:PVA (40:60) samples sample of the starch:PVA (40:60) samples containing SC3
containing SC3 and various PVAs, non-irradiated and irra- and various PVAs, non-irradiated and irradiated with gam-
diated with gamma rays applying doses of 25 kGy or 10 kGy. ma rays applying a dose of 25 kGy.
CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 23
cases (Fig.5), but simultaneously, a decrease in the [2]. Cieśla, K., Nowicki, A, & Buczkowski, M. (2010) Pre-
swelling parameters can be concluded in the cases liminary studies of the influence of starch irradiation
of all the pre-irradiated cornstarches – SC2, SC3 on physicochemical properties of films prepared using
starch and starch-surfactant systems. Nukleonika, 55,
and SC4 (Fig.6).
2, 233-242.
Accordingly, it can be concluded that the use [3]. Tang, X., & Alavi, S. (2011). Recent advances in starch,
of PVA1 (characterized by the highest molecular polyvinyl alcohol based polymer blends, nanocompos-
mass) and pre-irradiated high amylose cornstarch ites and biodegradability. Carbohydr. Polym., 85, 1-16.
enables to prepare the starch:PVA (40:60) films [4]. Cieśla, K., Watzeels, N., & Rahier, H. (2014). Effect of
characterized by the best properties, as well before gamma irradiation on thermophysical properties of
as after irradiation. However, the standard pre-ir- plasticized starch and starch surfactant films. Radiat.
radiated cornstarch SC3 can also be considered Phys. Chem., 99, 18-22.
as the promising substrate, particularly when the [5]. Cieśla, K., & Sartowska, B. (2016). Modification of
high cost of the SC4 starch is taken into account. the microstructure of the films formed by gamma irra-
The obtained results also suggest that the films diated starch examined by SEM. Radiat. Phys. Chem.,
118, 87-95.
obtained in the starch-PVA system can be applied
[6]. Abramowska, A., Cieśla, K.A., Buczkowski, M.J., No-
for the products predicted for radiation deconta- wicki, A., & Głuszewski, W.J. (2015). The influence of
mination. ionizing radiation on the properties of starch-PVA films.
The work was sponsored in the frame of IAEA Nukleonika, 60, 3, 669-677. doi: 10.1515/nuka-2015-
Research Contract No. 17493 (CRP F2206). -0088.
[7]. Ryzhkova, N., Jarzak, U., Schäffer, A., Bämer, M., &
References Swiderek, P. (2011). Modification of surface properties
[1]. Cieśla, K. (2009). Przekształcenia struktury nadcząs- of thin polysaccharide films by low energy electron ex-
teczkowej w polimerach naturalnych inicjowane pro- posure. Carbohydr. Polym., 83, 608.
mieniowaniem jonizującym. Warszawa: Instytut Che-
mii i Techniki Jądrowej, 223 p.
The issue of the use of ionizing radiation for the tors dealing with objects made of paper. The issue
preservation of objects of significant cultural heri- of radiation resistance of cellulose is also impor-
tage is still valid despite extensive scientific litera- tant from the point of view of packaging materials
ture on the subject [1]. A unique feature is the and preventive sterilization of postal items that
possibility of disinfestations and disinfections of could potentially be a source of bacteriological
a very large number of objects in a short (express) terrorist attack [4, 5].
time by radiation techniques [2]. For this purpose, If the protective phenomena in radiation chem-
both the electron beam (EB) and gamma radiation istry of polymers generally are defined as processes
are used worldwide [3]. In particular, radiation to restrain their degradation (deterioration of me-
techniques are an interesting offer for conserva- chanical 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 tem-
perature.
several possible ways to achieve this goal. The pro- porated in that case in the thermal degradation
tective effect may be the result of electron transfer process, and that phenomenon is also outside the
or the transfer of positive holes to the scavengers. scope of the paper.
This is the basic mechanism that prevents chemi- On the contrary, in the radiolytic decomposi-
cal changes in the polymer. We can also explain tion at room temperatures and even under cryo-
the protective effect of energy transfer from the genic conditions, hydrogen is the main constitu-
excited molecule to the aromatic additives. The ent of the gas phase above any hydrogen-bearing
concept of such a transfer mechanism is very in- products. For instance, in the case of all polymers,
teresting and could be explained by the ability of hydrogen dominates over the concentration of low
aromatic ring to dissipate energy. Protective addi- molecular weight debris of the degraded polymers.
tives may also react with free radicals, thereby In the specific case of radiolysis cellulose/lignin
competing with the processes of crosslinking and sulphonate mixture, the latter constituent had pro-
oxidation. It should be noted, however, that the tective effect due to the high contribution of aro-
network structure of a polymer material is often matic rings (Fig.1). It is confirmed both by the vol-
advantageous from the standpoint of mechanical ume of hydrogen emitted and oxidation consump-
properties. tion capacity. Quantitatively, the data also reveal
The study pointed out the protective effect of the influence of dose rate on radiolysis and postra-
lignin in the cellulose radiolysis. We have studied diation oxidation. The use of electron beam (15 000
the protective effects by gas chromatography (GC). kGy/h) instead of gamma rays (5 kGy/h) greatly
The prepared samples contained various percent- reduces oxidation of the cellulose (Fig.2).
age of lignin sulphonate (produced during the
processing of wood pulp) in the cellulose. Sulpho-
nate cellulose was dissolved in water and soaked
in the paper. The paper web was dried. Lignin con-
tent was determined by weight. They were used as
the cellulose Whatman paper. An aromatic com-
pound was lignin sulphonate (produced by Borre-
gaard, 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.
The experience gained during over ten years’ op- • VCO tuned with the analog signal from phase
eration of the LAE 10 accelerator shows a limited comparator;
reliability of microwave klystron driving genera- • dual-modulus prescaler. It takes the clock from
tors. The output power needed from the unit does the VCO and divides it down to a manageable
not exceed 20 mW. The problems concern usually frequency for the CMOS A and B counters. The
malfunction of generators’ output amplifier stage, prescaler is programmable. It can be set in soft-
it was observed highly elevated chassis tempera- ware to 8/9, 16/17, or 32/33 and is based on a
ture after several hours of operation. Probably that synchronous 4/5 core, along with the A and B
was the reason for last failure: damage of the non- counters, enabling the division ratio, N, to be
-volatile EEPROM containing generator’s output realized (N = BP + A);
stage calibration data. In addition, the services re- • A and B counters, in conjunction with the dual-
fused to fix the device which was too obsolete. -modulus prescaler, make it possible to generate
This situation led us to design a low cost, easy output frequencies that are spaced only by the
serviceable, dedicated RF generator equipped with reference frequency divided by R. The VCO fre-
external amplification/matching module. The basis quency equation is as follows:
for the construction was GaP monolithic integer-N fVCO = [(P B) + A] fREFIN/R
synthesizer and voltage controlled oscillator (VCO) where: fVCO – the output frequency of the VCO,
in one Analog Devices ADF4360 chip [1]. P – the preset modulus of the dual-modulus
A typical frequency range for LAE 10 accel- prescaler (8/9, 16/17, or 32/33), B – the preset
erator is 1.8174 GHz which should be tuned with divide ratio of the binary 13-bit counter (from 3
100 kHz step ±0.3 MHz span. The selected inte- to 8191), A – the preset divide ratio of the binary
grated synthesizer of ADF4360-x series is designed 5-bit swallow counter (from 0 to 31), fREFIN – the
for a centre frequency of 1750 MHz (version 3 de- external reference frequency oscillator.
noted in its symbol). The practical values of the counters selected for
As shown in Fig.1, the internal circuitry deter- the assumed performance are as follows: A = 30,
mining the output frequency consists of: B = 567, P = 32. They give n = 18 174 which
Alphanumerical LCD
Display
RF Power
Amplifier
Port A RF OUT
ATTINY 2313
Port B
Pre-Amp.
Fig.5. Plot from RF spectrum analyser.
ADF4360
PLL Synth. As shown in Fig.5, the generator is tested with
Board the RF spectrum analyser for the linearity of fre-
Control Panel quency sweep step, and the plot from its screen
displays the spectra of the output signal during
Fig.3. LAE 10 accelerator driving RF generator block dia- the routine tuning of accelerator. The peaks are
gram. sharp with well-defined frequency step, at least
30 dB distant from noise level, and there is no
As shown in Fig.2, a typical hardware configu- trace of spurs (frequency modulation VCO para-
ration recommended by the manufacturer as local sitic spectrum components).
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 pro-
jects 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 Commis-
sion (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 car-
bides. 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 Sep-
aration 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-den-
tate hydrophilic ligands – SO3-Ph-BTP and SO3-Ph-BTBP, especially the determination of
stability constants of these complexes in acidic aqueous solutions. Advanced quantum chemi-
cal 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 radioac-
tive wastes formed in the course of exploitation of nuclear power plants, with a special em-
phasis 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 radio-
nuclides 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 ultra-
filtration 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 dur-
ing 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 mem-
brane 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 nu-
clear 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 applica-
tions 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 macroeco-
nomical 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 eval-
uate the safety and identify the optimal location of shallow repository for low- and interme-
diate-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 ob-
tained 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 coopera-
tion 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 build-
ing 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 con-
tinued 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 pro-
cesses, a challenge for nuclear scientists” and the seminar on the possibility of implementa-
tion 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.
CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 29
Recycling of actinides from spent nuclear fuel by been developed which exhibit a very high selec-
their selective separation followed by transmuta- tivity for trivalent actinides (An) over lanthanides:
tion in fast reactors will optimize the use of natu- bis-triazinyl derivatives of pyridine (BTP), of bi-py-
ral uranium resources and minimize the long-term ridine (BTBP) and of 1,10-phenantroline (BTPhen)
hazard from high-level nuclear waste. This ap- [4] (Fig.1).
A
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 Apart from the AnIII/LnIII separation with the
cycle, should drastically reduce the potential long- use of the above lipophilic extractants (e.g. in the
-term threat to humans and the environment from regular SANEX process [3, 4]), another option
the radiotoxic nuclear waste. The new technologies has been proposed – to selectively strip the AnIII
will make the nuclear energy sustainable, enabling ions from the loaded organic phase to nitric acid
its broader development worldwide. This will re- solutions using hydrophilic AnIII-selective ligands
duce the global CO2 emissions, in line with the [4]. Such a ligand, 2,6-bis(5,6-di(sulphophenyl)-
agreement on the last UN Climate Change Con- 1,2,4-triazin-3-yl)pyridine (SO3-Ph-BTP, Fig.2),
ference (Paris, December 2015). Developing of an was synthesized and studied as an actinide-selec-
energy mix with a significant contribution from tive stripping agent by Geist and coworkers [5].
the zero-emission nuclear energy is the only real Later on, the usefulness of this anionic ligand for
option for our country (Polish Nuclear Power Pro- the separation of americium(III) from lanthanides
gramme, 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 re-
processing spent nuclear fuel. Basing on the strat-
egy of Partitioning and Transmutation, the acti-
nides separated (“partitioned”) from the spent fuel
will be transmuted into much shorter-lived and
stable nuclides by high energy (fast) neutrons, Fig.2. Structural formula of the SO3-Ph-BTP4– anion.
e.g. in fast nuclear reactors of Generation IV [2].
Various options, hydro- and pyrometalurgical, are (in the innovative-SANEX process [3, 4]) was
being developed and tested for the actinide parti- demonstrated in a laboratory-scale test carried out
tioning [3]. The most promising hydrometalurgi- in a multistage counter-current system [6]. Also
cal (solvent extraction) technologies utilize com- other sulphonated bis-1,2,4-triazine ligands, hydro-
pletely incinerable poly-N-dentate polyheterocyclic philic derivatives of BTBP and BTPhen appeared
‘CHON’ ligands which eagerly extract trivalent effective complexing reagents for separating acti-
f-electron metal ions from aqueous HNO3 solu- nides(III) from lanthanides(III) via selective for-
tions. Because the separation of americium from mation of aqueous actinide complexes [7, 8].
lanthanide fission products is an indispensable The knowledge of complexing properties of the
condition for the actinide transmutation [2, 4], novel ligands towards actinides allows us to pre-
novel lipophilic bis-[1,2,4]-triazinyl ligands have dict their usefulness for solvent extraction sep-
30 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY
arations. The studies on the extraction system for the Am3+ complexation by NO3– anions in the
N,N,N’,N’-tetraoctyl-diglycolamide (TODGA)/ aqueous phase:
SO3-Ph-BTP4– + HNO3 made possible to con- k
D0 W
j
clude that only two Am3+–SO3-Ph-BTP4– com-
plexes (1:1 and 1:2) co-existed in the aqueous L,i [L4 i
] D
1 NO3, j [NO3 ] (3)
1
j1 j1
phase [5]. Though no stability constants of these
complexes have been reported, such data are avail- The [L4–] values were calculated as the func-
able for the analogous complexes of Cm3+ (chemi- tions of the total concentrations of L, CL,tot, and
cal properties of which are very similar to those of HNO3, [H+], assuming the protonation constant
Am3+), determined using time-resolved laser fluo- of L4–, KH,1, to be an adjustable value which en-
rescence spectroscopy (TRLFS). Moreover, not sured the best fit of the calculated (3) to the
two but three (also 1:3) Cm3+–SO3-Ph-BTP4– corresponding experimental (D0/D – 1) values in
complexes have been found in a separate dilute the whole range of the CL,tot and [H+] variables
aqueous solution of pH 3 [9]. [10]. This “best fit” value, log KH,1 = 0.5 was equal
To conclude on the complex formation of to the literature value determined from UV-Vis
Am3+ ions with the SO3-Ph-BTP4– (L4–) ligand in spectra [10].
the aqueous phase and to determine the stability In each region of L4– concentration where a
constants of the complexes, we studied the de- complex of a given stoichiometry predominates,
pendence of two-phase distribution of Am3+ on Eq. (3) can be simplified and expressed in the
the concentration of the free ligand, [L4–]. The logarithmic form:
system consisted of 0.1 M TODGA in 5 vol%
D r
octanol-kerosene (the organic phase) and the log 0 1 log 1 NO3, j [NO3 ] j
SO3-Ph-BTP ligand (0.03 mM to 5 mM in total) D j1 (4)
in HNO3/NaNO3 solutions of various acidities 4
(0.02 M to 1 M) at a constant 1 M nitrate concen- i log [L ] log L,i
tration. The concentrations of Am in both phases Two such regions have been found in the ex-
at equilibrium at 25oC were measured radiometri- periment, corresponding to the two Am3+–L4– com-
cally (241Am tracer) [10]. plexes, 1:1 and 1:2 (Fig.3). Their stability con-
We based in this study on a simple model of stants, have been calculated by extrapolation of
Mn+ extraction in the system consisting of two the straight lines to the value log [L4–] = 0, and
competing ligands: lipophilic (TODGA) and hy- correcting the result on the complexation of Am3+
drophilic (L) in both liquid phases. It assumed by nitrates [10]. This way, the disagreement of
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:
S
[Am(TODGA) (NO ) ]
j1
j 3 3 org
D W k
(1)
[Am3 ] [Am(NO3 )3j j ] [AmL3i 4i ]
j1 i 1
[Am(TODGA) (NO ) ]
j1
j 3 3 org
D0 W
(2)
[Am3 ] [Am(NO3 )3j j
j1
ted as a function of log [L4–], which also accounts lines with the slopes of 1.00 and 2.00 are shown.
CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 31
the results obtained using the two-phase distribu- for uranyl and thorium under the experimental
tion and monophasic spectroscopy methods has conditions. The stability constants of these 1:1
been confirmed. In particular, no evidence has complexes have been arranged in the following
been found for the existence of the 1:3 complex in order: U(VI) Th(IV) < Am(III) < Pu(IV).
the aqueous phase of the two-phase system, in This report is based on the research carried
spite of much higher free SO3-Ph-BTP4– concen- out in parts within (i) the statutory research of
tration than that in the monophasic system where the Institute of Nuclear Chemistry and Technol-
the 1:3 Cm3+ complex had been detected (Table 1). ogy (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).
To explain this unexpected result, we have for- ject 31/CA/2014 “Coordination of actinides with
mulated a hypothesis that heteroleptic complexes hydrophilic ligands” – the bilateral agreement
can be formed in the two-phase system studied, between the INCT and the French Alternative
lipophilic and extractable from the acidic aqueous Energies and Atomic Energy Commission (CEA,
phase, e.g. [Am(TODGA)2(SO3-Ph-BTP)]– extract- Marcoule, France); and (iii) the TALISMAN, Col-
able as an ion pair with the TODGA·H+ cation laborative Project Grant co-funded by the Euro-
[10]. The search of such hypothetical species has pean Commission, JRP no. TALI-C06-15 “TRLFS
already been started by TRLFS in cooperation with search of heteroleptic Cm(III)/Eu(III) complexes
Dr. Geist’s team [12]. Preliminary results obtained with TODGA and SO3-Ph-BTP ligands in solvent
in a monophasic system, using a hydrophilic homo- extraction systems” studied in the Karlsruhe In-
logue of TODGA: N,N,N’,N’-te-traethyl-diglycol- stitute of Technology-Institute for Nuclear Waste
amide (TEDGA), allow to detect two unknown Disposal (KIT-INE, Karlsruhe, Germany).
heteroleptic complexes Cm(III)/TEDGA/SO3-Ph- The cooperation with our colleagues: Marie-
-BTP (1:1:1 and 1:2:1) in dilute slightly acidic -Christine Charbonnel and Philippe Moisy (CEA,
aqueous solutions. Unfortunately, no such com- Marcoule), as well as Christoph Wagner, Andreas
plexes have been found so far in the organic phase Geist and Petra J. Panak (KIT-INE) is kindly ac-
of the two-phase solvent extraction system con- knowledged.
taining TODGA [12]. The research is going on. It
is worth mentioning that also other authors pos- References
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ed solvates Ln(NO3)3-(TEDGA)n-DMDOHEMA of spent nuclear fuel. Separation of minor actinides
(where n = 1 or 2, and DMDOHEMA is a lipo- by solvent extraction. Annales UMCS, Ser. AA (Chem-
philic malonamide), as a reasonable interpreta- istry), in press.
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waste partitioning and transmutation within advanced
TEDGA with the lightest lanthanides in similar
fuel cycles: Achievements and challenges. Prog. Part.
systems [13, 14]. Nucl. Phys., 66, 144-166.
If the above hypothesis proves to be true one [3]. Bourg, S., Geist, A., & Narbutt, J. (2015). SACSESS
will need to take the following actions: (i) elabo- – the EURATOM FP7 project on actinide separation
rate the expanded model of solvent extraction of from spent nuclear fuels. Nukleonika, 60, 809-814.
metal ions in systems containing two competing [4]. Panak, P.J., & Geist, A. (2013). Complexation and
ligands, lipophilic and hydrophilic; (ii) validate the extraction of trivalent actinides and lanthanides by
values of stability constants of numerous metal triazinylpyridine N-donor ligands. Chem. Rev., 113,
complexes determined by this method and in- 1199-1236.
[5]. Geist, A., Müllich, U., Magnusson, D., Kaden, P.,
cluded in the tables and text books; and (iii) de-
Modolo, G., Wilden, A., & Zevaco, T. (2012). Acti-
sign new hydrophilic ligands which do not form nide(III)/lanthanide(III) separation via selective
heteroleptic actinide complexes with TODGA. The aqueous complexation of actinide(III) using a hy-
latter task can be of significant practical impor- drophilic 2,6-bis(1,2,4-triazin-3-yl)pyridine in nitric
tance because it can greatly increase the effec- acid. Solvent Extr. Ion Exch., 30, 433-444.
tiveness of stripping certain metal ions from load- [6]. Wilden, A., Modolo, G., Kaufholz, P., Sadowski, F.,
ed organic phases by the hydrophilic complexing Lange, S., Sypula, M., Magnusson, D., Müllich, U.,
agents. Geist, A., & Bosbach, D. (2015). Laboratory-scale
Using the same two-phase distribution method counter-current centrifugal contactor demonstration
we also studied complexation of some other acti- of an innovative-SANEX process using a water sol-
uble BTP. Solvent Extr. Ion Exch., 33, 91-108.
nides: U(VI) [15], Th and Pu(IV); by the SO3- [7]. Lewis, F.W., Harwood, L.M., Hudson, M.J., Geist,
-Ph-BTP4– ligand. The same two-phase extraction A., Kozhevnikov, V.N., Distler, P., & John, J. (2015).
system was applied (at some different TODGA Hydrophilic sulfonated bis-1,2,4-triazine ligands are
concentrations). Both 1:1 and 1:2 complexes of highly effective reagents for separating actinides(III)
all the metals studied were detected in the acidic from lanthanides(III) via selective formation of aque-
aqueous phases, with the 1:1 species dominating ous actinide complexes. Chem. Sci., 6, 4812-4821.
32 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY
[8]. Kaufholz, P., Sadowski, F., Wilden, A., Modolo, G., at Gothenburg Sweden (pp. 1-10). Amsterdam:
Lewis, F.W., Smith, A.W., & Harwood L.M. (2015). North-Holland Publ.
TS-BTPhen as a promising hydrophilic complexing [12]. Herdzik-Koniecko, I., Wagner C., Geist, A., Panak,
agent for selective Am(III) separation by solvent ex- P.J., & Narbutt J. (2016). On the formation of hetero-
traction. Nukleonika, 60, 815-820. leptic complexes in an innovative-SANEX system.
[9]. Ruff, C.M., Müllich, U., Geist, A., & Panak, P.J. In Sustainable Nuclear Energy Conference (SNEC),
(2012). Complexation of Cm(III) and Eu(III) with Nottingham, UK, 12-14 April 2016 (submitted).
hydrophilic 2,6-bis(1,2,4-triazin-3-yl)-pyridine studied [13]. Chapron, S., Marie, C., Arrachart, G., Miguirditchian,
by time-resolved laser fluorescence spectroscopy. M. & Pellet-Rostaing, S. (2015). New insight into
Dalton Trans., 41, 14594-14602. the americium/curium separation by solvent extrac-
[10]. Steczek, Ł., Rejnis, M., Narbutt, J., Charbonnel, tion using diglycolamides. Solvent Extr. Ion Exch.,
M.-C., & Moisy, P. (2016). On the stoichiometry and 33, 236-248.
stability of americium(III) complexes with a hydro- [14]. Pacary, V., Burdet F., & Duchesne, M.-T. (2012). Ex-
philic SO3-Ph-BTP ligand, studied by liquid-liquid perimental and modeling extraction of lanthanides
extraction. J. Radioanal. Nucl. Chem. DOI 10.1007/ in system HNO3-TEDGA-{DMDOHEMA-HDEHP}.
s10967-015-4663-7. Procedia Chem., 7, 328-333.
[11]. Stary, J. (1967). The use of solvent extraction of [15]. Steczek, L., Narbutt, J., Charbonnel, M.-Ch., & Moisy,
metal chelates for the investigation of complexation Ph. (2015). Determination of formation constants of
in aqueous solutions. In D. Dyrssen, J.-O. Liljenzin uranyl(VI) complexes with a hydrophilic SO3-Ph-BTP
& J. Rydberg (Eds.), Solvent Extraction Chemistry ligand, using liquid-liquid extraction. Nukleonika,
– Proceedings of the International Conference held 60, 809-813.
Radioactive wastes produced either from the civil Am3+ than the other metals ions [6]. However, the
or the military nuclear industry, as well as from nu- separation of the metal-loaded sorbent from the
clear medicine, still create many problems. They purified solution is often a problem to overcome.
are dangerous both to human life and to the natu- So the use of magnetic sorbents (in the following
ral environment. The majority of low- and me- called magsorbents, MS) to solve this technical
dium-level wastes contain different - and -emit- problem has received significant attention in re-
ters and a very small amount of actinides with cent years (e.g. [6-12]). These magnetic materials
specific activity below 107 kBq/m3. These wastes may be tailored to fix specific pollutants in waste-
require pretreatment both to fulfil the norms for water.
releasing them into the water flows and to mini- As a result, MS may become one of the prom-
mize the volume of radioactive materials to be ising methods for the removal of pollutants. This
stored in the disposal sites. According to the rec- process does not generate secondary waste and
ommendations for the drinking water published consequently produces no additional pollution.
by the European Union, radioactivity concentra- Moreover, this approach is particularly adapted
tions obtained from different radionuclides pre- when the conditions of separation are complex,
sent in water intended for human consumption e.g. when polluted water contains solid additives.
may range from 0.5 Bq/L to 11 Bq/L, with the Usually, purification of the aqueous metal so-
exception of this originating from carbon-14 (240 lutions by means of sorption is realized in the
Bq/L) [1]. two-stage batch process. First, sodium alginate is
Until now, adsorption technology has been con- added to water and particles of the magnetic ma-
sidered as one of the most effective methods for terial are suspended. Then, the above suspension
the removal of metal ions from water because it is is added drop-wise into the sodium-alginate solu-
convenient and easy to design and to operate. The tion for cross-linking and preparing the MS beads.
adsorption processes with various adsorbents, Finally, sorption is generally performed by batch
among other these of the biological and waste process or in the adsorption columns.
materials origin, have been recently extensively A detailed literature inspection on the purifi-
studied (e.g. [2-4]). It could be used most effec- cation of the wastewater containing heavy metals
tively in the metal concentration range below 100 has shown that when the polyvalent metal ions
mg/L, where other techniques are ineffective or exist at relatively high concentrations in the aque-
costly [5]. Thus, the development of novel, effec- ous media (i.e. above 100 ppm), sodium-alginate
tive and low-cost adsorbents and the adsorption solution may be directly dispensed into the solu-
procedures are welcome. tion circulating in a loop to produce the alginate
Among the most common biosorbents current- gels in situ that contain these metals [13]. Despite
ly used for industrial metal-bearing effluents are the fact that the method seems to be perspective,
alginates, biopolymers of alginic acid extracted a series of studies performed in the group headed
from different types of algae or from two forms of by L.K. Jang has not been undertaken. The objec-
bacteria, Pseudomonas and Azotobacter. It was tive of the present study was to investigate a novel
found that calcium alginate exhibits relatively variant of the procedure proposed by Jang with
higher uptake rate and distribution coefficient of application of the calcium alginate beads as MS
CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 33
for the treatment of the radioactive liquid wastes, Initial and equilibrium radioactivity concentra-
i.e. containing radioactive metals in the trace tions [Bq/L] (quotient of the activity of a material
amounts. and the volume of this material) of the radionu-
Till now, the most frequently used compounds clides in the solutions were determined radiomet-
as the magnetic cores were the hematite (iron(III) rically using a Perkin Elmer 2480 Wizard2® Auto-
oxide, Fe2O3) and the magnetite (mixed iron(II)/ matic Gamma Counter.
iron(III) oxide, Fe3O4). In contrast, in the present In the following, results of our studies were
study, carbonyl iron has been used. Carbonyl iron presented in terms of decontamination factor, YM
is a highly pure iron, prepared by chemical de- (ratio of activity prior to and after the deconta-
composition of purified iron pentacarbonyl. It is mination of radioactively contaminated objects,
commonly used in electronics for the production wastewater, air, etc. [16]).
of the magnetic high-frequency coils and as a com- Effect of the calcium chloride concentration
ponent of the radar-absorbing materials. Carbonyl In the present study, prior to the combined ge-
iron is also used in powder metallurgy and in phar- lation-sorption process, calcium chloride has been
maceutics for treating iron deficiency and as an added in the concentrations ranging from 5 g to
iron dietary supplement. If bought in bulk, the 25 g per each litre of the decontaminated solution.
price may be significantly smaller than 5 USD per Obtained values of decontamination factor for
1 kg [14]. caesium(I), strontium(II), europium(III) and ameri-
Synthesis of the alginate beads with simultaneous cium(III) radionuclides are presented in Fig.1.
sorption of the radionuclides It can be seen that for all metals studied, YM
Magnetic calcium alginate (MS) beads were does not depend significantly on the calcium chlo-
prepared by the following procedure [15]: homo- ride concentration. These values are about 100, 72
genous sodium-alginate solution with a concentra- and 29% for americium(III), europium(III) and
tion of 0.02 g/mL was prepared. Different amounts strontium(II), respectively, while the lack of sorp-
of the carbonyl iron were added to the sodium-al- tion for caesium(I).
ginate solution and the suspension was stirred for Effect of the iron concentration
90 min in room temperature. Obtained homoge- Obtained values of decontamination factor for
nous solution, constantly stirred, was dropped us- caesium(I), strontium(II), europium(III) and ame-
ing a peristaltic pump into the aqueous solution ricium(III) radionuclides for different amounts of
of the radionuclides after the addition of calcium iron added are presented in Fig.2. In the present
chloride (CaCl2; different amounts). Stirring of the study, calcium chloride has been added in the
solution containing the synthesized grains of sorb- constant amount of 25 g per each litre of the de-
ent was continued for 2 h. contaminated solution.
Fig.1. Effect of the calcium chloride concentration on the decontamination factors for the radionuclides sorbed by the
magnetic alginate spheres.
34 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY
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.
CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 35
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 tion of the health of the general public with regard
does not depend significantly on the amount of to radioactive substances in water intended for hu-
the iron added and are similar to these mentioned man consumption. Official Journal of the European
Union, L296/12. Retrieved 25 January 2016, from
above. It means that the magnetic characteristic of
http://eur-lex.europa.eu/legal-content/EN/TXT/
the obtained MS, which depends on the amount ?uri=CELEX%3A32013L0051.
of iron present in the inner core, is the main limit [2]. Song, W., Xu, X., Tan, X., Wang, Y., Ling, J.Y., Gao,
of the procedure. B.Y., & Yue, Q.Y. (2015). Column adsorption of per-
Effect of the acidity of the aqueous solution chlorate by amine-crosslinked biopolymer based
The initial acidity of the solution is one of resin and its biological, chemical regeneration prop-
the decisive factors determining the efficiency of erties. Carbohyd. Polym., 115, 432-438.
metal uptake from aqueous solutions. It affects [3]. Kalaivani, S.S., Vidhyadevi, T., Murugesan, A., Thir-
both surface of the sorbent and speciation of the uvengadaravi, K.V., Anuradha, D., Sivanesan, S., &
metal ion in solution which, additionally, depends Ravikumar, L. (2014). The use of new modified
poly(acrylamide) chelating resin with pendent ben-
on the concentration of the metal. To study the
zothiazole groups containing donor atoms in the
acidic dependence of sorption, pH was adjusted removal of heavy metal ions from aqueous solutions.
in the range from about 1.5 to about 7. The re- Water Resour. Ind., 5, 21-35.
sults are presented in Fig.3. It can be seen that [4]. Kabiri, S., Tran, D.H.N., Aitalhi, T., & Losic, D.
uptake of the metals oscillates slightly around the (2014). Outstanding adsorption performance of gra-
plateau being 99.9 ±0.2% for americum(III), 74.0 phene-carbon nanotube aerogels for continuous oil
±1.6% for europium(III), 32.2 ±3.7% for stront- removal. Carbon, 80, 523-533.
ium(II), while caesium(I) is not sorbed within the [5]. Schiewer, S. & Volesky, B. (1995). Modelling of the
whole range of the acidity. proton-metal ion exchange in biosorption. Environ.
Thermogravimetric studies of the sorbent Sci. Technol., 29, 3049-3058.
Performing thermal analyses were important [6]. Banerjee, A., & Nayak, D. (2007). Biosorption of
no-carrier-added radionuclides by calcium alginate
taking into account that in the industrial pro- beads using ‘tracer packet’ technique. Bioresource
cesses, heat is commonly used, and the thermal Technol., 98, 2771-2774.
decomposition of MS may yield a decreased solid [7]. Zhou, Y.-T., Nie H.-L., Branford-White, C., He, Z.-Y.,
radioactive waste mass. It is a textbook knowl- & Zhu, L.-M. (2009). Removal of Cu2+ from aque-
edge that organic matter breaks down into small ous solution by chitosan-coated magnetic nanopar-
molecular components if heated and does not re- ticles modified with alpha-ketoglutaric acid. J. Colloid
combine on cooling. Carbon dioxide, carbon mon- Interface Sci., 330, 29-37.
oxide and steam, with small quantities of acids, [8]. Huang, G., Yang, C., Zhang, K., & Shi, J. (2009). Ad-
aldehydes and volatile solids, are found as main sorptive removal of copper ions from aqueous solu-
thermal decomposition products of the carbohy- tion using cross-linked magnetic chitosan beads.
Chinese J. Chem. Eng., 17, 960-966.
drates [17].
[9]. Tran, H.V., Tran, L.D., & Nguyen, T.N. (2010). Prep-
For this purpose, thermogravimetric studies aration of chitosan/magnetite composite beads and
have been performed in the temperature range of their application for removal of Pb(II) and Ni(II) from
20-950oC. Raw material of the sorbent has been aqueous solution. Mater. Sci. Eng. C, 30, 304-310.
studied. Table 1 presents main results obtained. It [10]. Monier, M., Ayad, D.M., Wei, Y., & Sarhan, A.A.
can be seen that total mass loss of the sorbent is (2010). Preparation and characterization of mag-
about 70%; however, already in temperatures be- netic chelating resin based on chitosan for adsorp-
low 450oC, the sorbent loses about 50% of its mass. tion of Cu(II), Co(II), and Ni(II) ions. React. Funct.
The analysis of the pattern of the metal uptake, Polym., 70, 257-266.
as well as more results, will be published soon. [11]. Wang, J.-S., Peng, R.-T., Yang, J.-H., Liu, Y.-C., & Hu,
X.-J. (2011). Preparation of ethylenediamine-modified
Conclusions
magnetic chitosan complex for adsorption of uranyl
One-step procedure for the decontamination of ions. Carbohyd. Polym., 84, 1169-1175.
the radioactive wastes applying calcium alginate [12]. Hu, X.-J., Wang, J.-S., Liu, Y.-G., Li, X., Zeng, G.-M.,
with the magnetic inner-core from the iron carbonyl Bao, Z.-l., Zeng, X.-X., Chen, A.-W., & Long, F.
was found to be effective for the solutions contain- (2011). Adsorption of chromium (VI) by ethylenedi-
ing americium(III), europium(III) and strontium(II) amine-modified cross-linked magnetic chitosan resin:
radionuclides. The purification efficiency depends Isotherms, kinetics and thermodynamics. J. Hazard.
on the cation charge. Mater., 185, 306-314.
The magnetic sorbent is sufficiently stable to [13]. Jang, L.K., Geesey, G.G., Lopez, S.L., Eastman, S.L.,
have practical application in the treatment of waste- & Wichlacz, P.L. (1990). Use of gel-forming biopoly-
mer directly dispensed into a loop fluidized bed re-
waters, and its mass, when the radionuclide was
actor to recover dissolved copper. Water Res., 24,
loaded, can be diminished by heating below 450oC. 889-897.
[14]. http://www.alibaba.com/showroom/carbonyl-iron-
References powder.html.
[1]. Council Directive 2013/51/EURATOM of 22 Octo- [15]. Ani, I., Nur, S.M.I., Nursia, H., Effaliza, M., & Ngom-
ber 2013 laying down requirements for the protec- sik, A.-F. (2012). Synthesis of magnetic alginate beads
36 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY
The main goal of the Institute of Nuclear Chem- underwent carbothermic reduction in vacuum at
istry and Technology (INCT) which works on the T = 1600oC. It results from the X-ray diffraction
synthesis of uranium carbide (UC) by the com- (XRD) analysis that the main product was uran-
plex sol-gel process (CSGP) was to use ascorbic ium carbide with an additional UO phase. No
acid (ASC) as a carbon substrate for carbide ma- phases with higher contents of carbon and oxy-
terials [1, 2]. In the CSGP method, ascorbic acid gen were detected. In addition, a series of sols in
is a complexing agent and occurs in sol and gels’ which the molar ratio of UO3 to ASC were from
particles. So if the conditions of thermal treat- 1:0.9 to 1:1.9 was produced. For sols with a molar
ment are chosen accordingly, it will be possible to ratio 1.5, ammonia was added to pH 3.75, in
engage ascorbic acid to produce uranium carbide. order to eliminate the gels’ tendency to form a hard
In short, the processes leading from the gel stage crust. The dried microspheres of gels are spheri-
to uranium carbide can be presented as follows: cal with dense surface. Below, there are examples
T, inert atmosphere of the scanning electron microscopy (SEM) pic-
[UO3-ASC]gel UO2-x-C tures of gels with varying scope UO3:ASC (Figs.1
Ar / H 2 T, vacuum or Ar
UO2-C UC and 2).
Microspheres with molar ratio up to 1.3 look simi-
The gel sample (molar ratio UO3:ASC 1:0.82) lar. In Fig.1A,B,D there are visible bright areas on
was thermally treated. First, it was carbonized at the particle surface. The reasons for that are elec-
T = 700oC in Ar/5% H2 to UO2-C and then it tric 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 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 37
A A B
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 micro- Obviously, the appearance and shape of gel par-
spheres is usually smooth. But for a higher con- ticles in a large extent determine the appearance
tent of ascorbic acid (Fig.1D), a significantly no- of particles after the heat treatment.
ticeable deterioration of the particle quality may Powders of gels were reduced in the furnace
be observed. There are numerous cracks and de- (Nabertherm VHT series) to obtain uranium car-
laminations. In the case of gels containing am- bide in one cycle. Figure 3 shows a programme of
monia (Fig.2A), the particle surface is smoothed a thermal process for preparing uranium carbide.
and worsened again, at yet a higher content of as- In the beginning, powders of gels were carbonized
corbic acid (Fig.2B). There are also visible dimples by heating them in argon up to 300oC (1.5oC·min–1)
on the surface, whose image resembles a golf ball and then up to 900oC (3oC·min–1). Afterwards, at-
(Fig.2C). mosphere was shifted to the mixture Ar+5% H2
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 tion of the sample for analysis. Significant amount
mbar). Cooling of the samples took place in a of UO2 was observed for the sample 1:0.82, which
vacuum at a rate 10oC·min–1. Loose, dark-grey indicates an insufficient carbon amount during the
powders were obtained (Fig.4) and then were carbothermic reduction. For samples with a molar
analysed by the SEM and the XRD techniques. ratio higher than 1:1.1, only UC (JCPDS 09-0214)
The SEM analysis reveals some differences in and UC2 (JCPDS 06-0372) were detected. Also,
morphology of particles. It should be noted that the UC2 amounts increased with increasing molar
the microspheres are partially destroyed during ratio of UO3:ASC. In Fig.7, examples of diffracto-
sample’s preparation for the analysis. That means grams on a 2-theta scale for different samples of
their strength is not very high. Unfortunately, al- UO3:ASC are shown.
A B 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).
CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 39
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 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY
The XRD results indicate that the proper larnych jako prekursora paliwa do reaktorów nowej,
amount of ascorbic acid to UO3 for UC synthesis IV generacji. Polish Patent Application P-414768.
is in the range 1:0.9-1.0. [2]. Brykala, M., Rogowski, M., & Olczak, T. (2015). Car-
bonization of solid uranyl-ascorbate gel as an indirect
References step of uranium carbide synthesis. Nukleonika, 60, 4,
921-925.
[1]. Brykała, M., & Rogowski, M. (2015). Sposób wytwa-
rzania węglika uranu o ziarnach sferycznych i nieregu-
The issue of radioactive waste management ap- site for low- and intermediate-level radioactive
peared in Poland in 1958, when the first research waste.
reactor was put into operation at the Institute for Issues related to the new repository are, among
Nuclear Research in Świerk. Since then, there has other topics concerning the radioactive waste man-
been a large increase of applications of radioac- agement, discussed in recently developed docu-
tive isotopes in different areas of science and in- ment entitled “The National Plan of Radioactive
dustry. All those activities generate a waste, which Waste and Spent Nuclear Fuel Management”. This
requires special handling (collection, processing, document has been prepared in accordance with
solidification, transportation, storage and dispos- the provisions of the Atomic Law Act, as well as
al). the guidelines to the Council Directive 2011/70/
Radioactive waste of low and medium activity, Euratom of 19 July 2011, establishing Community
produced in Poland, is collected, processed, solidi- frameworks in regard to responsible and safe
fied and prepared for disposal by the state-owned management of spent nuclear fuel and radioac-
public utility – Radioactive Waste Management tive waste. The national plan is a result of coop-
Plant (RWMP). Subsequently, the waste is disposed eration between several institutions involved in
in the National Radioactive Waste Repository the management of radioactive waste and spent
(NRWR) in Różan site. The repository is a near- nuclear fuel, also considering experiences of other
-surface disposal site dedicated for processed countries.
short-lived, low- and intermediate-level radioac- According to this plan, there is a need to build
tive waste and sealed radioactive sources. a new surface repository taking into account the
The amount of all waste collected in Poland needs arising from the development of the Polish
every year is relatively not big; for example, in 2010, Nuclear Power Programme. It is planned that the
the total collected volume of stable waste was new repository will be put into operation after
51.3 m3 and 36.1 m3 of liquid radioactive waste. 2024 and will be operated by the year 2144. This
Low-level waste (LLW) constituted a volume of repository will accumulate low- and intermedi-
87 m3, while small amount of intermediate-level ate-level short-lived waste originating from their
waste (ILW) and alpha radioactive constituted applications in medicine and industry and, in the
about 1.1 m3. In addition, 17 500 smoke sensors case of the introduction of the Polish Nuclear
and 5300 sealed radioactive sources were collect- Power Programme, the waste produced during the
ed. All this radioactive waste after the selection operation of nuclear power plants (NNPs). The
and preparation were placed in containers and, in amounts of waste of various applications estimat-
this form, were disposed in Różan repository. ed according to “The National Plan of Radioactive
According to the present expectations, this re- Waste and Spent Nuclear Fuel Management” are
pository is foreseen to be completely filled by shown in Table 1.
2025. Therefore, Poland faces the challenge of The issue of a new repository is also the objec-
choosing a location for the new surface disposal tive 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.
methodology to evaluate the safety and identify- should also include 134Cs and 51Cr. However, tak-
ing the optimal location for surface repository for ing into account relatively short half-life of the
low and intermediate level waste” carried out by 51
Cr, this nuclide will have no impact on the total
consortium consisting of research institutes (Polish activity of potential effluents from the repository
Geological Institute-National Research Institute during the operation and after its closure.
– PGI-NRI; Institute of Geophysics of the Polish In addition to the type and activity of radionu-
Academy of Sciences – IGF PAS; the Mineral and clides, the exposure associated with the possible
Energy Economy Research Institute of the Polish release to the environment will depend on rate of
Academy of Sciences – MEERI PAS; Institute of their release and the rate of migration in the envi-
Nuclear Chemistry and Technology – INCT), geo- ronment. The parameter which allows estimating
logical company – Geoprojekt Szczecin Ltd. and the possibility of migration of a particular radio-
Radioactive Waste Management Plant. The main nuclide in aqueous solution in contact with the
objective of the project is to select the optimal solid phase in the surroundings of radioactive
location for the surface repository. Implementing waste repository is the partition coefficient (Kd).
this target must be preceded by many intermediate Due to the variety of parameters that affect
steps, which include: the migration of radionuclides, which include: the
• the preparation of projects of geological works; nature of the soil and suspended particles, mutual
• field tests; impact of radionuclides and other contaminants,
• the development of numerical models of the sorption/desorption processes, bacteriological ac-
2D layer system in order to simulate the migra- tivity, physicochemical properties of groundwater
tion of radionuclides in the geological environ- and the half-life of the radionuclides, the use of
ment for different scenarios of releases; partition coefficient in models of transport of ra-
• monitoring project of the future repository, dionuclides is always some estimation [2]. There-
taking into account the specificity of location; fore, for more thorough calculations, it is prefer-
• geological-engineering documentation for each able to determine the Kd values for the particular
of the three locations. type of soil in the laboratory or field, but such
Finally, for the optimal location, methodology tests are very time consuming.
for the safety assessment will be proposed. Partition coefficient is defined as the ratio of
Radionuclides, constituents of the waste stored equivalent concentrations of the studied compo-
in the repository, may move into the aquatic envi- nent in the two-phase system: a sorbent (soil)-the
ronment as a result of the natural evolution of the aqueous phase (ground water):
environment and the slow degradation of barriers. Cs
3
H, 60Co, 90Sr, 137Cs – due to their activity, ra- Kd
diotoxicity and mobility in the environment – and
Cw
the half-life, represent a group of significant radio- where Cs is a concentration of compound ad-
nuclides that should be taken into account when sorbed per unit of sorbent (soil) [mol/kg] and Cw
safety case for the surface repository is elaborated. is a concentration of compound in the liquid
As was mentioned above, in the new repository in phase at equilibrium [mol/L].
Poland, waste from NPP will also be stored; how- Thus, the Kd is associated with the distribution
ever, in this moment, neither the technology nor of the compound between the solid and the aque-
the type of the first NPP in Poland was selected ous phase. There are several methods used to de-
yet. From this reason, to assess a safety of the re- termine the Kd value, which include laboratory
pository, it is necessary to make simulations with methods, methods based on measurements in the
assumptions based on the available literature data. field (in situ) and computational methods. Each
When assessing the activity of radioactive waste of these methods has advantages and disadvan-
delivered to the new repository, as an example, tages, as well as a set of assumptions to calculate
waste from the economic simplified boiling water the Kd values based on experimental data. There-
reactor (ESBWR) from GE Hitachi was used [1]. fore, it is expected that the Kd values measured by
A list of the dominant radionuclides for the ESBWR various methods can be different. The values of Kd
reactor is given in Table 2. for the group of radionuclides dominated in the
According to this list, the group of significant waste, which will be stored in the surface reposi-
radionuclides stored in the surface repository tory of radioactive waste, are given in Table 3.
Table 2. Dominant radionuclides in solid waste from ESBWR type reactor.
Table 3. Value of Kd for different type of soil, determined using different methods.
Kd [L/kg]
Radionuclide The range of Kd [L/kg]
sand silt clay
7 [4]
4 [4]
3
H 0 [3] 0 [5] 26 [4]
0 [5]
0.04 [6]
51
Cr 1.7-1 729 [6]
1 000 [3]
60
Co 60 [4] 1 300 [4] 550 [4]
0.07-9 000 [6]
20 [3] 15 [4] 110 [4]
90
Sr 20 [4]
0.05-190 [6] 27 [5] 300 [5]
There are many issues to consider when meas- INCT, and some of the results have been publish-
uring Kd values and in selecting these values from ed [9]. The aim of studies was a simulation of the
the literature, among others, choice of simple or migration of radionuclides in environment, near
more complex test systems, the variability of site the radioactive waste repositories. The example
conditions (soil), issues related to the content of of radionuclide migration in geosphere concerns
gravel or creation of colloids. Crawford et al. [8] hypothetical release of radionuclide in saturated
summed up the uncertainty in the measurements porous media from a constant source. The com-
of the Kd values using the data in the literature. putational abilities of TOUGH2 simulator was a
These include the reasons for the uncertainty of the subject of the work. Simulator uses finite differ-
Kd values, such as random errors, mineralogical ential method for multiphase and multicompo-
variability of soil samples, the methodological de- nent modelling in porous and fractured media in
fects of measurement and interpretation of results unstable conditions [10]. Discretization scheme,
and the uncertainty associated with specific hydro- area localization in the coordinate system and the
logical and geochemical conditions (difficulty in boundary conditions of the model are shown in
determining the actual flow path and the type of Fig.1.
rocks encountered during water flow by fractured Two types of geological formations were dis-
rock). Consequently, the properties of the material tinguished in the modelled area – the permeable
are averaged, and therefore, the resulting Kd values and impermeable ones. The numeric calculations
are subject to have burdened with some errors. In were carried out for isothermal conditions using
addition, the state of geochemical parameters in the module (Equation of State) EOS7R intended
the future cannot be accurately determined due to for modelling the transport of radionuclides in geo-
the temporary effects of the flow. logical media. In the study, the migration of 137Cs
The issue of migration of radionuclides has radionuclide was modelled. Caesium radionuclide
been the subject of research conducted at the 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
per hour. Parallel generation of radionuclides and [2]. Krupka, K.M., Kaplan, D.I., Whelan, G., Serne, R.J.,
water simulates permeation of contaminated lea- & Mattigod, S.V. (1999). Understanding variation
chate into saturated geological formation. in partition coefficient, Kd, values. Review of geo-
chemistry and available Kd values for cadmium,
In Figs.2 and 3, the calculation results of the
cesium, chromium, lead, plutonium, radon, strontium,
contamination propagation after 100 years are pre- thorium, tritium (3H), and uranium. United States
sented. The extent of caesium contamination plum Environmental Protection Agency, Office of Air and
of 10–9 mass fraction concentration ranges up to Radiation Protection, 341 p. (EPA 402-R-99-004B).
500 m in 100 years. [3]. Nair, R.N., & Krishnamoorthy, T.M. (1999). Proba-
bilistic safety assessment model for near surface ra-
dioactive waste disposal facilities. Environ. Model.
Softw., 14, 447-460.
[4]. Heuel-Fabianek, B. (2014). Partition coefficients (Kd)
for the modelling of transport processes of radionu-
clides in groundwater. Julich: Forschungszentrum
Jülich, 51 p. (Berichte des Forschungszentrums Julich
4375).
[5]. Generic repository studies. Generic post-closure per-
formance 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 ma-
Fig.3. The concentration of 137Cs mass fraction after 100 jor soil types: a compendium. Health Phys., 59(4),
years from the beginning of radionuclide release from the 471-482.
source. [7]. Schwartz, M.O. (2012). Modelling groundwater con-
tamination above a nuclear waste repository at Gor-
The aim of the calculations was to test the leben, Germany. Hydrogeol. J., 20, 533-546.
computational capabilities of the TOUGH2 simu- [8]. Crawford, J., Neretnieks, I., & Malmström, M. (2006).
lator used for modelling radionuclide contamina- Data and uncertainty assessment for radionuclide
tion propagation in the geological environment Kd partitioning coefficients in granitic rock for
taking into account the decay of radionuclides in use in SR-Can calculations. Swedish Nuclear Fuel
time. and Waste Management Co., 117 p. (SKB Rapport
Despite the simplicity of the model, the pre- R-06-75).
[9]. Olszewska, W., Miśkiewicz, A., Zakrzewska-Kołtu-
sented problem confirms the possibility of using
niewicz, G., Lankof, L., & Pająk, L. (2015). Multi-
this software for modelling complex, three-dimen- barrier system preventing migration of radionuclides
sional issues related to the subject. from radioactive waste repository. Nukleonika, 60, 3,
557-563.
References [10]. Pruess, K., Oldenburg, C., & Moridis, G. (2012).
[1]. Energoprojekt Warszawa. (2013). Wariantowa kon- TOUGH2 user’s guide, Version 2. Berkeley, Califor-
cepcja programowo-przestrzenna składowiska odpa- nia: Earth Sciences Division, Lawrence Berkeley Na-
dów promieniotwórczych. Unpublished report, War- tional Laboratory, University of California, 197 p.
szawa.
Tacrine (1,2,3,4-tetrahydro-9-acridinamine – TAC) ing the enzyme that hydrolyses acetylcholine, the
is an oral medicament used to treat patients with concentration of acetylcholine in the brain in-
Alzheimer’s disease (AD) – the most common creases, resulting in the improvement in thinking
form of dementia. There is no cure for this disease and alleviation of the clinical symptoms of the
and worsens as it progresses leading to death [1, 2]. disease [5, 6]. Tacrine in the form of monohydro-
Tacrine belongs to the class of drugs which are chloride was the first drug approved by the United
cholinesterase inhibitors [3, 4]. Cholinesterase in- States Food and Drug Administration in 1993 for
hibitors inhibit the action of acetylcholinesterase palliative treatment of AD. Tacrine and its ana-
(AChE), the enzyme responsible for the degen- logues labelled with diagnostic radionuclide (e.g.
eration of acetylcholine. Acetylcholine is one of 125
I, 11C) were also studied from the point of view
several neurotransmitters in central nervous sys- of their application as potential diagnostic agent
tem (CNS) – chemicals which nerve cells use to able to define the specific site of action in the
communicate with one another. Reduced level of brain [7, 8]. However, the use of tacrine is limited
acetylcholine in the brain is believed to be respon- due to its significant incidence of hepatotoxicity,
sible for some of the symptoms of AD. By block- cardiovascular system impairment and mild cogni-
44 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY
tive benefits, but does not alter the course of the The coupling reactions between DOTA-NHS
disease [9]. Therefore, the search for new tacrine (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetra-
analogues is still of interest for scientists involved acetic acid mono-N-hydroxysuccinimidyl ester)
in AD research [10, 11]. and the three tacrine derivatives were performed
O O
HO HO
O O
N N N
OH N O
68
OH O Ga
N N
N O N O
O O
A
A)
NH2
BB) NH
C
C)
NH
a: n=7 N N N
b: n=8
c: n=9 NH2(CH2)nTAC DOTA-TACd 68Ga-DOTA-TACd
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 in DMF at 50oC and in the presence of Et3N
radioconjugates (Fig.1C, Table 1) containing the (Scheme 1). The molar ratio of the reagents used
68
Ga-DOTA complex and different tacrine deriva- in the coupling reactions was 1.3:1:4, respectively.
tives (TACd, Fig.1A, Table 1) as the biologically Crude DOTA-TACd-n products (Fig.1B, Table 1)
active molecules. The choice of the radioconju- were purified on a semi-preparative HPLC column
gate with the highest lipophilicity (blood-brain and lyophilized, with the yield 85%.
barrier can be crossed by compounds of sufficient- MS of DOTA-TACd-4: m/z: calcd. – 697.88, found
ly high lipophilicity [12]) and the determination – 698.46 [M+H+].
of physicochemical properties of this radioconju- MS of DOTA-TACd-7: m/z: calcd. – 711.91, found
gate are important from the radiopharmaceutical – 712.49 [M+H+].
point of view [13]. The tacrine derivatives used in MS of DOTA-TACd-9: m/z: calcd. – 725.93, found
syntheses contained in aliphatic chain: seven CH2 – 726.47 [M+H+].
groups (n = 7, TACd-7), eight CH2 groups (n = 8, The 68Ga-DOTA-TACd radioconjugates (Table
TACd-8) and nine CH2 groups (n = 9, TACd-9). 1) were synthesized according to the following
It was expected that TACd labelled with 68Ga may procedure: to the vial containing about 50 g of
serve as a diagnostic receptor radiopharmaceuti- lyophilized DOTA-TACd, 300 L of acetate buffer
cal, used in PET method, for the diagnosis of AD (pH = 5.89) and 50100 L of concentrated so-
at the very early stage of the disease. lution of 68GaCl3 from the 68Ge/68Ga generator
Table 1. Physicochemical properties of synthesized conjugates and radioconjugates.
MS analyses
Compound RT [min] Mw calcd. Mw found [M + H+] log P
[g/mol] [g/mol]
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
Ga-DOTA-TACd-9 13.10 793.6 794.37 −
CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 45
O
NH2
N
(CH2)n (CH2)n N
O O O HN
O HN N
H
N N O N N O O
HO HO
+ + N
N N OH N N N OH HO
O
O O
OH O OH
O
(70100 MBq) were added. The reaction mixture min), 68Ga-DOTA-TACd-9 (gamma detection, RT
was heated for 30 min at 95oC, and the reaction = 13.20 min) and Ga-DOTA-TACd-9 (UV/Vis
progress was checked by HPLC method. The radio- detection, RT = 13.10 min), synthesized in this
chemical yield of the synthesized conjugate was study, are shown in Fig.2. The conjugate 68Ga-
higher than 98%. -DOTA-TACd-9 was formed with high yield and
In order to verify the identity of the 68Ga-DOTA- purity. The non-radioactive reference conjugate
-TACd-9 radioconjugate synthesized in n.c.a. scale, Ga-DOTA-TACd-9 isolated from the reaction mix-
the non-radioactive reference compound – the ture was characterized by MS. Almost the same
Ga-DOTA-TACd-9 conjugate – was prepared in RT values of 68Ga-DOTA-TACd-9 and Ga-DOTA-
milligram scale, isolated by HPLC method and -TACd-9 conjugates confirmed the existence in
characterized by MS analysis (Table 1). n.c.a. scale of the 68Ga-DOTA-TACd-9 conjugate
MS of Ga-DOTA-TACd-9: m/z: calcd. – 793.6, in the reaction mixture.
found – 794.37 [M+H+]. The determined lipophilicity values of 68Ga-
The lipophilicity of 68Ga-DOTA-TACd-n radio- -DOTA-TACd-n radioconjugates increased with
conjugates isolated from the reaction mixture increasing number of CH2 groups (from 7 to 9) in
(using HPLC method) was characterized by the the aliphatic chain and were in the range from
determination of the logarithms of their partition -2.52 to -1.52 (Table 1), which indicates hydro-
coefficients, log P, in the n-octanol/PBS (pH 7.40) philic character of the designed compounds. How-
system (Table 1). The stability of the chosen ever, the log P values of 68Ga-DOTA-TACd-n radio-
68
Ga-DOTA-TACd-9 isolated radioconjugate was conjugates can be easily modified using macro-
investigated both as a function of time and in cyclic ligand DOTA in the form of the DOTA-
challenge experiments (in the presence of excess of -tris(tBu)ester.
histidine or cysteine), as well as in human serum The studied 68Ga-DOTA-TACd-9 conjugate ex-
and cerebrospinal fluid. hibited high stability. After about 5 h of incubation
Conditions of HPLC system were the follow- in 10 mM histidine or cysteine solution or in hu-
ing: Phenomenex Jupiter Proteo semi-preparative man serum, as well as in cerebrospinal fluid, the
column (4 m, 90 Å, 250 10 mm), UV/Vis de- obtained HPLC chromatograms have shown main-
tector (220 nm); elution conditions: solvent A – ly the existence of only one radioactive species in
water with 0.1% TFA (v/v), solvent B – acetoni- the solution, with the retention time characteristic
trile with 0.1% TFA (v/v); gradient – 0-20 min for the studied radioconjugate. Thus, we can con-
20% to 80% of solvent B, 20-35 min 80% solvent sider that the 68Ga-DOTA-TACd-9 radioconjugate
B; 2 mL/min. does not undergo the ligand exchange reactions
The HPLC chromatograms of the compounds with amino acids or other strongly competing
DOTA-TACd-9 (UV/Vis detection, RT = 12.60 natural ligands containing SH or NH groups. In
the case of studies on stability in human serum
and in cerebrospinal fluid, the protein compo-
nents were precipitated using ethyl alcohol and
the radioactivity of both the supernatant and pre-
cipitate (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 cere-
brospinal 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 physico-
chemical properties of the 68Ga-DOTA-TACd-9
conjugate can be an important basis for further
consideration of this conjugate as a potential di-
Fig.2. The HPLC analyses of the reaction mixtures after agnostic radiopharmaceutical. From the view-
the synthesis of DOTA-TACd-9 (A), 68Ga-DOTA-TACd-9 point of application in nuclear medicine, it is im-
(B) and Ga-DOTA-TACd-9 (C) compounds prepared in portant to note that the 68Ga-DOTA-TACd-n
this study. conjugates can be easily synthesized in hospital
46 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY
laboratories using previously prepared lyophilized est for the early diagnostics of Alzheimer’s disease.
kit formulations and the portable 68Ge/68Ga gen- Pharmazie, 61, 4, 269-273.
erator. 68Ga-DOTA-TACd-9 can be a useful tool [6]. Szymański, P., Markowicz, M., & Mikiciuk-Olasik,
for the diagnosis of early stage of AD. E. (2011). Synthesis and biological activity of deriva-
tives of tetrahydroacridine as acetylcholinesterase
The work has been supported by the statutory inhibitors. Bioorg. Chem., 39, 138-142.
activity of the Institute of Nuclear Chemistry and [7]. Kabalka, G.W., & Akula, M.R. (1999). Synthesis of
Technology (INCT). The authors thank Prof. S. 7-[123I]Iodotacrine: a potential SPECT agent to map
Siekierski (INCT) for the valuable discussion and acetylcholine esterase. J. Labelled Compd. Radio-
review of the text. pharm., 42, 959-964.
[8]. Tavitian, B., Pappata, S., Bonnot-Lours, S., Prenant,
References C., Jobert, A., Crouzel, C., & Di Giamberardino, L.
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& Hampel, H. (2011). Neuroimaging markers for methyl-tetrahydroaminoacridine (methyl-tacrine) in
the prediction and early diagnosis of Alzheimer’s baboon brain. Eur. J. Pharmacol., 236, 229-238.
disease dementia. Trends Neurosci., 34, 430-442. [9]. Davis, K.L., & Pochwik, P. (1995). Tacrine. Lancet,
[2]. Petrella, J.R., Coleman, R.E., & Doraiswamy, P.M. 345, 8950, 625-630.
(2003). Neuroimaging and early diagnosis of Alz- [10]. Musiał, A., Bajda, M., & Malawska, B. (2007). De-
heimer disease: A look to the future. Radiology, 226, velopment of acetylcholinesterase inhibitors for Alz-
325-336. heimer’s disease treatment. Curr. Med. Chem., 14,
[3]. Mehta, M., Adem, A., & Sabbagh, M. (2012). New 2654-2679.
acetylcholinesterase inhibitors for Alzheimer’s dis- [11]. Tumiatti, V., Minarini, A., Bolognesi, M.L., Milelli,
ease. Int. J. Alzheimer’s Dis., 2012, Article ID 728983, A., Rosini, M., & Melchiorre, C. (2010). Tacrine de-
8 p. rivatives and Alzheimer’s disease. Curr. Med. Chem.,
[4]. Szymański, P., Lázničková, A., Lázniček, M., Bajda, 17, 1825-1838.
M., Malawska, B., Markowicz, M., & Mikiciuk-Ola- [12]. Ambikanandan, M., Ganesh, S., Aliasgar, S., & Shre-
sik, E. (2012). 2,3-Dihydro-1H-cyclopenta[b]quino- nik, P.S. (2003). Drug delivery to the central nerv-
line derivatives as acetylcholinesterase inhibitors— ous system: a review. J. Pharm. Pharm. Sci., 6(2),
synthesis, radiolabeling and biodistribution. Int. J. 252-273.
Mol. Sci., 13, 10067-10090. [13]. Welch, M.J., & Redvanly, C.S. (2003). Handbook of
[5]. Szymański, P., Żurek, E., & Mikiciuk-Olasik, E. radiopharmaceuticals: radiochemistry and applica-
(2006). New tacrine-hydrazinonicotinamide hybrids tions. West Sussex, England: John Wiley and Sons
as acetylcholinesterase inhibitors of potential inter- Ltd.
The formation of molecular architectures driven approach to study low-energy vibrational excita-
by specific interactions such as hydrogen-bonds tions in molecular crystals by combining state-of-
(H-bonds) has been one of the most important -the-art theoretical calculations in the framework
areas of research in structural chemistry over the of solid-state density functional theory (DFT) with
last few decades. For the purpose of crystal engi- time-domain terahertz (TDs-THz) and inelastic
neering, the term supramolecular synthons has neutron scattering (INS) spectroscopy. Here we re-
been proposed, as referring to “building blocks” port the case study of (1:1) co-crystal of bromanilic
that control the molecular aggregation on a large acid and 2,6-dimethylpyrazine (BrA:2,6-DMP) [7].
scale [1]. In that sense, donor-acceptor type or- This report is constructed as follows. First, we
ganic complexes appear to be of vital importance, acquaint the reader with the basic principles of
being related both to the proton and electron this rather unique experimental methodology. Then
transfer phenomena. Of these, the family of anilic we illustrate the research on low-wavenumber
acids was found to be particularly interesting [2-6]. vibrational dynamics using BrA:2,6-DMP as an
From the scientific perspective, it is thus impor- example.
tant to deeper examine the crystallographic struc- In the well-established middle-infrared or Ra-
tures and competing intermolecular interactions man spectroscopy, one can routinely probe internal
therein. To this end, multiple complexes of hetero- molecular vibrations that can generally be attrib-
cyclic aromatic amines with bromanilic and chlo- uted to the presence of particular atoms or func-
ranilic acids have been synthesized. An extensive tional groups. These experiments are usually per-
physical-chemical characterization of these sys- formed at higher wavenumbers, since access to the
tems was conducted thanks to the long-term col- spectral range below 150 cm–1 is technically diffi-
laboration with the Joint Institute for Nuclear Re- cult. However, the terahertz features give the most
search (JINR) in Dubna, Russia. Thanks to this col- unique fingerprint arising from complex vibrations
laboration, we can provide a novel complementary of the entire molecules or from vibrations that can
CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 47
be ascribed to long-range inter-molecular vibra- tional to the factor k 2/. Therefore, a radia-
tions (external modes). tion of several thousand Å (), which is used in
Terahertz radiation can be loosely defined as Raman and infrared spectroscopy is only a few
the frequency between 0.1-10 THz (< 300 cm–1) thousandths of that of a typical Brillouin zone di-
and was called the “THz gap”, since one could mension. As a consequence, Raman, IR or TDs-THz
not access this region efficiently for a long time. refer to the Brillouin zone-centre phonons (-point
Nowadays, this gap is filled thanks to the photo- vibrations), where the selection rules are constrain-
conductive and electro-optic emitters, which have ed by the symmetry of each normal mode [9]. In
given rise to the so-called time-domain terahertz contrast, there is no such constraint in INS. Ad-
spectroscopy. A simplified scheme of a typical ditionally, the spectral intensity is defined here in
TDs-THz setup is illustrated in Fig.1A. In prin- a simple way, as it is directly proportional to the
ciple, in TDs-THz electron-hole pairs are generat- amplitude of atomic motion and incoherent neu-
ed in a semiconducting crystal (e.g. GaAs) using tron scattering cross-section of an atom (inc),
an ultra-short femtosecond pulse (e.g. < 100 fs which is an isotope-specific property independent
from Ti:Sapphire laser). These photo-excited charge of its chemical environment. Since the cross-sec-
carriers are further accelerated by an applied elec- tion value for hydrogen (80 barns) is far greater
tric field, emitting THz radiation. According to that of all other elements (typically ca. 5 barns),
Fig.1A, the a small portion of light is directed on the INS spectrum emphasizes the modes that in-
the THz receiver through an optical delay line, volve 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 Thanks to the long-term collaboration with
pump beam shines onto the THz emitter, result- the JINR, employees of the Institute of Nuclear
ing in a continuous spectrum covering the range Chemistry and Technology actively participate in
of ~0.1-3 THz (3-100 cm–1). The emitted radiation the experiments conducted at the IBR-2 neutron
follows an optical path and passes the sample source, including INS measurements with the
placed in a transparent matrix (e.g. HDPE). In the NERA spectrometer. The simplified scheme of
TDs-THz experiment, we observe a delay of the NERA has been given in Fig.1B (see [8] for more
signal due to sample absorption. The reference dis- details). In brief, NERA is an inverted-geometry
tance is therefore scanned by an optical delay line spectrometer, which means that the final energy
using the probe signal. Optionally, the Fourier of the scattered neutrons is fixed, and the wave-
transform (FT) is performed, converting the spec- length spectrum of polychromatic incident neu-
trum from the time- into the frequency domain. trons is analysed according to the de Broglie rela-
TDs-THz probes the absorption of terahertz tion by the time of flight on the ~110 m path. The
radiation due to vibrational excitations, where the scattered neutrons are Bragg reflected from a py-
transition probability is constrained by the same rolytic graphite analyser and higher-order reflec-
selection rules as in infrared spectroscopy. The tions beyond (002) are suppressed by cooled filters
transition arises from the interaction of the elec- so as to define the final energy of scattered neu-
tric component of the photon with the electronic trons at Ef as 4.65 meV. The spectrometer consists
cloud of the system. Alternatively, the low-wave- of two symmetrical sections, A and B, which both
number vibrational excitation may be induced by consist of eight chambers of 3He detectors for INS
an inelastic collision of the nucleus with an un- measurements. The spectrometer is also intended
charged, non-zero mass particle, that is the neu- for simultaneous measurements of INS, QENS
tron, which is then called inelastic neutron scatter- (quasi-elastic neutron scattering) and NPD (neu-
ing. tron powder diffraction), fully covering the low-
The major differences between vibrational neu- -wavenumber range [8].
tron and optical spectroscopy arise from the neu- BrA:2,6-DMP was synthesized and structur-
tron’s mass which leads to the significant transfer ally characterized with a low-temperature (100 K)
of both energy and momentum. The accessible single-crystal X-ray diffraction (using the Super-
wavevectors in the momentum space are propor- Nova Dual Source single-crystal diffractometer).
48 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY
The molecular structure of the system containing BrA:2,6-DMP crystal clearly illustrates that the
BrA and 2,6-DMP in a 1:1 molar ratio, is present- aforementioned methodology is capable of accu-
ed in Fig.2. rately 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 nu-
merical methodology allows one to achieve a very
Fig.2. The geometry of hydrogen-bonded synthon formed good match with the experimental spectra, allowing
in a (1:1) co-crystal of BrA and 2,6-DMP. for more complete interpretation of such a chal-
lenging spectral range. In Table 1, the full analysis
The studied system can be described as a su- of the external modes has been delivered.
pramolecular superstructure built by the hydro- By employing theoretical calculations it was
gen-bonded ···2,6-DMP···BrA··· chains, formed by also possible to probe the influence of the long-
alternating molecules, which are propagated to- -range dipole-coupling on the optical spectrum,
ward the crystallographic axis a. The neighbour- which has been shown to be of importance as it
ing acid and base molecules are linked into chains significantly affects the TDs-THz band intensities
by a pair of non-equivalent intermolecular hydro- (see LO and TO components in Fig.3).
gen bonds. The system crystallizes in the mono- By inspection of these data, one can find, for
clinic, centrosymmetric P21/c (C2h5) space group, example, that the most intense spectral feature in
with four molecules equivalent by symmetry per the TDs-THz can be attributed to the hydrogen
unit cell. The molecular chains in the crystal are bridge stretching, that is, the lowest-energy hydro-
arranged in the opposite directions (anticlinic con- gen-bond mode, which in fact cannot be studied
figuration), where the associated polarization vec- with any other technique. One can also note that
tors compensate each other, resulting in a centro- the analysed spectra could be generally divided into
symmetric structure. two parts, namely that above and below 50 cm–1.
The low-wavenumber vibrational response was While the upper range engages multiple librational
probed by combining TDs-THz (Teraview TPS modes of co-molecules, the lower part expresses the
3000) and INS spectroscopy (NERA) [8]. The ex- highly collective nature of the related vibrations,
perimental spectra are collected in Fig.3 and com- which involve rotational (screwing) and transla-
pared with the results of the first-principles calcu- tional motions (breathing, shearing) of the whole
lations for solid-state. hydrogen-bonded chains.
In 2015, we optimized the numerical proce- While the INS intensity is generally driven by
dure for predicting low-wavenumber optical and hydrogen contributions due to its large scattering
neutron spectra in the framework of density func- cross-section, the spectrum mainly reflects the con-
tional perturbation theory (DFPT), by taking peri- tributions coming from the methyl groups, that is,
odic boundary conditions into account [10, 11]. We the 2,6-DMP counterpart. Such modes are not vis-
have adopted the ab initio simulation method, ible on their own in optical vibrational spectros-
based on the plane-wave pseudopotential approach copy, since their motion does not affect the dipole
as implemented in CASTEP code [12]. In brief, moment (nor polarizability), but are the most in-
DFPT provides analytical solutions for the calcu- tense in INS spectroscopy. By contrast, the most
lation of lattice dynamics in solids, where the ionic intense features in the TDs-THz spectrum can be
displacement along with an external electric field associated with partially charged oxygen atoms,
are treated as perturbations acting on the equilib- whose motion affects the polarization in the crys-
rium crystal structure. The example analysis of the tal cell, that is, the BrA moieties.
A 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.
CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 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 longi-
tudinal (LO) optical components.
This research was supported in part by PL-Grid tion directing antiparallel to ionic displacement. Phys.
Infrastructure (grant IDs: phd2013, phd2014). Rev. Lett., 108, 23, 237601-237605. DOI: 10.1103/
K. Łuczyńska and K. Drużbicki gratefully ac- PhysRevLett.108.237601.
[6]. Adam, M.S., Parkin, A., Thomas, L.H., & Wilson, C.C.
knowledge the financial support of the Polish Go-
(2010). Bifurcated hydrogen-bonded synthons in mo-
vernment Plenipotentiary for the JINR in Dubna lecular complexes of picolines with chloranilic acid.
(grants no. 118-8/1069-5/2014; 44/27-01-2015/ CrystEngComm, 12, 917-924. DOI: 10.1039/B912539F.
7/1121/5) along with OMUS scholarship for the [7]. Łuczyńska, K., Drużbicki, K., Łyczko, K., & Dobro-
outstanding young scientists at the JINR. wolski, J.Cz. (2015). Experimental (X-ray, 13C CP/
MAS NMR, IR, RS, INS, THz) and solid-state DFT
References study on (1:1) co-crystal of bromanilic acid and 2,6-di-
[1]. Desiraju, G.R. (1995). Supramolecular synthons in methylpyrazine. J. Phys. Chem. B, 119, 6852-6872.
crystal engineering – A new organic synthesis. Angew. DOI: 10.1021/acs.jpcb.5b03279.
Chem., 34, 2311-2327. DOI: 10.1002/anie.199523111. [8]. Natkaniec, I., Chudoba, D., Hetmanczyk, Ł., Kazimi-
[2]. Horiuchi, S., & Tokura, Y. (2008). Organic ferroelec- rov, V.Yu., Krawczyk, J., Sashin, I., & Zalewski, S.
trics. Nat. Mater., 7, 357-366. DOI: 10.1038/nmat2137. (2014). Parameters of the NERA spectrometer for
[3]. Horiuchi, S., Kumai, R., & Tokura, Y. (2007). Supra- cold and thermal moderators of the IBR-2 pulsed re-
molecular ferroelectric realized by collective proton actor. J. Phys., Conf. Ser., 554, 012002. DOI: 10.1088/
transfer. Angew. Chem., 46, 3497-3501. DOI: 10.1002/ 1742-6596/554/1/012010.
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[4]. Horiuchi, S., Noda, Y., Hasegawa, T., Kagawa, F., & scattering spectroscopy of amino acids. Spectroscopy,
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[5]. Kobayashi, K., Horiuchi, S., Kumai, R., Kagawa, F., Lett.58.1861.
Murakami, Y., & Tokura, Y. (2012). Electronic ferro- [11]. Gonze, X. (1997). Dynamical matrices, born effective
electricity in a molecular crystal with large polariza- charges, dielectric permittivity tensors, and inter-
50 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY
atomic force constants from density-functional per- principles methods using CASTEP. Z. Kristallogr.,
turbation theory. Phys. Rev. B, 55, 10337-10354. DOI: 220, 567-570. DOI: 10.1524/zkri.220.5.567.65075.
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
Shale gas is natural gas that we use every day for Institute take an action to develop the new pro-
cooking or heating. This name does not describe ject that will create the prototype of installation
the special type of resources, but it is used to em- that can be used for the treatment of flowback
phasize specific properties of the rock where gas fluids from hydraulic fracturing of Polish gas-
is accumulated. The shale gas is extracted from -bearing shales. In this paper, the initial results of
these rocks using special exploration and produc- the studies on the examination of composition
tion technologies, namely, hydraulic fracturing. and purification of flowback fluids are presented.
The fracturing fluid is pumped under high pres- The fracturing fluids are very diverse in terms
sure into the borehole. The fluid pumping rate of chemical composition, depending on the bore-
typically ranges from 8 m3/min to 18 m3/min, and hole and fracturing technology applied. However,
the pumping pressure might be as high as 800 they consist of components such as water (more
bars. The hydraulic action of the fracturing fluid than 90%), proppants (quartz sand/resin-coated
crushes the rock formations and creates fractures. quartz sand/other high-resistance proppants, e.g.
This fluid is typically slurry of water, proppants zirconium oxide), natural polymers (derivatives of
and other chemical additives. The rocks contain Indian guar beans: Xantham gum, E415; guar
various metals that can be extracted by fracturing gum, E412), crosslinkers (boron, titanium and
fluids. zirconium compounds), buffers (inorganic acids
Table 1. The composition of selected fracking fluid used in Poland.
By-product of shale gas production is the huge and bases, e.g. hydrochloric acid, ammonium bi-
amounts of toxic fluids. These fluids are charac- sulphate), natural biocides, stabilizers (sodium
terized by high salinity and contain heavy metals, chloride, calcium chloride, isopropanol), surfac-
inter alia, also rare earth metals, radioactive ele- tants (amines, glycol ethers), viscosity breakers
ments and organic matter. (lithium hypochlorite, sulphates, peroxides), clay
Pyrocat Catalyse World, Institute of Nuclear and shale inhibitors – phosphonates, polyglycols,
Chemistry and Technology and Polish Geological 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
guar gum). The example of composition of the the environment, they must be treated prior to
fracking fluid, which was used in Poland, is re- further use or final disposal as treated sewage
ported in Table 1 [1]. that can be introduced into water or ground. The
Hydraulic fluid works as a lixiviant for many removal of heavy metals is one of the aims of pro-
minerals found in shales [2], and different minerals cessing. In addition, the separation of valuable
are leached during the hydraulic fracturing process. metals from the solution can improve the profit-
Flowback fluid typically contains large amounts ability 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
n.d. – not determined.
of salt, various quantities of metals including heavy The combined treatment scheme of membrane
metals and rare earth metals, and small amounts and ion exchange processes that can be used to
of naturally occurring radioactive elements and treat flowback fluids from shale gas wells being
organic matters. The flowback fluid composition Table 4. The content of organic and inorganic carbon
can vary depending on the location and the method [mg/L] found in selected flowback fluid samples (TOC –
of fracturing. The constituents of two flowback total organic carbon, TIC – total inorganic carbon).
fluids (B1 and L1) from fracturing in two loca-
tions in Poland are given in Tables 2, 3 and 4. Examined sample TOC TIC
The content of Na+, Ca2+ and Cl– in flowback
fluid is high. Compared to these ions, the other B1 108 14
ions, such as Sr2+ and Cs+, occur in low concen- L1 254 152
tration. Moreover, the fluid contains moderate con-
centration of organic materials, at 100-254 mg/L. n.d. – not determined.
The conductivity of the flowback fluid samples
is high on the level 130 mS/cm and pH is in the drilled in Poland was shown in Fig.1. At the be-
range 5.4-8.2. ginning, the fluid should be pretreated with using
The characteristics of presented fluids un- the depth filters. In this process, turbidity is signifi-
doubtedly show that to reduce negative effects on cantly reduced from 0.2 NTU to > 0.2 NTU. There
Fig.1. The possible scheme for the treatment of fluids after hydraulic fracturing.
52 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY
is also a reduction of the organic carbon content construction of the mobile installation which can
of about 20%. demonstrate the feasibility of technology at full
The filtration by the activated carbon bed, oxi- scale will complete the studies.
dation by Fenton reaction and ozonation are much
more suitable for the treatment of aqueous solu- References
tion with high organic content. Then, the adequate [1]. Organizacja Polskiego Przemysłu Poszukiwawczo-Wy-
sequence of cation and anion exchange resins will dobywczego. http://www.opppw.pl.
allow to separate rare earth elements and uranium. [2]. Chermak, J.A., & Schreiber, M.E. (2014). Mineralogy
and trace elements geochemistry of gas shales in the
The main result of the project will be the elab-
USA: Environmental implications. Int. J. Coal Geol.,
oration of cheap and efficient technology which 126, 32-44.
allows the treatment and reuse of flowback fluids
and recovery of valuable metals. The design and
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 devel-
opment of safe nuclear power engineering” from the National Centre for Research and Devel-
opment (SP/J/6/143 339/11), as well as in the “Development of a multi-parametric triage ap-
proach 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 re-
sponse 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 establish-
ing 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 net-
work 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, micronu-
clei 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 re-
sponders, disaster management units” and is the only Polish partner of the project. The re-
sults 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 mo-
lecular 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 nanopar-
ticles in response of microglia cells to -amyloid was studied in the frame of the project
UMO-2013/11/N/NZ7/00415.
54 CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY
Fig.2. Cluster analysis of 36 blood samples based on Ct values of GADD45A, CDKN1A, BBC3, BAX, DDB2, GDF15,
TNFSF4, FDXR.
CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY 55
DDB2, FDXR, GADD45A, GDF15, MDM2, PLK3, Thus, in the present study, we have selected and
SERPINE1, SESN2, TNFRSF10B, TNFSF4, and tested a new panel of radiation-responsive genes
VWCE) was assessed by reverse transcription proving its usefulness for biological dosimetry pur-
quantitative PCR 6, 12, 24, and 48 h after exposure poses. Our results confirm that the analysis of ex-
with ITFG1 and DPM1 used as reference genes. pression of a carefully selected group of genes can
The panel of radiation-responsive genes was select- provide sufficient information to discriminate be-
ed comprising GADD45A, CDKN1A, BAX, BBC3, tween irradiated and non-irradiated blood samples.
DDB2, TNFSF4, GDF15, and FDXR. The full description is available in [4].
Among radiation-responsive genes, a signifi-
cant difference between samples irradiated with References
0.6 Gy and 2 Gy was observed only for TNFSF4. [1]. Badie, C., Kabacik, S., Balagurunathan, Y., Bernard,
For the other genes, significant differences were N., Brengues, M., Faggioni, G., Greither, R., Lista, F.,
observed between irradiated samples and control Peinnequin, A., Poyot, T., Herodin, F., Missel, A., Ter-
brueggen, B., Zenhausern, F., Rothkamm, K., Meineke,
samples, but not between samples irradiated with
V., Braselmann, H., Beinke, C., & Abend, M. (2013).
different doses, even though a positive correlation Laboratory intercomparison of gene expression assays.
between the dose and mRNA level was observed. Radiat. Res., 180, 2, 138-148.
This lack of a sharp difference between samples [2]. Tucker, J.D., Divine, G.W., Grever, W.E., Thomas, R.A.,
irradiated with different doses is reflected in the Joiner, M.C., Smolinski, J.M., & Auner G.W. (2013).
cluster analysis, where one of the samples irradiat- Gene expression-based dosimetry by dose and time in
ed with 2 Gy is grouped with 0.6 Gy samples mice following acute radiation exposure. PLoS One,
(Fig.2). This result is in agreement with the data 8(12), e83390.
published by other authors, from which it appears [3]. Tucker, J.D., Joiner, M.C., Thomas, R.A., Grever, W.E.,
that gene expression analysis performs better in Bakhmutsky, M.V., Chinkhota, C.N., Smolinski, J.M.,
Divine, G.W., & Auner, G.W.J. (2014). Accurate gene
distinguishing between irradiated and non-irra- expression-based biodosimetry using a minima set of
diated samples than in predicting the actual ab- human gene transcripts. Int. J. Radiat. Oncol. Biol.
sorbed dose (e.g. [1-3]). Cluster analysis showed Phys., 88, 933-939.
that Ct values of the selected genes contained [4]. Brzoska, K., & Kruszewski, M. (2015). Toward the
sufficient information to allow discrimination be- development of transcriptional biodosimetry for the
tween irradiated and non-irradiated blood samples. identification of irradiated individuals and assessment
The samples were clearly grouped according to the of absorbed radiation dose. Radiat. Environ. Biophys.,
absorbed doses of radiation and not to the time 54, 3, 353-363.
interval after irradiation or to the blood donor.
Nowadays the use of nanoparticles (NPs) is very We investigated the genotoxic effects of AgNPs
widespread, both in everyday life (e.g. food addi- (20 nm) in leukocytes and erythrocyte precursors
tives, cosmetics, packaging systems) and in medi- of rats (male Wistar, 14-week old). AgNPs were ad-
cine (e.g. drug delivery, bioimaging, tissue engi- ministered to the animals (10 mg/kg body weight/
neering, detection of proteins, cancer treatment) day) intravenously, through the tail vein, or orally,
[1]. NPs can easily reach different parts of the body per os. After different time periods (from 24 h to
and accumulate; thus, it is reasonable to consider 28 days), the rats were sacrificed, blood was taken
the health consequences of their use. Silver nano- by heart puncture and bone marrow was flushed
particles (AgNPs) belong to the most commonly from the femora. The positive control were rats,
used, characterized by antimicrobial properties 24 h and 48 h after X-irradiation with the 3 Gy
arising from free radical formation and oxidative dose. The percentage of micronuclei in reticulo-
stress induction [2]. AgNPs present in consumer cytes – a measure of DNA damage in erythroid pre-
goods are released into the environment, where cursors – was evaluated both in the bone marrow
they could be bioaccumulated or enter the food and blood. The bone marrow was prepared and
chain or drinking water supplies, potentially result- stained with acridine orange, according to the mod-
ing in adverse and unpredictable effects. Hence, ified method of Hayashi et al. [3], then examined
estimation of their genotoxicity in vivo may bring under fluorescence microscope (Nikon, Japan). For
important information on their impact on human micronucleus test in blood, a cytometric method
health. of Harada et al. [4] was applied, with additional
56 CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY
References
[1]. Yang, F., Jin, C., Subedi, S., Lee, C.L., Wang, Q., Jiang,
Fig.1. Percentage of micronucleated reticulocytes (% MN Y., Li, J., Di, Y., & Fu, D. (2012). Emerging inorganic
in RET) in bone marrow and in blood after intravenous nanomaterials for pancreatic cancer diagnosis and treat-
injection (24 h or 28 days) or oral (per os, 7 days or 28 ment. Cancer Treat. Rev., 38, 6, 566-579.
days) administration of AgNPs. Bars show means (N 6) [2]. Gaillet, S., & Rouanet, J.M. (2015). Silver nanopar-
+ 95% confidence intervals. In rats X-irradiated with a ticles: their potential toxic effects after oral exposure
dose of 3 Gy, the level of micronuclei in bone marrow in- and underlying mechanisms – a review. Food Chem.
creased to 23.3% and 44.6% after 24 h and 48 h, respec- Toxicol., 77, 58-63.
tively, while in blood the corresponding values were 1.4% [3]. Hayashi, M., Morita, T., Kodama, Y., Sofuni, T., & Ishi-
and 6.4% (not shown). data, M. (1990). The micronucleus assay with mouse
peripheral blood reticulocytes using acridine orange-
In spite of a very thorough analysis by several -coated slides. Mutat. Res., 245, 245-249.
methods both of cells present in the bone marrow [4]. Harada, A., Matsuzaki, K., Takeiri, A., Tanaka, K., &
and blood no significant damage was found. No Mishima, M. (2013). Fluorescent dye-based simple
differences were found in micronuclei frequency staining for in vivo micronucleus test with flow cyto-
in reticulocytes independently of the way of nano- meter. Mutat. Res., 751, 85-90.
particle administration or of the time of estima- [5]. Kruszewski, M., Green, M.H., Lowe, J.E., & Szumiel,
I. (1995). Comparison of effects of iron and calcium
tion (Fig.1). The same applied to the directly esti- chelators on the response of L5178Y sublines to X rays
mated DNA damage by the comet assay in peri- and H2O2. Mutat. Res., 326, 155-163.
pheral blood lymphocytes (Fig.2A). In contrast, [6]. Kruszewski, M., Wojewódzka, M., Iwaneńko, T., Col-
the oxidative DNA damage in these cells was sig- lins, A.R., & Szumiel, I. (1998). Application of the
nificantly increased 7 days after per os adminis- comet assay for monitoring DNA damage in workers
CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY 57
exposed to chronic low dose irradiation. II. Base dam- L.M., Kruszewski, M., Lankoff, A., Sandberg, W.J.,
age. Mutat. Res., 416, 37-57. Refsnes, M., Skuland, T., Schwarze, P., Brunborg, G.,
[7]. Kruszewski, M., Grądzka, I., Bartłomiejczyk, T., Chwa- Bjøras, M., Collins, A., Miadoková, E., Gálová, E., &
stowska, J., Sommer, S., Grzelak, A., Zuberek, M., Lan- Dušinská, M. (2012). Silver nanoparticles induce pre-
koff, A., Dusinska, M., & Wojewódzka, M. (2013). mutagenic DNA oxidation that can be prevented by
Oxidative DNA damage corresponds to the long term phytochemicals from Gentiana asclepiadea. Muta-
survival of human cells treated with silver nanopar- genesis, 27, 6, 759-769.
ticles. Toxicol Lett., 219, 2, 151-159.
[8]. Hudecová, A., Kusznierewicz, B., Rundén-Pran, E.,
Magdolenová, Z., Hasplová, K., Rinna, A., Fjellsbø,
Halloysite clay nanotubes have been developed for ZrO2 show the highest stability under similar
a controlled release of anticorrosion agents [1] sus- conditions. In result of incubation in the LHC-9
tained release of drugs and proteins has also been medium the size of HNs increases to > 1 m.
obtained. The latter property was the reason of in- To characterize the in vitro effect of HNs
creased interest in halloysite application for drug and compare it with that of CeO2 and ZrO2 we
delivery. Modified halloysite was used in in vitro used adenocarcinomic human alveolar basal epi-
experiments for drug delivery (e.g. [1, 2]). Yet the thelial cells, A549, and their normal counterpart,
effects of its presence in culture medium on mam- BEAS-2B. The cell cultures seeded 24 h earlier
malian cells are not recognized. Here, unmodified were then incubated for 24 h or 72 h in cell cul-
halloysite preparation (nanotubes, 100 nm of ture medium containing the studied nanoparticles
length, Sigma-Aldrich) was used to check its effect at various concentrations. To estimate the meta-
under cell culture conditions and compare it to bolic activity/viability of nanoparticle-treated cells
other nanomaterials: cerium oxide (CeO2) and zir- the Alamar Blue test was applied, where resazurin,
conium oxide (ZrO2) nanoparticles (NPs). The a non-fluorescent indicator dye, is converted to
cerium oxide NPs exhibit a considerable ability to bright red-fluorescent resorufin via the reduction
induce oxidative stress in mammalian cells [3]. In reactions of metabolically active cells i.e. able to
contrast, zirconium oxide NPs have vast technical maintain a reducing environment within the cyto-
applications, whereas they rarely exert pronounced sol. The fluorescence measured is proportional to
cytotoxic effects. However, they are known to in- the number of living cells and corresponds to the
hibit cell proliferation, induce DNA damage and metabolic activity/viability.
apoptosis by reducing the cell defense mechanism Under the conditions applied none of the exam-
against oxidative stress [4]. ined nanoparticles exerted a significant cytotoxic
To characterize the halloysite nanotubes (HNs) effect, as shown in Table 1. The measure of the
applied here we measured their hydrodynamic di- NPs effect was IC90 or IC50, that is, NPs concen-
ameter, zeta potential and aggregation (polydis- tration that reduced the metabolic activity by 10%
persity index) and compared the results with those or 50% as compared to the control. There was a
obtained for the other two nanoparticles. We used similar weak response of BEAS-2B cells to all
the DLS (dynamic light scattering) method and three NPs. The largest difference was between IC50
the Zetasizer Nano ZS (Malvern) at various in- values for 72 h incubation of A549 cells between
tervals after sonication in water and transfer into CeO2 and HNs. Since both NPs tend to aggregate
culture media used for the cell lines investigated. in serum-supplemented cell culture medium, ag-
HNs and CeO2 tend to aggregate in cell culture gregation is not the causal factor. Rather, the dif-
media supplemented with fetal calf serum; this ference may be due to NP-specific interactions
tendency is particularly strong in HNs, whereas 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.
culture media or on cell surface. In that case, the [2]. Lee, Y., Jung, G.E., Cho, S.J., Geckeler, K.E,. & Fuchs,
adverse effect may be observed in the absence of H. (2013). Cellular interactions of doxorubicin-load-
NPs internalization. In summary, in tests in vitro, ed DNA-modified halloysite nanotubes. Nanoscale, 5
(18), 8577-8585.
HNs seem not to be a harmful nanomaterial.
[3]. Park, E.J., Choi, J., Park, Y.K., & Park, K. (2008). Oxi-
Nevertheless, further studies with the use of dif- dative stress induced by cerium oxide nanoparticles in
ferent experimental models are needed to clarify cultured BEAS-2B cells. Toxicology, 245 (1-2), 90-100.
this point. [4]. Asadpour, E., Sadeghnia, H.R., Ghorbani, A., & Boro-
ushaki, M.T. (2014). Effect of zirconium dioxide nano-
References particles on glutathione peroxidase enzyme in PC12 and
[1]. Lvov, Y., Aerov, A., & Fakhrullin, R. (2014). Clay nano- n2a cell lines. Iran. J. Pharm. Res., 13 (4), 1141-1148.
tube encapsulation for functional biocomposites. Adv.
Colloid Interface Sci., 207, 189-198.
Carbon nanomaterials are becoming increasing- (adenocarcinomic human alveolar basal epithelial
ly common in everyday life. Among them, single cells) were treated with a range of doses of SWCNTs
walled carbon nanotubes (SWCNTs) are attract- and DEPs. The alkaline comet assay with the for-
ing significant attention as a novel material in the mamido-pyrimidine glycosylase (FPG) was carried
field of medicine for molecular imaging, biodetec- out to estimate the extent of oxidative DNA dam-
tion of disease markers, tissue engineering, devices age. Percent of DNA in comet’s tail was chosen
for drug delivery and nanotargeted radionuclides as a measure of DNA breakage. Cytotoxicity of
for tumour nuclear imaging and internal radio- SWCNTs and DEPs was determined with the
therapy [1]. Such common applications in medi- sulphorhodamine B assay (not shown) and clono-
cal field raise concerns regarding the interaction genic survival assay.
of SWCNTs with biological molecules in the hu- Figure 1 shows that the extent of X-ray (2 Gy)
man body. Moreover, apart from medical exposure, induced SSB (single strand breaks) is not modified
SWCNTs can be absorbed into the body by inha- by SWCNTs or DEPs treatment. In contrast, the
lation of engine emissions containing diesel ex- treatment considerably decreases the rate of re-
haust particles (DEPs) during the combustion of pair of the oxidative DNA damage induced by 2
diesel and biodiesel fuels in the urban environ- 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 vival data and shows that the difference between
possible adverse effects of SWCNTs and DEPs is SWCNTs and DEPs cytotoxicity is not significant.
very imperative and urgent. However, the obtained data indicate that the ex-
Taking this into consideration the aim of our posure to SWCNTs and DEPs decreases the colony
study was to determine the impact of SWCNTs forming ability of A549 cells and also the colony
and DEPs on DNA repair and cell survival in forming ability of A549 cells irradiated with 2 Gy
A549 cells. The exponentially growing A549 cells of X-rays.
CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY 59
A 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 [2]. Wang, J., Sun, P., Bao, Y., Liu, J., & An, L. (2011).
and DEPs in various biological models shows a Cytotoxicity of single-walled carbon nanotubes on
complicated pattern of damaging effects depend- PC12 cells. Toxicol. In Vitro, 25, 1, 242-250.
[3]. Kumarathasan, P., Breznan, D., Das, D., Salam, M.A.,
ing both on particle characteristics, cellular models
Siddiqui, Y., MacKinnon-Roy, C., Guan, J., de Silva,
and end-points analysed [2-4]. N., Simard, B., & Vincent, R. (2015). Cytotoxicity of
This project is funded from Norway grants in carbon nanotube variants: A comparative in vitro ex-
the Polish-Norwegian Research Programme oper- posure study with A549 epithelial and J774 macro-
ated by the National Centre for Research and De- phage cells. Nanotoxicology, 9, 2, 148-161.
velopment: Pol-Nor/201040/72/2013 (FuelHealth). [4]. Durga, M., Nathiya, S., Rajasekar, A., & Devasena, T.
(2014). Effects of ultrafine petrol exhaust particles on
References cytotoxicity, oxidative stress generation, DNA damage
[1]. De Volder, M.F.L., Tawfick, S.H., Baughman, R.H. & and inflammation in human A549 lung cells and murine
Hart, A.J. (2013). Carbon nanotubes: present and future RAW 264.7 macrophages. Environ. Toxicol. Pharmacol.,
commercial applications. Science, 339, 6119, 535-539. 38, 2, 518-530.
OC
L
CCC
A
1 2 3 4 5 6 7 8 9
# #
OC
L
CCC
B
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 endonu-
clease (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 abun- [3]. Gorbunov, N.V., Yalowich, J.C., Gaddam, A., Tham-
dant antioxidant, GSH. This sheds new light on patty, P., Ritov, V.B., Kisin, E.R., Elsayed, N.M., & Ka-
the iron-related protective effect of NO under the gan, V.E. (1997). Nitric oxide prevents oxidative dam-
age produced by tert-butyl hydroperoxide in erythro-
circumstances of oxidative stress.
leukemia cells via nitrosylation of heme and non-heme
References iron. Electron paramagnetic resonance evidence. J.
Biol. Chem., 272, 19, 12328-12341.
[1]. Lewandowska, H., Kalinowska, M., Brzóska, K., Wój- [4]. Lewandowska, H., Sadło, J., Męczyńska, S., Stępko-
ciuk, K., Wójciuk, G., & Kruszewski, M. (2011). Ni- wski, T.M., Wójciuk, G., & Kruszewski, M. (2015).
trosyl iron complexes – synthesis, structure and biology. Formation of glutathionyl dinitrosyl iron complexes
Dalton Trans., 40, 33, 8273-8289. protects against iron genotoxicity. Dalton Trans., 44,
[2]. Lu, C., & Koppenol, W.H. (2005). Inhibition of the 28, 12640-12652.
Fenton reaction by nitrogen monoxide. J. Biol. Inorg.
Chem., 7, 732-738.
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 applica-
tion in a nuclear chemical engineering, radiobiological and environmental problems associat-
ed 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 lab-
oratories of the INCT and provides analytical services for them as well as for the outside in-
stitutions. The Laboratory is a producer of certified reference materials (CRMs) for the pur-
pose 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 absorp-
tion 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 pro-
tection.
In 2015, the Laboratory participated in the strategic research project from the National
Centre for Research and Development (NCBR), Poland “New technologies supporting devel-
opment 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 scien-
tific institutes. Within the scope of the MODAS project, the Laboratory was involved in prep-
aration 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 Har-
monized Protocol (2006).
62 LABORATORY OF NUCLEAR ANALYTICAL METHODS
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 tion (LOD) in the range 0.12-0.66 mg/L, while
persistence of perfluorinated organic compounds with additional solid-phase extraction step, the de-
(PFCs) received worldwide attention in recent termination of 50 g/L was possible. A reversed-
two decades [1, 2]. They are widely produced for -phase HPLC method was developed based on
various applications in recent decades as stable derivatization of the PFCAs with 3-bromoacetyl
and efficient surfactants, are utilized in syntheses coumarin [18]. With a 100-fold SPE preconcen-
of fluorinated polymers and are applied in house- tration, the LOD values in the range 43-75 ng/L
hold products and cosmetics [3]. Their unusual sta- were reported. Different approaches using solid-
bility in the environment and resistance to chemi- -phase extraction methodology for preconcentra-
cal and biochemical degradation result in a wide tion of PFCAs have been developed. For the de-
global proliferation, including remote regions with- termination with LC/MS, the methodology using
out and anthropogenic activity. They are present C18 sorbents has been mainly used by various
commonly in groundwater and drinking waters [4] authors, which is limited for long-chain acids [19].
and in human organisms [5, 6]. It is commonly Also the application of polymeric sorbents Oasis
known of their accumulation in particular organs HLB and Oasis WAX mixed-mode weak anion-ex-
and incorporation into a lipid cell wall. The two change reversed phase for PFCAs’ preconcentra-
most commonly detected species such as perfluoro- tion has been presented [20].
octanoic acid (PFOA) and perfluorooctane sul- A large number and diversity of PFCs occur-
phonic acids (PFOS) globally occur in human ring in environment, as well as the complexity of
bloods and serum samples at g/L level, hence their identification and determinations, create in-
wide investigations concerning the toxicity of those creasing interest in the evaluation of the valuable
compounds for humans [7, 8]. The suspected ef- and informative general parameter known as total
fects include hepatotoxicity, carcinogenicity, im- organic fluorine (TOF) [21]. The determination of
munotoxicity and developmental toxicity. Recent TOF with sufficient selectivity and low detection
studies show concern about hepatotoxicity of limit is necessary to obtain a mass balance of TOF
PFOA for the occupationally exposed humans and in environmental and biological samples, as well
immunotoxicity by PFOS [9]. Some effects of as, e.g. for monitoring of degradation processes of
PFCs on reproductive hormones in humans were fluorinated organic compounds. Such determina-
also discovered [10]. The presence of PFCs is in- tions can be carried out directly, e.g. by using 19F
vestigated also in indoor and outdoor air; how- NMR [22], but most commonly, they are carried
ever, exposure via inhalation appears a minor out by the release of fluorine from organic com-
pathway [11]. An increasing attention is also fo- pounds and analytical determination of fluoride
cused in recent decade on the monitoring of their ion. The release of fluorine can be achieved with
content in foods, which, besides water, is the most different methods, including combustion with oxy-
significant exposure route for humans [12]. gen in the furnace at 900-1000ºC [23] or by the
Monitoring PFCs’ concentration in trace level reaction with sodium biphenyl (SBP), which was
in complex matrices is a serious analytical chal- reported in our earlier work [24]. In the latter
lenge. Reliable methods of extraction, separation case, the hydrolysis of the reaction mixture leads
and identification in complex matrixes are necess- to the formation of inorganic fluoride, which can
ary. The difficulty in determining PFCs is very low be then determined with various methods, for in-
concentration in the samples (ng-pg/L or ng-pg/g) stance, by potentiometry with ion-selective elec-
and complexity of matrices [13, 14]. Numerous trode or ion chromatography. In our earlier works,
analytical methods have been developed to deter- we have found a method originally used for the
mine PFCs and most of them are chromatographic determination of fluoride by gas chromatography
methods [15, 16]. For the determination of per- to be especially convenient in terms of detectabil-
fluorinated carboxylic acids (PFCAs), one of the ity and selectivity [25]. It is based on reaction of
most frequently occurring and determined group fluoride with trimethylhydroxysilane to form tri-
of PFCs, in analytical procedures without deriva- methylfluorosilane, and following this principle,
tization, liquid chromatography with mass spectro- we used triphenylhydroxysilane (TPSiOH) for
metry detection (LC/MS) and electrospray ioniza- fluoride derivatization (R – phenyl):
tion are most commonly used in the analysis of R3SiOH + H+ + F– R3SiF + H2O
environmental and biological samples. Also in- The obtained triphenylfluorosilane (TPSiF)
strumentally simpler methods such as, e.g. ion can be determined by gas chromatography (GC)
chromatography with conductivity detection for with MS or flame ionization (FID) detections [26],
the separation of PFCAs having C3-8 alkyl chains as well as with reversed-phase HPLC with UV de-
have also been proposed [17] with limit of detec- tection [27].
LABORATORY OF NUCLEAR ANALYTICAL METHODS 63
The aim of the conducted investigations was phase was taken for GC/FID analysis. Parallel pre-
the comparison of results of the determination of pared preconcentrated samples were taken for
TOF by GC/FID with defluorination using SBP LC/MS analysis for the determination of PFACs
and derivatization with TPSiOH in natural waters from C3 to C12 and PFOS.
and milk samples with results of the determina- Chromatograms are shown in Fig.1, which were
tion of selected PFOAs and PFOS using LC/MS. recorded for GC/FID determinations of TOF us-
The efficiency of TOF determination was also ex- ing gas chromatograph HP 5890 Series II (Agi-
amined for selected fluorinated pharmaceuticals lent). Figure 1A shows chromatograms for reac-
and pesticides using HPLC with UV detection. tion mixture after derivatization with TPSiOH for
The samples of natural waters were filtered with water as blank and for 10 M standard fluoride
0.45 m filters and preconcentrated from 400 mL solution, which indicated a very satisfactory se-
using Sep-Pak Vac C18 (Waters) columns with lectivity and chromatographic efficiency of fluo-
500 mg sorbent bed, then retained analytes were ride determination with developed method. Figure
eluted with methanol and acetonitrile (ACN) and 1B shows chromatograms recorded for 50 ng/L
evaporated almost to dryness in argon atmosphere. standard PFOA solution, cow milk and cow milk
Samples of milk (5 mL of human milk samples and sample spiked with 50 ng/L PFOA, as well as blank
100 mL of cow milk Łaciate 0%) were diluted of deionized water with signal below LOD for de-
with 0.1 mM formic acid solution and analytes veloped method.
A B Deionized water
10 ng/L PFOA standard
Milk
Milk spiked with 10 ng/L PFOA
Detector response
Detector resposne
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) As natural samples were taken tap waters and
columns with 60 mg bed and then eluted with 1 mL river waters collected in Warsaw, and also in Tar-
of 1% NH3 in ACN [28]. Using LC/MS, individual nów, in vicinity of large chemical plant producing
PFCs were determined, while after evaporation fluorinated compounds, including Polish polytetra-
almost to dryness, defluorination with SBP was fluoroethylene. The examined milk samples includ-
carried out. To the sample evaporated for defluor- ed commercial cow milk Łaciate 0% and two sam-
ination, 300 L SBP solution was added, and after ples of human milk obtained from the Regional
10-min reaction, 700 L of water was added. After Women Milk Bank in Holy Trinity Hospital in
hydrolysis was processed, to the aqueous phase Warsaw. The LC/MS determinations of individual
the solution of TPSiOH in ACN was added and PFCs were carried out using HPLC system equip-
HClO4, and after 10 min reaction, the organic ped 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 de-
rivatization with TPSiOH. C7-PFCA – perfluoroheptanoic acid, C9-PFCA – perfluorononoic acid, C10-PFCA – per-
fluorodecanoic 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).
Sample C7-PFCA PFOA C9-PFCA C10-PFCA PFOS F 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 LABORATORY OF NUCLEAR ANALYTICAL METHODS
and reversed-phase C18 Eclipse XDB column (5 of commonly occurring PFOA and PFOS was ob-
m, 250 mm, 4.6 mm I.D.) from Agilent, with gra- served (except PFOS in tap water from Warsaw).
dient elution using 10 mM formic acid solution From examined PFCAs, in river water samples,
and increasing content of ACN. different levels of C7-PFCA and C9-PFCA were
Fig.2. Determination of fluorinated and perfluorinated Fig.3. Determination of fluorinated and perfluorinated
organic compounds using HPLC and LC/MS and TOF us- organic compounds using HPLC and LC/MS and TOF us-
ing GC/FID in natural water samples after solid-phase ing GC/FID in human and cow milk samples after solid-
preconcentration using Waters Sep-Pak Vac C18 columns, -phase preconcentration using Waters Sep-Pak Vac C18
defluorination with sodium biphenyl and derivatization columns, defluorination with sodium biphenyl and deri-
with TPSiOH. vatization with TPSiOH.
The obtained results are presented in Table 1, found, while in milk samples, mostly C7-PFCA
and Figs.2 and 3 show the results on histograms. was detected. In all examined samples, the con-
As it can be expected from the vast literature, in tent of other non-identified perfluorinated com-
all examined water and milk samples, the presence pounds range from 12-13% up to 60-80% in case
Table 2. Characteristics and applications of selected fluorinated pharmaceuticals and pesticides examined for their recov-
ery in the procedure for TOF determination used for perfluorinated organic compounds.
Anti-inflammatory
Dexamethasone Up to 22.6 ng/L in wastes [30]
steroid
of water samples. These results convincingly con- in consumer products in Norway – A pilot study.
firm the importance of the determination of TOF Chemosphere, 88, 8, 980-987.
as the most informative parameter indicating the [4]. Eschauzier, C., Raat, K.J., Stuyfzand, P.J., & De Voogt,
P. (2013). Perfluorinated alkylated acids in ground-
content for that class of compounds in examined
water and drinking water: identification, origin and
samples. mobility. Sci. Total Environ., 458-460, 477-485.
As a supplementary investigation for these [5]. Kärrman, A., Domingo, J.L., Llebaria, X., Nadal, M.,
studies, the efficiency of the developed method Bigas, E., van Bavel, B., & Lindström, G. (2010). Bio-
for TOF determination was examined for selected monitoring perfluorinated compounds in Catalonia,
fluorinated pharmaceuticals and pesticides, which Spain: concentrations and trends in human liver
are widely used nowadays, and some of them were and milk samples. Environ. Sci. Pollut. Res., 17(3),
already examined in environmental samples (Table 750-758.
2). As it is shown in histogram in Fig.4, except [6]. Fromme, H., Tittlemeier, S.A., Völkel, W., Wilhelm,
5-fluorouracil, for the investigated level of 20 M, M., & Twrdella, D. (2009). Perfluorinated compounds
– Exposure assessment for the general population in
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similarly to included in the same histogram PFCAs [7]. Kudo, N., & Kawashima, Y. (2003). Toxicity and toxi-
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reversed-phase HPLC with UV detection at 254 [8]. Lau, C., Anitole, K., Hodes, C., Lai, D., Pfalhles-
nm, with the use C18 column type Grace™ Grace- -Hutchens, A., & Seed J. (2007). Perfluoroalkyl acids:
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methanol with acetic acid solution and increasing
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[10]. Vested, A., Ramlau-Hansen, C.H., Olsen, S.F., Bonde,
J.P., Kristensen, S.K. Halldorsson, T.I., Becher, G.,
Haug, L.S., Ernst, E.H., & Toft, G. (2013). Associa-
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Radioisotopes 90Sr and 99Tc belong to the most tant, however in the automated radionuclides de-
commonly determined radionuclides for environ- termination, the analyst is not exposed to emitted
mental, industrial, medical and food control pur- radiation due to remote computerized control of
poses [1, 2]. Usually, their determination with ra- whole system. Thus, flow systems became promis-
diometric methods or mass spectrometry (MS) in ing tools to apply for continuous monitoring of
complex matrix detection requires a laborious and radionuclides for industrial or environmental pur-
time-consuming sample processing, hence perform- poses. These studies were focused on optimization
ing such a processing in mechanized or automat- of the active sample processing in MSFIA-LOV
ed flow systems is especially attractive, offering system for 99Tc determination and on some addi-
shortened analyses time, enhancing safety of op- tional aspects of the procedure reported in Ref.
erations and improving the precision and accuracy [5] for the flow-injection determination of 90Sr
of numerous operations [3, 4]. Operations carried with inductively coupled plasma mass spectrometry
out in flow systems may include both preconcen- (ICP-MS) detection.
tration of the analyte and separation from other The essential feature of the MSFIA-LOV sys-
sample components, which may interfere in the tem (Crison Instruments, Spain) used in this work
detection. In the case of traditional manual tech- is the use of so-called lab-on-valve (LOV), a ro-
niques, the whole analysis may take even several tary, computer-controlled multiposition valve in-
days, while the automated flow methods may corporating a sorbent mini-column (microcolumn)
shorten analysis time to several minutes. The lab- (1.6 mm I.D./16 mm long) for conducting a pre-
oratory flow instrumentation, such as, for instance, concentration and separation processes. The mi-
a multisyringe system using the advanced lab-on- crocolumn can be automatically filled with re-
-valve (MSFIA-LOV) for sorbent bed renewal, newable beads of 40 mg of Sr-resin or 50 mg of
which is used in this study, offers the possibility of TEVA resin, which were contained in a 1 mL
conducting mechanized operations of active sample plastic syringe mounted on the outlet of one of
processing with small volumes of reagents and gen- microchannels of the LOV. A glass fibre prefilter
erated radioactive wastes. What is the most impor- (Millipore) is used at the end of the column to pre-
LABORATORY OF NUCLEAR ANALYTICAL METHODS 67
Fig.3. A calibration curve for the determination of 90Sr in The processed samples are off-line measured by
the activity range up to 1000 Bq/mL with ICP-DRC-MS ICP-MS. The scheme of developed procedure is
detection using methane as a reaction gas. shown in Fig.4, while their details are as follows:
• The TEVA resin is loaded into a microcolumn:
detection of reactor coolant in real sample ob- 1 mL of sorbent suspension (50 mg in 0.1 M
tained from research nuclear reactor in Świerk HNO3) is aspirated at a flow rate of 1 mL/min
(Poland). The 1 L sample of simulated reactor first to the holding coil and then to the micro-
water containing 130 Bq/L of 90Sr was analysed column built in the LOV.
in developed MSFIA-LOV system with program- • Conditioning of TEVA resin: the sorbent bed
med preconcentration and separation processes. is conditioned with 3 mL of 0.1 M HNO3 as-
First, whole sample in 10 mL portions (determined pirated by port 3 of LOV to the holding coil
by a volume of a syringe of the MSFIA unit) was and then to the microcolumn at flow rate of 2
loaded at a flow rate 10 mL/min to outer column mL/min.
filled with cation-exchange resin to preconcentrate • Sample loading: 1 mL of 250 g/L rhenium so-
90
Sr. The retained analyte was eluted with 3 mL lution, which was prepared in 0.1 M HNO3
of 8 M HNO3 and directly introduced to Sr-resin from 10 mg/L sodium perrhenate solution, is
microcolumn in LOV, where the separation process aspirated by port 4 in LOV to the holding coil
took place. Finally, strontium was eluted with 10 at a flow rate of 5 mL/min and then injected to
mL of water and measured by ICP-DRC-MS. The TEVA resin bed packed in the microcolumn at
total recovery of 90Sr was 69% and the whole pro- a flow rate of 0.6 mL/min.
cedure took 6 h; however, some further attempts • Removal of interferences: The potential inter-
will be focused on shortening the analysis time. ferences are removed from TEVA bed by inject-
LABORATORY OF NUCLEAR ANALYTICAL METHODS 69
ing 1 mL of 0.1 M HNO3 from port 3 at a flow are shown in Fig.5. They demonstrate that all iso-
rate of 5 mL/min to the holding coil and then baric interferences have weak affinity to TEVA
aspirated through the microcolumn at a flow resin, and hence they can be almost completely
rate of 2 mL/min. 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 microcol-
umn 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 only up to 10% of their initial content can be pre-
the resin is eluted with 1 mL of 8 M HNO3 at a sent in the final eluate with the analyte.
flow rate of 2 mL/min. The conducted optimization also included the
• ICP-MS detection: The solutions of rhenium examination of the TEVA resin bed durability in re-
eluted from the column are collected and dilut- peated retention/elution cycles. The portion of the
ed 20 times with 2% HNO3 containing 5 g/L sorbent (50 mg) loaded into the microcolumn al-
of indium as an internal standard prior to the lowed to carry out at least 30 successive analyses.
measurement. The analysis included injection of 1 mL sample of
In the optimization of the flow procedure for rhenium solution (250 g/L), elimination of inter-
99
Tc determination, the first studied aspect was ferences by washing the column with 2 mL of 0.1
the elimination of potential interferences that M HNO3 solution, and elution of the analyte with
may disturb the used ICP-MS detection. 99Ru and 1 mL of 8 M HNO3. The collected fractions were
98
Mo1H are considered as the main isobaric inter- analysed with ICP-MS. The results of the experi-
ferences. In the literature, one can find two differ- ment are presented in Fig.6. In further research,
ent methods applied in purpose to separate tech-
netium from molybdenum and ruthenium on TEVA
resin. First one assumes the elimination of the
mentioned interferences by use diluted HNO3 so-
lution [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 re-
sults in application in flow procedure. In the con-
ducted experiment, the potential isobaric inter-
Fig.6. Recovery of rhenium in repeated cycles of retention/
ferences molybdenum and ruthenium were added
elution on 50 mg bed of TEVA resin of 50-100 m particle
to the rhenium sample in equal concentration of size, evaluated by the determination of strontium in each
250 g/L. After loading and conditioning the TEVA stage of the procedure: () injection of 1 mL sample con-
resin bed in the microcolumn, 1 mL of analysed taining 250 g/L of rhenium into the column, () removal
solution was introduced into the sorbent bed and of interferences with 2 mL of 2 M HNO3, () final elution
then the interferences were removed with three of rhenium with 1 mL of 8 M HNO3.
successive 1 mL portions of 0.1 M HNO3 solu-
tion. Finally, the retained analyte was eluted with an attempt will be made to replace the same pur-
1 mL of 8 M HNO3. The collected fractions were pose of extracting TEVA resin with conventional
measured with ICP-MS, and the obtained results polymeric anionite.
70 LABORATORY OF NUCLEAR ANALYTICAL METHODS
Certified reference materials (CRMs) are refer- tent of elements to be certified in time. There are
ence materials accompanied by documentation various causes of instability of this type of CRMs
issued by authority institutions giving one or more such as decomposition of the analyte or matrix,
specified property values with associated uncer- autocatalysis and the activity of the microorgan-
tainties and consistencies using the procedures of isms. In order to test the stability of CRM, the
proven regularity. These materials play an impor- samples of the candidate CRM were stored at vari-
tant role in the chemical measurements in analyti- ous temperatures and analysed after the chosen
cal laboratories [1-3]. They are used to validate time intervals [13]. The obtained results were sub-
analytical methods, quality assurance and quality jected to the statistical analysis.
control, check skills of laboratories and analysts In this work, we have studied the stability of
[4-6]. The process of preparation and certification the new Polish reference materials of biological
of a candidate for reference material is a complex origin: MODAS-3 Herring Tissue (M-3 HerTis),
task. The general strategy of the production of new MODAS-4 Cormorant Tissue (M-4 CormTis) and
CRMs is based on the procedures from the Lab- MODAS-5 Cod Tissue (M-5 CodTis).
oratory of Nuclear Analytical Methods INCT [3-5], Long-term stability of the CRMs was examin-
which follow the requirements of ISO Guides [7]. ed by comparing analytical results of their elemen-
The manufacture of CRMs consists of the follow- tal composition obtained at 0, 2, 4, 6, 10, 12 and
ing steps: (a) choice of the type of material, (b) 15 months of storage. The samples were taken
collection of the suitable amount of material, (c) from CRMs stored under controlled conditions
preparation of the material (comminution, grind- (temperature – 20oC). Isochronous testing was ap-
ing, sieving, homogenization), (d) preliminary ho- plied, then the samples were frozen at -20oC and
mogeneity and stability tests, (e) distribution of analysed together at the end of the study. Then,
the material into containers and radiation sterili- the samples were mineralized in a high-pressure
zation, (f) procedure of the determination of dry microwave system using concentrated mineral
mass, (g) final check of homogeneity and stability acids. Samples of mass ca. 250 mg were digested
tests, (h) organization of the certification inter- with 6 mL of HNO3 and 2 mL of H2O2. After di-
laboratory comparison, (i) evaluation of results, gestion, all obtained solutions were diluted using
(j) printing of the certificate and finally (k) CRM 2% HNO3 and selected element content was deter-
ready – starting distribution and sale [5, 7-9]. The mined by inductively coupled plasma mass spectro-
important thing is to prepare the materials as ho- metry (ICP-MS). The elements to be determined
mogeneous and stable as possible [10-12]. Stabil- were Ag, As, Ba, Cd, Co, Cr, Cu, Fe, Mn, Mo, Pb,
ity testing is one of the ISO guides requirements. Sr, U, V and Zn. To study the short-time stability
CRMs for the purpose of inorganic trace analysis (associated with transport), the CRMs were stored
should be characterized with stability of the con- in the CO2 incubator (ASAB) at 37oC, 100% hu-
LABORATORY OF NUCLEAR ANALYTICAL METHODS 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).
November February
January 2014 March 2014 May 2014 July 2014 March 2015
Elements 2014 2015
[g/g] [g/g] [g/g] [g/g] [g/g]
[g/g] [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
Cu 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
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
Zn 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
HerTis - - - - - - -
Se 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
CormTis 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
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 3.67 ±0.07 3.47 ±0.02 3.80 ±0.11
CormTis 0.260 ±0.07 0.206 ±0.02 0.240 ±0.01 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
Cd 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
As 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
midity and 5% CO2 for two months. Then, the was applied. Functions c = a t + b were calcu-
samples were taken and analysed by ICP-MS. lated for the following elements: MODAS-3
To check the stability, we have applied the Herring Tissue – U, Ba, Zn, Mn, Co, Cd, Th, Cu,
ICP-MS method for the determination of selected Pb, Sr, Cr, Al, V, Mg, Ni, Fe, Mo, Li, Be, As, Ag,
elements in new CRMs: Herring, Cod, Cormorant Tl, Sb; MODAS-4 Cormorant Tissue – U, Ba, Zn,
Tissue. The obtained results are shown in Table 1. Mn, Co, Cd, Th, Cu, Pb, Sr, Cr, Al, V, Mg, Ni, Mo,
The results were evaluated using the regression Li, Be, As, Ag, Tl, Sb, Se and MODAS-5 Cod
analysis. It was assumed that the relation c = f(t), Tissue – Ba, Zn, Mn, Co, Cu, Sr, Cr, Al, V, Mg, Fe,
where: c – element concentration, t – time, could Li, As, Se. An example of the regression line is
be described as a straight line, i.e. the changes if shown in Fig.1.
occurring were small. The least square method For all the determined elements in the studied
Concentration, mg kg-1 CRMs, no evidence of any trend (value of a did
1.0 not differ in a statistically significant way from 0)
0.9
M-3 HerTis was revealed. The contribution of uncertainty as-
Cd sociated with long-time stability to standard un-
0.8
certainty of CRM was evaluated. The uncertainty
0.7
of stability was calculated as the standard devia-
0.6 tion of the slope of the regression line. The uncer-
0.5 tainty of short-time stability was found to be in-
0.4
significant. The obtained results allowed to con-
clude that the prepared materials M-3 HerTis,
0.3
M-4 CormTis and M-5 CodTis meet the require-
0.2 ments for CRMs and are sufficiently stable.
0.1 This project is financed in the framework of
0.0
grant entitled “Production and attestation of new
0 5 10 15 20 types of reference materials crucial for achieving
Time, months European accreditation for Polish industrial lab-
Fig.1. Concentration of cadmium in MODAS-3 Herring oratories” attributed by the National Centre for
Tissue during storage. Research and Development.
72 LABORATORY OF NUCLEAR ANALYTICAL METHODS
A A
B
B
[1]. Arnold, L., Averlant, G., Marx, S., Weickert, M., Mül-
ler, U., Mertel, J., Horch, C., Peksa, M., & Stallmach, F.
LABORATORY OF MATERIAL RESEARCH 77
The study of the composition and the content of of the early mediaeval Central Europe coins. The
the trace elements of ancient coins provides valu- Sachsenpfenning struck from the mid-tenth cen-
able information about the metallurgy and economy tury till the end of the eleventh century were se-
of the time of minting the coins. A material re- lected for the examination. For comparison, the
search on the historical artefact constitutes an Otto and Adelheid denarii (AD 991-995), Arabic
important additional factor that helps us to choose dirhams, Hungarian and Czech denarii as well as
the proper conservation methods. The goal of the the Polish ones, the Bolesław Chrobry, Bolesław
research project was to characterize a few groups Śmiały, Władysław Herman and the Paltine Sie-
ciech 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
Saxon coin type I – obverse, reverse
(PIXE) may not result in reliable bulk composi-
tion data due to silver enrichment of the near sur-
face layers. In our work, the prompt-gamma acti-
vation analysis (PGAA) method was chosen as the
analytical method largely on the basis of ready ap-
plication 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
Saxon coin type I – obverse, reverse 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 de-
termine their silver and copper content. Indeed,
the PIXE measurements of the test samples taken
from different surface points of one particular coin
Saxon coin type II – obverse, reverse show very inhomogeneous composition. Conse-
quently, 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
Saxon coin type V – obverse, reverse
different sensitivities. In principle, it is possible to
determine both the major and the trace elements
100
prompt
10
decay
background
1
Intensity (cps)
0.1
0.01
0.001
0.0001 10
108
Ag 110
0 1000 2000 3000 4000 5000 6000 Ag
Intensity (cps)
E (keV) 1
0.001
110Ag 24.6 s 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 identical sample can be returned to the user. How-
matrix-dependent. The measurements do not re- ever, one has to be careful with irradiation of Ag
quire sample preparation; they give prompt re- because (n,) the reaction on silver produces a
sults. Moreover, usually after some days of cool- long-life radioactive daughter (see below). Because
ing (i.e. decay of radioactive products), the same of the limited irradiation time and the complexity
OAP type IV
2,5
denarii type VI-C
Cu/Ag
2,0
denary krzyżówe typ VI-E
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.
LABORATORY OF MATERIAL RESEARCH 79
of elemental silver’s spectrum, we decided to de- urement time for one individual coin varied be-
termine the Cu/Ag ratios, instead of trace ele- tween 460 s and 3700 s.
ments’ identification. Although in most of the practical applications
PGAA is based on the detection of gamma-ray in archaeometry [4, 5], PGAA is suitable for the
photons, which are emitted after the capture of determination of both major and trace compo-
thermal or subthermal neutrons into the atomic nents, and in the case of silver objects it is almost
nuclei, i.e. the (n,) reaction. The photon energies impossible to detect significant trace elements.
range between 50 keV and 11 MeV and are char- First, the limited irradiation time was not suffi-
acteristic for a given element. The element identi- cient to reach the detection limits of most traces;
fication is based on the precise determination of second, the complexity of the elemental silver spec-
gamma photon energies and intensities. The de- trum and the high spectral density of prompt-
tected gamma-ray intensity is directly proportion- -gamma peaks cause numerous peak overlaps,
al to the mass of a given element, the analytical which makes the element identification much more
sensitivity and the measurement time. difficult than in the case of most other matrixes.
Instead of direct determination of every indi- In order to determine the Cu/Ag mass ratios, the
vidual component’s mass, we apply the compara- practically interference-free 277.993 keV prompt-
tor method, or k0-method, which is widely used in -gamma peak of Cu and the 198.522 keV prompt-
instrumental neutron activation analysis (INAA). -gamma peak of Ag were chosen (Fig.3). The pos-
The k0 factors have been previously determined sible peak overlapping was investigated, based on
from standardization measurement at the Buda- BNC PGAA data library [5]. The theoretically
pest PGAA laboratory. A much more detailed overlapping peaks for Cu – 277.993 keV (viz. Co
standardization procedure is described by Révay – 277.199 keV, Ir – 278.328 keV) and for Ag –
and Molnár [2]. 198.522 keV (viz. Ga – 198.002 keV, Cs – 198.111
The PGAA measurements were performed at keV, Er – 198.267 keV, As – 198.701 keV, Gd –
neutron-induced prompt-gamma spectroscopy fa- 199.421 keV, Re – 199.439 keV and Ho – 199.659
cility (Fig.2) at the Budapest Neutron Centre keV) were excluded based on practical considera-
(BNC). A guided cold neutron beam, obtained tions.
from the 10 MW Budapest Research Reactor, is Obtained results for all the 55 coins are shown
used for the purpose of PGAA analysis. The ther- in Table 1. The bulk analysis of the coins has re-
mal neutrons, which exit the reactor core, are vealed an increasing Cu/Ag ratio as a function of
cooled by a liquid hydrogen cell down to 16 K. time. The mass ratio varies from about 0.03 to
Consequently, the achieved thermal equivalent about 4.24. The significant increase of Cu con-
neutron flux is 5 107 cm–2s–1 [3]. The size of the tent, which is impossible to state by visual obser-
neutron beam was restricted to 1 1 cm2 area. vation, can be discovered in Fig.4. This tendency
The investigated coins were packed in thin teflon probably indicates the course of inflation at that
(FEP) films and were placed in a well-defined po- historical period.
sition of the sample holder chamber. In fact, be- Prompt-gamma activation analysis is a useful
cause of the unacceptably high long-lived radio- non-destructive tool to investigate the bulk com-
activity of 64Cu and 110Ag isotopes, which were position of valuable archaeological objects. In com-
produced during (n,) reaction, we had to reduce parison with X-ray fluorescence analysis, it pro-
the beam intensity. For this purpose, a perforated vides bulk silver content, which is free from errors
plastic sheet, containing 6Li, was introduced. due to surface leaching and diffusion of copper
According to a relative flux monitored by a thin during the corrosion process.
Cd-sheet, the estimated actual neutron flux was This work has been performed at the Budapest
as low as 1.7 106 cm–2s–1. The emitted gamma Neutron Centre, Hungary, within the contract
photons were detected with a complex HPGe-BGO CHARISMA of the EU.
detector system in Compton-suppression mode;
the signals were processed with a multichannel References
analyser. The spectra were evaluated with Hyper- [1]. Pańczyk, E., Sartowska, B., Waliś, L., Dudek, J., Weker,
met-PC software; the element identification was W., & Widawski, M. (2015). The origin and chronol-
performed on the basis of BNC prompt-gamma ogy of medieval silver coins based on the analysis of
chemical composition. Nukleonika, 60, 3, 657-663.
element library.
[2]. Révay, Zs., & Molnár, G.L. (2003). Standardisation
During the investigation of silver coins, we have of the prompt gamma activation analysis method.
focused on the determination of Cu/Ag ratio. The Radiochim Acta, 91, 361-369.
peaks of interest were fitted by Hypermet-PC and [3]. Révay, Zs., Belgya, T., Kasztovszky, Zs., Weil, J.L., &
mass ratios were calculated. The combined stand- Molnár, G.L. (2004). Cold neutron PGAA facility at
ard uncertainties of the mass ratios depend on Budapest. Nucl. Instrum. Meth. B, 213, 385.
the uncertainty of the counting statistics, the un- [4]. Szakmány, Gy., & Kasztovszky, Zs. (2004). Prompt
certainty of efficiency function and the uncertainty Gamma Activation Analysis: a new method in the
of k0 factors. The most dominating of them is the archaeological study of polished stone tools and
uncertainty of counting statistics. their raw materials. Eur. J. Mineral., 16(2), 285.
[5]. Révay, Zs., Molnár, G.L., Belgya, T., Kasztovszky, Zs.,
The method was previously checked on a set & Firestone, R.B. (2000). A new gamma-ray spectrum
of copper-silver standard alloys, obtained from the catalog for PGAA. J. Radioanal. Nucl. Chem., 244(2),
Institute of Standards for Noble Metals, Hungary, 383.
and a good agreement was found [4]. The meas-
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 tech-
nologies as flue gas and water treatment, wastewater purification, processing of different in-
dustrial 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).
POLLUTION CONTROL TECHNOLOGIES LABORATORY 83
One of the most dangerous pollutants in the air is dependencies between the concentrations of main
sulphur dioxide (SO2) and nitrogen oxides (NOx), species and time of irradiation, changes in remov-
especially NO and NO2. All of them are compo- al efficiencies of both pollutants within the time
nents of acid rain, which leads to the damage of of irradiation and the influence of absorbed dose
historical buildings and monuments as well as na- on the concentration of SO2 and NOx [1].
ture. Nitrogen oxides also cause eutrophication of This year, we validated the model by compar-
lakes, which results in lower content of oxygen in ing the results obtained by mathematical compu-
water. SO2 and NOx are produced in many indus- tation with the experimental results [2]. Condi-
trial processes, burning of fossil fuels or chemical tions of experiments and modelling are as shown
processes. To avoid releasing these oxides into the in Tables 1 and 2 giving the comparisons between
atmosphere, there are many methods that are used the results.
for the removal of these pollutants from exhaust- The average relative deviations for SO2 and
ed gases. One of the most promising methods is NOx are 9.5% and 11.5%, respectively. It shows
electron beam flue gas treatment (EBFGT), which that the model is in a good agreement with results
uses electron beam from accelerator to oxidize and obtained experimentally.
remove SO2 and NOx from gases. As it is a novel In order to provide a more thorough study of
approach, the intensified work is implemented to the influence of conditions on results, we decided
optimize the technology as well as to find out the to implement the factorial experiment and check
mechanisms of reactions, which are occurring dur- the response of the model in three cases: the worst,
ing the process. base and the best conditions for removal of NOx
Previously, the mathematical model based on and SO2. We decided to study five parameters as
the system of first-order differential equations was follows: irradiation dose, humidity content, NO
developed in programming environment MATLAB, initial concentration, temperature and ammonia
which finally contained 1034 reactions, where 115 stoichiometry. Conditions of experiment no. 3 were
species were involved. As a result, we obtained the 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 POLLUTION CONTROL TECHNOLOGIES LABORATORY
Table 2. Comparisons between the removal efficiencies of SO2 and NOx obtained from experiments and modelling.
relative deviation between modelling and experi- That can be explained by the fact that at this high
mental results for both pollutants. The best con- irradiation dose and high temperature, the rates
ditions for NOx removal were as follows: high dose of reactions, which lead to the generation of NOx,
and humidity, low NO initial concentration, high are increased. In the case of SO2, trends are more
temperature and concentration of ammonia. For straightforward leading to the conclusion that the
SO2 removal, the best conditions were almost the removal efficiency increases with higher doses.
same, with the difference in temperature (low tem- The other parameter, which significantly influ-
perature for the best case). The worst conditions ences the removal efficiency, is humidity. With in-
were reverse to the best case. Values are present- crease in content of water, the removal efficiency
ed in Table 3. increases for both pollutants. The decrease of tem-
Table 3. Parameter values used in factorial experiment.
The influence of the dose on the NOx and SO2 perature can slightly improve SO2 removal effi-
removal efficiencies in three different cases are ciency; however, the influence on NOx removal ef-
shown in Figs.1 and 2, respectively. Irradiation ficiency is not linear. During the worst conditions,
dose has a major effect on the removal of both the higher temperature is beneficial, on the con-
pollutants, especially when the dose is lower than trary to the best conditions when the lower tem-
10.2 kGy, the removal efficiencies drop signifi- perature is preferable. When the base case scenario
cantly. It can be noticed that when the best condi- is applied, the temperature effect is negligible. The
tions are applied, rising the dose over 10.2 kGy effect of inlet concentration of NO shows a similar
does not improve NOx removal efficiency, and it trend to temperature when considering the NOx re-
decreased in comparison to base condition case. moval efficiency. High inlet concentration is pref-
POLLUTION CONTROL TECHNOLOGIES LABORATORY 87
Fig.1. Influence of the dose on NOx removal efficiency in Fig.2. Influence of the dose on SO2 removal efficiency in
the worst, base and best case. the worst, base and best case.
erable only in the best condition scenario. Further- responsible for NO2 generation, which is caused
more, the SO2 removal efficiency decreases with by high dose and high temperature in the best
increase of NO inlet concentration. The growth of case scenario.
ammonia ratio significantly improves the removal • The removal efficiency of SO2 depends on dose,
efficiency of SO2 as well as NOx. Only in the best humidity, temperature, inlet concentration of
condition scenario, the content of ammonia does NO and ammonia stoichiometry. The depend-
not improve the removal of NOx. encies in the case of SO2 removal efficiency are
The conclusions are as follows: more straightforward than those related to NOx
• The developed model was in a good agreement removal efficiency.
with experimental results. With a good level of
accuracy, it can predict the behaviour of species References
involved in a process of electron beam flue gas [1]. Zwolińska, E., Gogulancea, V., Lavric, V., & Sun, Y.
treatment. (2014). Modelling study of the abatement of SO2 and
• The removal efficiency of NOx strongly depends NOx from the accelerated electron beam by using
MATLAB. In INCT Annual Report 2014 (pp. 95-96).
on a dose, humidity and ammonia ratio. The in-
Warszawa: Institute of Nuclear Chemistry and Tech-
fluence of temperature and inlet concentration nology.
of NO is dependent on other parameters. Model- [2]. Chmielewski, A.G., Tymiński, B., Dobrowolski, A., Il-
ling shows that when very high dose is applied, ler, E., Zimek, Z., & Licki, J. (2000). Empirical models
the removal efficiency in best case scenario is for NOx and SO2 removal in a double stage flue gas
lower than that with moderate conditions. This irradiation process. Rad. Phys. Chem., 57, 527-530.
can be explained by accelerating reaction rates DOI: 10.1016/S0969-806X(99)00419-3.
STABLE ISOTOPE LABORATORY
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 com-
position 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, envi-
ronmental 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 Guard-
ian (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 – profi-
ciency testing scheme).
The Stable Isotope Laboratory is open for any form of cooperation. We are ready to under-
take 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 composi-
tion. 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 spectro-
metry (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 STABLE ISOTOPE LABORATORY
Stable isotope analyses have been useful tool for Table 1. Carbon isotopic composition 13C for CO2 of dif-
food authenticity control. An important limitation ferent origin [1-4].
of the application isotopic method for food authen- Origin of CO2 13C – CO2 [‰]
ticity control is a lack of database of stable isotope
composition for different origin food. Stable Iso- Fermentation:
tope Laboratory of the Institute of Nuclear Chem- – C3 sugar -26 ÷ -20
istry and Technology (INCT) from many years – C4 sugar -12 ÷ -9
carries out a study on isotopic composition of food Air -8 ÷ -7
for the elaboration and implementation of new iso-
tope ratio mass spectrometry (IRMS) methods and Fossil fuels combustion:
– coal -33 ÷ -22
database for some food from Polish market. – petroleum -31 ÷ -25
Some of the most popular European sparkling – natural gas -75 ÷ -15
wines are as follows: French Champagne, Italian
Spumante, Portuguese Espumante, Spanish Cava, Carbonate sediments -14 ÷ 1
German Sekt and Russian Sovietskoye Shampan- Natural mineral water -7 ÷ -4
skoye. Other alcoholic sparkling drinks are cider
and beer. Sparkling wines can be in every type: Carbonated mineral waters -45 ÷ -28
extra brut, brut, sec, demi-sec, asti, doux. Non-al-
coholic sparkling beverages are natural and artifi- in sparkling drink from natural source (natural
cial carbonated mineral waters and a lot of car- fermentation or from spring) or by artificial car-
bonated soft drinks. bonation of those drinks? In the study, the stable
For sparkling wine is allowed only natural isotope method for the control (natural or exog-
methods of bubbles CO2 production by addition enous carbonation) of CO2 bubbles will be elabor-
of sugar to fermentation. The addition of sugar to ated to control the quality of sparkling drink and
produce CO2 bubbles in wine is allowed during their compliance with labelling.
the first fermentation or second fermentation. The The GasBench vials were initially filled by
addition of beet sugar (C3 plants – Calvin cycle) or flushing with helium 5.0 for 1 min. After that,
cane sugar and corn syrup (C4 plans – Hatch-Slack 100 l of CO2 gas was taken from the headspace
pathway) results in different isotopic composi- of the bottle with the sparkling drinks with the
tion of CO2. Artificial carbonated drinks typically use of the gastight syringe. CO2 was transferred to
using CO2 from industrial source results in other the GasBench vials with septum cap. The bottles
13C value (Table 1). with sparkling drinks were stabilized at room tem-
Subject of the study is to investigate the stable perature. The GasBench vials were put to the
carbon isotope composition of the CO2 bubbles of GasBench tray for the normal procedure of CO2
sparkling drinks for the control of authenticity of gas measurements.
the drinks. The basic aim was to identify the The isotopic composition was determined us-
source of CO2 in these drinks. Our method is to ing GasBench II (ThermoQuest) connected in con-
look for the range of the 13C values for authentic tinuous flow mode to DELTAplus (FinniganMat)
sparkling drinks. Basic problem is: Is the CO2 gas mass spectrometer. Every sample was measured
MW10
MW11
MW12
MW1
MW2
MW3
MW4
MW7
MW9
MW5
MW6
MW8
SW1
SW2
SW3
SW4
SW5
SW6
SW7
c1g
c2g
c3g
c4g
c5g
c6g
c7g
c8g
B1
B2
B3
-5
-10
-15
δ13C - CO2 [‰]
-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.
STABLE ISOTOPE LABORATORY 91
six times for carbon isotopic composition. The • The study will be continued for different com-
standard deviation of the values obtained from mercial sparkling drinks and the database for
measurements for 13C was 0.2‰. Polish mineral waters, ciders and beers will be
The isotopic composition of 13C in CO2 is fi- constructed. The correlation between a carbon
nally expressed by the following equation: isotopic composition 13C in CO2 and C2H5OH
for different authentic, alcoholic drinks will be
13 C 13 C tested.
12 C 12
SAMPLE C STANDARD References
13C vsPDB 1000 0 00
13 C [1]. Gonzalez-Martin, I., Gonzalez-Perez, C., & Marques-
12 C -Macias, E. (1997). Contribution to the study of the
STANDARD origin of CO2 in Spanish sparkling wines by determi-
nation of the 13C/12C isotope ratio. J. Agric. Food Chem.,
The measured values of 13C of sparkling drinks
45, 1149-1151.
are presented in Fig.1. [2]. Gaillard, L., Guyon, F., Salagoity, M.-H., & Medina, B.
We can see a big difference in carbon isotopic (2013). Authenticity of carbon bubbles in French ciders
composition 13C in CO2 in every group of prod- through multiflow-isotope ratio mass spectrometry
ucts. This is connected with different origin of the measurements. Food Chem., 141, 2103-2107.
CO2. Biggest difference we can see between min- [3]. Martinelli, L.A., Moreira, M.Z., Ometto, J.P.H.B., Al-
eral waters which contained a natural gas from carde, A.R., Rizzon, L.A., Stange, E., & Ehleringer, J.R.
spring and carbonated by industrial gas. This is (2003). Stable carbon isotopic composition of the wine
agreeable with the foreseen of these gases’ origin and CO2 bubbles of sparkling wines: detecting C4
(Table 1). sugar additions. J. Agric. Food Chem., 51, 2625-2631.
[4]. Cabañero, A.I., San-Hipólito, T., & Rupérez, M. (2007).
Conclusions are the following: GasBench/isotope ratio mass spectrometry: a carbon
• The final product of the study is a new simplified isotope approach to detect exogenous CO2 in spar-
method for origin control of CO2 in sparkling kling drinks. Rapid Commun. Mass Spectrom., 21(20),
drinks. It is necessary to test the sensitivity of 3323-3328.
the method for big population samples with
good origin confirmed.
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, accredita-
tion 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 “Issle-
dovatel” 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 LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES
In accordance with the recommendations of the A plan for the validation of methods for meas-
standard PN-EN ISO/IAC 17025:2005 [1], valida- uring the dose using calorimeters was prepared.
tion is the confirmation by examination and the It included the following:
provision of objective evidence that the particular • three groups of calorimeters manufactured by
requirements for a specific intended use are ful- the High Dose Laboratory, Risø: polystyrene –
filled. Validation of methods of measurement is old (nos. 829, 830, 904), polystyrene – new (nos.
documented course of action that repeatedly gets 1167, 1168, 1169), graphite (nos. 1191, 1192,
results that match the given criteria of acceptance. 1193);
Calibration of all types of calorimeters applied in • determination of calibration curves for doses
dosimetry system and used as routine dosimeters of electron radiation in the range 5-40 kGy;
should be checked by comparison with reference • creating a balance of uncertainty for calorimetric
standard or transfer standard dosimeter. A detail- method;
ed guidance on the experiment is shown in the • criterion for acceptance of calorimeter method
standard ISO/ASTM 51631:2013(E) [2]. – expanded uncertainty U (k = 2) 8%.
The Laboratory for Measurements of Technol- 45
ogical Doses (LMTD) has nine calorimeters manu-
Absorbed dose - alanine NPL [kGy]
40
factured by the High Dose Laboratory, Risø, Den- 35
mark. Manufacturer’s recommendations were to 30
calibrate the calorimeters by the user in real oper- 25
ating conditions and each time after receiving a 20
dose of total 2000 kGy. The calorimeters were 15 Calorimetr 829
irradiated with 10-MeV electron beams from an 10 Calorimetr 830
industrial 10-kW linear accelerator radiation (ac- 5 Calorimetr 904
celerator Elektronika 10/10). For control of ap- 0
plied doses, the alanine reference dosimeters hav- 0 5 10 15 20 25 30 35 40 45
ing the traceable to a primary standard maintained Absorbed dose - polistyrene calorimeters - old [kGy]
by the National Physical Laboratory – NPL (Ted- Fig.1. Examples of calibation curves DNPL = f(Dcal).
dington, UK) were used. The mean electron energy
measured by the wedge method was in the range For all three groups of calorimeters, calibra-
9.6-9.8 MeV. Approved doses range 5-40 kGy, cor- tion curves were determined as a function of
responding to routine sterilization process in the DNPL = f(Dcal). Examples of calibration curves are
Institute of Nuclear Chemistry and Technology shown in Fig.1. Results for alanine and calori-
(INCT). Dose measurements were performed us- meter dose measurements are given in Table 1 (in
ing software Caldose, Risø. example only dose 20 kGy). The results show the
Table 1. Results for alanine NPL and calorimeter dose measurements (~20 kGy).
agreement between doses measured with alanine rimeters and irradiation in accelerator Electronics
reference dosimeters and the calorimeters with a 10/10 did not exceed 8%.
Table 3. Measurement uncertainties of routine calorimetric dosimetry systems.
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 certifi-
cate 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 cer-
tificate, 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 de-
tection 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 assort-
ment 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 sup-
plement, food extracts are delivered from our domestic and foreign customers for examina-
tion 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 para-
magnetic 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 spec-
troscopy 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 spec-
troscopy 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 recommend-
ed 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 con-
taining 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 deter-
mination 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 organi-
zation of the control and monitoring of irradiated food around the country.
In May 2015, the Laboratory was invited to join the “Intercomparative exercise for qual-
ity 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 par-
ticipation of specialized analytical laboratories from many countries.
LABORATORY FOR DETECTION OF IRRADIATED FOOD 99
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.
the dish with thin layer of the sample. The weight The samples were examined as purchased and
of samples equalled to 3.0 ±0.2 g. Petri dishes then for the second time after calibrated irradia-
with sample powder were stored in dark before tion of samples with 60Co gamma rays from Gamma
the measurement, in order to avoid accidental ex- Chamber 5000 with the dose 5 kGy (dose rate –
position to bright light. The PPSL measurements 3.262 kGy/h). The obtained results (multiplier
were carried out with the reader produced by the flash counts) express correspond to the intensity of
Scottish University Research Reactor Centre PPSL of the sample. The obtained results are re-
(SURRC), actually an only producer of PPSL in- ferred to critical threshold values. If the number of
struments known. The analytical procedure of counts is less than 700 counts, the sample is classi-
PPSL measurements and the instrument adjust- fied non-irradiated, and if the number of counts
ments were based on European standard EN-13751. exceeds 5000, the sample is classified irradiated.
LABORATORY FOR DETECTION OF IRRADIATED FOOD 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 Number of counts Number of counts sample
of products investigated [kGy] [g] untreated samplea) irradiated with 5 kGya)
0 3.0674 374 1 245
T1A – Humavit
0.5 3.1298 1 183 2 881
diet supplement
5 3.0912 2 393 3 891
0 3.4826 148 4 692
T2B – Extra Spasmina
0.5 3.3127 1 283 3 934
diet supplement
5 3.4652 1 884 1 905
0 3.0612 339 74 892
T3A – PilexTM
0.5 3.0162 160 389 194 899
diet supplement
5 3.0116 320 201 520 260
0 3.0467 423 36 304
T1B – horsetail
0.5 3.0706 17 993 18 324
powdered
5 3.0707 10 417 13 631
0 3.0917 277 27 728
T2A – nettle leaves
0.5 3.0689 155 875 12 113
powdered
5 3.0587 23 613 26 022
0 3.0877 360 29 812
T2B – lemon balsam
0.5 3.0857 20 692 28 229
leaves
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
T3C – neem
0.5 3.0371 36 817 59 308
(Melia azadirachta)
5 3.0142 54 341 61 329
0 3.0269 297 2 410
T3C – amalaki
0.5 3.0753 3 253 4 225
(Emblica offcinalis)
5 3.1417 3 227 11 448
0 3.1032 439 918
DermoSkrzyp Forte
0.5 3.0120 608 1 241
diet supplement
5 3.0624 1 060 2 194
a)
Number of counts represents mean value of two measurements (deviation ±15%).
Table 2 comprehends the results obtained with diet -irradiated samples was extremely low, while for
supplements and their vegetal components obtain- samples irradiated with both 0.5 kGy and 5 kGy
ed with the use of PPSL method. was found too low to be classified as samples ir-
The PPSL measurements on samples designat- radiated (intermediate result between 700 counts
ed T3C, T1B, T1C, T2B, T2C, T3B and T3C deliver- and 5000 counts). Similar results were obtained
ed positive result. It means that both non-irradiat- after the examination of DermoSkrzyp Forte, a
ed and irradiated samples were classified properly diet supplement which was found irradiated by
(Table 2). The obtained numbers of counts were the producer. The described measurements con-
lower than 700 counts (non-irradiated samples) or clusively show that three of the five investigated
were higher than 5000 counts (samples irradiat- diet supplements did not deliver satisfactory re-
ed). These results have been confirmed after cali- sults as examined by the PPSL method.
brating irradiation of enumerated samples with 5 Conclusions
kGy. The investigation on three diet supplements
The measurements of samples designated T1A and six vegetal components of the latter showed
and T2A (diet supplements – Humavit and Extra that both groups of products can be investigated
Spasmina), which were done before and after cali- effectively whether irradiated by the TL method.
brating irradiation, did not deliver satisfactory It is not the case, however, with the PPSL method
results. The number of counts obtained with non- which was studied in parallel to the latter. The
102 LABORATORY FOR DETECTION OF IRRADIATED FOOD
PPSL examination of these samples was effective lower). Thus, both methods are suitable and ef-
in the studies on diet supplement vegetal compo- fective for the control of food articles irradiated
nents but was not satisfactory by the examination with low doses. These kinds of food products are
of diet supplements, the complex products. The quite probably present in food market as the con-
limited range of the usage of the PPSL method to sequence of the development and implementation
prove radiation treatment of diet supplements is of combined microbial decontamination methods
due to the small release of stimulated photolumi- such as thermal/radiation treatment.
nescence from investigated diet supplements in
contrast to their vegetal components. Diet sup- References
plement processing destroys probably in some de- [1]. FAO/WHO. General Standard for Irradiated Foods.
gree the structure of rigid parts of dried vegetal Codex Stan 106-1983, Rev.1-2003.
components suitable to trap irradiation energy giv- [2]. European Committee for Standardization. Foodstuffs –
Thermoluminescence detection of irradiated food from
ing rise to luminescence. The PPSL method for
which silicate minerals can be isolated. EN-1788:2001.
the detection of irradiation in food is relatively [3]. European Committee for Standardization. Foodstuffs
simple contrast to more complex and time con- – Detection of irradiated food using photostimulated
suming but more universal thermoluminescence luminescence. EN-13751:2009.
method. It remains very useful and reliable by the [4]. Directive 1999/2/EC of the European Parliament and
examination of irradiation of less complex prod- of the Council on the approximation of the laws of the
ucts such as spices, herbs, seasoning, etc. Member States concerning foods and food ingredients
The important achievement of the present study treated with ionizing radiation.
was that it was ascertained that both methods of [5]. Directive 1999/3/EC of the European Parliament and
the detection of irradiated food, TL an PPSL, are of the Council on the establishment of a Community
list of foods and food ingredients treated with ioniz-
suitable for the identification of food irradiated ing radiation.
with low doses of ionizing radiation (0.5 kGy and
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 indus-
try, medicine and protection of the environment;
• construction and industrial testing of a gamma scanner for diagnostics of industrial installa-
tions;
• 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 ma-
terials;
• 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 trans-
mission 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 measur-
ing equipment is used in a gamma scanner for diagnostics of large industrial installations.
104 LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS
In exploiting big multiphase installations, a very emission of soft beta radiation – 0.018 MeV. Total
important task is to maintain their proper technical applied activity was 6000 Bq. The tracer was in-
conditions. jected instantaneously in the input of fermenter
During the process run, some emergency states while charging the mixture from hydrolyser to fer-
can be observed, and it is important to identify their menter. The samples of materials were taken on
reasons and the places of their location. The appli- output of fermenter during the periodic discharge.
cation of nuclear techniques such as tracer method The activity of samples was measured with liquid
and scanning technique or computational fluid dy- scintillator Wallac-Guardian application. Taking
namics (CFD) method is very profitable in solving into account the requirement of clarity of measur-
these kinds of problems. The application of these ing samples, all taking from fermenter samples
techniques is presented in the example of big lab- were distillated before measuring procedure. The
oratory fermentation installation for biogas pro- mean flow, Q, during the experiment was 3.8
duction. 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 ground cutting and with data extrapolation are
cylindrical hydrolyser of volume V1 = 57 dm3 and presented in Fig.4.
fermenter with volume V2 = 531 dm3 was con- The experimental RTD curve is exhibited with
structed. From the process engineering point of the measured curve, tracer concentration vs. time
view, it was important to investigate the biogas of experiment.
production process (gas composition and gas Taking into account the construction of fer-
quantity per 1 kg of dry mass) and also optimize menter, the scheme of flow was simulated by the
of mixing efficiency and check the liquid-phase simple model comprising plug flow and two units
residence time distribution (RTD) function inside of perfect mixing. The result of fitting the experi-
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 hydro-
gen isotope tritium in the form of tritium water was
used. Half-time of tritium is T1/2 = 4510 days, Fig.3. General view of installation.
LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS 105
PUBLICATIONS IN 2015
ARTICLES
42. Krawczyńska A., Dziendzikowska K., Gromadzka-Ostrowska J., Lankoff A., Herman A.P., Oczko-
wski 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., Lumni-
czky 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., Sobie-
szczańska-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: Syn-
thesis, 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., Chło-
picki 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/lan-
thanide complexation and solvent extraction separation – a theoretical approach.
Dalton Transactions, 44, 2657-2666 (2015).
110 PUBLICATIONS IN 2015
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 tech-
niques, 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.
Acta Physica Polonica A, 128, 5, 923-926 (2015).
65. Skotnicki K., Bobrowski K.
Molecular hydrogen formation during water radiolysis in the presence of zirconium dioxide.
Journal of Radioanalytical and Nuclear Chemistry, 304, 473-480 (2015).
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 over-
expression 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.
Acta Physica Polonica A, 127, 5, 1471-1474 (2015).
PUBLICATIONS IN 2015 111
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 con-
taining 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’]hemihy-
drate].
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., Jastrzęb-
ski 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 promie-
niowania na organizmy żywe (The National Centre for Research and Development strategic research
project “Technologies supporting development of safe nuclear power engineering”. Task no. 6 “Develop-
ment 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).
Postępy Techniki Jądrowej, 58, 2, 42-46 (2015).
92. Ciupek K., Krajewski P., Kozak K., Śliwka I., Pliszczyński T., Polkowska-Motrenko H.
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 1:
Opracowanie ogólnej koncepcji i metod badań środowiskowych (w tym zdrowotności) dla przewidy-
wanej 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).
Postępy Techniki Jądrowej, 58, 2, 35-41 (2015).
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”).
Postępy Techniki Jądrowej, 58, 2, 16-28 (2015).
PUBLICATIONS IN 2015 113
94. Głuszewski W.
Innowacje w przemyśle tworzyw polimerowych (Innovation in the plastics industry).
Postępy Techniki Jądrowej, 58, 3, 34-35 (2015).
95. Głuszewski W.
Radiacyjna sterylizacja opakowań. Niewidoczne, ale pracowite (Radiation sterilization packaging. In-
visible but busy).
Packing Polska, 5, 24-25 (2015).
96. Głuszewski W.
Unikatowe cechy radiacyjnej konserwacji dużych zbiorów obiektów o znaczeniu historycznym (Unique
features of radiation conservation of large object collections of historical importance).
Postępy Techniki Jądrowej, 58, 1, 19-23 (2015).
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 napro-
mieniowania żywności (Evaluation of detection of potential radiation treatment of foodstuff samples
using EPR, TL and PPSL methods).
Postępy Techniki Jądrowej, 58, 4, 13-16 (2015).
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).
Postępy Techniki Jądrowej, 58, 1, 16-18 (2015).
101. Michalik J.
Chemiczne aspekty energetyki jądrowej w projekcie Narodowego Centrum Badań i Rozwoju „Techno-
logie 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”).
Postępy Techniki Jądrowej, 58, 2, 14-15 (2015).
102. Michalik J., Kocia R.
Strategiczny projekt badawczy Narodowego Centrum Badań i Rozwoju pt. „Technologie wspomagające
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 Develop-
ment strategic research project “Technologies supporting development of safe nuclear power engineer-
ing”. 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”).
Postępy Techniki Jądrowej, 58, 3, 8-14 (2015).
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?).
Postępy Techniki Jądrowej, 58, 4, 38-41 (2015).
104. Sommer S.
RENEB (Realizing the European Network in Biodosimetry) w stronę Europejskiej Sieci Biodozyme-
trycznej (RENEB (Realizing the European Network in Biodosimetry) towards the European Biodo-
simetry Network).
Ekoatom, 17, 28-34 (2015).
105. Sommer S.
Ryzyko niskich dawek promieniowania a ochrona radiologiczna (Risk of low doses of radiation in radio-
logical protection).
Bezpieczeństwo Jądrowe i Ochrona Radiologiczna, 4, 33-38 (2015).
114 PUBLICATIONS IN 2015
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).
Postępy Techniki Jądrowej, 58, 3, 29-33 (2015).
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 emito-
wanego 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 sytua-
cjach awaryjnych z propozycjami działań na rzecz podniesienia poziomu bezpieczeństwa jądrowego.
Zadanie wykonane w ramach projektu strategicznego NCBR Technologie wspomagające rozwój bez-
piecznej 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 jądro-
wych z propozycjami działań na rzecz podniesienia poziomu bezpieczeństwa jądrowego. Zadanie wyko-
nane 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 Tech-
nology. 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).
PUBLICATIONS IN 2015 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).
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. 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
1955-2015. Pod red. dra inż. L. Walisia. Instytut Chemii i Techniki Jądrowej, Warszawa 2015, pp. 283-286.
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 radionu-
clides-corrosion products).
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. 45-57.
6. Chajduk E., Kulisa K., Samczyński Z.
Weryfikacja szczelności prętów paliwowych na podstawie oznaczania produktów wybranych radioizo-
topów w wieloskładnikowych roztworach wodnych (Verification of the assessing fuel integrity based on
the determination of chosen radionuclides in water solutions).
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. 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 ex-
changers for Cs and other fission products removal from the spent fuel storage basins and the nuclear
reactor primary water circuit).
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. 117-133.
8. Chmielewski A.G.
Okruchy wspomnień – moja praca w IChTJ (Scraps of memories – my work in the INCT).
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. 43-75.
9. Chmielewski A.G.
IChTJ – nowe rozdanie (The INCT – new deal).
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. 297-316.
10. Chmielewski A.G., Iller E., Palige J.
Inżynieria chemiczna i procesowa (Chemical and process engineering).
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. 191-200.
11. Chmielewski A.G., Sun Y.
Electron accelerators application in air pollution control.
116 PUBLICATIONS IN 2015
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).
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. 161-189.
13. Deptuła A.
Wspomnienia obecnie najstarszego (stażem) pracownika (Memories today oldest (internships) employee).
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. 77-92.
14. Dybczyński R.S., Polkowska-Motrenko H.
Zakład Chemii Analitycznej (Department of Analytical Chemistry).
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. 137-160.
15. Gryczka U., Migdał W., Chmielewska-Śmietanko D.
Application of electron beam accelerators for food irradiation.
In: The industrial and environmental applications of electron beams. Ed. D. Chmielewska-Śmietanko.
Institute of Nuclear Chemistry and Technology, Warszawa 2015, pp. 51-58.
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).
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. 23-37.
17. Łyczko M., Filipowicz B., Łyczko K., Bilewicz A.
Opracowanie ulepszonych technologii wydzielania radionuklidów będących produktami korozji z pły-
nów dekontaminacyjnych (Elaboration of the separation methods for isolation corrosion product radio-
nuclides from decontamination solutions).
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. 106-115.
18. Migdał W.
Samodzielna Pracownia Radiacyjnego Utrwalania Płodów Rolnych (Pilot Plant for Food Irradiation).
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. 267-273.
19. Ostyk-Narbutt J.
60 lat radiochemii na Żeraniu (Sixty years of radiochemistry at Żerań).
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. 93-136.
20. Pałyska W.
Zakład IIA Chemicznej Inżynierii Jądrowej (Department of Chemical Nuclear Engineering IIA).
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. 247-250.
21. Parus J.L.
Zakład Chemicznej Inżynierii Jądrowej (Department of Chemical Nuclear Engineering).
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. 243-245.
22. Pieńkos J.P.
Zakład Aparatury i Metod Jądrowych (XVA) (Department of Radioisotope Instruments and Methods
– XVA).
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. 259-265.
PUBLICATIONS IN 2015 117
In: Analiza procesów generacji wodoru w reaktorze jądrowym w trakcie normalnej eksploatacji i w sy-
tuacjach awaryjnych z propozycjami działań na rzecz podniesienia poziomu bezpieczeństwa jądrowego.
Zadanie wykonane w ramach projektu strategicznego NCBR Technologie wspomagające rozwój bez-
piecznej energetyki jądrowej. Red. nauk. J. Michalik, R. Kocia. Instytut Chemii i Techniki Jądrowej,
Warszawa 2015, pp. 43-54.
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]).
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. 7-40.
34. Waliś L.
Od „Dwudziestki” do „Jedynki” (From Department XX to Department I).
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. 225-241.
35. Wiśniewski A.
NSZZ “Solidarność”.
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. 287-289.
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 appli-
cations. 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).
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. 191-223.
38. Zimek Z.
Introduction to electron beam accelerators.
In: The industrial and environmental applications of electron beams. Ed. D. Chmielewska-Śmietanko.
Institute of Nuclear Chemistry and Technology, Warszawa 2015, pp. 7-18.
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 (Mix-
ing, ventilation and control systems and active and passive equipment for hydrogen removal from con-
tainment during severe accidents of nuclear reactor).
In: Analiza procesów generacji wodoru w reaktorze jądrowym w trakcie normalnej eksploatacji i w sy-
tuacjach awaryjnych z propozycjami działań na rzecz podniesienia poziomu bezpieczeństwa jądrowego.
Zadanie wykonane w ramach projektu strategicznego NCBR Technologie wspomagające rozwój bez-
piecznej energetyki jądrowej. Red. nauk. J. Michalik, R. Kocia. Instytut Chemii i Techniki Jądrowej,
Warszawa 2015, pp. 119-142.
3. Analiza procesów zachodzących przy normalnej eksploatacji obiegów wodnych w elektrowniach jądro-
wych z propozycjami działań na rzecz podniesienia poziomu bezpieczeństwa jądrowego. Zadanie wyko-
nane w ramach projektu strategicznego NCBR Technologie wspomagające rozwój bezpiecznej ener-
getyki 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 engi-
neering).
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 Tech-
nology. 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
9. Rafalski A.
Kontrola dozymetryczna radiacyjnej sterylizacji wyrobów medycznych (Dosimetry of radiation sterili-
zation of medical devices).
XIII Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 22-23.10.2015,
[6] p.
10. Rafalski A.
Sterylizacja radiacyjna na tle innych metod wyjaławiania (Radiation sterilization compared to other
sterilization methods).
XIII Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 22-23.10.2015,
[3] p.
11. Rafalski A.
Wiadomości niezbędne dla klientów Stacji Sterylizacji Radiacyjnej (Information for Radiation Sterili-
zation Plant clients).
XIII Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 22-23.10.2015,
[2] p.
12. Sadowska M.W.
Samodzielne Laboratorium Identyfikacji Napromieniowania Żywności. Identyfikacja napromieniowa-
nej żywności w IChTJ (Laboratory for Detection of Irradiated Food. Identification of irradiated food in
the INCT).
XIII Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 22-23.10.2015,
[6] p.
13. Schreinemachers C., Middendorp R., Bukaemskiy A.A., Modolo G., Brykała M., Rogowski M., Dep-
tuła 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 Sep-
tember 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 ion-
izing 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).
XIII Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 22-23.10.2015,
[5] p.
16. Zimek Z.
Akceleratory elektronów dla potrzeb sterylizacji radiacyjnej (Electron accelerators for radiation steri-
lization).
XIII Szkoła Sterylizacji i Mikrobiologicznej Dekontaminacji Radiacyjnej, Warszawa, Poland, 22-23.10.2015,
[6] p.
CONFERENCE ABSTRACTS
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, S924 (2015).
4. Bobrowski K., Filipiak P., Hug G.L., Pogocki D., Marciniak B.
Stabilization of monomeric sulfur cations in methionine-containing peptides with oligoprolines back-
bones.
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 elek-
trowniach 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 wyko-
rzystaniem 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 histo-
rycznych (The complementary use of INAA and ICP-MS in the analysis of metallic historical objects).
IX Polska Konferencja Chemii Analitycznej „Chemia analityczna to ciągłe wyzwania”, Poznań, Poland,
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 Sebas-
tian, 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 PUBLICATIONS IN 2015
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. Toxi-
cology 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.
Mądralin-2015: Wybrane aspekty bezpieczeństwa elektrowni jądrowej w Polsce. Wspólna konferencja
naukowo-techniczna PTN i SFEN, Mądralin, Poland, 24-25.11.2015, p. 32.
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
ionizing radiation, Brdo, Slovenia, 15-17.06.2015, [1] p.
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 Re-
search – 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., Hadjide-
kova V., Hatzi V., Pantelias G., Terzoudi G., Lindholm C., Sabatier L., Moreno M., Prieto M., Bura-
czewska 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.
International Conference RICOMET 2015: Risk perception, communication and ethics of exposures to
ionizing radiation, Brdo, Slovenia, 15-17.06.2015, [1] p.
43. Kużelewska I., Chajduk E., Polkowska-Motrenko H.
Zastosowanie neutronowej analizy aktywacyjnej i spektrometrii mas ze wzbudzeniem w plazmie induk-
cyjnie sprzężonej do badania trwałości certyfikowanych materiałów odniesienia o matrycy biologicznej
(Application of neutron activation analysis and inductively coupled plasma mass spectrometry to sta-
bility testing of certified reference materials with biological origin).
IX Polska Konferencja Chemii Analitycznej „Chemia analityczna to ciągłe wyzwania”, Poznań, Poland,
6-10.07.2015, p. 50.
44. Kużelewska I., Polkowska-Motrenko H., Danko B.
Opracowanie procedury oznaczania chromu w próbkach środowiskowych z zastosowaniem neutrono-
wej analizy aktywacyjnej (NAA) (Procedure of chromium determination in enviromental materials by
neutron activation analysis (NAA)).
XXIV Poznańskie Konwersatorium Analityczne „Nowoczesne metody przygotowania próbek i ozna-
czania 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-in-
duced 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.
International Conference RICOMET 2015: Risk perception, communication and ethics of exposures to
ionizing radiation, Brdo, Slovenia, 15-17.06.2015, [1] p.
PUBLICATIONS IN 2015 125
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. 414.
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 Net-
work of Biodosimetry – RENEB.
ConRad 2015, Global Conference on Radiation Topics – Preparedness, Response, Protection and Re-
search – 21st Nuclear Medical Defence Conference, Munich, Germany, 4-7.05.2015, [2] p.
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 con-
struction of new repositories for radioactive waste in Poland.
International Conference RICOMET 2015: Risk perception, communication and ethics of exposures to
ionizing radiation, Brdo, Slovenia, 15-17.06.2015, [1] p.
63. Oszczak A., Fuks L.
Sorption of selected radionuclides from liquid radioactive wastes by alginate beads.
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. 510.
64. Oszczak A., Fuks L., Herdzik-Koniecko I.
Polisacharydy jako sorbenty w procesie zatężania ciekłych odpadów promieniotwórczych (Polysaccha-
rides as a sorbents of liquid radioactive waste in the concentrating process).
Mądralin-2015: Wybrane aspekty bezpieczeństwa elektrowni jądrowej w Polsce. Wspólna konferencja
naukowo-techniczna PTN i SFEN, Mądralin, Poland, 24-25.11.2015, p. 44.
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 emer-
gencies.
International Conference RICOMET 2015: Risk perception, communication and ethics of exposures to
ionizing radiation, Brdo, Slovenia, 15-17.06.2015, [1] p.
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 disinfec-
tion 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)).
Mądralin-2015: Wybrane aspekty bezpieczeństwa elektrowni jądrowej w Polsce. Wspólna konferencja
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., Mon-
teiro Gil O., Gregoire E., Hadjidekova V., Hatzi V., Lindholm C., M’kacher R., Kulka U., Montoro A.,
PUBLICATIONS IN 2015 127
Moquet J., Moreno Domene M., Noditi M., Oestreicher U., Palitti F., Pantelias G., Prieto M.J., Pope-
scu 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.
ConRad 2015, Global Conference on Radiation Topics – Preparedness, Response, Protection and Re-
search – 21st Nuclear Medical Defence Conference, Munich, Germany, 4-7.05.2015, [1] p.
70. Roubinek O., Palige J., Szołucha M., Kalbarczyk P.
Odzysk uranu z pokopalnianych hałd rud uranowych (Uranium recovery from postmining heap of
uranium ores).
Mądralin-2015: Wybrane aspekty bezpieczeństwa elektrowni jądrowej w Polsce. Wspólna konferencja
naukowo-techniczna PTN i SFEN, Mądralin, Poland, 24-25.11.2015, p. 47.
71. Rzepna M., Przybytniak G.
Ocena oddziaływania promieniowania jonizującego na poliestry biodegradowalne (Assessment of the
impact of ionizing radiation on biodegradable polyesters).
ChemSession’15 – XII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 8.05.2015,
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).
IX Polska Konferencja Chemii Analitycznej „Chemia analityczna to ciągłe wyzwania”, Poznań, Poland,
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 in-
organic 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 Organo-
metallic 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 zesta-
lania odpadów promieniotwórczych (Synthesis of ceramic (Ti) matrixes based on hollandite, intended
for solidifying radioactive waste by sol-gel method).
Mądralin-2015: Wybrane aspekty bezpieczeństwa elektrowni jądrowej w Polsce. Wspólna konferencja
naukowo-techniczna PTN i SFEN, Mądralin, Poland, 24-25.11.2015, p. 50.
128 PUBLICATIONS IN 2015
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., Pope-
scu 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 net-
work 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.
International Conference RICOMET 2015: Risk perception, communication and ethics of exposures to
ionizing radiation, Brdo, Slovenia, 15-17.06.2015, [1] p.
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).
Mądralin-2015: Wybrane aspekty bezpieczeństwa elektrowni jądrowej w Polsce. Wspólna konferencja
naukowo-techniczna PTN i SFEN, Mądralin, Poland, 24-25.11.2015, p. 53.
83. Szkliniarz K., Bilewicz A., Choiński J., Jakubowski A., Jastrzębski J., Leszczuk E., Łyczko M., Sto-
larz A., Trzcińska A., Was B., Zipper W.
New results on the radioisotope 211At produced using the alpha particle beam.
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. 222.
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 ion-
izing radiation.
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. 501.
85. Vaidyanathan G., McDougald D., Choi J., Koumarianou E., Pruszyński M., Osada T., Lyerly H., La-
houtte T., Zalutsky M.R.
An anti-HER2 nanobody labeled with 18F using a residualizing label for assessing HER2 status.
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, S102 (2015).
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 promieniotwór-
czych (Synthesis of silica glasses used for solidification of radioactive waste by sol-gel).
Mądralin-2015: Wybrane aspekty bezpieczeństwa elektrowni jądrowej w Polsce. Wspólna konferencja
naukowo-techniczna PTN i SFEN, Mądralin, Poland, 24-25.11.2015, p. 58.
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 Depres-
sion).
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 Re-
search, 21st Nuclear Medical Defence Conference, Munich, Germany, 4-7.05.2015, [1] p.
PUBLICATIONS IN 2015 129
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).
In: Rozwój technik i technologii wspomagających gospodarkę wypalonym paliwem i odpadami promie-
niotwórczymi. Red. nauk. L. Fuks. Instytut Chemii i Techniki Jądrowej, Warszawa 2014, pp. 167-170.
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.
In: Rozwój technik i technologii wspomagających gospodarkę wypalonym paliwem i odpadami promie-
niotwórczymi. Red. nauk. L. Fuks. Instytut Chemii i Techniki Jądrowej, Warszawa 2014, pp. 105-113.
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., Kor-
man 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 bio-
terrorism 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 promie-
niotwórczymi. 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).
In: Rozwój technik i technologii wspomagających gospodarkę wypalonym paliwem i odpadami promie-
niotwórczymi. Red. nauk. L. Fuks. Instytut Chemii i Techniki Jądrowej, Warszawa 2014, pp. 135-147.
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 promienio-
twórczymi. Zadanie wykonane w ramach projektu strategicznego NCBR Technologie wspomagające
PUBLICATIONS IN 2015 131
rozwój bezpiecznej energetyki jądrowej (Development of spent nuclear fuel and radioactive waste man-
agement techniques and technologies. Task realized in the frame of the NCBR strategic project Tech-
nologies 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).
In: Rozwój technik i technologii wspomagających gospodarkę wypalonym paliwem i odpadami promie-
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Badania stabilności radiacyjnej cieczy jonowych stosowanych w ekstrakcji plutonu i aktynowców
mniejszościowych (Radiation stability of ionic liquids used in plutonium and minor actinides extrac-
tion).
In: Rozwój technik i technologii wspomagających gospodarkę wypalonym paliwem i odpadami promie-
niotwórczymi. Red. nauk. L. Fuks. Instytut Chemii i Techniki Jądrowej, Warszawa 2014, pp. 47-63.
23. Trojanowicz M.
Applications of gold nanoparticles in electroanalysis. (Chapter 11).
In: Gold nanoparticles in analytical chemistry. Comprehensive analytical chemistry. Vol. 66. Eds. M. Val-
cárcel, 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 Syn-
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In: Rozwój technik i technologii wspomagających gospodarkę wypalonym paliwem i odpadami promie-
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Bisignate resonance Raman optical activity: a pseudo breakdown of the single electronic state model
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Rozwój technik i technologii w zakresie przerobu i postępowania z nisko- i średnioaktywnymi odp-
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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)
bauer spectroscopy
R. Konieczny, R. Idczak
NUKLEONIKA 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 nano-
crystalline 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 transforma-
tion
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
J. Pasley, I.A. Bush, A.P.L. Robinson, P.P. Rajeev, S. Mondal, A.D. Lad, S. Ahmed, V. Narayanan, G. Ra-
vindra 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. Mos-
kalenko
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
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 offici-
nalis – EPR examination
M. Zdybel, B. Pilawa
Regular papers
21. A Monte Carlo study on dose enhancement and photon contamination production by various nanopar-
ticles 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 nano-
particles 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
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 de-
structive 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
235
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 nano-
particles. 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. Kor-
cyl, 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. Ka-
mińska, 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. Wie-
czorek, W. Wiślicki, M. Zieliński, B. Zgardzińska, P. Moskal
12. Studies of unicellular microorganisms Saccharomyces cerevisiae by means of positron annihilation life-
time 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. Niedź-
wiecki, 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 Ma-
halanobis distance
N.G. Sharma, M. Silarski, T. Bednarski, P. Białas, E. Czerwiński, A. Gajos, M. Gorgol, B. Jasińska, D. Ka-
mińska, 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 poly-
styrene 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-posi-
tronium 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
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
INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY
NUKLEONIKA
Dorodna 16, 03-195 Warszawa, Poland
phone: +48 22 504 11 32, fax: +48 22 811 15 32, e-mail: nukleon@ichtj.waw.pl
Full texts are available on-line at http://www.nukleonika.pl
POSTĘPY TECHNIKI JĄDROWEJ 141
EDITORIAL BOARD
Stanisław Latek (Editor-in-Chief), Wojciech Głuszewski, Maria Kowalska, Łukasz Kuźniarski, Andrzej
Mikulski, Marek Rabiński, Edward Rurarz, Elżbieta Zalewska
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 tech-
niques and technologies”)
L. Fuks, A. Oszczak
6. 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” (The Na-
tional Centre for Research and Development strategic research project “Technologies supporting devel-
opment 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
7. Strategiczny projekt badawczy Narodowego Centrum Badań i Rozwoju pt. „Technologie wspomagające
rozwój bezpiecznej energetyki jądrowej”. Zadanie nr 6 „Rozwój metod zapewnienia bezpieczeństwa jądro-
wego i ochrony radiologicznej dla bieżących i przyszłych potrzeb energetyki jądrowej”. Cel 1: Opracowa-
nie ogólnej koncepcji i metod badań środowiskowych (w tym zdrowotności) dla przewidywanej lokali-
zacji 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”. Objec-
tive 1: General concept and methodology for baseline environmental research and public health investi-
gation in the foreseen location of NPP)
K. Ciupek, P. Krajewski, K. Kozak, I. Śliwka, T. Pliszczyński, H. Polkowska-Motrenko
8. Strategiczny projekt badawczy Narodowego Centrum Badań i Rozwoju pt. „Technologie wspomagające
rozwój bezpiecznej energetyki jądrowej”. Zadanie nr 6 „Rozwój metod zapewnienia bezpieczeństwa jądro-
wego i ochrony radiologicznej dla bieżących i przyszłych potrzeb energetyki jądrowej. Cel 2: Rozwój metod
dozymetrii biologicznej oraz biofizycznych markerów i indykatorów wpływu promieniowania na organiz-
my 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”. Objec-
tive 2. Development of the biodosimetry and biophysics markers of ionizing radiation in living beings)
K. Brzóska, M. Kowalska, M. Kruszewski, A. Lankoff, S. Sommer
Information
INSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY
POSTĘPY TECHNIKI JĄDROWEJ
Dorodna 16, 03-195 Warszawa, Poland
phone: +48 22 504 12 48, fax: +48 22 811 15 32, e-mail: PTJ-redakcja@ichtj.waw.pl
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 Re-
search – 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.
THE INCT PATENTS AND PATENT APPLICATIONS IN 2015 145
PATENTS
1. Prekursor radiofarmaceutyku, sposób jego wytwarzania, radiofarmaceutyk oraz jego zastosowanie (Pre-
cursor 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 elektrycz-
nych 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
Russian Patent 2542358
9. A selective extraction of uranium and protactinium from material containing thorium
P. Kalbarczyk, H. Polkowska-Motrenko, E. Chajduk
Russian Patent 2578538
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
Polish Patent Application P-411028
146 THE INCT PATENTS AND PATENT APPLICATIONS IN 2015
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 SEP-
TEMBER 2015, WARSZAWA, POLAND
Organized by the Institute of Nuclear Chemistry and Technology
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.
CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2015 149
Ph.D. THESES
D.Sc. THESES
1. Ewa Gniazdowska, Ph.D. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)
Projektowanie nowych potencjalnych radiofarmaceutyków receptorowych opartych na analogach pepty-
dów 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)
Institute of Nuclear Chemistry and Technology, 10.04.2015
EDUCATION 151
EDUCATION
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 pro-
tection 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 publi-
cation;
• 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 instru-
ments – 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: A.Bilewicz@ichtj.waw.pl);
• secretary: Ewa Gniazdowska, Ph.D., D.Sc., professor in INCT
(phone: +48 22 504 11 78, e-mail: E.Gniazdowska@ichtj.waw.pl).
152 EDUCATION
TRAINING OF STUDENTS
Number
Institution Country Period
of participants
Cardinal Stefan Wyszyński University in Warsaw,
Poland 2 1 month
Faculty of Mathematics and Natural Sciences
Maria Curie-Skłodowska University Poland 1 1.5 months
1 1 month
Medical University of Warsaw Poland
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
University of Warsaw, Faculty of Chemistry Poland
3 1 month
3 3 months
1 1 month
University of Warsaw, Faculty of Physics Poland
2 1.5 months
Warsaw University of Life Sciences – SGGW Poland 34 one-day course
2 3 weeks
Warsaw University of Technology, Faculty of Chemistry Poland
6 1 month
Warsaw University of Technology,
Poland 3 one-day course
Faculty of Environmental Engineering
24 one-day course
Warsaw University of Technology, Faculty of Physics Poland
2 1 month
Warsaw University of Technology,
Poland 2 3 months
Faculty of Power and Aeronautical Engineering
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 dekontaminacyj-
nych 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
RESEARCH PROJECTS AND CONTRACTS 153
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 ni-
trosyl complexes of iron.
supervisor: Hanna Lewandowska-Siwkiewicz, Ph.D.
2. Chiral cores/monomers of drugs and conducting polymers: from calculations to experimental charac-
teristics.
supervisor: Prof. Jan Cz. Dobrowolski, Ph.D., D.Sc.
3. Nanobodies labelled with alpha emitters as potential radiopharmaceuticals in targeted radioimmuno-
theraphy.
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.
supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc.
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 frac-
turing 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 RESEARCH PROJECTS AND CONTRACTS
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).
supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc.
3. The integrated system of sewage treatment, biogas production and its enrichment in the methane.
supervisor: Jacek Palige, Ph.D.
4. Syntheses of radiopharmaceuticals based on scandium radionuclides for positron emission tomography
(Petscand).
supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc.
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.
supervisor: Prof. Jerzy Narbutt, Ph.D., D.Sc.
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 treat-
ment and biogas production plants.
supervisor: Jacek Palige, Ph.D.
13. Electron beam for preservation of biodeteriorated cultural heritage paper-based objects.
supervisor: Dagmara Chmielewska-Śmietanko, M.Sc.
14. Laboratory and feasibility study for industrial wastewater effluents treatment by radiation.
supervisor: Zbigniew Zimek, Ph.D.
RESEARCH PROJECTS AND CONTRACTS 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
OF SAFE NUCLEAR POWER ENGINEERING”
1. Scientific problem no. 7: Study of hydrogen generation processes in nuclear reactors under regular op-
eration 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.
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 treat-
ment 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 RESEARCH PROJECTS AND CONTRACTS
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
supervisor: Dagmara Chmielewska-Śmietanko, M.Sc.
1. Introducing and harmonizing standardized quality control procedures for radiation technologies.
RER 1014
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 ap-
proach (ARCADIA).
principal investigator: Prof. Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc.
6. FP7 – Enhancing education, training and communication processes for informed behaviors and deci-
sion-making related to ionizing radiation risks (EAGLE).
principal investigator: Prof. Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc.
7. FP7 – Building a platform for enhanced societal research related to nuclear energy in Central and
Eastern Europe (PLATENSO).
principal investigator: Prof. Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc.
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).
supervisor: Prof. Jerzy Narbutt, Ph.D., D.Sc.
RESEARCH PROJECTS AND CONTRACTS 157
PROJECTS GRANTED
BY THE FOUNDATION FOR POLISH SCIENCE
IN 2015
ERASMUS+ PROGRAMME
1. Joint innovative training and teaching/learning program in enhancing development and transfer knowl-
edge 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
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 tech-
nologies.
• Task 7: Study of hydrogen generation processes in nuclear reactors under regular operation condi-
tions 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 Chem-
istry and Technology, Institute of Nuclear Physics PAS, Institute of Electronic Materials Technology,
AGH University of Science and Technology, Maria Curie-Skłodowska University – Faculty of Chem-
istry 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 radioac-
tive 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 Tech-
nology – Faculty of Chemical and Process Engineering, and Silesian University of Technology – Insti-
tute 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 thermo-
catalytic processes taking place on the surface of zircaloy claddings at temperatures above 1000oC was
THE NCBR STRATEGIC RESEARCH PROJECT 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 contami-
nation 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 hy-
droxyl 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 experi-
mental 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 hydro-
gen 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 recom-
biners (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 impor-
tant factors decisive on safe reactor exploitation. Cooling water of primary system contains radionu-
clides 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.
160 LIST OF VISITORS TO 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 steri-
lization 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 de-
velopment”, 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.
LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2015 163
12. Cieśla K.
Application of radiation modified polysaccharide hydrogels.
Erasmus+ TL-IRMP “Joint innovative training and teaching/learning program in enhancing develop-
ment 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.
Erasmus+ TL-IRMP “Joint innovative training and teaching/learning program in enhancing develop-
ment and transfer knowledge of application of ionizing radiation in materials processing”, Palermo,
Italy, 28.09.-02.10.2015.
14. Cieśla K.
Characterization of natural polymers systems, their structural properties, related applications and de-
sirable modification. Part I. Basic components and raw materials.
Erasmus+ TL-IRMP “Joint innovative training and teaching/learning program in enhancing develop-
ment and transfer knowledge of application of ionizing radiation in materials processing”, Palermo,
Italy, 28.09.-02.10.2015.
15. Cieśla K.
Characterization of natural polymers systems, their structural properties, related applications and de-
sirable modification. Part II. Composites/nanocomposites and nanoparticles.
Erasmus+ TL-IRMP “Joint innovative training and teaching/learning program in enhancing develop-
ment and transfer knowledge of application of ionizing radiation in materials processing”, Palermo,
Italy, 28.09.-02.10.2015.
16. Cieśla K.
Chemical and physical modification of polysaccharide systems: specific features of electromagnetic
radiation.
Erasmus+ TL-IRMP “Joint innovative training and teaching/learning program in enhancing develop-
ment and transfer knowledge of application of ionizing radiation in materials processing”, Palermo,
Italy, 28.09.-02.10.2015.
17. Cieśla K.
Radiation degradation of polysaccharides and modification of activity of active polysaccharides.
Erasmus+ TL-IRMP “Joint innovative training and teaching/learning program in enhancing develop-
ment and transfer knowledge of application of ionizing radiation in materials processing”, Palermo,
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.
Erasmus+ TL-IRMP “Joint innovative training and teaching/learning program in enhancing develop-
ment and transfer knowledge of application of ionizing radiation in materials processing”, Palermo,
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.
Erasmus+ TL-IRMP “Joint innovative training and teaching/learning program in enhancing develop-
ment and transfer knowledge of application of ionizing radiation in materials processing”, Palermo,
Italy, 28.09.-02.10.2015.
20. Cieśla K.
Radiation modification of polysaccharide composites for packaging.
Erasmus+ TL-IRMP “Joint innovative training and teaching/learning program in enhancing develop-
ment and transfer knowledge of application of ionizing radiation in materials processing”, Palermo,
Italy, 28.09.-02.10.2015.
21. Cieśla K.
Radiation modification of polysaccharide composites: potential for the other areas.
Erasmus+ TL-IRMP “Joint innovative training and teaching/learning program in enhancing develop-
ment and transfer knowledge of application of ionizing radiation in materials processing”, Palermo,
Italy, 28.09.-02.10.2015.
22. Dybczyński R.S.
Neutronowa analiza aktywacyjna i jej rola w metrologii chemicznej (Neutron activation analysis and
its role in chemical metrology).
164 LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 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 de-
sirable 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 de-
sirable modification. Part II. Composites/nanocomposites and nanoparticles.
Hacettepe University, Department of Chemistry, Ankara, Turkey, 04.05.2015.
LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2015 165
4. Cieśla Krystyna
Adsorbents. Classics and the current directions in research.
Hacettepe University, Department of Chemistry, Ankara, Turkey, 05.05.2015.
5. Cieśla Krystyna
Radiation processes in biopolymer system.
Hacettepe University, Department of Chemistry, Ankara, Turkey, 05.05.2015.
6. Cieśla Krystyna
Biopolymer hydrogels. Application of radiation modification.
Hacettepe University, Department of Chemistry, Ankara, Turkey, 06.05.2015.
7. Cieśla Krystyna
Edible and biodegradable films and coatings based on proteins and polysaccharides.
Hacettepe University, Department of Chemistry, Ankara, Turkey, 07.05.2015.
8. Cieśla Krystyna
Radiation modification of composites. Part I. Modification of the properties of biodegradable plastics.
Hacettepe University, Department of Chemistry, Ankara, Turkey, 07.05.2015.
9. Cieśla Krystyna
Radiation modification of composites. Part II. Radiation processes in nanotechnology, technical and
food industries, agriculture and the other areas.
Hacettepe University, Department of Chemistry, Ankara, Turkey, 08.05.2015.
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 – chem-
istry 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.
16. Zakrzewska-Kołtuniewicz Grażyna
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.
17. Zakrzewska-Kołtuniewicz Grażyna
Współczesne zastosowania technik jądrowych (Modern applications of nuclear techniques).
General Tadeusz Kościuszko Military Academy of Land Forces, Wrocław, Poland, 22.10.2015.
18. Zakrzewska-Kołtuniewicz Grażyna
Odpady promieniotwórcze – nie takie straszne? (Radioactive waste – not that terrible?).
University of Gdańsk, Faculty of Law and Administration, Gdańsk, Poland, 28.10.2015.
19. Zakrzewska-Kołtuniewicz Grażyna
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
36. Pro Masovia commemorative medal awarded by the Marshal of the Mazowieckie Voivodeship for out-
standing services and activity for the Mazovia Voivodship
Marcin Kruszewski
37. Pro Masovia commemorative medal awarded by the Marshal of the Mazowieckie Voivodeship for out-
standing services and activity for the Mazovia Voivodship
Wiesława Łada
38. Pro Masovia commemorative medal awarded by the Marshal of the Mazowieckie Voivodeship for out-
standing services and activity for the Mazovia Voivodship
Wojciech Maciąg
39. Pro Masovia commemorative medal awarded by the Marshal of the Mazowieckie Voivodeship for out-
standing services and activity for the Mazovia Voivodship
Wojciech Migdał
40. Pro Masovia commemorative medal awarded by the Marshal of the Mazowieckie Voivodeship for out-
standing services and activity for the Mazovia Voivodship
Marta Walo
41. Pro Masovia commemorative medal awarded by the Marshal of the Mazowieckie Voivodeship for out-
standing services and activity for the Mazovia Voivodship
Tomasz Zawisza
42. Pro Masovia commemorative medal awarded by the Marshal of the Mazowieckie Voivodeship for out-
standing services and activity for the Mazovia Voivodship
Zbigniew Zimek
43. Honorary Medal of Merit for Economic Development in the Polish Republic
Rajmund S. Dybczyński
44. Honorary Medal of Merit for Economic Development in the Polish Republic
Jacek Michalik
45. Honorary Medal of Merit for Economic Development in the Polish Republic
Jerzy Ostyk-Narbutt
46. Honorary Medal of Merit for Economic Development in the Polish Republic
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 No-
wicki, 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 pub-
lished articles, participation in the actions organized and co-organized by the Institute and participa-
tion 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 partici-
pation 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 pub-
lished articles, participation in the actions organized and co-organized by the Institute and participa-
tion 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 di-
rector proxy for student practices
Marta Pyszynska
170 INDEX OF THE AUTHORS
A Korzeniowska-Sobczuk Anna 94
Kowalska Magdalena 58
Abramowska Anna 20, 50
Kozera Klaudia 23
Apel Pavel 75
Koźmiński Przemysław 43
B Kruszewski Marcin 54, 55, 58, 59
Kubera Hieronim 23
Bartłomiejczyk Teresa 55, 57
Kużelewska Iga 70
Bojanowska-Czajka Anna 66
Brykała Marcin 36 L
Brzóska Kamil 54
Lankof Leszek 40
Buczkowski Marek 20, 75
Lankoff Anna 58
Bułka Sylwester 25, 83
Lavric Vasile 85
Buraczewska Iwona 55
Lewandowska Hanna 59
C Licki Janusz 83
Lisowska Halina 58
Chajduk Ewelina 66
Liśkiewicz Grażyna 99
Chmielewski Andrzej G. 83, 85
Chorąży Katarzyna 62 Ł
Cieśla Krystyna 20
Łada Wiesława 36
D Łuczyńska Katarzyna 46
Łyczko Krzysztof 46
Dalecka Wanda 32
Deptuła Andrzej 36 M
Dobrowolski Andrzej 104
Dobrowolski Jan Cz. 46 Maróti Boglarka 77
Drużbicki Kacper 46 Masłowska Katarzyna 43
Dudek Jakub 66 Męczyńska-Wielgosz Sylwia 57, 58, 59
Dziendzikowska Katarzyna 55 Mikiciuk-Olasik Elżbieta 43
Mirkowski Krzysztof 17
F Miśkiewicz Agnieszka 40, 50
Fuks Leon 32 N
G Narbutt Jerzy 29
Gajda Dorota 50 Nowicki Andrzej 17
Głuszewski Wojciech 23
O
Gniazdowska Ewa 43
Gogulancea Valentina 85 Olczak Tadeusz 36
Grądzka Iwona 54, 55, 57 Olszewska Wioleta 40
Gromadzka-Ostrowska Joanna 55 Ołdak Wiesław 104
Guzik Grzegorz P. 99 Orelovitch Oleg 75
Oszczak Agata 32
H
P
Herdzik-Koniecko Irena 29
Pająk Leszek 40
I Palige Jacek 104
Iwaneńko Teresa 55, 58 Pańczyk Ewa 77
Polkowska-Motrenko Halina 70
K Przybytniak Grażyna 17
Karlińska Magdalena 94
Kasztovszky Zsolt 77 R
Kiegiel Katarzyna 50 Rejnis Magdalena 29
Koc Mariusz 62 Rogowski Marcin 36
Kołacińska Kamila 66 Roubinek Otton 104
INDEX OF THE AUTHORS 171
S W
Sadło Jarosław 59 Waliś Lech 77
Sadowska Magdalena W. 99 Wasyk Iwona 55, 57
Samczyński Zbigniew 66, 70 Wawszczak Danuta 36
Sartowska Bożena 75 Weker Władysław 77
Sikorska Katarzyna 55 Węgierek-Ciuk Aneta 58
Smoliński Tomasz 36 Widawski Maciej 77
Sochanowicz Barbara 54 Wierzchnicki Ryszard 90
Sołtyk Wojciech 104 Wojewódzka Maria 57, 58
Sommer Sylwester 55 Wojtowicz Patryk 36
Stachowicz Wacław 99 Wójciuk Grzegorz 59
Starosta Wojciech 75
Steczek Łukasz 29 Z
Stępkowski Tomasz M. 59 Zakrzewska-Kołtuniewicz Grażyna 40, 50
Sun Yongxia 83, 85 Zapór Lidia 57
Szumiel Irena 59 Zimek Zbigniew 25
Szymański Paweł 43 Zwolińska Ewa 83, 85
T
Trojanowicz Marek 62, 66
INSTITUTE OF NUCLEAR
CHEMISTRY AND TECHNOLOGY
Dorodna 16, 03-195 Warszawa, Poland
phone: +48 22 504 12 05, fax: +48 22 811 15 32
e-mail: sekdyrn@ichtj.waw.pl
www.ichtj.waw.pl