annual report 2016 - ichtj · numerical simulation of nox and so2 removal under electron beam...

ANNUAL REPORT2016

ANNUAL REPORT2016

INSTITUTE OF NUCLEAR CHEMISTRY

AND TECHNOLOGY

© Copyright by the Institute of Nuclear Chemistry and Technology, Warszawa 2017

EDITORSProf. Jacek Michalik, Ph.D., D.Sc.

Ewa Godlewska-Para, M.Sc.

CONTENTS

GENERAL INFORMATION 9

MANAGEMENT OF THE INSTITUTE 11

MANAGING STAFF OF THE INSTITUTE 11

HEADS OF THE INCT DEPARTMENTS 11

SCIENTIFIC COUNCIL (2015-2019) 11

ORGANIZATION SCHEME 13

SCIENTIFIC STAFF 14

PROFESSORS 14

SENIOR SCIENTISTS (Ph.D.) 14

CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY 17 THREE-ELECTRON BONDED, DIMERIC RADICAL CATIONS DERIVED FROM 2-THIOURACIL DERIVATIVESK. Skotnicki, K. Taras-Goślińska, K. Bobrowski 19

CHANGES IN COLLAGEN AND ITS MAIN COMPONENTS UNDER THE INFLUENCE OF IONIZING RADIATIONE.M. Kornacka, G. Przybytniak, Z. Zimek 20

MATURATION OF NEWLY DEPOSITED CALCIUM-PHOSPHATE CRYSTALS IN HUMAN ADIPOSE DERIVED STEM CELLS CULTURE AFTER CELL DIFFERENTIATION TO OSTEOBLAST IN VITROM. Kołodziejczyk, J. Sadło, M. Lewandowska-Szumieł 23

INFLUENCE OF POST-RADIATION OXIDATION FOR POLYETHYLENE FOAM DENSITYW. Głuszewski, A. Stasiek, A. Raszkowska-Kaczor, D. Kaczor 25

IONIZING RADIATION TREATMENT OF BRINE PURIFICATION SUSPENSIONM. Sudlitz, Z. Zimek 27

MODIFICATIONS INTRODUCED INTO ILU-6 ACCELERATOR SYSTEM IN ORDER TO OBTAIN LOW ENERGY ELECTRON BEAMS. Bułka, Z. Zimek 31

CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY 33ON THE SYNTHESES AND EVALUATION OF SUBSTANCE P FRAGMENTS LABELLED WITH 99mTc AND 177Lu AS POTENTIAL RECEPTOR RADIOPHARMACEUTICALS IN GLIOMA TREATMENTA. Majkowska-Pilip, E. Gniazdowska, P. Koźmiński, A. Wawrzynowska, T. Budlewski, B. Kostkiewicz 35

LABELLED ANTIBIOTICS WITH TECHNETIUM-99m AS POTENTIAL RADIOPHARMACEUTICALS FOR DIABETIC FOOT IMAGINGP. Koźmiński, E. Gniazdowska, A. Piądłowska, M. Gumiela, M. Pruszyński 39

5,6-DIHALOGEN-1,10-PHENANTROLINE COMPLEXES WITH Eu(III) AND Am(III) IONS. A COMPUTATIONAL STUDYJ.Cz. Dobrowolski, J.E. Rode, S. Ostrowski, M.H. Jamróz 42

APPLICATION OF INDUSTRIAL WASTES AS AN ENGINEERING BARRIER IN RADIOACTIVE WASTE REPOSITORIES: SORPTION OF Cs(I), Sr(II), Eu(III), AND Am(III) IONS ON THE CLAY-SALT SLIMES OF THE JOINT STOCK COMPANY “BELARUSKALI”L. Fuks, I. Herdzik-Koniecko, L. Maskalchuk, T. Leontieva 48

STUDY AND CHARACTERIZATION OF U-Nd PARTICLES AFTER THERMAL TREATMENTM. Rogowski, M. Brykała, T. Olczak, D. Wawszczak, T. Smoliński 53

THE STUDY OF MEMBRANE FOULING BY USING PHOTOACOUSTIC SPECTROSCOPYA. Miśkiewicz, G. Zakrzewska-Kołtuniewicz, B. Sartowska, S. Pasieczna-Patkowska 57

PURIFICATION OF FLOWBACK FLUIDS FROM HYDRAULIC FRACTURING OF POLISH GAS-BEARING SHALES BY HYBRID METHODS K. Kiegiel, A. Abramowska, D.K. Gajda, A. Miśkiewicz, G. Zakrzewska-Kołtuniewicz 60

CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY 63 RECONSTRUCTION OF IONIZING RADIATION DOSE – A CASE STUDYT. Bartłomiejczyk, I. Buraczewska, K. Sikorska, M. Kowalska, S. Sommer 64

IMPACT OF NANOPARTICLES ON SURVIVAL OF HepG2 CELLS TREATED WITH TUMOUR NECROSIS FACTOR I. Grądzka, K. Sikorska, T. Stępkowski, K. Brzóska 65

FORMATION OF A DINITROSYL IRON COMPLEX WITH LOW-DENSITY LIPOPROTEIN AND ITS APPLICATION AS IRON CARRIERH. Lewandowska, S. Męczyńska-Wielgosz, K. Sikorska, G. Wójciuk, J. Sadło, J. Dudek, M. Kruszewski 67

LABORATORY OF NUCLEAR ANALYTICAL METHODS 69MODIFICATION OF A POLYMER MONOLITHIC COLUMN WITH CROWN ETHER FOR SEQUENTIAL INJECTION CHROMATOGRAPHY WITH ICP-MS DETECTIONK. Kołacińska, P. Koźmiński, A. Bojanowska-Czajka, M. Pyszynska, J. Dudek, E. Chajduk, S. Prohazkova, M. Trojanowicz 70

POSSIBILITY OF USING MODIFIED GRAPHENE OXIDE WITH MnO2 IN NEUTRON ACTIVATION ANALYSIS AND INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY E. Chajduk, P. Kalbarczyk, H. Polkowska-Motrenko, L. Stobiński, E. Miśta 75

LABORATORY OF MATERIAL RESEARCH 79THE MODIFICATION OF ZIRCONIUM ALLOY SURFACE LAYER BY TIG METHODSW. Starosta, M. Barlak, P. Kołodziejczak 81

COATINGS BASED ON SILICON COMPOUNDS ON ZIRCONIUM ALLOYS FOR HIGH TEMPERATURE CORROSION RESISTANCE IMPROVEMENTB. Sartowska, M. Miłkowska, W. Starosta 84

CHARACTERIZATION OF SILVER WŁADYSŁAW JAGIEŁŁO CROWN HALF-GROSCHEN MADE BY THE POLISH MINT IN KRAKÓW IN 1394-1434 BY THE X-RAY FLUORESCENCE METHODE. Pańczyk, J. Kierzek, L. Waliś, M. Zawadzki, M. Widawski, W. Weker 87

INVESTIGATION OF THE RELATIONSHIP BETWEEN ORIGIN, TECHNOLOGY AND DURABILITY OF GLASS, WITH A SPECIAL FOCUS ON LATE 17th AND 18th CENTURY GLASSJ.J. Kunicki-Goldfi nger, S.P. Koob 93

POLLUTION CONTROL TECHNOLOGIES LABORATORY 95NUMERICAL SIMULATION OF PERFLUOROOCTANOIC ACID DEGRADATION IN WATER UNDER IONIZATION RADIATIONH. Nichipor, Y. Sun, A.G. Chmielewski 97

NUMERICAL SIMULATION OF NOx AND SO2 REMOVAL UNDER ELECTRON BEAM IRRADIATION WITH TWO COMPUTER PROGRAMS: KINETIC AND MATLABE. Zwolińska, Y. Sun, H. Nichipor 100

STABLE ISOTOPE LABORATORY 105STUDY OF STABLE ISOTOPE COMPOSITION OF POLISH CIDERSR. Wierzchnicki, R. Adamska 106

LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES 109MEASUREMENT TRACEABILITY OF 60Co GAMMA SOURCE ISSLEDOVATELA. Korzeniowska-Sobczuk, M. Karlińska 110

LABORATORY FOR DETECTION OF IRRADIATED FOOD 113INVESTIGATION WITH THERMOLUMINESCENCE METHOD OF LOW DOSE IRRADIATED DRIED FRUITSM.W. Sadowska, G. Liśkiewicz 115

ADVANTAGE OF NEW THERMOLUMINESCENCE READER-ANALYSER INSTALLED IN THE LABORATORY FOR DETECTION OF IRRADIATED FOODG. Guzik 117

LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS 119RADIOMETRIC METHOD FOR MEASURING AND MODELLING MULTIPHASE SYSTEMS TOWARDS PROCESS MANAGEMENTJ. Palige, O. Roubinek, A. Dobrowolski, W. Sołtyk 120

PUBLICATIONS IN 2016 122

ARTICLES 122

CHAPTERS IN BOOKS 128

THE INCT PUBLICATIONS 129

CONFERENCE PROCEEDINGS 129

CONFERENCE ABSTRACTS 129

SUPPLEMENT LIST OF THE PUBLICATIONS IN 2015 139

NUKLEONIKA 140

POSTĘPY TECHNIKI JĄDROWEJ 145

INTERVIEWS IN 2016 147

THE INCT PATENTS AND PATENT APPLICATIONS IN 2016 148

PATENTS 148

PATENT APPLICATIONS 148

CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2016 150

Ph.D. THESES IN 2016 152

EDUCATION 153

Ph.D. PROGRAMME IN CHEMISTRY 153

TRAINING OF STUDENTS 153

MASTER’S AND BACHELOR’S DISSERTATIONS 154

RESEARCH PROJECTS AND CONTRACTS 156

RESEARCH PROJECTS GRANTED BY THE NATIONAL SCIENCE CENTRE IN 2016 156

PROJECTS GRANTED BY THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT IN 2016 156

IAEA RESEARCH CONTRACTS IN 2016 157

IAEA TECHNICAL AND REGIONAL CONTRACTS IN 2016 157

PROJECTS WITHIN THE FRAME OF EUROPEAN UNION FRAME PROGRAMMES IN 2016 158

OTHER INTERNATIONAL RESEARCH PROGRAMMES IN 2016 158

ERASMUS+ PROGRAMME 158

LIST OF VISITORS TO THE INCT IN 2016 159

THE INCT SEMINARS IN 2016 160

LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2016 162

LECTURES 162

SEMINARS 166

AWARDS IN 2016 168

INDEX OF THE AUTHORS 171

9GENERAL INFORMATION

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.

The INCT is Poland’s most advanced institution in the fi elds 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 fi eld 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 modifi cation of polymers; for removal of SO2 and NOx from fl ue gases; for food hygiene. The electron beam fl ue 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 Scientifi c Council has the rights to grant D.Sc. and Ph.D. degrees in the fi eld of chemistry. The Institute carries out third level studies (doctorate) in the fi eld of nuclear and radiation chemistry and in 2016 four Ph.D. theses were defended. One Ph.D. thesis was defended at the University of Montpellier 2 (Co-tutelle).

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 fi ll up the gap of education quality between different region of EU countries.

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 Col-laborating Centre in Radiation Processing and Industrial Dosimetry. In 2016, the IAEA made an evaluation of the Collaborating Centre’s activity in the period of 2011-2015 and approved the Centre’s status for next fi ve years.

The INCT is editor of the scientifi c journal “Nukleonika” (www.nukleonika.pl) and the scientifi c-information journal “Postępy Techniki Jądrowej” (www.ptj.waw.pl).

In 2013, the Evaluation Committee of Scientifi c 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;• 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;

10 GENERAL INFORMATION

• PLATENSO: Building a platform for enhanced societal research related to nuclear energy in Central and Eastern Europe;

• SACSESS: Safety of actinide separation processes;• EUCARD-2 WP4: Applications of accelerators: The industrial and environemntal ap-

plications of electron beams.In 2016, the INCT scientists published 57 papers in scientifi c journals registered in

the Philadelphia list, among them 50 papers in journals with an impact factor (IF) higher than 1.0. Eight chapters of books were written by the INCT research workers.

The following annual awards of the INCT Director-General for the best publica-tions and application achievements were granted in 2016:• fi rst degree team award to Michał H. Jamróz, Katarzyna Łuczyńska, Krzysztof Łyczko,

Monika Łyczko, Sławomir Ostrowski, Joanna E. Rode, Wojciech Starosta, Jan Cz. Do-browolski for a series of twenty original publications on the application of quantum chemistry methods and graph theory for interpretation and prediction of the results of X-ray and vibrational spectroscopy structural studies;

• second degree team award to Anna Lankoff, Kamil Brzóska, Sylwia Męczyńska-Wielgosz, Katarzyna Sikorska, Tomasz M. Stępkowski, Maria Wojewódzka, Marcin Kruszewski for a series of fi ve publications on the study of nanoparticles effect on human and animal cells;

• third degree team award to Krzysztof Bobrowski, Dariusz Pogocki, Gabriel Kciuk for a series of four publications dedicated to the radiation- and photochemically-induced radical processes in amino acids and sulphur-containing peptides;

• third degree team award to Jerzy Ostyk-Narbutt, Łukasz Steczek, Magdalena Rejnis-Strze-lak for a series of four publications on effective separation of minority actinides from fi ssion products of uranium in spent nuclear fuel;

• second degree team award to Zbigniew Zimek, Andrzej Rafalski, Sylwester Bułka, Sta-nisław Celiński-Mysław, Izabela Fąfrowicz-Janowska for the application achievements in 2014-2015 – the technology for radiation modifi cation of semiconductor devices used in photovoltaic sources using the low energy electrons;

• second degree team award to Yongxia Sun, Ewa Zwolińska for the application achieve-ments in 2014-2015 – the process for removing sulphur dioxide and nitrogen oxides from exhaust gases with high content of carbon dioxide using high-energy electron beams.

In 2016, the research teams in the INCT were involved in the organization of 11 scien-tifi c meetings.

11MANAGEMENT OF THE INSTITUTE

MANAGEMENT OF THE INSTITUTE

MANAGING STAFF OF THE INSTITUTE

DirectorProf. Andrzej G. Chmielewski, Ph.D., D.Sc.

Deputy Director for Research and DevelopmentProf. Jacek Michalik, Ph.D., D.Sc.

Deputy Director of FinancesWojciech Maciąg, M.Sc.

Deputy Director of Maintenance and MarketingRoman Janusz, M.Sc.

Accountant GeneralMaria Małkiewicz, M.Sc.

HEADS OF THE INCT DEPARTMENTS

• Centre for Radiation Research and TechnologyZbigniew Zimek, Ph.D.

• Centre for Radiochemistry and Nuclear ChemistryProf. Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc.

• Centre for Radiobiology and Biological DosimetryProf. Marcin Kruszewski, Ph.D., D.Sc.

• Laboratory of Nuclear Control Systems and MethodsJacek Palige, Ph.D.

• Laboratory of Material ResearchWojciech Starosta, Ph.D.

• Laboratory of Nuclear Analytical MethodsHalina Polkowska-Motrenko, Ph.D., D.Sc., professor in INCT

• Stable Isotope LaboratoryRyszard Wierzchnicki, Ph.D.

• Pollution Control Technologies LaboratoryYongxia Sun, Ph.D., D.Sc., professor in INCT

• Laboratory for Detection of Irradiated FoodWacław Stachowicz, Ph.D./Grażyna Liśkiewicz

• Laboratory for Measurements of Technological DosesAnna Korzeniowska-Sobczuk, M.Sc.

SCIENTIFIC COUNCIL (2015-2019)

1. Prof. Aleksander Bilewicz, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology

2. Prof. Krzysztof Bobrowski, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology

3. Prof. Ewa Bulska, Ph.D., D.Sc.University of Warsaw

4. Sylwester Bułka, M.Sc.Institute of Nuclear Chemistry and Technology

5. Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology

6. Tomasz Ciach, Ph.D., D.Sc., professor in WUTWarsaw University of Technology

7. Prof. Jan Czesław Dobrowolski, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology

8. Prof. Rajmund Dybczyński, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology

12 MANAGEMENT OF THE INSTITUTE

9. Prof. Zbigniew Florjańczyk, Ph.D., D.Sc.(Chairman)Warsaw University of Technology

10. Prof. Zbigniew Galus, Ph.D., D.Sc.University of Warsaw

11. Prof. Janusz Gołaszewski, Ph.D., D.Sc.University of Warmia and Mazury

12. Prof. Henryk Górecki, Ph.D., D.Sc.Wrocław University of Technology

13. Edward Iller, Ph.D., D.Sc., professor in NCBJNational Centre for Nuclear Research

14. Michał Jamróz, Ph.D., D.Sc., professor in INCTInstitute of Nuclear Chemistry and Technology

15. Prof. Marek Janiak, Ph.D., D.Sc.Military Institute of Hygiene and Epidemiology

16. Rafał Kocia, Ph.D.Institute of Nuclear Chemistry and Technology

17. Prof. Marcin Kruszewski, Ph.D., D.Sc.(Vice-chairman)Institute of Nuclear Chemistry and Technology

18. Krzysztof Kulisa, Eng.Institute of Nuclear Chemistry and Technology

19. Prof. Anna Lankoff, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology

20. Prof. Marek Wojciech Lankosz, Ph.D., D.Sc.AGH University of Science and Technology

21. Prof. Jacek Michalik, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology

22. Wojciech Migdał, Ph.D., D.Sc., professor in INCTInstitute of Nuclear Chemistry and Technology

23. Prof. Jarosław Mizera, Ph.D., D.Sc. Warsaw University of Technology

24. Prof. Jan Namieśnik, Ph.D., D.Sc. Gdańsk University of Technology

25. Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology

26. Andrzej Pawlukojć, Ph.D., D.Sc., professor in INCTInstitute of Nuclear Chemistry and Technology

27. Halina Polkowska-Motrenko, Ph.D., D.Sc., professor in INCT(Vice-chairman)Institute of Nuclear Chemistry and Technology

28. Marek Pruszyński, Ph.D.Institute of Nuclear Chemistry and Technology

29. Grażyna Przybytniak, Ph.D., D.Sc., professor in INCTInstitute of Nuclear Chemistry and Technology

30. Prof. Janusz Rosiak, Ph.D., D.Sc.Technical University of Łódź

31. Yongxia Sun, Ph.D., D.Sc., professor in INCTInstitute of Nuclear Chemistry and Technology

32. Prof. Marek Trojanowicz, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology

33. Lech Waliś, Ph.D.Institute of Nuclear Chemistry and Technology

34. Maria Wojewódzka, Ph.D.Institute of Nuclear Chemistry and Technology

35. Prof. Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc.(Vice-chairman)Institute of Nuclear Chemistry and Technology

HONORARY MEMBERS OF THE INCT SCIENTIFIC COUNCIL (2015-2019)

1. Prof. Sławomir Siekierski, Ph.D.2. Prof. Zbigniew Szot, Ph.D., D.Sc.

3. Prof. Irena Szumiel, Ph.D., D.Sc.

13MANAGEMENT OF THE INSTITUTE

DIRECTOR

ORGANIZATION SCHEME

Scientifi c Council

Laboratory of Nuclear Control Systems and Methods

Deputy Director for Research and Development

Centre for Radiobiology and Biological Dosimetry

Centre for Radiochemistry and Nuclear Chemistry

Deputy Director of Maintenance and Marketing

Accountant General

Laboratory of Nuclear Analytical Methods

Stable Isotope Laboratory

Pollution Control Technologies Laboratory

Laboratory for Detection of Irradiated Food

Laboratory of Material Research

Laboratory for Measurements of Technological Doses

Centre for Radiation Research and Technology

Deputy Director of Finances

14 SCIENTIFIC STAFF

SCIENTIFIC STAFF

PROFESSORS

1. Bilewicz Aleksanderradiochemistry, inorganic chemistry

2. Bobrowski Krzysztofradiation chemistry, photochemistry, biophysics

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

4. Cieśla Krystyna, professor in INCTphysical chemistry

5. Dobrowolski Jan Cz.physical chemistry

6. Dybczyński Rajmundanalytical chemistry

7. Gniazdowska Ewa, professor in INCTchemistry

8. Jamróz Michał, professor in INCTchemistry, physics

9. Kruszewski Marcinradiobiology

10. Lankoff Annabiology

11. Lipkowski Januszphysical chemistry

12. Michalik Jacekradiation chemistry, surface chemistry, radical chemistry

13. Migdał Wojciech, professor in INCTchemistry, science of commodies

14. Ostyk-Narbutt Jerzyradiochemistry, coordination chemistry

15. Pawlukojć Andrzej, professor in INCTchemistry

16. Pogocki Dariusz, professor in INCTradiation chemistry, pulse radiolysis

17. Polkowska-Motrenko Halina, professor in INCTanalytical chemistry

18. Przybytniak Grażyna, professor in INCTradiation chemistry

19. Siekierski Sławomirphysical chemistry, inorganic chemistry

20. Sun Yongxia, professor in INCTchemistry

21. Szumiel Irenacellular radiobiology

22. Trojanowicz Marekanalytical chemistry

23. Zakrzewska-Kołtuniewicz Grażynaprocess and chemical engineering

SENIOR SCIENTISTS (Ph.D.)

1. Bartłomiejczyk Teresabiology

2. Boguski Jacekchemistry

3. Bojanowska-Czajka Annachemistry

4. Brykała Marcinchemistry

5. Brzóska Kamilbiochemistry

6. Chajduk Ewelinachemistry

7. Danilczuk Marekchemistry

8. Dobrowolski Andrzejchemistry

9. Dudek Jakubchemistry

10. Fuks Leonchemistry

15SCIENTIFIC STAFF

11. Głuszewski Wojciechchemistry

12. Grądzka Iwonabiology

13. Herdzik-Koniecko Irenachemistry

14. Kciuk Gabrielchemistry

15. Kiegiel Katarzynachemistry

16. Kocia Rafałchemistry

17. Kornacka Ewachemistry

18. Koźmiński Przemysławchemistry

19. Kunicki-Goldfi nger Jerzyconservator/restorer of art

20. Latek Stanisławnuclear physics

21. Lewandowska-Siwkiewicz Hannachemistry

22. Łyczko Krzysztofchemistry

23. Łyczko Monikachemistry

24. Majkowska-Pilip Agnieszkachemistry

25. Męczyńska-Wielgosz Sylwiachemistry

26. Miśkiewicz Agnieszkachemistry

27. Nowicki Andrzejorganic chemistry and technology, high-temperature technology

28. Ostrowski Sławomirchemistry

29. Palige Jacekmetallurgy

30. Pawelec Andrzejchemical engineering

31. Pruszyński Marekchemistry

32. Ptaszek Sylwiachemical engineering

33. Rafalski Andrzejradiation chemistry

34. Rode Joannachemistry

35. Roubinek Ottonchemistry

36. Sadło Jarosławchemistry

37. Samczyński Zbigniewanalytical chemistry

38. Sartowska Bożenamaterial engineering

39. Sochanowicz Barbarabiology

40. Sommer Sylwesterradiobiology, cytogenetics

41. Starosta Wojciechchemistry

42. Sterniczuk Macinchemistry

43. Strzelczak Grażynaradiation chemistry

44. Szreder Tomaszchemistry

45. Waliś Lechmaterial science, material engineering

46. Walo Martachemistry

47. Wawszczak Danutachemistry

48. Wierzchnicki Ryszardchemical engineering

49. Wiśniowski Pawełradiation chemistry, photochemistry, biophysics

50. Wojewódzka Mariaradiobiology

51. Wójciuk Grzegorzchemistry

52. Wójciuk Karolinachemistry

53. Zimek Zbigniewelectronics, accelerator techniques, radiation processing

CENTRE CENTRE FOR RADIATION RESEARCH FOR RADIATION RESEARCH

AND TECHNOLOGYAND TECHNOLOGY

The electron beams (EB) offered by the Centre for Radiation Research and Technology lo-cated at the Institute of Nuclear Chemistry and Technology (lNCT) are dedicated to basic research, R&D study, and practical applications of radiation technology.

The Centre, in collaboration with the universities from Poland and abroad, applies EB tech-nology to fundamental research on electron beam-induced chemistry and the transformation of materials. Research in the fi eld 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 for direct time-resolved observation of short-lived intermediates (typically within the nanosecond to millisecond time domain), and is complemented by steady-state radiolysis, stopped-fl ow absorption spectrofl uorimetry, and product analysis using chromatographic methods. Studies on radiation-induced interme-diates are dedicated to the processes of energy and charge transfer, to radical reactions in model compounds of biologically relevant aromatic thioethers, peptides and proteins, and also to the observation of atoms, clusters, and radicals by electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR). Further, these studies are also focused on research problems in nanophase chemistry and the radiation-induced crosslinking of selected and/or modifi ed 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 mate-rial properties. Electron accelerators provide streams of electrons to initiate chemical reac-tions or break down chemical bonds more effi ciently than the existing thermal and chemical approaches, thus helping to reduce energy consumption and thereby decrease the cost of the processes. The Centre currently offers fi ve electron accelerators to study the effects of accel-erated electrons on a wide range of chemical compounds with a focus on electron beam-in-duced polymerization, polymer modifi cation, and the controlled degradation of macromol-ecules. EB technology has great potential to promote innovation, including new ways to save energy and reduce the use of hazardous substances, as well as to enable more eco-friendly manufacturing processes.

Advanced EB technology offered by the Centre provides a unique platform to be used for some of the following applications: sterilization of medical devices, pharmaceutical materials, shelf-life extension food products, advanced polymer materials, air pollution removal technol-ogy, and others. EB accelerators replace frequently thermal and chemical processes for cleaner, more effi cient, lower cost manufacturing.

The Centre offers EB in the energy range of 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 is supported by unique laboratory equipment such as: • nanosecond pulse radiolysis and laser photolysis set-ups, • stopped-fl ow experimental set-up, • EPR spectroscopy for solid materials investigation, • pilot installation for polymer modifi cation, • experimental stand for removal of pollutants from gas phase, • polymer characterization laboratory, • pilot facility for radiation sterilization, polymer modifi cation, and food product processing.

The unique technical core makes it possible to organize a wide internal and international cooperation in the fi eld of radiation chemistry and radiation processing including programmes

supported by the European Union and the International Atomic Energy Agency (IAEA). It should be noted that currently there are no other suitable European experimental platforms for the study of radiation chemistry, physics and radiation processing in a full range of elec-tron energy and beam power.

Since 2010, at the INCT and based on 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 the capability and great potential of concentrated equipment, as well as of the employed methods and staff working towards the application of innovative radiation technology.

19CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY

THREE-ELECTRON BONDED, DIMERIC RADICAL CATIONS DERIVED FROM 2-THIOURACIL DERIVATIVES

Konrad Skotnicki1/, Katarzyna Taras-Goślińska2/, Krzysztof Bobrowski1/

1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland2/ Adam Mickiewicz University, Poznań, Poland

2-Thiouracil (2TU) derivatives, sulfur analogs of the DNA base uracil, have gained a lot of atten-tion recently, due to their varied biological activ-ity. 2-Thiouracil has been used in the diagnosis, as well as in a treatment, of melanoma, since it binds to melanin polymers [1-3]. 6-Methyl-2-thio-uracil (6MeTU) has been used in the treatment of thyroid related diseases, including hyperthyroid-

ism [4]. Moreover, modifi ed DNA bases, including sulfur or halogen-containing purines and pyrimi-dines, are thought to be potential radiosensitizing agents in cancer therapy [5]. Despite these im-portant applications, not much is known about the radical chemistry of thiouracil and its derivatives, in contrast to the regular uracil base [6]. In the presented work, the OH and N3

-induced oxida-tion of thiouracil derivatives (2-thiouracil, 5-me-

thyl-2-thiouracil (5MeTU), and 6-methyl-2-thio-uracil) has been studied in aqueous solutions at neutral pH.

Oxidation of 2TU by OH radicals in aqueous solutions led to the formation of at least two dis-tinct absorption maxima, located at = 325 and 420 nm. In principle, we observed the same prod-ucts for all the examined compounds, but with

various radiation chemical yields. The highest ab-sorption recorded 1 s after an electron pulse was observed at = 325 nm for 5MeTU, followed by absorptions observed for 6MeTU and 2TU (Fig. 1A). On the other hand, 5MeTU showed the low-est absorption at = 420 nm in comparison to the other compounds. When the results from simi-lar experiments, performed with a higher concen-tration of solutes (2 10–3 M), were compared, the

Fig. 1. Transient absorption spectra (uncorrected for the ground-state absorption) recorded 6 s after an electron pulse in N2O-saturated aqueous solution containing 0.125 mM (A), and 2 mM (B) of the respective thiouracil derivatives at pH 7. In both spectra: 2TU (), 5MeTU (○), 6MeTU (Δ).

A B

Fig. 2. Transient absorption spectra (uncorrected for the ground-state absorption) recorded 6 s after an electron pulse in: (A) N2O-saturated aqueous solutions containing 0.1 mM of the respective thiouracil derivatives and 0.1 M NaN3 at pH 7; (B) in O2-saturated acetonitrile solution containing 0.1 mM of the respective thiouracil derivatives. In both spectra: 2TU (), 6MeTU (○), 5MeTU (Δ).

A B

20 CENTRE FOR RADIATION RESEARCH AND TECHNOLOGY

difference in yields of the 420 nm absorption was even more pronounced (Fig. 1B). The highest rate constant for the formation of the 325 nm ab-sorption was observed for 2TU (1 1010 M–1s–1), followed by 5MeTU (8 109 M–1s–1) and 6MeTU (6 109 M–1s–1). All the rates measured were close to the diffusion controlled rates.

Since the OH radical is not a pure one-elec-tron oxidant, additional experiments were perform-ed by changing either the oxidizing agent to the N3 radical, or the solvent from water to acetoni-trile. In both cases, one can expect the formation of one-electron oxidized species derived from thiouracils. Oxidation by N3

led to an absorption band with a single absorption maximum localized at = 325 nm for all thiouracil derivatives (Fig. 2A). It is worth mentioning that the absorption observed in solutions containing 2TU was ca. 50% lower in comparison to the other compounds. The reaction in oxygenated acetonitrile (Fig. 2B) led to the formation of a single absorption band, identical to that observed during oxidation by N3 radicals. This is due to the fact that the radical cation derived from acetonitrile (CH3CN+) is also a strong one-electron oxidant.

The results obtained led to several conclu-sions. Firstly, a product characterized by the ab-sorption band with max = 325 nm in water and acetonitrile can be clearly assigned to a radical cation of the respective thiouracil derivative. Sec-ondly, spectral and kinetic data obtained in this work, along with the data reported in the litera-ture [6], suggest that the absorption band with max = 425 nm can be assigned to the 2c,3e-bond-ed, intermolecular sulfur-sulfur radical cations (Fig. 3). Such odd-electron sulfur-sulfur bonded radicals have been exhaustively studied by pulse

radiolysis and observed in many aliphatic com-pounds, for instance in thioethers. On the other hand, there is almost no knowledge about three--electron bonded radicals of aryl compounds. Therefore, more work is needed to undoubtedly confi rm their existence and to elucidate the pos-sible consequences for medical applications.

References[1]. Dencker, L., Larsson, B., Olander, K., Ullberg, S., & Yo-

kota, M. (1979). False precursors of melanin as selec-tive melanoma seekers. Brit. J. Cancer, 39 (4), 449-452.

[2]. Tjarks, W., & Gabel, D. (1991). Boron-containing thiouracil derivatives for neutron-capture therapy of melanoma. J. Med. Chem., 34 (1), 315-319.

[3]. Napolitano, A., Palumbo, A., d’Ischia, M., & Prota, G. (1996). Mechanism of selective incorporation of the melanoma seeker 2-thiouracil into growing melanin. J. Med. Chem., 39 (26), 5192-5201.

[4]. Cooper, D.S. (2005). Antithyroid drugs. New Engl. J. Med., 352 (9), 905-917.

[5]. Westphal, K., Skotnicki, K., Bobrowski, K., & Rak, J. (2016). Radiation damage to single stranded oligonu-cleotide trimers labelled with 5-iodopyrimidines. Org. Biomol. Chem., 14 (39), 9331-9337.

[6]. Prasanthkumar, K., Suresh, C., & Aravindakumar, C. (2012). Oxidation reactions of 2-thiouracil: A theoreti-cal and pulse radiolysis study. J. Phys. Chem. A, 116 (44), 10712-10720.

Fig. 3. The proposed mechanism for the formation of two-centered, three-electron bonded uracil dimeric radical cations.

CHANGES IN COLLAGEN AND ITS MAIN COMPONENTS UNDER THE INFLUENCE OF IONIZING RADIATION

Ewa Maria Kornacka, Grażyna Przybytniak, Zbigniew Zimek

Skin allographs are valuable biomaterials, which can be used as wound dressings in the case of skin burns, trophic ulcers, or tumours. Cell-free allo-graphs preserve native porous architecture and retain the original chemical structure of the col-lagen matrix. In order to apply the material for biomedical purposes, sterilization is necessary as a preliminary treatment prior to further cell cul-ture. It is generally accepted that exposure to ion-izing radiation is the most certain and reliable process to eliminate pathogens in this type of ma-terials. However, some reports in the literature suggest that radiation sterilization of the colla-gen-based materials results in their degradation, followed by a deterioration in their mechanical properties, and an increase in their susceptibility to enzymatic digestion and to dissolving in neu-tral and acidic media. The adverse macroscopic consequences arising from the generated radicals result from the modifi cation of collagen structure, as well as from the development of oxidative deg-

radation [1]. Similar processes are created under native conditions in skin via metabolic pathways and as a result of external factors, e.g. exposure to ultraviolet radiation [2].

Collagen is a simple protein, composed of three -helixes wound together in a triple helix. It is the most abundant component of skin. When exposed to ionizing radiation to eliminate bioburdens, col-lagen may partially loss functionality due to radia-tion-induced modifi cation. Radical processes cause removal of some functional groups (e.g. amine groups, disruption of the hydrogen bonding sys-tem, and the insertion of new, usually oxygen containing substituents, etc. The changes have an infl uence on the spatial structure of the protein.

Chiapara et al. [3] investigated the radical pro-cesses in collagen irradiated with protons at room temperature. The superposition of an anisotropic singlet of a peroxyl radical and a quintet from alkyl radicals were noted by EPR (electron para-magnetic resonance) spectroscopy. The presence


of the second species proves that the scission of macromolecules is an important consequence of irradiation.

Irradiation of L-proline and 4-hydroxy-L-pro-line solutions triggers reactions leading to the opening of the pyrrolidine ring or to hydrogen ab-straction from the methylene groups. The indirect effect of ionizing radiation is observed in this case, so the results cannot be straightforwardly extra-polated to anhydrous conditions.

Radical products generated by gamma rays were identifi ed in lyophilized collagen and in mi-crocrystalline powders of glycine, L-proline, and L-hydroxyproline. Reagents irradiated at 77 K were studied by EPR spectroscopy in the range of 100-350 K using a temperature control system. The samples in quartz tubes were exposed to gamma rays in a BRIT Gamma Chamber 5000 at a dose rate of 4.1 kGy/h. The irradiation was per-formed at liquid nitrogen temperature with a dose of 5 kGy. EPR spectra were recorded using a Bru-ker EMXplus–A EPR spectrometer system, operat-ing at X-band and equipped with a high sensitiv-ity probe head and a Bruker EMX 41VT tempera-ture control system. The experimental signals were recorded using the following parameters: modu-lation amplitude – 0.1 mT, sweep width – 70.0 mT, resolution – 7000 points, and microwave power – 0.107 mW. The number of scans was ad-justed to the intensity of the spectra and was 4-8 for amino acids and 8-16 for collagen.

Glycine is one of the main component of col-lagen, since it appears as every third residue in its structure. Polycrystalline glycine in zwitterionic form, when irradiated under cryogenic condi-tions, showed two lines at a distance of 50.4 mT, attributed to the released hydrogen atoms (out of range in Fig. 1), and a doublet of hyperfi ne split-

ting (hfs) 2.57 mT and g = 2.0038, probably cor-responding to the radical anion G1 (Fig. 1). This primary intermediate (presented in Scheme 1) was a precursor of two carbon-centred species, created either via release of hydrogen (G2) or by deamination (G3) [4, 5], showing a quintet and a triplet, respectively.

Collagen is a proline-rich protein. The L-pro-line spectrum detected just after irradiation at 100 K showed a symmetric singlet (Fig. 2) and two lines separated by about 50.4 mT, attributed to hydrogen. Triplet lines with a ratio of 1:2:1 and hfs 2.06 mT arising above 100 K were assigned to the radical P2 presented in Scheme 2 [6]. Interest-ingly, for LD-proline an analogous pattern of lines already appeared at 100 K, whereas at elevated temperatures a distinct quintet 1:4:6:4:1 emerged, which suggested that in this case the most thermo-dynamically stable species was the DL-P3 rad-ical.

In the well-established collagen repeating se-quence (glycine-X-Y)n the X and Y positions are

Fig. 1. EPR spectra of glycine gamma-irradiated with a dose of 5 kGy at 77 K.

310 320 330 340 350

290 K

Sim. 170 K

170 K

140 K

100 K

Magnetic field / mT

Scheme 1. Glycine radicals initiated by ionizing radiation.

310 320 330 340 350

quartz tube

DL-proline, 350 K

350 K

140 K

120 K

100 K

Magnetic field / mTFig. 2. EPR spectra of proline gamma-irradiated with a dose of 5 kGy at 77 K.


often occupied by proline or hydroxyproline (HyP). The HyP spectra were multiline and com-plex (Fig. 3). However, it seemed that two dis-tinct patterns could be selected – the fi rst one at a lower temperature and the second one at a higher temperature. The prevailing signal could be repro-duced by the triplet of triplets structure presented in Fig. 3, Sim. 100 K. To simulate the dominant component, the hyperfi ne splitting of the two hy-drogen atoms of the amino group was taken into account and also the interactions of the and protons at their carbon atoms, respectively. The relevant fi gures were a(HN1,2) = 1.0 mT, a(H) = 1.6 mT, and a(H) = 3.6 mT. Such a signal could be attributed to the radical HyP1 presented in Scheme 3.

Apart from the main signal, there were many weak lines corresponding to the symmetric spec-trum appearing in a pronounced shape at 350 K.

The 0.7 mT splitting could be attributed to the hydrogen atom attached to the secondary amino group. To simulate the signal recorded at 350 K, the following parameters were used: a(H) = 1.6 mT, a(H1) = 3.10 mT, a(H2) = 1.4 mT, a(HN1,2) = 0.7 mT, and a(N) = 0.35 mT. The radical HyP2, presented in Scheme 3, was a product of decar-boxylation of HyP, followed by the capture of an electron.

The spectra of irradiated collagen are shown in Fig. 4. The signal detected at 100 K was com-posed of a broad singlet and a triplet of hfs = 2.06 mT, corresponding to Col1 (Scheme 4); the signal slowly decayed between 100 and 200 K. The un-paired spin localized in the proline or hydroxy-proline residues of the peptide interacted with

Scheme 3. Hydroxyproline radicals initiated by ionizing radiation.

Fig. 3. EPR spectra of L-hydroxyproline gamma-irradiated with a dose of 5 kGy at 77 K.

310 320 330 340 350

Sim. 350 K

350 K

290 K

Sim. 100 K

100 K

Magnetic field / mT

Scheme 2. Proline radicals initiated by ionizing radiation.

Fig. 4. EPR spectra of collagen gamma-irradiated with a dose of 5 kGy at 77 K.

310 320 330 340 350

Col2

Col1

quartz tube

Sim. 290 K

290 K

Sim. 140 K

140 K

100 K

Magnetic field / mT


two protons. The corresponding radical was also identifi ed in proline as the P2 intermediate (Scheme 2).

The sextet clearly outlined at 290 K as a weak-ly resolved signal was also present in the form of wide external lines in the spectrum measured at 100 K. The intensity of these wings did not change in the range of 100-290 K, demonstrating that the radical showing such a signal was already generated during irradiation. The sextet of split-ting a(H) = 1.5 mT was attributed to the Col2 radical with one and four equivalent protons.

The radicals identifi ed in collagen by EPR did not affect the hydrogen bonding system, since the active centres were situated at carbon atoms and, even more importantly, unpaired spins do not in-teract with groups playing the role of proton do-nors or acceptors. Additionally, the intermediates found by EPR spectroscopy were not terminal radicals that would be produced by chain scission. Thus, if such a process did occur, it would be trig-gered by subsequent oxidative degradation, rather

than the reactions of carbon-centred radicals. The radicals identifi ed in collagen were situated in the proline ring. If unpaired spin is localized at the carbon to the carbonyl group, it is conceivable that the hydroxyproline radical is also involved.

Th e work was performed in the framework of the National Centre for Research and Develop-ment project No. 269807, STRATEGMED2/ 269807/14/NCBR/2015 (acronym: BIOOPA).

References[1]. Headlam, H.A., Mortimer, A., Easton, C.J., & Davies,

M.J. (2000). -scission of C-3 (-carbon) alkoxyl rad-icals on peptides and proteins: A novel pathway which results in the formation of -carbon radicals and the loss of amino acid side chains. Chem. Res. Toxicol., 13, 1087-1095. DOI: 10.1021/tx0001171.

[2]. Herrling, Th., Jung, K., & Fuchs, J. (2006) Measure-ments of UV-generated free radicals/reactive oxygen species (ROS) in skin. Spectrochim. Acta Part A, 63, 840-845. DOI: 10.1016/j.saa.2005.10.013.

[3]. Chipara, M., Romero, J.R., Ignat, M., Constantinescu, B., & Secu, C. (2003). ESR studies on collagen irra-diated with protons. Polym. Degrad. Stab., 80, 45-49. DOI: 10.1016/S0141-3910(02)00381-6.

[4]. Aydin, M., & Osmanoglu, Y.E. (2011). EPR study of free radicals in amino acids derivatives irradiated by gamma rays. Rom. J. Phys., 56 (9-10), 1156-1161.

[5]. Weidong, H., Jianwei, H., Xiangqing, W., Zengliang, Y., & Yuheng, Z. (1998). keV ion irradiation of solid gly-cine: an EPR study. Nucl. Instrum. Meth. Phys. Res. B, 140, 137-142.

[6]. Ban, F., Gauld, J.W., & Boyd, R.J. (2000). Theoretical studies of the radiation products of hydroxyproline. J. Phys. Chem. A, 104, 8583-8592. DOI:10.1021/jp001692g.

Scheme 4. Collagen radicals initiated by ionizing radiation.

MATURATION OF NEWLY DEPOSITED CALCIUM-PHOSPHATE CRYSTALS IN HUMAN ADIPOSE DERIVED STEM CELLS CULTURE

AFTER CELL DIFFERENTIATION TO OSTEOBLAST IN VITROMałgorzata Kołodziejczyk1/, Jarosław Sadło2/, Małgorzata Lewandowska-Szumieł1/

1/ Medical University of Warsaw, Department of Histology and Embryology, Warszawa, Poland2/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland

Mineralization in cell culture is commonly con-sidered to be a marker of osteoblast maturity and functionality. Numerous techniques are currently used to demonstrate biological mineralization; however the reliably documented data regarding characterization of mineral noodles remains mod-est.

The aim of this study was to verify whether the min eral deposits that appear during prolonged cell culture are the result of the cells activity, or are merely calcium phosphate precipitates. Using a wide battery of tests and comparative studies, we sought to exhibit morphological and physico-chemical features similar to that of natural bone apatite.

Two types of cells were used, i.e. human adi-pose derived stem cells (hASC) and human bone marrow mesenchymal stem cells (hBMSC). In both cases we used two types of culture medium (DMEM, FBS10%, antibiotic, Glu, dex, Asc2P) en-

riched with both BMP-2 and -glycerophosphate (fi rst system) or with NaH2PO4 (second system).

The following time points were applied for EPR (electron paramagnetic resonance) measure-ments: 21st, 28th, 35th and 42th day. At this time, the mineral which appeared in the culture was analysed by means of Alizarin Red staining and EPR.

Alizarin Red S (40 mM) was prepared in dH2O and the pH was adjusted to 4.1-4.3 using 0.5% (v/v) ammonium hydroxide. At each of the specifi ed time points of osteogenic differentiation, cells were washed with PBS (phosphate-buffered saline) followed by fi xation in 10% buffered for-malin for 20 min. The monolayers were then wash-ed twice with excess dH2O prior to the addition of 1.5 mL of 40 mM Alizarin Red S per well. The plates were incubated at room temperature for 30 min with gentle shaking. After aspiration of the unincorporated dye, the wells were washed four


times with 2 mL of dH2O while shaking for 5min. Stained monolayers were then visualized by phase microscopy using an inverted microscope.

For quantifi cation of staining, 1 ml of 10% (v/v) cetylpyridinium chloride was added to each well, and the plate was incubated at room temperature for 1 h with shaking. The dye was then removed and 100-L aliquots were transferred to a 96-well plate prior to reading at 560 nm.

The cells grown on the culture plates (with mineral and extracellular matrix) were fi xed in 2.5% glutaraldehyde solution in a 0.2 M cacodyl buffer, washed, and then were scraped off the bottom of the culture plate into the media. Col-lected samples were pelleted by centrifugation at 50 000 rpm for 10 min at 4oC, were dehydrated through a graded ethanol series, and then were air-dried. All samples were irradiated at room tem-perature at the Institute on Nuclear Chemistry and Technology, Poland, with a dose of 12 kGy in a 60Co gamma source “Issledovatel”, with a dose rate of 0.6 kGy/h. Then, the samples were placed into thin-walled spectrosil tubes. The EPR meas-urements at X-band (9.5 GHz) were carried out at room temperature with the Bruker ESP-300

Fig. 1. EPR spectra of irradiated hASC samples after 21 days (a) and 42 days (b) of maturation. (c) EPR signal of irradiated human bone.

Fig. 2. Comparison of the presence of red colour of samples after Alizarin Red treatment and the EPR signal in hASC samples.


INFLUENCE OF POST-RADIATION OXIDATION FOR POLYETHYLENE FOAM DENSITY

Wojciech Głuszewski1/, Andrzej Stasiek2/, Aneta Raszkowska-Kaczor2/, Daniel Kaczor2/

1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland2/ Institute for Engineering of Polymer Materials and Dyes, Toruń, Poland

spectrometer. The spectrometer was equipped with a precise frequency counter Hewlett Pack-ard 5342A, and gaussmeter Bruker ER035M. A wide range of microwave powers and modula-tion amplitudes were tested in order to optimize the detection conditions. A standard polycrystal-line DPPH (diphenylpicrylhydrazyl) sample (g = 2.0036) was used for accurate g-tensor determi-nation. The measurement parameters were deter-mined to be the following: modulation frequency – 100 kHz, modulation amplitude – 0.1 mT, and microwave power – 1-10 mW.

EPR signals of both irradiated cell cultures after a short-term incubation were broad singlets with a g-value of g = 2.0045 (Fig. 1a). After a longer incubation time (42 days), a new signal appeared characterized as an axial singlet with g = 2.003 and gll = 1.997 (Fig. 1b). The signal has an identical g-value as the signal that occur-red due to the CO2

– radical in irradiated bone (Fig. 1c) or/and in hydroxyapatite.

Results from the EPR do not correlate with the Alizarin Red results. The samples began to be-come red after only 28 days of maturation, and after 35 days they were fully red (Fig. 2). The ob-tained results indicate that the mineral which oc-curred in the prolonged culture of cells changes over time, namely it becomes more mature and gains increased biological similarity to the native bone forming mineral. However, our data also in-dicate that Alizarin Red staining (the most com-monly used marker for mineralization confi rma-tion) in culture is not suffi cient to distinguish between immature and mature minerals, which may lead to false conclusions. Only the battery consisting of different, well-selected methods employed in the study allowed us to not only de-tect mineral, but also monitor the maturation of mineral in the cell and in cell culture.

Crosslinked polyethylene (PE) foams are charac-terized by good thermal insulation properties, low density, low thermal conductivity, high sound absorption and chemical resistance. These prop-erties aid their broad usage in construction, auto-motive production, the packaging industry, and sports.

The process of polymer extrusion is carried out to introduce interesting physical and technologi-cal properties, i.e. a reduction in the weight and cost of a product, a reduction in material con-sumption, improvement of noise damping effects and heat, and to create products with new appli-

cations [1]. The process for preparing chemical-ly/radiation crosslinked foams consisted of the following steps: preparation of powder mixtures, extrusion of pellets, extrusion of fi lm, and lastly foaming of crosslinked materials [2]. Radiation technology methods are an interesting alternative to traditional chemical crosslinking methods [3-6]. The primary aim of this work is to evaluate the effect of post-radiation oxidation on the density of polyethylene foams. Generally mutual compe-tition of free radicals between the processes of oxidation and crosslinking is observed. The sum-mary highlights the advantages of the process of

Sample number PromoterComposition [%]

promoter porophor content antioxidant polyethylene

1

zinc oxide

1 15 0.2 83.8

2 3 15 0.2 81.8

3 5 15 0.2 79.8

4

tracryl

1 15 0.2 83.8

5 3 15 0.2 81.8

6 5 15 0.2 79.8

7

zinc oxide and tracryl

0.5/0.5 15 0.2 83.8

8 0.7/0.3 15 0.2 83.8

9 0.3/0.7 15 0.2 83.8

10 1.5/1.5 15 0.2 81.8

11 2/1 15 0.2 81.8

12 1/2 15 0.2 81.8

Table 1. Composition of samples used in tests.


radiation crosslinking using electron beams (EB) and gamma rays.

The polyethylene used for foam production was low density polyethylene (LDPE) type Malen FGAN 23-D003 (density – 0.922 g/cm3) and MFR (melt fl ow index; 190oC/2.16 kg, 0.31 g/10 min) from Lyonellbasell. Azodicarbonamide type Uni-cell D1500TSK from Tramaco was used as a foam-ing agent. Other components used include: zinc oxide, zinc stearate, Tracryl PO 3501, and Irganox PS 802 FL (Ciba Specialty Chemicals), all listed in Table 1. The polymer fi lm was obtained using lab equipment that consisted of a single screw ex-truder type Plasti-Corder PLV 151 (Brabender) with a fl at die and polishing rolls. The foaming process was conducted in silicone oil bath at 225oC for 1.5 min.

An electron accelerator with energy of 10 MeV and a beam power of 10 kW was used in this study. For comparison, we also conducted radia-tion treatment by gamma irradiation with an aver-age energy of 1.25 MeV.

The total apparent density (a) was determined from both crosslinked and foamed samples. Three samples for each fi lm were studied with approxi-mate dimensions 50 mm 50 mm. Overall dimen-

sions of the samples were measured in accordance with the European standard [7].

Characterization of the sample was performed on a test stand equipped with a scanning electron microscope Hitachi SU8010 (Japan, 2011) and Cressington sputter coater module measuring the thickness of the sputtered gold layer (Germany, 2011). The microscope is equipped with a cold cathode fi eld emission, SE and BSE detectors, and an EDX detector for X-ray microanalysis.

A gas chromatograph Shimadzu (thermal con-ductivity detector, molecular sieves 5A) was used to determine the radiation yield of hydrogen evo-lution (GH2) and the absorption of oxygen (-GO2) from the dose of radiation given ranging from 5 to 20 kGy. Samples were irradiated in air, in closed vessels with gas phase, and subjected to gas chro-matographic analysis at room temperature.

Table 2 shows the performance of oxygen ab-sorption for two methods of radiation: gamma and electron beam. They are listed here with the cor-responding density of crosslinked foams.

Figures 1-3 show foam obtained from cross-linked polyethylene using EB radiation, gamma radiation, and peroxides. Here we see that the

Table 2. Comparison processes: gamma radiation (dose rate – 4 kGy/h) and EB radiation (dose rate – 14 000 kGy/h). Absorbed dose of radiation was 100 kGy.

Sample numberDensity [g/cm3] Ratio of density

/EB-GO2 [mol/J] Ratio of -GO2

/EB EB EB

1 0.47 0.13 3.6 0.939 0.511 1.8

2 0.23 0.17 1.4 0.714 0.377 1.9

3 0.22 0.1 2.2 0.591 0.187 3.2

4 0.36 0.08 4.5 0.812 0.351 2.3

5 0.28 0.45 0.6 0.904 0.274 3.3

6 0.33 0.41 0.8 1.265 0.343 3.7

7 0.24 0.22 1.1 0.856 0.209 4.1

8 0.18 0.08 2.3 0.857 0.245 3.5

9 0.26 0.1 2.6 0.876 0.153 5.7

10 0.27 0.06 4.5 2.572 0.251 10.2

11 0.6 0.04 15.0 1.695 0.352 4.8

12 0.68 0.08 8.5 2.516 0.269 9.4

Fig. 1. Radiation crosslinked foams – 100 kGy, EB radia-tion.

Fig. 2. Radiation crosslinked foam – 100 kGy, gamma ra-diation.


greater crosslinking of the polyethylene, the lower the density of the obtained foam.

Table 3 compares the foam radiation and chemi-cal crosslinking procedures. Foams with smaller pores and thus a lower thickness can be obtained though the use of radiation crosslinking.

Gas chromatography and DRS (diffuse refl ec-tion spectroscopy) proved to be good analytical methods to observe the processes of post-radia-tion oxidation of polymers.

The method of radiation employed is an im-portant determiner for the density of the resulting crosslinked foams.

It can be assumed that competition between the crosslinking reaction and oxidation reaction is important for the fi nal effect.

It is not clear what the protective effect of aro-matic antioxidants is in the process of radiolysis with the different types of mixtures used.

References[1]. Stasiek, A., Raszkowska-Kaczor, A., & Bajer, K. (2013).

Wpływ obecności środka wspomagającego sieciowanie oraz zawartości środka porującego na właściwości poli-etylenowych pianek chemicznie sieciowanych. Prze-mysł Chemiczny, 92, 6, 1038-1041.

[2]. Raszkowska-Kaczor, A., Stasiek, A., Janczak, K., & Olewnik-Kruszkowska, E. (2015). Chemically cross-linked polyethylene foams of limited fl ammability. Po-limery, 60, 4, 283-285.

[3]. Raszkowska-Kaczor, A., Głuszewski, W., & Stasiek, A. (2016). Zastosowanie radiacyjnego sieciowania w pro-dukcji polietylenowych pianek. Tworzywa Sztuczne w Przemyśle, 5, 47-48.

[4]. Głuszewski, W., Zagórski, Z.P., & Rajkiewicz, M. (2014). Protective effects in radiation modifi cation of elastomers. Radiat. Phys. Chem., 105, 53-56.

[5]. Głuszewski, W., Zagórski, Z.P., & Rajkiewicz, M. (2014). Synergistic effects in the processes of cross-linking of elastomers. Radiat. Phys. Chem., 94, 36-39.

[6]. Głuszewski, W., Zagórski, Z.P., & Rajkiewicz, M. (2015). The comparison of radiation and a peroxide crosslinki ng of elastomers. KGK – Kautschuk, Gummi, Kunststoffe, 15, 11/12, 46-49.

[7]. ISO. (2006). Cellular plastics and rubbers – Determi-nation of apparent density. ISO 845:2006.

Table 3. Comparison of chemical and radiation crosslinking.

Parameters Radiation crosslinking Chemical crosslinking

Process control easy complicated

Production rate fast slow

Device (production line) rather simple simple

Costs decrease with the volume of production relatively constant

Choice of foaming simple more complicated

Thickness [mm] 3-6 5-16

Cell size [mm] 0.2-0.4 0.5-0.8

Degree of crosslinking 30-40 60-70

IONIZING RADIATION TREATMENT OF BRINE PURIFICATION SUSPENSION

Marcin Sudlitz, Zbigniew Zimek

The radiation processing method may offer a uni-que possibility to recycle wastes when common processes are too expensive or do not offer requir-ed effi ciency. Suitable evaluation procedures need to be applied to ensure development status, tech-nical feasibility, retrofi t ability, process reliability, energy consumption, resources requirements, and economical aspects of the radiation process. It was found that the sedimentation capabilities of a va-riety of sediments were signifi cantly improved by using non-selective radiation-induced processes. These processes are based on free radical reactions

and surface effects in the adsorption on solids, as well as on the systematic interaction between sedi-mentation and the electrical fi eld. The substantial amount of research performed over the years has confi rmed that radiation technology can be suc-cessfully used as an effective and feasible process method.

The Solvay process is a major industrial pro-cess used for the production soda ash. It is a well--established technology that was fi rst implement-ed with success many years ago. Soda ash is used in many industrial processes what including: glass

Fig. 3. Chemically crosslinked foams.


making, water treatment (to soften water), mak-ing soaps and detergents, paper making, and as a common alkali in baking soda, fi re extinguishers, the pharmaceutical industry among others. The raw materials needed for this process, namely salt brine and limestone, are readily available and in-expensive. Soda ash (predominantly sodium car-bonate (Na2CO3)) is produced in the Solvay pro-cess from brine (as a source of sodium chloride (NaCl)) and limestone (as a source of calcium car-bonate (CaCO3)). The overall process formula can be written as:

2NaCl + CaCO3 Na2CO3 + CaCl2 (1) In the fi rst step of the process, carbon dioxide

(CO2) passes through a concentrated aqueous so-lution of sodium chloride and ammonia in the fol-lowing reaction:

NaCl + CO2 + NH3 + H2O NaHCO3 ++ NH4Cl (2)

In practice the reaction is carried out by fi rst passing concentrated brine though ammonia bub-bles, and subsequently carbon dioxide bubbles up through the ammoniated brine. This allows for the precipitation of sodium bicarbonate (NaHCO3) out of the solution, which is less water-soluble than sodium chloride. Relatively little ammonia is consumed in the reaction due to the fact that the necessary ammonia is reclaimed in a later step. The carbon dioxide required for the reaction is produced by heating (calcinations) of the lime-stone at 950-1100oC in the following reaction:

CaCO3 CO2 + CaO (3)The sodium bicarbonate precipitate is fi ltered

out from the hot ammonium chloride (NH4Cl) solution, and the solution then reacts with the quicklime (calcium oxide (CaO)) that reamids after heating the limestone as per the following reaction:

2NH4Cl + CaO 2NH3 + CaCl2 + H2O (4)The ammonia from the reaction is then recycl-

ed back to the initial brine solution reaction. The sodium bicarbonate is converted to the fi nal prod-uct, sodium carbonate, by calcinations (160-230oC)

that produce water and carbon dioxides as by-prod-ucts as follows: 2NaHCO3 Na2CO3 + H2O + CO2 (5)

The carbon dioxide is then recovered and re-used.

The major inputs to the Solvay process are salt, limestone and thermal energy. The principal by-product is calcium chloride (CaCl2) in aqueous solution, which can be sold as road salt. Additional wastes and by-products result from the process as well. Waste generated during soda ash fabrication in the Solvay process can be divided based on nonorganic solid particles and the liquid phase. Here, not all of the limestone that is calcinated is converted to quicklime and carbon dioxide, thus the residual calcium carbonate and other compo-nents of the limestone are waste. In addition, the salt brine used by the process is usually purifi ed to remove magnesium and calcium ions, typically to form carbonates; otherwise, these impurities would lead to scale in the various vessels and towers that perform the reactions. Consequently, these carbonates are additional waste products. In inland plants, the by-products have been de-posited in “waste beds” which have led to water pollution, principally by calcium and chloride. At seaside plant locations, the calcium chloride solu-tion may be discharged directly into the sea, with-out substantial environmental harm.

The typical Solvay process plant is capable of producing soda ash amounts of 0.5-0.6 Mt/y, and an adequate waste quantity is produced here as well. 1 t of soda ash production requires the fol-lowing components:• NaCl (salt brine) – 1525-1555 kg,• CaCO3 (limestone) – 1206-1370 kg,• carbon (coke) for limestone calcination pro-

cess – 98-105 kg,• carbon for NaHCO3 calcination process –

120-140 kg,• ammonia water – 4-8 kg.

Poland is one of the biggest producers of soda, as a result of an abundance of the natural re-

Fig. 1. Flow sheet of the soda production facility equipped with a waste processing plant.


sources salt and calcium carbonate. Unfortunate-ly, the production process of 1 t of soda generates 10 m3 of waste in the form of liquid suspension. It was recognized that in common process condi-tions, solid particle waste amounts totalled up to 200 kg per 1 t of suspension. The solid particle waste consists of calcium carbonate and magnes-ium hydroxide in the case of brine purifi cation sludge, or alternatively calcium carbonate, gypsum (CaSO4·2H2O), silica and some amounts of mag-nesium and calcium hydroxide in the case of post- -distillation sludge obtained in reaction (2). The liquid phase from the post-distillation suspension is dominated by the presence of calcium chloride (110 g/l), as well as unreacted sodium chloride (55 g/l), and some quantities of other compounds like KCl, NH4Cl, Ca(HCO3)2 with concentra-tions ranging from 0.3-3.0 g/l. To solve this, new methods to discard solid waste are being devel-oped. One of them involves irradiating the sus-pension resulting from brine purifi cation to make it sediment faster and thus easier to remove from the sodium chloride. This waste, which is in fact calcium carbonate and magnesium hydroxide, can be used as a fertilizer after reducing the sodium chloride content to a safe level for plants [1-5]. The main task of the treatment process is sediment separation with limited chloride content (< 0.5% of dry mass).

After conventional treatment, the liquid phase will be reused in industrial processes. It should be mentioned that the application of coagulating agents is excluded to avoid distortion of the main industrial process. On the other hand, separated sediment can also be a marketable product and can be applied as a component of agriculture fer-

tilizers or building materials. Figure 1 illustrates the fl ow of a waste processing plant equipped with electron accelerator.

Sediments were taken from a soda ash plant in Janikowo (CIECH group) and employed in sub-sequent research studies. Concentrations of cat-ions and anions in the hard solvable part of sedi-ment resulting from the brine purifi cation process and from the hard solvable part of sediment after the distillation process were evaluated. The ob-tained data are presented in Tables 1 and 2.

Suspensions were irradiated with a dose up to 10 kGy using Gamma Chamber 5000 60Co source. Afterwards, irradiation coagulation of sludge was observed. In Fig. 2 the formation of layer frac-tions over the time of the sedimentation process of raw waste that was irradiated with a dose of 2.5 kGy. In preliminary studies regarding the ra-diation-induced sedimentation process, a number of experiments were performed. The fi rst set of data was obtained when raw waste was irradiated (before sedimentation tank). Results are display-ed in Fig. 2.

The formation of a layer of sediment in a pro-cess initiated by irradiation only vs. dose is pre-sented in Fig. 3. An irradiation dose of 2.5 kGy was found to be optimal regarding the economi-cal effectiveness of the irradiation process.

The non-irradiated and irradiated sediment samples after distillation process are displayed in Fig. 4. The infl uence of ionizing radiation on the size of the agglomerates can be observed. In Fig. 4A, several agglomerates of approximately 40 m can be observed despite the fact that the sample was not irradiated. For the irradiated sample, the

Table 1. Concentrations of cations and anions measured in the hard solvable part of sediment from the brine purifi ca-tion process.

Table 2. Concentrations of cations and anions measured in the hard solvable part of sediment after the distillation process.

Cations Anions

ion concentration [mg/l] ion concentration

[mg/l]Na+ 0.761 F– 0.228

NH4+ 0.335 Cl– 43.270

K+ 0.164 NO3– 1.732

Mg2+ 0.018 SO42– 2.682

Ca2+ 96.932

Cations Anions

ion concentration [mg/l] ion concentration

[mg/l]

Na+ 16.494 F– 0.158

K+ 0.64 Cl– 69.037

Mg2+ 4.808 NO2– 0.431

Ca2+ 18.452 NO3– 0.365

SO42– 3.697

Fig. 3. Formation of the layer of sediment in a process ini-tiated by irradiation.

Fig. 2. Formation of layers with different volume fractions upon sedimentation of raw waste for dose level 2.5 kGy.


agglomerates are much larger at a size of approxi-mately 160 m.

The experiments using model brine were car-ried out to explain the mechanism of the infl uence of the irradiation on the sedimentation process. Model brine was composed as a solution of sod-ium chloride at a concentration of 307 g/l, calc-ium chloride and magnesium sulphate to achieve a calcium ions concentration of 0.008 M, and mag-nesium ions at a concentration of 0.012 M. These values were close to the concentrations of their respective ions in the raw brine. This composi-tion of raw brine from literature data is presented in Table 3. The main difference between raw brine and model brine is the absence of some ionic pol-lutants such as: Fe3+, K+ and Al3+.

Experiments with model brine were carried out in the same way as with the brine purifi ca-tion sludge. The results demonstrated a complete lack of the infl uence of ionizing radiation on the speed of sedimentation for model brine. No co-agulation was observed after the irradiation of the suspension obtained from model brine. The reason for this may be due to the presence of transition metals cations in the raw brine, which could react with the products of water radiolysis. That may result in an increase in their valence [6] thus making them better coagulants in accord-

ance with the Hardy-Schulze law. Additional ex-periments are planned with the new composition of model brine containing an adequate ion con-tent to defi ne its infl uence on the speed of sedi-mentation.

In conclusion, it has been confi rmed that the treatment of wastewater by radiation to infl uence the physical-chemical separation of highly con-centrated nonorganic pollutants deposited in spe-cifi c industrial waste can be performed. The sedi-ment should be irradiated with a certain dose to obtain the highest process effi ciency. Accordingly, an irradiation dose of 2.5 kGy was found to be optimal. An assumption can be formulated from the point of view of both technical and economic aspects of the waste treatment process to deter-mine: • optimum radiation facility type, complexity and

size; • electrical energy consumption of the techno-

logical process;• by-product market value;• cost effectiveness of the removal process.

References[1]. Dramiński, M., & Grzybowski, P. (2016). Czy jest moż-

liwe zagospodarowanie osadów posodowych? Prze-gląd Techniczny, 11-12, 17-19.

[2]. Steinhauser, G. (2008). Cleaner production in the Sol-vay Process: general strategies and recent develop-ments. J. Clean. Prod., 16, 833-841.

[3]. Bukowski, A. et al. (1958). Technologia sody – praca zbiorowa. Warszawa: Państwowe Wydawnictwo Tech-niczne.

[4]. Bortel, E., & Koneczny, H. (1992). Zarys technologii chemicznej. PWN.

[5]. Morawska, P.M. (2008). Wpływ parametrów proceso-wych na oczyszczanie solanki surowej w przemyśle sodowym. Unpublished masters dissertation, Nicolaus Copernicus University in Toruń, Poland.

[6]. Rush, J.D., & Bielski, B.H.J. (1986). Pulse radiolysis studies of alkaline Fe(III) and Fe(VI) solutions. Ob-servation on transcient iron complexes with interme-diate oxidation states. J. Am. Chem. Soc., 108, 523-525.

Fig. 4. Image of sediments after the distillation process: A – not irradiated, B – irradiated with a dose 10 kGy. Scale bar is 10 m.

A B

Table 3. Example of raw brine composition [3].

Ion Concentration [g/dm3]

Na+ 120.93

K+ 1.08

Ca2+ 0.81

Mg2+ 0.32

Cl– 188.47

SO42– 1.65

CO32– 0.18


Accelerator ILU-6 was installed in 1988 at the De-partment of Radiation Chemistry and Technology pilot plant for research and technology applica-tions using an electron beam in the energy range of 0.5-2 MeV. This device is produced according to standard procedures in the Institute of Nu-clear Physics in Novosibirsk (Russia). The above--mentioned electron energy range is typical for industrial applications, e.g. the modifi cation of plastics via radiation technology (polymerization, crosslinking). Basic parameters of the accelerator are listed in Table 1. The development of surface

treatment technologies (grain hygienization, thin foil crosslinking) requires the use of electron beams with energies in the range of 300 keV or less. Therefore, it is necessary to be able to change the operating parameters of accelerator systems to those with a lower energy of accelerated elec-trons while still ensuring safety and stable opera-

tion with regard to design requirements and con-straints.

Analysis of the working conditions of accel-erator equipment have shown that reducing the electron energy level to between 0.15-0.3 MeV requires the following:• Modifi cations to the pulse power supply switch-

ing system in order to lower the output voltage by introducing an additional system reducing high frequency power generator voltage, while maintaining the actual current level of RF gen-erator at the pre-excitement baseline.

During the tests of the existing pulse modula-tor, the measurement of RF generator pulse power electrical parameters provided informa-tion that there is a certain limit regarding the possibility of a reduction in voltage pulse power, primarily due to thyristor switch instability at low current rates.

Parameter Value

Accelerating structure type resonant RF (127 MHz)

Electron energy range 0.5-2 MeV

Electron beam power up to 20 kW

Electron beam average current up to 20 mA

Electron beam mode pulse Tp = 400 s

Pulsing rate 2, 3, 5, 10, 15, 25 and 50 Hz

Electron beam pulse current up to 0.7 A

Electron beam single pulse energy up to 400 J

Scanning width up to 80 cm

Table 1. Main parameters of the ILU-6 accelerator.

Fig. 1. Confi guration of pulse modulator dedicated for low energy ILU-6 mode.

MODIFICATIONS INTRODUCED INTO ILU-6 ACCELERATOR SYSTEM IN ORDER TO OBTAIN LOW ENERGY ELECTRON BEAM

Sylwester Bułka, Zbigniew Zimek


In this case, an alternative system (shown in Fig. 1) based on transistor switches has been proposed, which has no restrictions regarding voltage pulse power and ensures fl exibility of the selection of generated pulse parameters. The new system includes the circuits respon-sible for coupling the new interlock system with the existing one to assure unaltered safety fea-tures in the modifi ed installation.

• Changes in the electron gun circuitry to im-prove electrons emission at low electric fi eld strengths in the space around the cathode.The thermal cathode emits electrons that should be intercepted by an electric fi eld, Ua; they run further and then become accelerated – when this fi eld is very weak, there is no suffi cient in-terception and the beam current is too low to be useful. In order to facilitate the intercep-tion, the additional negative voltage, -Ubias (Fig. 2) is introduced, resulting in the repul-sion of electrons from the cathode. The accel-erator operates in pulse mode, but the bias is provided as constant DC voltage.

• Since low energy electrons are more susceptible to magnetic defl ection, the signifi cant losses at

the side walls of the beam scanner might occur due to excess sweeping trace. Thus, it was necessary to change the step-down rate of the voltage transformer, taking care of maintaining the linearity of the sweeping current, which de-termines the uniformity of the dose distribution under the accelerator EB extraction window.The electron beam produced by the ILU-6 ac-

celerator was tested by irradiation of dosimetric

foils (PVC thick – 200 m and B3 thick – 19 m). The qualitative visualization of the electron range was demonstrated in PVC (Fig. 3) to compare the two preset accelerating voltages. For this energy range, it was determined that the more suitable dosimeter is B3 due to its low thickness which allows it to achieve a dose depth profi le as shown in Fig. 3.

After modifi cations, the range of electron beam energy obtainable ranges from about 120 (limited by electrons absorption in 50 m titanium foil) to 340 keV at a pulse current of 50 mA. Other para-meters of the accelerator remain unchanged, i.e. frequency selection, pulse duration and scanning width.

Fig. 3. PVC foil irradiated at low electron beam energy – dose depth visualization.

Fig. 2. Accelerator electron gun and its equivalent diode model.

CENTRE FOR RADIOCHEMISTRY CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRYAND NUCLEAR CHEMISTRY

Chemical issues of nuclear power and radiopharmaceutical chemistry are the main research areas of the Centre for Radiochemistry and Nuclear Chemistry. In 2016, the Centre worked on research projects fi nanced 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 collaboration was focused on development of the European Commission (FP7 Euratom, Fission) and other (IAEA, COST) projects. The in-dividual projects of young scientists funded under the specifi c subsidy of the Ministry were important elements for the development of the human resources of the Centre.

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 fi nalized 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 team of Radiochemical Separation Method Laboratory continued the research on actinide/lanthanide separation by solvent extraction, in the frame of the European Colla-borative 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 thermody-namic characteristics of the complexes of actinide cations from Th to Am, at different oxida-tion levels (+3 to +6) with the newly synthesized (Karlsruhe Institute of Technology-Ins-titute for Nuclear Waste Disposal – KIT-INE), tri- and tetra-N-dentate hydrophilic ligands: SO3-Ph-BTP and SO3-Ph-BTBP, especially the determination of stability constants of these complexes in acidic aqueous solutions. Advanced quantum chemical calculations, which al-lowed explaining the reason of actinide selectivity of some ligands used for solvent extraction separation of actinides from lanthanide fi ssion products, were performed. The result of coop-eration with the CEA Marcoule and the studies on partitioning of actinides was the fi naliza-tion in 2016 of the doctoral thesis carried out in the Cotutelle system.

The knowledge based on molecular modelling may allow to design and synthesize novel, more selective ligands for such separations. Design of chiral molecules for applications in medicine and manufacturing of conductive polymers was examined in the frame of research project implemented by a scientifi c consortium composed of the departments of chemistry in Polish universities and research institutes. The experimental work was supported by calcula-tions and molecular modelling with the software developed by researchers from the Centre.

Recovery of uranium and accompanying metals from various types of industrial wastes like phosphogypsum or waste from fl otation of copper ores was studied in the scope of the IAEA CRP. Various aspects related to the management and storage of spent nuclear fuel and radioactive wastes formed in the course of exploitation of nuclear power plants, with a spe-cial emphasis on the Polish Nuclear Power Programme, were studied. Within the statutory research, novel methods were examined by the Membrane Processes group, for the treatment of “problematic” nuclear waste, based on integrated processes (membrane fi ltration com-bined with sorption, advanced oxidation-membrane process), as the basis for further techno-logical advancement in radioactive waste processing fi eld.

The application of membrane systems in nuclear desalination was tested within the frame of another 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 in membrane units was continued in the scope of the NCN research project on the development of sensitive methods for studying concentration polarization and membrane fouling. The combination of radiotracers with optic techniques like SEM (scanning electron microscopy), FTIR/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 frames 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 governmental institutions.

Research on radiopharmaceutical chemistry (Laboratory of Radiopharmaceuticals Syn-thesis and Studies) was focused on obtaining and studying novel potential radiopharmaceu-ticals, 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 Ana-lyses, Medical University of Łódź and with 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. The development of new cyclotron method for 47Sc production was continued in the scope of a new IAEA Research Contract. Also potential therapeutic radiopharmaceuticals were obtained and studied. Peptides and pro-teins were labelled with alpha emitters (211At, 225Ac and 223Ra) 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 affi nity and high radiotoxicity. Nanobodies labelled with either beta or alpha emitters were studied in coop-eration with Vrije Universiteit, Brussels. Multifunctional nanoparticles for magnetic hyper-thermia and indirect radiation therapy were studied in cooperation of international consor-tium in the frame of COST project.

The interest in energy related issues and the expertise in separation methods allowed building the industrial consortium capable to develop a research project devoted to elabora-tion of the technology for treatment of fl uids 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 com-petence.

Two teams of the Centre were awarded with Director’s prize for publications presented in 2014-2015.

The international and national scientifi c 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, seminars and trainings of students.

The scientists of the Centre were involved in activities of large number of organizations, societies, and editorial boards of scientifi c journals in the country and abroad.

35CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY

ON THE SYNTHESES AND EVALUATION OF SUBSTANCE P FRAGMENTS LABELLED WITH 99mTc AND 177Lu

AS POTENTIAL RECEPTOR RADIOPHARMACEUTICALS IN GLIOMA TREATMENT

Agnieszka Majkowska-Pilip1/, Ewa Gniazdowska1/, Przemysław Koźmiński1/, Anna Wawrzynowska2/, Tadeusz Budlewski3/, Bogusław Kostkiewicz4/

1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland2/ Warsaw University of Life Sciences – SGGW, Faculty of Agriculture and Biology, Warszawa, Poland,

on leave3/ Central Clinical Hospital of the Ministry of the Interior and Administration, Radionuclide Therapy

Ward, Warszawa, Poland4/ Central Clinical Hospital of the Ministry of Interior and Administration, Clinical Department

of Neurosurgery, Warszawa, Poland

Gliomas are the most frequent primary brain tu-mours in adult patients. The most malignant of them is glioblastoma multiforme (GBM). GMB, also called glioblastoma or grade IV astrocytoma, is a very aggressive primary brain tumour, the etiol-ogy of which is unknown in most cases [1]. GBM appears to account for over 50% of brain tumour cases and more than 20% of all intracranial tu-mours. The infi ltrating character of the tumour (these tumours do not have clearly defi ned mar-gins) and the signifi cant morphological cell hetero-geneity of the tumour tissue (containing many types of cells), as well as the protective effect of the blood-brain barrier, are the main causes of un-successful treatment (surgery, radio- and chemo-therapy). Currently, tumour recurrence occurs at the original tumour location or within a distance of 2 cm in about 90% of patients. About 50% of the people diagnosed with GBM die within one year, while 90% do so within three years [2, 3]. GMB displays resistance to almost all current anti-cancer approaches: chemo- or radiotherapy, and even to the induction of apoptosis. Median sur-vival with standard-of-care radiation and chemo-therapy is 15 months. Median survival without treatment is 4.5 months. Despite recent advances in cancer treatment, brain tumours remain in-herently diffi cult to treat, and the prognosis for these patients remains extremely poor.

NK-1R (neurokinin 1 receptor) is the main re-ceptor of peptides belonging to the tachykinin family [4]. It is now known that overexpression of NK-1R is present in a broad variety of tumours (e.g. melanoma, glioma, pancreatic, larynx, stom-ach, and breast cancers). The number of NK-1Rs expressed on tumour cells is much greater than that on normal human cells and is correlated with the degree of malignancy [4-7]. The presence of an overexpression of NK-1R on tumour cells has prompted the use of neuropeptide substance P (the physiological ligand of NK-1R) in cancer treat-ment [8].

Substance P (SP) is a neuropeptide containing 11 amino acids (Arg1Pro2Lys3Pro4Gln5Gln6Phe7

Phe8Gly9Leu10Met11), widely distributed in the peripheral and central nervous system. Together with other neurotransmitters, such as serotonin or dopamine, SP acts as a neuromodulator [7].

The interaction of SP with the NK-1 receptor con-sists of the internalization of the peptide into the cell’s endosome by the action of the clathrin-de-pendent mechanism, where the complex of the peptide and receptor dissociates, due to the more acidic conditions within the endosome. The re-leased receptor returns to the cell membrane and the absorbed peptide particles couple with the lysosome, where they are appropriately processed for further application by the cell (transmission of morphological information) [6]. The fragment of SP responsible for its affi nity towards the NK-1 receptor is a sequence of fi ve amino acids, Phe7Phe8Gly9Leu10Met11, located at the C-termi-nus of the peptide. Currently (starting from March 2012), at the Department of Nuclear Medicine, Central Clinical Hospital, Warszawa, in coopera-tion with the Institute for Transuranium Elements (JRC-ITU, Karlsruhe), a modifi ed form of sub-stance P ([Thi8,Met(O2)11]-substance P) labelled with 213Bi [9] is used as an experimental medical procedure for glioblastoma multiforme treatment. The 213Bi-DOTA-[Thi8,Met(O2)11]-substance P peptide is applied to patients that have been diag-nosed with recurrent critically-located GBM, inde-pendently of routine treatments (surgery, radio- and chemotherapy). It is administrated locally into the solid cancer or into the cavity formed after surgical removal of a tumour. Such a method al-lows for the administration of a higher concentra-tion of drug into the tumour, while avoiding the blood-brain barrier. A disadvantage noted with the treatment with 213Bi-DOTA-[Thi8Met(O2)11]-sub-stance P is its poor effective migration into the walls of the post-surgery cavity, which makes it diffi cult for it to reach any remaining tumour cells (including stem cells) and destroy them.

The aim of this work was to synthesize two series of radioconjugates (99mTc-NS3CN-SP and

177Lu-DOTA-SP, Fig. 1), containing the diagnostic radionuclide 99mTc (emitter, t1/2 = 6.01 h, Emax = 0.141 MeV) or the therapeutic radionuclide 177Lu (– emitter, t1/2 = 6.71 days, Emax = 0.497 MeV) and different analogues of SP. In 99mTc-radiocon-jugates, the Tc(III) cation was coordinated by the tetradentate NS3 tripodal chelator (tris(2-mer-captoethyl)-amine, also known as 2,2’,2’’-nitrilo- triethanethiol) and a monodentate isocyanide

36 CENTRE FOR RADIOCHEMISTRY AND NUCLEAR CHEMISTRY

species CN-BFCA (a bifunctional coupling agent, isocyanobutyric acid succinimidyl ester), previous-ly coupled with the SP fragment. In 177Lu-radio-conjugates, the Lu(III) cation was coordinated by the macrocyclic ligand DOTA, also previously coupled with the SP fragment.

The labelled SP analogues (Fig. 2) were: sub-stance P(1-11) and its modifi ed form [Thi8,Met (O2)11]substance P(1-11), substance P(4-11), sub-stance P(5-11) and its modifi ed form [Thi8,Met (O2)11]substance P(5-11). The log P values of the SP analogues, estimated using the program Mar-vinSketch (values determined theoretically, show-ing only the trend in changes of lipophilicity) are presented in Table 1. In order to evaluate the pos-sibility of the application of different SP frag-ments (especially these characterized with lower molecular weight and higher lipophilicity) as vec-tors leading the diagnostic or therapeutic radio-nuclide to NK-1 receptors, their physicochemical properties (important from the viewpoint of re-ceptor radiopharmaceuticals [10]) have been de-termined.

The coupling reactions between CN-BFCA (isocyanobutyric acid succinimidyl ester) and four SP analogues (SP(1-11), SP(4-11), SP(5-11), and [Thi8,Met(O2)11]SP(5-11)) were performed in DMF

at 50oC in the presence of Et3N (Scheme 1). The molar ratio of the reagents used in the reactions was approximately 1.2:1:4, respectively. Crude CN-SP products were purifi ed on a semi-prepara-tive HPLC column and lyophilized, giving a yield 95%. MS of CN-SP(1-11): m/z: calcd. – 1441.77, found – 1442.33 [M+H+].MS of CN-SP(4-11): m/z: calcd. – 1061.26, found – 1062.11 [M+H+].MS of CN-SP(5-11): m/z: calcd. – 964.17, found – 965.49 [M+H+].MS of CN-[Thi8,Met(O2)11]SP(5-11): m/z: calcd. – 1003.21, found – 1004.41 [M+H+].

The coupling reactions between DOTA-NHS (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetra-acetic acid mono-N-hydroxysuccinimidyl ester) and three shorter SP analogues (SP(4-11), SP(5-11), and [Thi8,Met(O2)11]SP(5-11)) were performed in DMF at 50oC in the presence of Et3N (Scheme 2). The molar ratio of the reagents used in the reac-tions was approximately 1:1:4, respectively. Crude DOTA-SP products were purifi ed on a semi-pre-

parative HPLC column and lyophilized, giving a yield 85%. MS of DOTA-SP(4-11): m/z: calcd. – 1351.66, found – 1352.88 [M+H+].

Fig. 1. Structures of 99mTc-NS3CN-SP and 177Lu-DOTA-SP radioconjugates synthesized in this work.

Fig. 2. Structures of substance P peptide and its analogues used in this work.


MS of DOTA-SP(5-11): m/z: calcd. – 1254.61, found – 1255.51 [M+H+].MS of DOTA-[Thi8,Met(O2)11]SP(5-11): m/z: calcd. – 1292.55, found – 1293.78 [M+H+].The conjugates DOTA-SP(1-11) and DOTA-[Thi8, Met(O2)11]SP(1-11) were commercially avail-able.

The 99mTc-NS3CN-SP radioconjugates were synthesized in two steps. In the fi rst step, 1 mL of eluate from the 99Mo/99mTc generator (100-200 MBq) was added to a kit formulation containing 1 mg of Na2EDTA, 5 mg of mannitol, and 0.08 mg of SnCl2 in freeze-dried form under nitrogen. The mixture was allowed to stand at room tempera-ture for 20 min. The radiochemical purity of the intermediate 99mTc-EDTA/mannitol compound was checked by HPLC and TLC. In the second step, the 99mTc-EDTA/mannitol compound reacted with 300 g of the NS3 ligand and with about 50 g of the isocyanide-modifi ed peptide CN-SP. The reac-tion progress and radiochemical purity were con-trolled by HPLC. The fi nal radiochemical yields of the 99mTc-NS3CN-SP radioconjugates were in the range 96-98%.

The 177Lu-DOTA-SP radioconjugates were syn-thesized according to the following procedure: to a vial containing 15 nmol of lyophilized DOTA-SP dissolved in 300 L of 0.4 M acetate buffer (pH = 5.0), a solution of 177LuCl3 (5 MBq) in acetate buffer (pH = 6.0) was added. The reaction mix-ture was heated for 60 min at 95oC, and the reac-

tion’s progress was checked by TLC. The radio-chemical yields of the 177Lu-DOTA-SP radiocon-jugates were higher than 98%.

The lipophilicity of 99mTc-NS3CN-SP and 177Lu--DOTA-SP radioconjugates was characterized by the determination of the logarithms of their parti-tion coeffi cients, log P, in the n-octanol/PBS (pH = 7.40) system.

The stability of the 99mTc-NS3CN-SP and 177Lu--DOTA-SP radioconjugates was investigated in dif-ferent physiological solutions, namely phosphate buffered saline (PBS), histidine, and cysteine, us-ing HPLC and ITLC. For the 177Lu-DOTA-SP ra-dioconjugates, stability studies were also perform-ed in human serum (HS) and cerebral spinal fl uid (CSF). In this case, the protein components were precipitated using ethyl alcohol, and the radioac-

Scheme 2. Coupling reaction of DOTA-NHS with SP fragments.

Table 1. Physicochemical properties of 99mTc-NS3CN-SP and 177Lu-DOTA-SP radioconjugates.

Scheme 1. Coupling reaction of CN-BFCA with SP fragments.

Compound RT [min] Log P Log P of SP fragments used in the work*

99mTc-NS3CN-SP(1-11) 15.95 -0.26 ± 0.05 SP(1-11) -5.899mTc-NS3CN-[Thi8,Met(O2)11]SP(1-11) - - SP(1-11)modifi ed -7.4

99mTc-NS3CN-SP(4-11) 17.53 0.09 ± 0.02 SP(4-11) -2.599mTc-NS3CN-SP(5-11) 18.41 1.14 ± 0.01 SP(5-11) -2.7

99mTc-NS3CN-[Thi8,Met(O2)11]SP(5-11) 17.06 0.64 ± 0.02 SP(5-11)modifi ed -4.7

Compound RT [min] Log P

Stability in HS: % of intact radioconjugate after

1 h 2 h 4 h 24 h177Lu-DOTA-SP(1-11) 12.53 -5.12 ± 0.06 100 100 100 72.2

177Lu-DOTA-[Thi8,Met(O2)11]SP(1-11) 11.67 -5.28 ± 0.02 97.7 100 100 74.8177Lu-DOTA-SP(4-11) 13.21 -2.93 ± 0.01 100 92.1 81.0 17.2177Lu-DOTA-SP(5-11) 13.23 -2.68 ± 0.01 18.6 8.3 3.6 0

177Lu-DOTA-[Thi8,Met(O2)11]SP(5-11) 11.97 -3.94 ± 0.01 100 79.2 56.4 4.0

* The values estimated using the program MarvinSketch (values determined theoretically indicating only the direction of the changes in lipophilicity of SP fragments).


tivities of both the supernatant and precipitate (protein) fractions were measured.

The conditions for the HPLC system were the following: Phenomenex Jupiter Proteo semi-pre-parative column (4 m, 90 Å, 250 mm 10 mm), UV/Vis detector (220 nm); elution conditions: solvent A – water with 0.1% TFA (v/v); solvent B – acetonitrile with 0.1% TFA (v/v); gradient – 0-20 min 20 to 80% of B, 20-35 min 80% solvent B; 2 mL/min.

All the 99mTc-NS3CN-SP and 177Lu-DOTA-SP radioconjugates were formed with yields in the range 96-98% and purities higher than 98%.

The obtained lipophilicity values of the 99mTc--NS3CN-SP and 177Lu-DOTA-SP radioconjugates are presented in Table 1. In general, it can be said that the lipophilicity value of the radioconjugate depended very strongly on the hydrophilic-hydro-phobic properties of the radionuclide complex. In the series of 99mTc-NS3CN-SP radioconjugates, the lipophilicity values were several orders of magnitude higher than those in the series of 177Lu-DOTA-SP radioconjugates (due to the high-ly lipophilic character of the NS3 ligand and the hydrophilic character of the DOTA macrocyclic li-gand). Analysis of the obtained values also showed that radioconjugates containing shorter SP frag-ments were characterized by higher lipophilicity parameters, while the replacement of the amino acids at positions 8 and 11 (Phe and Met, respec-tively, by Thi and Met(O2)) led to the lipophilicity decreasing. The observed nature of the changes in lipophilicity values was the same in both series.

The studied 99mTc-NS3CN-SP and 177Lu-DOTA- -SP radioconjugates were shown to be stable in PBS buffer, as well as in 10 mM histidine and/or cysteine solutions. On the recorded HPLC chro-matograms (in the case of 99mTc-NS3CN-SP com-pounds after 24 h of incubation and in the case of 177Lu-DOTA-SP compounds after 15 days of in-cubation), only one peak was observed, having an RT corresponding to the RT value of the tested radioconjugate. Thus, we can consider that the studied radioconjugates do not undergo ligand ex-change reactions with amino acids or other strong-ly competing natural ligands containing SH or NH groups.

Stability studies of 177Lu-DOTA-SP radiocon-jugates in HS showed enzymatic biodegradation of all SP fragments (Fig. 3, Table 1). On the re-corded HPLC chromatograms of liquid phases (after precipitation and separation, about 8-11% of the 177Lu-DOTA-SP radioconjugate was bound by protein components present in human serum) new peaks appeared, and simultaneously the peak corresponding to the studied radioconjugate dis-appeared. It can be observed that in the case of

radioconjugates containing shorter SP fragments, the enzymatic biodegradation was quicker com-paring to that of radioconjugates containing SP molecules with all 11 amino acids.

However, stability studies in CSF showed no enzymatic biodegradation of the tested 177Lu--DOTA-SP radioconjugates (the protein content in CSF is about 200-fold lower than in HS [11]). The percentage of 177Lu-DOTA-SP radioconjugate that had been bound by cerebrospinal fl uid com-ponents was in the range of 1-4%, while about 96% of the studied compound remained in the liquid phase in unchanged form. After 15 days of incubation, the recorded HPLC chromatograms showed the existence of mainly one radioactive species in the solution, with the retention time characteristic for the studied radioconjugate.

In conclusion, the results obtained showed that lipophilicity parameters of radioconjugates strongly depend on the hydrophilic-hydrophobic properties of the radionuclide complex and the structure of the SP fragment. Radioconjugates containing shorter SP fragments were character-ized by lower molecular weight and higher lipo-philicity (which can allow more effective migra-tion into GBM tissue, or into the walls of the post-surgery cavity), while replacement at posi-tion 8 of Phe by Thi and at position 11 of Met by its oxidized form MetO2 (in order to increase the half-life of the peptide) resulted in a decrease in lipophilicity.

Stability studies of the 99mTc-NS3CN-SP and 177Lu-DOTA-SP radioconjugates showed that all the preparations were stable in different physio-logical solutions (PBS, histidine, cysteine).

The 177Lu-DOTA-SP radioconjugates were also stable in cerebrospinal fl uid, but not stable

Fig. 3. Stability studies of 177Lu-DOTA-SP radioconjugates in HS.


enough in human serum, while radioconjugates containing shorter SP fragments were character-ized by lower stability.

To summarize, among the SP fragments tested in the work, the SP(4-11) analogue turned out to be the best potential vector (taking into account the lipophilicity and stability of 177Lu-DOTA-SP radioconjugates), able to lead diagnostic or thera-peutic radionuclides to NK-1 receptors. Since the preparation is administrated directly into the solid cancer, or into the cavity after surgical removal of the tumour, as a glioblastoma treatment, the SP(4-11) fragment can be considered as a biolo-gically-active molecule used for the synthesis of potential receptor radiopharmaceuticals. Never-theless, preparations based on the SP(4-11) ana-logue would not meet all the requirements for radiopharmaceuticals, so our future studies will focus on the search for other vectors, covering both peptidic and nonpeptidic antagonists of the NK-1 receptor.

The work has been supported by the statutory activity of the Institute of Nuclear Chemistry and Technology.

References[1]. Zhang, X. Zhang, W., Cao, W.-D., Cheng, G., &

Zhang, Y.-Q. (2012). Glioblastoma multiforme: Mol- ecular characterization and current treatment strat-egy (Review). Exp. Ther. Med., 3, 9-14.

[2]. Ramirez, Y.P., Weatherbee, J.L., Wheelhouse, R.T., & Ross, A.H. (2013). Glioblastoma multiforme therapy and mechanisms of resistance. Pharmaceuticals, 6, 12, 1475-1506.

[3]. Carlsson, S.K., Brothers, S.P., & Wahlestedt, C. (2014). Emerging treatment strategies for glioblastoma multi-forme. EMBO Mol. Med., 6, 11, 1359-1370.

[4]. Garcia-Recio, S., & Gascón, P. (2015). Biological and pharmacological aspects of the NK-1-receptor. Biomed Res. Int., 2015. DOI: 10.1155/2015/495704.

[5]. Muñoz, M., Bernabeu-Wittel, J., & Coveñas, R. (2011). NK-1 as a melanoma target. Expert Opin. Ther. Tar-gets, 15 (7), 889-897.

[6]. Muñoz, M., Martinez-Armesto, J., & Coveñas, R. (2012). NK-1 receptor antagonists as antitumor drugs: a survey of the literature from 2000 to 2011. Expert Opin. Ther. Pat., 22 (7), 735-746.

[7]. Łazarczyk, M., Matyja, E., & Lipkowski, A. (2007). Substance P and its receptors – a potential target for novel medicines in malignant brain tumour therapies (mini-review). Folia Neuropathol., 45 (3), 99-107.

[8]. Muñoz, M., Coveñas, R., Esteban, F., & Redondo, M. (2015). The substance P/NK-1 receptor system: NK-1 receptor antagonists as anti-cancer drugs. J. Biosci., 40 (2), 441-463.

[9]. Cordier, D., Forrer, F., Bruchertseifer, F., Morgen-stern, A., Apostolidis, C., Good, S., Müller-Brand, J., Mäcke, H., Reubi, J.C., & Merlo, A. (2010). Target-ed alpha-radionuclide therapy of functionally criti-cally located gliomas with 213Bi-DOTA-[Thi8,Met (O2)11]-substance P: a pilot trial. Eur. J. Nucl. Med. Mol. Imaging, 37, 1335-1344.

[10]. Oyen, W.J.G., Bodei, L., Giammarile, F., Maecke, H.R., Tennvall, J., Luster, M., & Brans, B. (2007). Targeted therapy in nuclear medicine – current status and future prospects. Ann. Oncol., 18, 1782-1792.

[11]. Kandel, E.R., Schwar tz, J.H., & Jessell, T.M. (2000). Principles of neural science (4th ed.). New York: The McGraw-Hill Companies, Inc.

LABELLED ANTIBIOTICS WITH TECHNETIUM-99m AS POTENTIAL RADIOPHARMACEUTICALS

FOR DIABETIC FOOT IMAGINGPrzemysław Koźmiński1/, Ewa Gniazdowska1/, Agata Piądłowska2/, Magdalena Gumiela1/,

Marek Pruszyński1/

1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland2/ University of Warsaw, Faculty of Physics, Insitute of Experimental Physics, Warszawa, Poland,

on leave

Scintigraphic imaging of infection and inflamma-tion is a powerful diagnostic tool in the manage-ment of patients with infectious or inflammatory diseases. Radiolabelled leukocytes are still con-sidered the gold standard to detect infectious and inflammatory lesions in patients. However, their preparation is time-consuming, laborious, and has risks associated with the handling of potentially contaminated blood. There is still a great interest in the development of new radiopharmaceuticals for infection imaging.

Technetium-99m is the most widely used diag-nostic radionuclide, due to its nearly ideal nuclear properties (low radiation dose to the patient, op-timum gamma-energy profi le, short physical and biological half-lives), rich coordination chemistry [1, 2], and easy commercial availability via gen-erators.

Cefepime (CFM, Fig. 1) belongs to the cephalo-sporin family of antibiotics and has a broad spec-trum of activity against gram-positive and gram--negative bacteria. This antibiotic selectively and irreversibly inhibits bacterial cell wall synthesis by binding to specifi c penicillin binding proteins (PBP). The mechanism of action of cephalospor-ins, in which the compound disrupts the ratio be-

Fig. 1. Chemical structure of the cefepime molecule.


tween PBP mediated peptidoglycan synthesis and murein hydrolase activity, results in autolysis of the cell wall [3, 4].

Cefepime is used against Pseudomonas aerugi-nosa and Staphylococcus aureus, the most inten-sively studied bacterial pathogens, which frequent-ly cause severe tissue damage in the feet of dia-betics [5-8].

The aims of this work were to label cefepime with technetium-99m using the DTPA chelator (in the form of its dianhydride, DTPA-da), to deter-mine the best conditions for labelling, to test the stability of the obtained 99mTc-DTPA-CFM radio-conjugate, and to design a ready to use single-vial kit containing appriopriate amounts of DTPA-CFM conjugate and the reducing agent SnCl2. Synthesis of ligand-antibiotic conjugate

The DTPA-CFM conjugate was synthesized as described below (Scheme 1).

To 0.026 mmol (12.41 mg) of cefepime dis-solved in 150 L of DMF, a solution of 0.034 mmol (12 mg) DTPA-da in 200 L of DMF was added dropwise over 5 min. The reaction mixture was allowed to stay overnight at room tempera-ture under argon. After completion of the reaction, the solvent was removed in vacuo to afford crude

product. HPLC analysis of the reaction mixture showed a main product, DTPA-CFM (RT = 10.21 min, C33H46N9O14S2

+), and a minor compound, DTPA-(CFM)2 (RT = 11.46 min, C52H69N15O18S4

2+). The analysis was accomplished on a LiChro-spher® 100 RP-18 analytical column (5 m par-ticle size, 4.6 mm 250 mm) from Merck (Ger-many). The solvent and gradient conditions were as follows: solvent A, 0.1% (v/v) trifl uoroacetic acid (TFA) in water; solvent B, 0.1% (v/v) trifl u-

oroacetic acid (TFA) in acetonitrile; gradient: 0-15 min 5 to 50% of B, 15-17 min 50 to 95% of B, 17-22 min 95% of B; 1 mL/min; UV detection (220-400 nm). The crude DTPA-CFM product was purifi ed by HPLC and lyophilized.

The reaction products were identifi ed by mass spectrometry (MS): MS for C33H46N9O14S2

+, TOF MS ES+: m/z: calcd. – 855.26, found – 856.28 [M+H+].MS for C52H69N15O18S4

2+, TOF MS ES+: m/z: calcd. – 1318.38, found – 1319.48 [M+H+].Radiolabelling procedure and quality control

The labelling was carried out by adding 1 mL of freshly eluted 99mTcO4

– to a vial containing 1.5-2 mg of lyophilized DTPA-CFM conjugate and 80-100 g of stannous chloride as a reducing agent. The vial was then shaken virgorously and left to stand at room temperature for 10 min.

The lipophilicity of the 99mTc-DTPA-CFM ra-dioconjugate was characterized by the determi-nation of the logarithm of its partition coeffi cient, log P, in n-octanol/PBS (pH 7.40).

The stability of the 99mTc-DTPA-CFM radio-conjugate was investigated in different physiolo-gical solutions (phosphate buffered saline – PBS, histidine, and cysteine), as well as in human se-

rum, using HPLC and/or ITLC methods. In the case of the stability studies in human serum, the protein components were precipitated using ethyl alcohol, and the radioactivities of both the super-natant and precipitate (protein) fractions were measured. Results and discussion

The radiochemical purity was determined by TLC using silica gel-coated fi berglass sheets. The samples of radioactive reaction mixture were spot-

Scheme 1. Coupling reaction of DTPA-da with CFM.


ted onto the strip. To determine the reduced/hy-drolysed 99mTcO2 (colloid) and free 99mTcO4

–, two mobile phases were used: (A) acetone and (B) 0.9% NaCl (Fig. 2). In system (A), free 99mTcO4

– migrated with the front of the mobile phase, Rf 1, while the colloid and 99mTc-DTPA-CFM radiocon-jugate stayed at the origin, Rf 0. The second strip was developed in system (B), where the colloid remained at the origin, while the radioconjugate and free 99mTcO4

– moved with the solvent, Rf 1. The distribution of radioactivity on the strip was determined using a home-made automatic TLC analyser SC-05 (Institute of Nuclear Chemistry and Technology) or a Cyclone® Plus storage phos-phor system (PerkinElmer).

The radiochemical yield of the labelled CFM was higher than 95%. The optimum labelling yield and purity was achieved when 2 mg of DTPA-CFM and 80 g of SnCl2 were used.

The determined lipophilicity value of the 99mTc-DTPA-CFM radioconjugate was found to be 4.00 ± 0.14 (n = 6).

The 99mTc-DTPA-CFM radioconjugate was char-acterized by high stability in solutions of cysteine and histidine, as well as suffi cient stability in hu-man serum. After about 20 h of incubation of the radioconjugate in these solutions, only one radio-active species was present, with the RT and/or Rf values characteristic for the studied radioconju-gate.

In conclusion, the 99mTc-DTPA-CFM product described in this paper meets the requirements for a potential radiopharmaceutical for use in medical diagnostics. It can be synthesized direct-

ly in hospital laboratories from previously pre-pared lyophilized kit formulations.

This work was been supported by the statutory activity of the Institute of Nuclear Chemistry and Technology.

References[1]. Volkert, W.A., & Hoffmann, T.J. (1999). Therapeutic

radiopharmaceuticals. Chem. Rev., 99, 2269-2292. [2]. Ibrahim, I.T., Motaleb, M.A., & Attalah, K.M. (2010).

Synthesis and biological distribution of 99mTc–norfl ox-acin complex, a novel agent for detecting sites of in-fection. J. Radioanal. Nucl. Chem., 285, 3, 431-436.

[3]. Richards, D.M., Heel, R.C., Brogden, R.N., Speight, T.M., & Avery, G.S. (1984). Ceftriaxone. A review of its antibacterial activity, pharmacological properties and therapeutic use. Drugs, 27 (6), 469-527.

[4]. Barradell, L.B., & Bryson, H.M. (1994). Cefepime. A review of its antibacterial activity, pharmacokinetic properties and therapeutic use. Drugs, 47 (3), 471-505.

[5]. Muthu, S.E., Aberna, R.A., Mohan, V., Premalatha, G., Srinivasan, R.S., Thyagarajan, S.P., & Rao, U.A. (2006). Phenotypes of isolates of Pseudomonas aeruginosa in a diabetes care center. Arch. Med. Res., 37, 95-101.

[6]. Eliopoulos, G.M. (2004). Current and new antimicro-bial agents. Am. Heart J., 147, 4, 587-592.

[7]. Kaul, A., Hazari, P.P., Rawat, H., Singh, B., Kalawat, T.C., Sharma, S., Babbar, A.K., & Mishra, A.K. (2013). Preliminary evaluation of technetium-99m-labeled ceftriaxone: infection imaging agent for the clinical diagnosis of orthopedic infection. Int. J. Infect. Dis., 17 (4), e263-e270.

[8]. Muratani, T., Inatomi, H., Ando, Y., Kawai, S., Akasa-ka, S., & Matsumoto, T. (2008). Single dose 1 g ceftri-axone for urogenital and pharyngeal infection caused by Neisseria gonorrhoeae. Int. J. Urol., 15, 9, 837-842.

Fig. 2. TLC analysis of 99mTc-DTPA-CFM in: (A) acetone and (B) 0.9% NaCl.


5,6-DIHALOGEN-1,10-PHENANTHROLINE COMPLEXES WITH Eu(III) AND Am(III) IONS. A COMPUTATIONAL STUDY

Jan Cz. Dobrowolski, Joanna E. Rode, Sławomir Ostrowski, Michał H. Jamróz

Partitioning, i.e., the extractive removal of long--lived, highly toxic isotopes of minor actinides (An) from high-level radioactive waste, has at-tracted intense and sustained attention for dec-ades [1]. The partitioning of actinides, the minor part of the waste, from a much larger mass of fi s-sion product lanthanides (Ln), requires sophisti-cated complexing agents [2]. Indeed, An and Ln have very similar chemical properties and, in par-ticular, close ionic radii. This is why Ln serve as An surrogates and operational routines developed for them may also be applied to An. Am(III) and Eu(III) complexes may serve as a model for the general problem of An/Ln separation.

According to a review by Hancock [3], “selec-tivity ratio for An(III) over Ln(III) ions of up to about 103 has been found for N-donor ligands such as: BTP, TPEN, 4,7-diphenyl-Phen, BTBP, BTTP, BTPhen, TPTZ and ODP”. Recently, it has been shown that replacing a fl exible bipyridine unit in BTBP (bis-triazinyl bipyridine) with the rigid Phen (1,10-phenanthroline) core in BTPhen (Scheme 1) increases the effi ciency and selectiv-ity of the Am/Eu separation. This is due to the greater rigidity of Phen in comparison to the BP core [4]. Recently, the diamide-Phen tetradentate ligand has appeared to be an excellent agent for the selective extraction of hexavalent, tetravalent, and trivalent An from Ln in highly acidic solu-tions [5-7].

A motivating impulse for this study was given by the demonstration that a 5-Br or 5,6-di-Br sub-stituted Phen core in the BTPhen ligand (Scheme 1) enhanced the Am(III) from Eu(III) separation factor in 4 M HNO3 even further, from 180 (for unsubstituted BTPhen) to ca. 250 and 800, re-spectively [8]. Therefore, it seemed interesting to look at the changes in the interaction energy be-tween Am(III) and Eu(III) ions and 5,6-dihalo-gen substituted Phen complexes with respect to changes in the halogen atoms. Calculations

Structure optimization was carried out using the DFT B3LYP functional [9, 10]. The 6-31G** basis set [11-13] was used for H, C, N, and all the halogen atoms except for I, for which the 6-311G** basis set was applied [14]. For the Eu and Am atoms, the ECP28MWB_SEG [15, 16]

and ECP60MWB_SEG [17-19] Stuttgart/Cologne Group (SDB) basis sets with quasi-relativistic pseudopotentials were used. All the studied sys-tems were true local minima exhibiting no im-aginary frequencies. All calculations were perform-ed using the Gaussian 09 program [20].5,6-dihalogeno-1,10-phenanthrolines

The halogens’ electron donor acceptor prop-erties and atomic and ionic radii change smoothly [21-25]. Firstly, we tried to establish whether the halogens’ main infl uence was through the - or -electron system, or due to other factors, such as interhalogen repulsion. However, unlike the whole set of sEDA and pEDA substituent effect descrip-tors which do not intercorrelate [21], for halo-gens their correlation was excellent. Thus, due to the goodness of fi t for the correlation between the sEDA and pEDA of the halogens, it was not pos-sible to distinguish whether the effect was due to halogen infl uence on the - or -electrons of the substituted Phen system (Table 1, Fig. 1A). It should be noted that, although for sole halogens the correlations between the d(N1N10) distance and sEDA or pEDA were excellent, the point cor-responding to the H “substituent” deviated from the regression line (Figs. 1B and C).

On the other hand, the halogen atoms attached to the neighboring C5 and C6 atoms repulsed each other the more the larger the X atom or X1– radius (Table 1). Interestingly, the correlations be-tween the d(C5C6), d(C11C12), and d(N1N10) dis-tances and the X1– ionic radii were strong (Figs. 1D and E). The d(C5C6) distance increased and the d(C11C12), and d(N1N10) distances decreased with the increase in the X1– radius. Thus, it is rea-sonable to suppose that the X substituents’ repul-sion played a key role in the change of the dis-tance between the Phen N atoms. Indeed, if the -electron withdrawing abilities of the halogens were the major factor, one could expect a decrease in the d(C5C6) distance with an increase in the halogen mass and the sEDA descriptor. However, the -electron donating abilities decreased from F to I and should eventually contribute to an in-crease in the C5C6 bond order and a shortening in the d(C5C6) distance which, however, is not the case.

The 5,6-disubstitution also changed the elec-tric, geometric, and magnetic parameters of the Phen A (pyridine) and B (disubstituted benzene) rings (Scheme 1). Substitution with F decreased the charge on the -valence electron system of the B ring, s(B), while the charge on the -valence electron system, p(B), was signifi cantly increased. The charge s(B) then increased through Cl and Br to I, while p(B) decreased (Table 1). Such a be-havior was in line with the substituent properties expressed by the sEDA and pEDA descriptors [21].

Halogens are -electron withdrawing and -electron donating substituents: the potencies of

Scheme 1. The BTPhen ligand and its Phen fragment used in this model study.

NNN

NN N

N

N

R R

Phen

BTPhen

AB


both attributes decreased from F to I (Table 1). On the other hand, the charge in both the - and -electron systems of the pyridine A ring, s(A) and p(A), increased for F and then decreased through Cl and Br to I (Table 1). Interestingly, the -charge at Phen correlated linearly and the

-charge correlated non-linearly with the sEDA and pEDA descriptors (Fig. 2). This meant that the impact of the two halogen substituents on the -electron system of Phen was additive, whereas on the -electron system it was visibly non-addi-tive. Such a behavior had already been observed

Parameter X H F Cl Br I

Distances & angles

d(N1N10) [Å] 2.7623 2.7735 2.7324 2.7236 2.7088

d(C5C6) [Å] 1.3609 1.3593 1.3691 1.3685 1.3722

d(C11C12) [Å] 1.4589 1.4589 1.4574 1.4566 1.4546

d(C6X) [Å] 1.0870 1.3460 1.7494 1.9079 2.1488

d(XX) [Å] 2.4681 2.7159 3.1467 3.3253 3.6253

a(C5C6X) [deg] 120.62 120.26 120.54 120.85 121.62

X radiiIR(1-) [Å] 1.45* 1.33** 1.81** 1.96** 2.20**

AR(0) [Å] 0.30 0.64 0.99 1.14 1.33

Lone pairs’ charge, HO & LU global & local

states

qLP(N) [e] 1.924 1.923 1.922 1.915 1.92

HOAO(N) [eV] -0.1588 -0.1690 -0.1715 -0.1722 -0.1712

LUAO(N) [eV] 0.85741 0.84882 0.84679 0.84947 0.84845

local gap [eV] -1.0163 -1.0178 -1.0183 -1.0216 -1.0196

HOMO [eV] -0.2300 -0.2318 -0.2383 -0.2361 -0.2330

LUMO [eV] -0.0494 -0.0603 -0.0701 -0.0698 -0.0683

global gap [eV] -0.1806 -0.1715 -0.1683 -0.1663 -0.1647

SE descriptors

sEDA [e] 0.000 -0.621 -0.264 -0.197 -0.114

pEDA [e] 0.000 0.078 0.062 0.057 0.042

s(A) [e] 0.000 0.018 -0.010 -0.010 -0.016

p(A) [e] 0.000 0.025 -0.007 -0.011 -0.016

s(B) [e] 0.000 -1.272 -0.548 -0.409 -0.233

p(B) [e] 0.000 0.177 0.196 0.186 0.160

s(A-B) [e] 1.447 2.737 1.985 1.846 1.665

p(A-B) [e] 0.063 -0.089 -0.140 -0.134 -0.114

Ring A

HOMA 0.881 0.884 0.887 0.885 0.877

EN 0.047 0.043 0.042 0.041 0.043

GEO 0.072 0.072 0.072 0.074 0.080

NICS(0) [ppm] -8.82 -8.97 -9.16 -9.2 -9.48

NICS(1) [ppm] -11.57 -11.53 -11.7 -11.7 -11.85

Ring B

HOMA 0.443 0.484 0.408 0.400 0.356

EN 0.323 0.284 0.388 0.392 0.444

GEO 0.234 0.233 0.204 0.208 0.201

NICS(0) [ppm] -6.67 -9.59 -6.9 -6.37 -5.78

NICS(1) [ppm] -9.06 -9.42 -8.5 -8.27 -8.13

* The radial expectation value obtained from local spin density treatment of the free anion [22].** Effective ionic radius for the six-coordinate anion [23].

Table 1. The selected intramolecular distances in 5,6-X Phen calculated at the B3LYP/6-31G**/6-311G**(I) level, and some other X substituent parameters: IR(-1) ionic and AR(0) atomic radii, sEDA and pEDA denote the substituent effect (SE) descriptors [21] demonstrating the number of electrons donated to or withdrawn from the (s) and (p) electron system by the substituent. s(A), s(B) and p(A), p(B) denote the number of - and -electrons in the rings A and B, while s(A-B) and p(A-B) denote the difference between the number of electrons in the rings A and B, respec-tively. HOMA and NICS(0) and NICS(1) are ring aromaticity indices, and EN and GEO are HOMA components. The partial charge localized at the N atom lone electron pair was estimated using the NBO method, the energy of the HOAO and LUAO states and the HOAO-LUAO gap at the N atoms, and the energy of the HOMO and LUMO states and the HOMO-LUMO gap.


by us for ortho-substituted benzenes and pyri-dines [26, 27].

To better characterize the 5,6-X Phen ligands, the energies of the global HOMO and LUMO as well as the local HOAO and LUAO states at the N atoms were estimated (Table 1). This allowed us to evaluate changes in the global and local hardness of the ligands with the halogen change. As Am(III) is considered to be softer than Eu(III) [28, 29], the size of gaps can appear helpful in the search for ligand selectivity in the Am(III)/Eu(III) separation. In particular, we supposed that it might appear indicative that the local charge at the N atoms and the HOAO-LUAO gap at N atoms was minimal for the 5,6-Br Phen, while the HOMO-

-LUMO gap and the N1N10 distance reached their extreme for other halogens (Table 1). Multiplicity of the studied Eu(III) and Am(III) complexes

The Eu and Am atoms have the [Xe]4f76s2 and [Rn]5f77s2 confi gurations, whereas Eu(III) and Am(III) ions correspondingly exhibit the [Xe]4f6 and [Rn]5f6 ones. The 7F term is the only state in the f6 confi guration [30]. Recent measurements for EuCl3·6H2O [31] and calculations for Am(III) [32] have again confi rmed this fact. To verify whether the 7F term is also the fundamental state for the Eu(Phen)3+ and Am(Phen)3+ complexes at the applied level of theory, they were calculated in the singlet, triplet, quintet, and septet spin states

Fig. 1. Correlations between the sEDA and pEDA descriptors of halogens and the H atom (A), and between the descrip-tors and the change in the d(N1N10) distance in 5,6-X Phen (B) and (C). Correlations between the X1– radius of halogens and the H1– ion and the change of the d(C5C6), d(C11C12), and d(N1N10) distances in 5,6-X Phen (D), (E), and (F), re-spectively.

f = (1+a*x)/(b+c*x)R=0.9997

sEDA

-0.6 -0.4 -0.2 0.0

pED

A

-0.02

0.00

0.02

0.04

0.06

0.08

0.10

F

ClBr

I

H

A

f = y0+a*x+b*x2

R=1.0

pEDA

0.00 0.02 0.04 0.06 0.08 0.10

d(N

1N10

)

2.70

2.71

2.72

2.73

2.74

2.75

2.76

2.77

2.78

F

H

Cl

Br

I

C

f = y0+a*x+b*x2

R=0.9993

X1- Ion Radius

1.2 1.4 1.6 1.8 2.0 2.2 2.4

d(C

11C

12)

1.454

1.455

1.456

1.457

1.458

1.459

1.460

F H

Cl

Br

I

E

f = y0+a*x+b*x2

R=0.9998

sEDA

-0.6 -0.4 -0.2 0.0

d(N

1N10

)

2.70

2.71

2.72

2.73

2.74

2.75

2.76

2.77

2.78

H

F

Cl

Br

I

B

f = (a+b*x)/(1+c*x)R=0.9999

X1- Ion Radius

1.2 1.4 1.6 1.8 2.0 2.2 2.4

d(N

1N10

)

2.70

2.71

2.72

2.73

2.74

2.75

2.76

2.77

2.78

F

H

Cl

Br

I

F

f = y0+a*xR=0.976

X1- Ion Radius

1.2 1.4 1.6 1.8 2.0 2.2 2.4

d(C

5C6)

1.358

1.360

1.362

1.364

1.366

1.368

1.370

1.372

1.374

F

H

ClBr

ID


and it was shown that the relative Gibbs free en-ergies of Eu(Phen)3+ were 132, 137, 73, and 0 kcal/mol, while for Am(Phen)3+ the values were 130, 114, 50, and 0 kcal/mol, respectively. There-fore, in further calculations the septet states of the Eu(III) and Am(III) complexes with the sub-stituted Phen were assumed.

The Eu(III) and Am(III) complexes with 5,6-X Phen

Calculation of the Eu(5,6-X Phen)3+ and Am(5,6-X Phen)3+ complexes demonstrated that the BSSE (basis set superposition error) corrected complex stabilization energy [33], EBSSE, varied with the halogen substituent (Table 2). Correla-tions between EBSSE and the sEDA and pEDA substituent effect descriptors, the X1– ion radius, and the HOMO-LUMO gap in the sole ligand, as well as between the d(N1N10) distances in the free

ligand and in the Eu(5,6-X Phen)3+ and Am(5,6-X Phen)3+ complexes are shown in Fig. 3.

It appeared that the interaction energy of the Am(5,6-X Phen)3+ complex correlated non-linear-ly with that of the Eu(5,6-X Phen)3+ complex (Fig. 3A). It quickly increased from I, through Br, to Cl substituted Phen ligands, and reached a plateau

for H and F. The d(N1N10) distances in the free ligand and in the two types of complexes were also strongly correlated (Fig. 3B). However, for the I substituent the concordance of the shape plots was no longer seen, suggesting that this very bulky halogen could allow differentiation be-tween the properties of the Am(III) and Eu(III) complexes with the 5,6-I Phen ligand. The corre-lations of the EBSSE with the sEDA and pEDA substituent effect descriptors (Figs. 3C and D) were regular but non-linear and, additionally, the

Fig. 2. Correlations between the - and -electron charge, s(.) and p(.), respectively, at the A and B rings of the 5,6-X Phen system and the sEDA and pEDA substituent effect descriptors.

sEDA

-0.6 -0.4 -0.2 0.0

s(A)

-0.020

-0.015

-0.010

-0.005

0.000

0.005

0.010

0.015

0.020F

ClBr

I

H

f = y0+a*xR=0.990

A

f = y0+a*xR=1.0

sEDA-0.6 -0.4 -0.2 0.0

s(B)

-1.4

-1.2

-1.0

-0.8

-0.6

-0.4

-0.2

0.0 H

ClBr

I

F

C

f = y0+a*exp(b*x)R=1.0

pEDA

0.00 0.02 0.04 0.06 0.08 0.10

p(A

)

-0.02

-0.01

0.00

0.01

0.02

0.03

H

F

ClBr

I

B

f = y0+a*x+b*x2

R=0.998

pEDA

0.00 0.02 0.04 0.06 0.08 0.10

p(B)

-0.05

0.00

0.05

0.10

0.15

0.20

0.25

FClBr

I

H

D

Table 2. The B3LYP/6-31G**/SDB(Am/Eu)/6-311G**(I) calculated Eu(5,6-X Phen)3+ and Am(5,6-X Phen)3+ com-plexes in the 7F states, d(N1N10) distance, q(N) Mulliken partial charge at the N atoms, and the interaction energies of the complexes corrected for BSSE.

Substitution Eu Am

d(N1N10) [Å] q(N) [e] EBSSE [kcal/mol] d(N1N10) [Å] q(N) [e] EBSSE [kcal/mol]

I 2.711 -0.628 -410 2.764 -0.611 -375

Br 2.749 -0.598 -405 2.752 -0.610 -361

Cl 2.757 -0.597 -399 2.760 -0.608 -354

F 2.796 -0.600 -323 2.796 -0.609 -347

H 2.795 -0.594 -392 2.793 -0.609 -348


points corresponding to the H “substituent” de-viated from the overall trends. In contradiction to our assumptions that local, not global, hardness plays a signifi cant role in the formation of the complex with the Am and Eu ions, the size of the local HOAO-LUAO gap did not correlate with the interaction energy, whereas quite a fi ne change of EBSSE with respect to the HOMO-LUMO gap was observed (Fig. 3E). Finally, a smooth change of EBSSE with the X1– ion radius (Fig. 3F) indi-cated that size of the substituent and intersub-stituent repulsion could play a pivotal role.

In conclusion, this study of the infl uence of ha-logens in positions 5,6- of disubstituted 1,10-phe-

nanthrolines on the properties of such ligands, and on the interaction energy of the complexes formed with the Eu(III) and Am(III) ions, allowed us to fi nd several regularities between the types of halo-gen present and the substituted phenanthrolines’ properties and complex interaction energies. The correlations of the interaction energy with the ha-logen X1– ion radius and with the HOMO-LUMO gap of the free ligand seem to be the most promis-ing. However, a larger set of substituents should be examined to verify these fi ndings. Also, a larger ligand, such as bis-triazine functionalized phenan-throline (BTPhen), and uncharged complexes should be examined in further studies.

Fig. 3. Correlations for the Eu(5,6-X Phen)3+ and Am(5,6-X Phen)3+ complexes: (A) the complex interaction energies of the complexes corrected for BSSE [kcal/mol] of the two metal ions; (B) d(N1N10) distance [Å] in the free ligand and in the complexes; the complex interaction energy and: (C) sEDA descriptor [e], (D) pEDA descriptor [e], (E) HOMO-LUMO gap [eV] in the free ligand, and (F) X1– radius [Å] of the substituent.

Eu: y=aebx+cAm:y=a(1-e-bx)+c

pEDA (e)

0.00 0.02 0.04 0.06 0.08 0.10

EB

SS

E (k

cal/m

ol)

-420

-400

-380

-360

-340

-320

-300

EuAm

H

H

F

F

Cl

ClBr

Br

I

I

D

Eu: y=ae-bx+ce-dx; R=0.993Am: y=ax2+bx+c; R=0.999

X1- Ion Radius

1.2 1.4 1.6 1.8 2.0 2.2 2.4

EB

SS

E (k

cal/m

ol)

-420

-400

-380

-360

-340

-320

-300

EuAm

H

H

F

FCl

ClBr

I

Br

I

F

y=ax2+bx+c

sEDA (e)

-0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0

EB

SS

E (k

cal/m

ol)

-420

-400

-380

-360

-340

-320

-300

EuAm

H

H

F

F

Cl

ClBr

Br

I

I

C

y= ax/(b+x)+cx/(d+x)Eu: R=0.998, F excludedAm: R=0.999

HOMO-LUMO Gap in 5,6-X Phen ligand

-0.180 -0.175 -0.170 -0.165

EB

SS

E (k

cal/m

ol)

-420

-400

-380

-360

-340

-320

-300

EuAm

F

FH

H

Cl

ClBr

Br

I

I

E

Eu: y=ax2+bx+c; R=0.997Am: y=ax3+bx2+cx+d; R=0.999

d(N1N10) (A) in Phen ligand

2.70 2.72 2.74 2.76 2.78

d(N

1N10

) (A

) in

Me(

Phe

n)3+

com

plex

2.70

2.72

2.74

2.76

2.78

2.80

2.82

EuAm

I

I

F

Cl

Br

H

B

f = (1+a*x)/(b+c*x); R=0.989

EBSSE (Eu) (kcal/mol)

-420 -400 -380 -360 -340 -320 -300

EB

SS

E (A

m) (

kcal

/mol

)

-380

-375

-370

-365

-360

-355

-350

-345

-340

I

Br

Cl

H F

A


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APPLICATION OF INDUSTRIAL WASTES AS AN ENGINEERING BARRIER IN RADIOACTIVE WASTE REPOSITORIES: SORPTION

OF Cs(I), Sr(II), Eu(III), AND Am(III) IONS ON THE CLAY-SALT SLIMES OF THE JOINT STOCK COMPANY “BELARUSKALI”

Leon Fuks1/, Irena Herdzik-Koniecko1/, Leanid Maskalchuk2/, Tatjana Leontieva2/

1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland2/ Belarusian State University, International Sakharov Environmental Institute, Minsk, Belarus

The sorption of radionuclides on mineral sor-bents is an effective and general method for their elimination from aqueous solutions [1-4]. Among the many diverse sorbents, aluminosilicates de-serve special interest, as they are the major com-ponents of many rocks, clays, and minerals depo-sited in the neighborhood of ground water. Because of their high chemical, thermal, and radiation re-sistance, as well as their high affi nity for metal ions, aluminosilicates (e.g. bentonite or montmo-rillonite) have been proposed as ideal backfi ll ma-terials for geological repositories for radioactive wastes [5]. However, due to their large surface area and favorable sorption properties, alumino-silicates can also play an important role in the migration of radionuclides in the aquatic environ-ment [6].

The surface complex formation between alu-minosilicate and metal ions can be described as:n{Al, Si–OH} + Mn+ = {(Al, Si–O)nM} + nH+

where the symbol {Al, Si-OH} represents the alu-minol/silanol groups on the surface of the sorbent.

In the present work, we evaluated the sorptive properties of clay-salt slimes (CSS) produced as industrial waste from the Joint Stock Company (JSC) “Belaruskali” (Soligorsk, Belarus). The crude material was taken from the warehouse and wash-ed fi ve times with distilled water to remove soluble salts (mainly NaCl and KCl). After drying at 50oC for 6 h, a constant mass was achieved. The ob-tained material was referred to as 1A sorbent. A portion of the 1A sorbent was treated with 0.1 M hydrochloric acid to destroy the carbonates pre-sent, washed with distilled water, and dried (50oC, 6 h) to a constant mass. This treated material was referred to as 1B sorbent. For the main properties of both materials, see the papers by Maskalchuk et al., e.g. [7].

The main components of these minerals after treatment are still aluminosilicates. The present studies are a continuation of the work commenced at the Institute of Nuclear Chemistry and Tech-nology in the framework of Task 4 “Development

of spent nuclear fuel and radioactive waste man-agement techniques and technologies” of the gov-ernmental strategic research project “Technologies supporting development of safe nuclear power engineering”. Those studies concerned the sorp-tion of selected radionuclides using domestic alu-minosilicates [8].

In the present work, we investigated the sorp-tion of Cs(I), Sr(II), Eu(III), and Am(III) ions on the CSS by recording and analyzing the decon-tamination factors for their removal from water as a function of numerous factors, in order to de-sign an effective technological process.

Previous studies have shown that CSS con-sists of about 30-35 wt% of water-soluble chlo-rides (potassium and sodium salts) and about 40-50 wt% of superfi ne aluminosilicates (illite, feldspar, and others) [9]. The latter were extract-ed from the CSS by fi ltering the suspension through a “Trumem” sintered metal membrane with a pore size of 1.0 and 0.2 mm, with a ratio of the solid to liquid phase equal to 1:30.

Before starting the studies, the homogeneity of both sorbents was checked. With this aim, fi ve randomly selected 50 mg lots were equilibrated with equal volumes of an initial solution contain-ing all the radionuclides. It was found, that the values of the metal removal effi ciency (YM = (C0 – Ceq)/C0 100%) of all the samples did not differ from each other. The materials, were thus assum-ed to be homogeneous and suitable to be used for the entire study. The results of their sieve analysis are shown in Fig. 1. It can be seen that both sor-bents were rather fi ne materials, with the diame-ter of the main fraction being 0.2 mm smaller than that of crude CSS. It was found that about 98 percent of the particles were greater than 0.05 mm.

Further studies were performed using the un-fractioned sorbents.

The removal of the radionuclides from aqueous solutions was determined in batch experiments, looking primarily at the dependence of the re-


moval on the contact time between adsorbent and adsorbate, but also looking at all the main factors that were important for the design of the separa-tion procedure.

Contact time is an important parameter for sorption experiments, in view of the design of the purifi cation process. Figure 2 shows the increas-ing amount of strontium(II) adsorbed as a func-tion of time. It may be seen that the percentage sorption attained its saturation value in 40 min.

Other radionuclides behaved similarly. In de-tail, the mean uptake of the metals for times of contact ranging from 40 to 180 min for the 1A sorbent were found to be: 99.0 ± 0.3%, 99.0 ± 0.4%, 91.1 ± 0.6%, and 97.4 ± 0.2% for Cs(I), Sr(II), Eu(III), and Am(III), respectively. For the 1B sorbent, in turn, the corresponding values were: 98.6 ± 0.2%, 98.4 ± 0.3%, 87.0 ± 0.5%, and 92.3 ± 0.2%. Therefore, it was decided that in all subsequent experiments, as well in the de-sign of future separation procedures, the equili-bration time for sorption should be at least 1 h.

The acidity of the purifi ed solution is an im-portant factor infl uencing the removal effi ciency of the sorbent for the metals, due to metal specia-tion and the dissociation of the binding sites on the surface, both determining the charges of the reacting species [10]. Figure 3 shows the data on the sorption of strontium(II) as a function of pH. It was found that the percentage sorption does not change signifi cantly within a broad range of pH. However, the complicated interplay of the speciation and dissociation mentioned above may be clearly seen. A similar, non-uniform course of changes appeared for the other radionuclides studied.

The effect of sorbent dosage on the sorption of strontium(II) when all the other conditions re-

Fig. 1. Results of the sieve analysis of the sorbents.

0,0 0,2 0,4 0,6 0,8 1,0-5

0

5

10

15

20

25

30

35

0

5

10

15

20

25

%

sieve mesh, mm

1A

%

1B

Fig. 2. Kinetics of strontium(II) sorption by 1A and 1B sorbents (a) and uptake of all the radionuclides by these sorbents after 1 h equilibration (b).

(b)

Cs-137 Sr-85 Eu 152/152 Am-24180

85

90

95

100

80

85

90

95

100

ake,%

radionuclide

1A

ake,

1B

upta

ke,%

upta

ke,%

(a)

0 20 40 60 80 100 120 140 160 180 200

02

92

94

96

98

100

02

92

94

96

98

100

time, min.

Sr(II); 1A

Sr(II); 1B

upta

ke,%

upta

ke,%


mained constant is presented in Fig. 4. It may be observed that the percentage removal of the metal ions increased with an increase in the adsorbents’ doses up to 2 g/L, and further increase in the ad-sorbents’ doses did not provide any more increase in the percentage of the metal ion removed. There-fore, when application of the 1A or 1B sorbents is planned, a 2 g/L dose of the adsorbents may be

proposed. The increase in the percentage of the metal ion removal with the increase in adsorbent dose may be related to the greater availability of the exchangeable sites or surface area at higher concentrations of the adsorbent. The lack of sig-nifi cant increase observed when the adsorbent doses exceed this value has been observed previ-ously, e.g. in the studies of Mittal and Jiao et al. [11, 12]. The aforementioned trend and the max-imum dosage have been shown to be similar for other metal ions studied.

The treatment of liquid radioactive wastes quite often demands the use of special decontamination solutions. Among the most popular, the CANDEREM (Canadian decontamination and re-mediation process) solution and the CANDECON (Canadian decontamination process) may be men-tioned. The approximate composition of the solu-tion is: 0.3 g/l oxalic acid, 0.2 g/l citric acid, and

Fig. 3. Uptake of strontium(II) by 1A and 1B sorbents, showing its dependence on the initial acidity of the purifi ed solu-tion.

Fig. 4. Uptake of strontium(II) by 1A and 1B sorbents, showing its dependence on the mass of the sorbent used.

0 2 4 6 8 1002

92

94

96

98

100

02

92

94

96

98

100

uptake, %

sorbent, g/L

Sr(II); 1A

Sr(II); 1B

uptake,%

Fig. 5. Uptake of strontium(II) by 1A and 1B sorbents from water as compared to that from the solution contain-ing complexing agents.

upta

ke,%

Decon Water Decon Water

90

100

1B

ake,

1A


0.5 g/l EDTA (i.e. about 2 10–3 M, each) [13]. To check the sorbents studied in the pretreatment and storage of low level radioactive waste (LLRW) solutions, it was tested by sorption of all four ra-dionuclides from the artifi cial CANDEREM de-contamination liquid. Figure 5 shows the results obtained for strontium(II) as compared to the values obtained for sorption from the pure water. As may be seen, within experimental error both values are close to each other.

Additionally, it was found that complexation of Am(III), Eu(III), and Cs(I) by mixing with strong chelating agents, such as the citrate, oxa-late, and EDTA, did not diminish the sorption ef-fi ciency of these sorbents. It implies that the pro-cessing of radioactively contaminated water by means of clay-salt slimes may be widely applied.

The stability of the sorbent is one of the most fundamental problems to be considered when dealing with sorption. In order to make it more attractive for large scale use, the sorbent must ap-proximately retain its initial properties during the whole process. For this purpose, the leaching of different metals by water was performed by equili-brating 1 g of the sorbent with 25 mL of water for 120 min. Data presented in Table 1 in comparison with the regulations of the WHO for drinking water and the composition of drinking water taken in the INCT show that the both sorbents do not fulfi ll the requirements for being applied in the production of drinking water.

Basing on our previously acquired knowledge, it is expected that a nanofi ltration (NF) process should be effective in the removal of the released contaminants. This problem, however, is not the object of this study.

Another problem that should be taken into ac-count in designing potential application of the

sorbents is the strength of binding of the radionu-clides once they are sorbed. Contrary to the previ-ous data, the prolonged equilibration of the radio-nuclide-loaded sorbents with water showed the extremely good stability of the material (in the case of strontium(II) – Fig. 6). All other radionu-clides were also poorly released from the sorbents.

Finally, the radiation stability of the sorbents was also checked. Both sorbents were irradiated

Table 1. Chemical composition of water after equilibration with sorbents 1A and 1B in relations to the standards of the WHO.

Anion/cationWHO [14] Water INCT Sorbent 1A Sorbent 1B

[mg/L]

F– 1.5 0.047 0.58 0.79

Cl– 250 0.144 0.99 458.46

SO42– 250 0.471 1789.1 986.21

NO3– 3 0.60 0.26

PO43– 2.66

Na(I) * 0.247 0.94 0.66

K(I) * 0.125 12.98 8.42

Mg(II) * 0.196 23.43 81.06

Ca(II) * 0.362 562.29 419.84

Sr(II) * 27.7 22.24

Zn(II) * 0.101 0.054

Fe(III) 0.3 2.400 0.169

Mn(III) 0.1 21.702 0.321

Ni(II) 0.07 0.016

* Not established a guideline value; not of health concern at levels found in drinking water.

Fig. 6. Removal of strontium(II) from the metal loaded 1A and 1B sorbents.

0 20 40 60 80 100 120

0

2

0

2

uptake, %

time, hrs

Sr(II); 1A

Sr(II); 1B

uptake,%


with a radiation dose of 250 kGy with a cobalt-60 gamma radiation source. Their high radiation sta-bility, i.e. the insignifi cant changes of the sorbents’ structure upon irradiation, was proven by two in-dependent methods. In the fi rst case, the sorption properties of the materials were shown to be the same for both raw materials with the appropriate irradiated sorbents (Fig. 7).

Moreover, infra-red vibrational spectra of all the materials studied were recorded, and pairs of spectra before and after irradiation were com-pared by numerical methods. According to the proposition of Sadlej-Sosnowska et al. [15], cal-culation of the Pearson’s correlation coeffi cient (c.c.) seems to be the most powerful methods of comparison. The c.c. may range from a value of -1 to 1. A zero value implies a lack of correlation between both spectra, i.e. they are totally differ-ent. On the other hand, values close to ± 1 indi-cate the similarity of the compared spectra and, consequently, of the identity of the substances be-ing compared.

Vibrational spectra recorded for both pairs of the studied sorbents in the fi ngerprint spectral range of 2000-400 cm–1, i.e. for the raw materials and the corresponding irradiated sorbents, re-vealed c.c. values of 0.97 and 0.98 for the sor-bents 1A and 1B, respectively. It means that the spectra of the irradiated sorbents were very simi-lar to those recorded for the original materials, and the conclusion concerning the high radiation stability of both sorbents is justifi ed.

We also decided to compare the aforemention-ed results obtained under laboratory conditions with the metal uptake from solutions with com-positions resembling real liquid radioactive waste. In the commonly available literature, data on the above compositions are rare and diffi cult to ob-tain. Aiming to perform this comparison, we chose the composition of liquid radioactive waste men-tioned by Liu et al. [16] (all salts in g/L): NaNO3 – 31.560, Al(NO3)3 – 13.670, Fe(NO3)3 – 7.460, Cr(NO3)2 – 0.960, Ni(NO3)2 – 2.670, KNO3 – 0.620, Ba(NO3)2 – 0.014, Sr(NO3)2 – 0-0.1 and CsNO3 – 0.175. For strontium(II), such as com-parison is presented in Fig. 8. The fi gure clearly shows that due to the co-sorption of the salts, one

should apply a quadruple sorbent dosage to obtain full strontium(II) uptake. The results for the other radionuclides were similar to those for strontium.

Our conclusions are as follows:• Decontamination of radioactive waste by ap-

plying the clay-salt slimes from the industrial waste of the JSC “Belaruskali” was found to be effective for solutions containing Cs(I), Sr(II), Eu(III), and Am(III) radionuclides.

• Both sorbents appear to be suffi ciently stable for practical application in the treatment of wastewaters.

• Hea vy metal ions released to the water in the course of the sorption may be removed by the nanofi ltration method.

References[1]. Rajec, P., Mátel, L., Orechovská, J., Šúcha, J., & No-

vák, I. (1996). Sorption of radionuclides on inor-ganic sorbents. J. Radioanal. Nucl. Chem., Articles, 208, 477-486.

[2]. Galamboš, M., Suchánek, P., & Rosskopfová, O. (2012). Sorption of anthropogenic radionuclides on natural and synthetic inorganic sorbents. J. Radio-anal. Nucl. Chem., 293, 613-633.

[3]. Thomson, B.M., Smith, Ch.L., Busch, R.D., Siegel, M.D., & Baldwin, C. (2003). Removal of metals and radionuclides using apatite and other natural sorb-ents. J. Environ. Eng., 129, 492-499.

[4]. Abdel Rahman, R.O., Ibrahium, H.A., & Hung, Y.-T. (2011). Liquid radioactive wastes treatment: A re-view. Water, 3, 551-565.

[5]. Legoux, Y., Blain, G., Guillaumont, R., Ouzounian, G., Brillard, L., & Hussonnois, M. (1992). Kd meas-urements of activation, fi ssion and heavy elements in water/solid phase systems. Radiochim. Acta, 58/59, 2, 211-218.

[6]. Evans, L.J. (1989). Chemistry of metal retention by soils. Environ. Sci. Technol., 23, 9, 1046-1056.

[7]. Maskalchuk, L., Baklay, A., & Leontieva, T. (2016). Chemical and mineralogical aspects of clay-salt slimes

Fig. 7. Radiation stability of the sorbents studied by sorp-tion of strontium(II).

Fig. 8. Comparison of the strontium uptake from water with that from the simulated radioactive waste: 1A sor-bent (a), 1B sorbent (b).

upta

ke,%

1A 1A irrad. 1B 1B irrad. 1A 1A irrad. 1B 1B irrad.

85

90

95

100

pH=5.13

ke,

pH=2.53

0

25

50

75

100

uptake,%

water waste

0 5 10 15 200

25

50

75

100

uptake%

dosage, g/L

water waste

(a)

(b)


STUDY AND CHARACTERIZATION OF U-Nd PARTICLES AFTER THERMAL TREATMENT

Marcin Rogowski, Marcin Brykała, Tadeusz Olczak, Danuta Wawszczak, Tomasz Smoliński

of “Belaruskali” using for the preparation of nano-structured sorbents of radionuclides. Procedia Chem., 21, 394-400.

[8]. Grabias, E., Solecki, J., Gładysz-Płaska, A., Fuks, L., Oszczak, A., & Majdan, M. (2015). 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 L. Fuks (Ed.), Rozwój technik i technologii wspomagających gos-podarkę wypalonym paliwem i odpadami promienio-twórczymi (pp. 105-114). Warszawa: Instytut Chemii i Techniki Jądrowej.

[9]. Maskalchuk, L., Baklay, A., & Leontieva, T. (2012). Synthesis and properties of the composite sorbents on the basis of alumosilicates separated from the clay-salt slimes. J. Environ. Sci. Eng., A1, 1356-1361.

[10]. Akar, T., Tunali, S., & Cabuk, A.S. (2007). Study on the characterization of lead(II) biosorption by fungus Aspergillus parasiticus. Appl. Biochem. Biotechnol., 136, 389-405.

[11]. Mittal, A. (2006). Removal of the dye, amaranth from waste water using hen feathers as potential ad-sorbent. Electron. J. Environ. Agric. Food Chem., 5, 1296-1305.

[12]. Jiao, L., Qi, P., Liu, Y., Wang, B., & Shan, L. (2015). Fe3O4 nanoparticles embedded sodium alginate/PVP/calcium gel composite for removal of Cd2+. J. Nanomater., 2015. DPI:10.1155/2015/940985.

[13]. Dulama, M., Deneanu, N., Pavelescu, M., & Pasăre, L. (2009). Combined radioactive liquid waste treat-ment processes involving inorganic sorbents and micro/ultrafi ltration. Rom. J. Phys., 54, 851-859.

[14]. WHO. (2011). Guidelines for drinking-water quality (4th ed.). WHO. Retrieved December 28, 2015, from http://apps.who.int/iris/bitstream/10665/44584/ 1/9789241548151_eng.pdf.

[15]. Sadlej-Sosnowska, N., Ocios, A., & Fuks, L. (2006). Selectivity of similar compounds’ identifi cation using IR spectrometry: -Lactam antibiotics. J. Mol. Struct., 792-793, 110-114.

[16]. Liu, M., Dong, F., Kang, W., Sun, S., Wei, H., Zhang, W., Nie, X., Guo, Y., Huang, T., & Liu, Y. (2014). Bio-sorption of strontium from simulated nuclear waste-water by Scenedesmus spinosus under culture con-ditions: Adsorption and bioaccumulation processes and models. Int. J. Environ. Res. Public Health, 11, 6, 6099-6118.

Uranyl-ascorbate gels with 10-40 mol% of neo-dymium have been previously obtained. Uranium trioxide, neodymium nitrate, ascorbic acid, and

ammonia were used to synthesize these gels. Initially, there were problems obtaining spherical grains of gels. However, after selection of the ap-

Fig. 1. SEM images of gels samples reduced at 1100oC with 10 mol% of Nd (A) and 30 mol% of Nd (B), and 1200oC with 20 mol% of Nd (C) and 40 mol% of Nd (D).

BA

C D


propriate parameters for the gelation process, spherical grains with a diameter of less than 150 m have been obtained. Non-destructive thermal conditions of the calcination process of gels to mixture of uranium and neodymium oxides were selected afterwards, as they were optimal. Cur-rently the works are focused on selection of the appropriate reduction conditions to UxNd1-xO2. The purpose of these works is to manufacture gels with a spherical particle shape preserved, a mini-mum quantity of cracks, and a smooth grain sur-face, while maintaining their suffi cient mechani-cal strength. It is also important that the mixed

uranium-neodymium dioxide is only present in a single crystalline phase.

After the reduction process the U-Nd powders were loose, non-agglomerated, and black-gray in colour. Below are some examples of SEM (scan-ning electron microscopy) images (using SE2, sec-ondary electron detector) showing the morphol-ogy of spherical UxNd1-xO2 grains at various mag-nifi cations (Fig. 1). It should be noted that the microspheres are partially destroyed during sample preparation for analysis. Thus, their strength is not very high. Basically, the appearance of the micro-spheres’ is similar. They have preserved a spheri-

Fig. 3. SEM images of spheres surface at high magnitude: (A) 1200oC, 10 mol% of Nd; (B) 1100oC, 10 mol% of Nd; (C) 1200oC, 30 mol% of Nd; (D) 1200oC, 40 mol% of Nd.

Fig. 2. SEM images of divided microspheres reduced at 1100oC with 20 mol% of Nd (A) and 1200oC with 40 mol% of Nd (B).

A B

D

A B

C


(Nd) theoretical [mol%]

Examined areaof the sample At% urani um At% neodymium At% oxygen (Nd) EDX

[mol%]

10surface 24.57 2.40 60.75 8.90

centre 24.65 3.35 62.00 11.96

20surface 23.38 7.18 58.27 23.49

centre 23.40 5.42 60.17 18.81

30surface 19.53 7.97 62.02 28.98

centre 18.31 8.11 62.98 30.70

40surface 15.68 9.32 64.59 37.28

centre 16.11 10.17 63.44 38.70

Table 1. Results of EDX analysis of samples after reduction at 1200oC.

Fig. 4. SEM images for EDX analysis of UxNd1-xO2 samples in the middle (A) and near the surface (B) of the micro-sphere.

A B

Fig. 5. XRD pattern of sample UxNd1-xO2 (x = 0.2). Reduction temperature – 1200oC.


cal shape and only have small cracks on their sur-faces.

In the middle of the divided spheres, one can see longitudinal and/or branched voids with a length up to several micrometres and a diameter up to 0.5 m (Fig. 2). These voids are not de-pendent on the reduction temperature. In addi-tion, they had been already present in the cal-cined samples, even though the heating rate of gels powders was only 0.5oC·min–1.

In Fig. 3 you can see the surface of the micro-spheres at high magnifi cation. Crystallites of a size up to 500 nm (average 200 nm) can be seen clear-ly. The structure of the surface is not solid, but shows numerous single mesopores with an aver-age diameter of 100 nm (Fig. 3B). These mesopores combine with each other to form elongated pores (Fig. 3C). Using the AsB detector (angle selective back-scattered detector), the homogeneity of the sample can be determined on the basis of differ-

ences in crystallographic contrasts (Fig. 3D). In this case, there is practically no difference in con-trast, and thus there is no signifi cant segregation of the UO2 and Nd2O3 phases.

For samples reduced at 1200oC, EDX (energy dispersive X-ray) analysis was performed. Measure-ments were performed on two areas inside of the microsphere: in the middle and near the surface (Fig. 4). Traces of sodium and aluminum were de-tected, which were probably impurities that re-sulted from the stages of preparation of sols and gels and powders annealing in the alundum boats.

In Table 1, results of the EDX analysis are pre-sented. The exact neodymium content was calcu-lated using the following formula:

n(Nd) 100%(Nd)n(Nd) n(U)

The neodymium content varies in the range up

to 5 mol%, and usually the quantity is higher in the middle than at the surface of the microspheres.

For all samples reduced at 1100 and 1200oC, XRD (X-ray diffraction) analysis was performed. In each case, only one phase was detected, name-ly the UO2 (database entry JCPDS 41-1422) phase. In Fig. 5 an exemplary and representative diffrac-togram is presented.

Figure 6 shows the results of the lattice para-meter a [Å] as a function of neodymium content (Nd) and reduction temperature. It contains re-sults from previous studies as well as those obtain-ed in the current studies. The lattice parameter

decreases linearly with an increase in neodymium content. The effect of temperature is minor and higher temperatures lead to an increase in the lattice parameter. A nonlinear relationship for samples containing more than 30 mol% of neo-dymium is also observed, but not for the sample reduced at 900oC. For the sample reduced at 1200oC a trend line was determined, because in that case it intersects the Y axis at 5.47 Å, which corresponds to the pure UO2.

Successful reduction processes of gels with amount of 10-40 mol% neodymium were per-

Fig. 6. Lattice parameter a of a UO2/Nd2O3 system as a function of neodymium concentration and the reduction tem-perature.


THE STUDY OF MEMBRANE FOULING BY USING PHOTOACOUSTIC SPECTROSCOPY

Agnieszka Miśkiewicz1/, Grażyna Zakrzewska-Kołtuniewicz1/, Bożena Sartowska1/, Sylwia Pasieczna-Patkowska2/

1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland2/ Maria Curie-Skłodowska University, Lublin, Poland

Membrane processes currently employed in nu-clear applications posses many benefi ts including high separation factors and relatively low energy consumption. Among the drawbacks of membrane methods include the tendency of decreases in ef-fi ciency resulting from the decline in fl ux over time due to membrane fouling.

Membrane fouling is a permanent and often irreversible change in the permeability of mem-branes; it causes an increase in the resistance to fl ow, and consequently a decrease in fi ltration ef-fi ciency. These effects result from blocking of the membrane due to the deposition of particulates, colloids, and other macromolecular compounds. Elimination of this blocking phenomenon by all available means is important for the effi cient op-eration of membrane apparatuses. Similarly, un-derstanding the nature of the phenomena that cause membrane fouling by using carefully select-ed methods of surface analysis is equally vital.

There are many methods which are already widely practiced in the investigation of mem-brane fouling [1-5]. There are also many studies examining the membrane blocking phenomenon which utilized spectroscopic methods such as at-tenuated total refl ection Fourier-transform infra-red (ATR-FTIR) spectroscopy [6-8].

In this paper, membrane fouling is investigated via a Fourier-transform infrared photoacoustic spectroscopy (FTIR-PAS), shortly: photoacoustic spectroscopy (PAS) approach. PAS permits meas-urements of material surfaces, regardless of the sample form. It can be used to analyse different materials, including optically neutral samples that do not transmit or refl ect incident light. PAS can also be used to examine irregularly shaped samples and surfaces with different coverage (i.e. layered samples) [9, 10]. The overall advantages of this method include: non-contact measurement, non-destructive, and depth profi ling (resolving) capability, among others, which all make PAS a very promising technique for the characterization of membrane surfaces [11].

PAS is based on the measurement of the effect of electromagnetic energy absorbed by matter via acoustic detection. The energy absorbed from light causes local heating through the thermal expan-sion of pressure waves or sound. PAS involves in-termittent light irradiation of a sample and simul-taneous detection of periodic temperature fl uctua-

tions in the sample as pressure fl uctuations. This process is illustrated in Fig. 1.

The photoacoustic (PA) signals depend on many factors, including the intensity and modula-tion frequency of light, and the thermal, optical and geometric properties of the sample, cell, and media.

The photoacoustic signal originating from a homogeneous solid sample is described as the pressure variation of the gas in the photoacoustic cell, P(t), according to the Eq. (1) [11]:

0 g s

g 0

P T (0, )P(t) exp I t

42l T

(1)

where: – the angular modulation frequency of the incident light, – the ratio of the specifi c heats (Cp/Cv) of the sample, P0 – the static pressure of the photoacoustic cell gas, T0 – the average tem-perature of the photoacoustic cell gas, Ts(0, ) – the complex temperature at the solid-gas bound-ary (surface), lg – the distance from the surface of the sample to the cell window, g – the thermal diffusion depth of the cell gas, t – time, I – the light intensity, – the phase difference of acoustic signal.

The photoacoustic signal phase contains spa-tial information about the signal origin, and thus it is of great importance in spectral depth profi l-

Fig. 1. Scheme of photoacoustic signal generation and de-tection.

0 g s0

g 0

P Texp I t

42l T

formed. In this process, we achieved good-looking spherical grains. Further, XRD analysis revealed the existence of only one phase of UO2. We also ob-served changes in the lattice parameter depending

on the amount of neodymium in the sample and the reduction temperature. Lastly, we note that the calcination step of the gels is critical with re-gard to the presence of cracks in the microspheres.


ing analysis. PA signals would exhibit phase lags with respect to the optical modulation because thermal diffusion is much slower than optical penetration. The phase lags depend on the modu-lation frequency, the instrument, and the spatial origin of the signals. A fi nite time delay, t, for a PA signal generated from a deeper layer of a sample to reach the microphone with respect to the sur-face PA signal can be related to the phase differ-ence, by Eq. (2): 2f(t) (2)where f is the phase modulation frequency.

PA signals originating from deeper parts of a sample have greater phase lags than those from shallower parts. Additionally, smaller phase lags are associated with stronger bands from the same layer when this layer is thermally thick (the layer is thicker than the thermal diffusion depth) or op-tically opaque (the layer is thicker than the opti-cal penetration depth).

Experiments aimed at determining the rate of membrane blocking by poly(acrylic acid) were carried out in a batch stirred cell (Model 8010, Amicon, Millipore, USA) with an initial volume

Fig. 2. FTIR-PAS spectra of a pure PES membrane and membranes with poly(acrylic acid) deposited on their surface, within the 4000-2000 cm–1 range (the baselines are displaced vertically to avoid overlap).

Fig. 3. FTIR-PAS spectra of a pure PES membrane and membranes with poly(acrylic acid) deposited on their surface, within the 2000-400 cm–1 range.


of 0.01 L. These experiments used commercial fl at-sheet membranes made of polyethersulphone (P ES) with a molecular cut-off of 10 000 kDa, a diameter of 25 10–3 m, and an effective mem-brane area of 4.1 10–4 m2 provided by Millipore. The fi ltration cell was stirred with a magnetic stirrer at 400 rpm. The applied pressure was ad-justed by pressurized air at 0.2 MPa. The feed so-lution of poly(acrylic acid) with a concentration of 500 mg/L was introduced into the fi ltration cell and fi ltered for periods of 1, 5, 10 and 20 min. After fi ltration, membranes were removed from the cell, dried and then subjected to spectroscopic measurements. A new membrane was used for each fi ltration period. The values of average per-meate fl ux were calculated based on the masses of the permeate samples collected during each fi l-tration period.

FTIR-PAS spectra of membranes were record-ed using the Bio-Rad Excalibur 3000 MX spectro-meter equipped with the photoacoustic detector MTEC300 (in a helium atmosphere) at RT over the 4000-400 cm–1 range at a resolution of 4 cm–1 and maximum source aperture. Spectra were nor-

malized by computing the ratio of sample spec-trum to the spectrum of a MTEC carbon black standard. The membrane sample was placed in a stainless steel cup for measurement. Before each data collection, the photoacoustic cell was purged with dry helium for 5 min. Interferograms of 1024 scans were averaged for each spectrum.

The membrane samples were analysed by means of photoacoustic spectroscopy before (sample P0) and after fi ltration of poly(acrylic acid) for 1, 5, 10 and 20 min (samples: P1, P2, P3 and P4, respec-tively). Figures 2-4 show the FTIR-PAS spectra of these membrane samples.

Although most of the IR bands derived from poly(acrylic acid) overlap with those of PES, and the presence of poly(acrylic acid) on the mem-brane surface is visible as the band at 1732 cm–1 (C=O stretching in COOH group) (Figs. 3 and 4). This band is absent in the pure PES membrane spectrum and its presence on the membrane after fi ltration may be used to evaluate the amount of deposited poly(acrylic acid).

The studies described in this paper have dem-onstrated that the PAS method is very sensitive

Fig. 5. SEM images of pure membrane samples (A) and membrane samples after 5 min (B) and 20 min (C) of fi ltration of poly(acrylic acid) solution.

Fig. 4. FTIR-PAS spectra of a pure PES membrane and membranes with poly(acrylic acid) deposited on their surface, within the 1850-1500 cm–1 range.

BA C


and allows for the distinction of small differences in the thickness of deposit layers accumulated on the membrane surface.

Results obtained with the application of the photoacoustic spectroscopy were also confi rmed by the technique of scanning electron microscopy (SEM). The same membrane samples were ob-served under the microscope, and representative images are presented in Fig. 5. As can be observ-ed, the surface of the membrane was blocked by poly(acrylic acid) more intensively following the fi ltration process. Samples No. 2 and No. 4, which were subject to fi ltration for 5 and 20 min, respec-tively, are covered with aggregated polymer par-ticles. Alternatively, sample No. 0, which is a new membrane sample, is not fouled by poly(acrylic acid).

To summarize, photoacoustic spectroscopy can be an alternative for other methods used for the investigation of membrane fouling. This technique allows for estimation of even slight changes in the deposit thickness. The PAS method can also be used to assess the effectiveness of methods used for membrane cleaning. Additionally, results from photoacoustic experiments were confi rmed by an optic method.

The studies were supported by the National Science Centre, Poland, grant No. DEC-2013/11 /D/ST8/03328 entitled “Studies on the phenom-ena occurring in the membrane boundary layer during the fi ltration of aqueous solutions and sus-pensions proceeding in membrane apparatuses with different confi gurations”.

References[1]. Arndt, F., Roth, U., Nirschl, H., Schutz, S., & Guthau-

sen, G. (2016). New insights into sodium alginate fouling of ceramic hollow fi ber membranes by NMR imaging. AIChE, 62 (7), 2459-2467. DOI: 10.1002/aic.15226.

[2]. Benavente, L., Coetsier, C., Venault, A., Chang, Y., Causserand, C., Bacchin, P., & Aimar, P. (2016). FTIR mapping as a simple and powerful approach to study

membrane coating and fouling. J. Membr. Sci., 520, 477-489. DOI: 10.1016/j.memsci.2016.07.061.

[3]. Ho, J.S., Low, J.H., Sim, L.N., Webster, R.D., Rice, S.A., Fane, A.G., & Coster, H.G.L. (2016). In-situ monitoring of biofouling on reverse osmosis mem-branes: Detection and mechanistic study using elec-trical impedance spectroscopy. J. Membr. Sci., 518, 229-242. DOI: 10.1016/j.memsci.2016.06.043.

[4]. Tunga, K.-L., Damodara, H.-R., Damodara, R.-A., Wua, T.-T., Li, Y.-L., Lina, N.-J., Chuanga, C.-J., Youa, S.-J., & Hwang, K.-J. (2012). Online monitor-ing of particle fouling in a submerged membrane fi l-tration system using a photointerrupt sensor array. J. Membr. Sci., 407-408, 58-70. DOI: 10.1016/j.mem-sci.2012.03.013.

[5]. Li, W., Liu, X., Wang, Y.-N., Chong, T.H., Tang, C.Y., & Fane, A.G. (2016). Analyzing the evolution of membrane fouling via a novel method based on 3D Optical Coherence Tomography imaging. Environ. Sci. Technol., 50, 6930-6939. DOI: 10.1021/acs.est. 6b00418.

[6]. Thygesen, O., Hedegaard, M.A.B., Zarebska, A., Be-leites, C., & Krafft, C. (2014). Membrane fouling from ammonia recovery analyzed by ATR-FTIR imaging. Vib. Spectrosc., 72, 119-123. DOI: 10.1016/j.vib-spec.2014.03.004.

[7]. Rabiller-Baudry, M., Le Maux, M., Chaufer, B., & Begoin, L. (2002). Characterisation of cleaned and fouled membrane by ATR-FTIR and EDX analysis coupled with SEM: application to UF of skimmed milk with a PES membrane. Desalination, 146, 123-128. DOI: 10.1016/S0011-9164(02)00503-9.

[8]. Bass, M., & Freger, V. (2015). Facile evaluation of coating thickness on membranes using ATR-FTIR. J. Membr. Sci., 492, 348-354. DOI: 10.1016/j.mem-sci.2015.05.059.

[9]. McClelland, J.F., Jones, R.W., & Bajic, S.J. (2002). FT-IR photoacoustic spectroscopy. In J.M. Chalmers & P.R. Griffi ths (Eds.), Handbook of vibrational spectroscopy (pp. 1231-1251). Chichester: John Wiley & Sons.

[10]. Ryczkowski, J. (2007). Application of infrared photo-acoustic spectroscopy in catalysis. Catal. Today, 124, 11-20. DOI: 10.1016/j.cattod.2007.01.044.

[11]. Jiang, E.Y. (2003). Advanced FT-IR spectroscopy: Principles, experiments and applications. Madison: Thermo Electron Corp.

PURIFICATION OF FLOWBACK FLUIDS FROM HYDRAULIC FRACTURING OF POLISH GAS-BEARING SHALES BY HYBRID METHODS Katarzyna Kiegiel, Anna Abramowska, Dorota K. Gajda, Agnieszka Miśkiewicz,

Grażyna Zakrzewska-Kołtuniewicz

Gas-bearing shales are impermeable sedimentary rocks that require special stimulation to release shale gas, which is trapped therein. The shale gas is extracted by using special exploration and pro-duction technologies, namely hydraulic fracturing [1]. During the fracking, action fl uid is pumped into a wellbore under high pressure and causes crushing of the rock formations and fracture for-mation. Huge amounts of toxic fl uids are a by--product of shale gas production. These fl uids cre-ate a serious environmental problem to be solved in the context of the future exploitation of shale deposits. It is necessary to treat these fl uids for reuse and to reduce the environmental impact of gas extraction technology.

The primary physicochemical chracteristics of the fl owback fl uid are shown in Table 1. The fl uid is characterized by a very high concentration of chloride (entry 11) and sodium (entry 24). The value of total dissolved solids (TOC) is also high (entry 9). The sample analysis performed by alpha spectrometry shows that uranium radioisotopes are present in fl owback fl uid, among of other metals (Table 2). The level of radioactivity detect-ed in the samples collected from Polish wellbores is higher than the average activity of radionu-clides in inland water reservoirs [2]. In the ana-lysed fl owback fl uids, radioisotopes of Ra-226, Pb-214, Bi-214, Pb-212, Tl-208, and K-40 (Table 3) were also found. The activity of these isotopes


was higher than the natural background present in deep water in Poland, which is rated on 0.04 Bq/L for Ra-226 and 4 Bq/L for K-40 in references [2]. Other radionuclides are relatively short--lived and do not pose a threat to the environ-ment.

Toxicity of the fl owback fl uid was measured using the bioluminescent bacteria Vibrio fi scheri with a Microtox® test. The toxicity parameters were on the level of TU50 = 6.3 and TU20 = 19. The value of TU20 indicated that in order to re-duce the toxicity of the analysed liquid sample below the hazard value, the sample should be di-luted 19-fold.

The purifi cation process of the fl uid obtain-ed after hydraulic fracturing proposed in the pro-ject begins from the mechanical purifi cation step, which is necessary to obtain a clear and homoge-neous solution (Fig. 1). In the second step, the soluble organic compounds are removed by sorp-

tion on activated carbons or in advanced oxida-tion processes, e.g. the Fenton reaction [3] or ozonation [4]. In this work, the special modifi ed Impex BAK 40 carbon was examined. Sorption on this particular carbon resulted in reduction of organic substances up to 85%. Lastly, nanofi ltra-tion and reverse osmosis (RO) are used for fi nal treatment and water recovery. In addition, heavy

Entry Parameter Value

1 pH 5.79

2 conductivity 124 mS/cm

3 NH4 134 mg/mL

4 HCO3 976 mg/L

5 TOC 53 mg/L

6 chemical oxygen demand 65 mg/L

7 surfactant content 40 mg/L

8 turbidity 0.2 NTU

9 total dissolved solid 103.189 mg/L

10 Br 670 mg/L

11 Cl 66.400 mg/L

12 NO2 15.7 mg/L

13 NO3 30.5 mg/L

14 B 44.4 mg/L

15 Ba 226 mg/L

16 Ca 7520 mg/L

17 Cu 0.062 mg/L

18 Fe 20 mg/L

19 K 515 mg/L

20 Li 11.286 mg/L

21 Mg 865 mg/L

22 Mn 9.7 mg/L

23 Mo 0.009 mg/L

24 Na 24.590 mg/L

25 SiO2 50 mg/L

26 Sr 1110 mg/L

RadionuclideActivity of radionuclides

in fl owback fl uidAverage activity of radionuclides in water reservoirs [2]

underground and groundwater oceans (to 400 m) potable water

[Bq/m3]

U-238 578 ± 42 14 40 2

U-234 416 ± 32 150 46 -

U-235 22 ± 6 no data no data no data

Radionuclide* Flowback fl uidA/Abackground

Ra-226 8

Pb-214 11.5

Bi-214 6

Pb-212 6

Tl-208 2

Ac-228 -

K-40 activity at the level of natural background

Table 2. The content of uranium isotopes in the fl ow-back fl uid.

Table 3. Comparison of the content of radionuclides in the fl owback fl uid sample to the typical ground water natural background surrounding the drilling place (0.04 Bq/L).

Table 1. Characterization of fl owback fl uid.

Fig. 1. The proposed scheme for treatment of fl owback fl uids from hydraulic fracturing.

Depth Filter

Active carbon Ozonation

Backflow fluid

Cation Exchange Resin

Nanofiltration Reverse Osmosis

Anion Exchange Resin

Reverse Osmosis

organic compounds removal

desalin

organic compounds removal

desalination

A

* Extended uncertainty of the measurement: Ra-226 – 5%, Pb-214 – 2%, Bi-214 – 2%, K-40 – 0.2%, Tl-208 – 0.5%, Ac-228 – 2%, Pb-212 – 3%.


metals fl ushed out from the wellbore, which are concentrated in retentate after nanofi ltration, can be separated by commercial ion-exchangers. The reverse osmosis method was found to be an effec-tive separation process that can be used as the fi nal step in the purifi cation of the feedback fl uids. Signifi cant reduction in the content of divalent ions (magnesium, calcium, strontium, sulphates) as well as monovalent ions (lithium, sodium, po-tassium and chlorides) was observed in this pro-cess. In the case of divalent ions, 96% content reduction was achieved, while 92% reduction was achieved in the case of monovalent ions. In addi-tion, it was observed that a high degree of remov-al of all the analysed ions was obtained just after 30 min of the RO process. At this time, the reten-tion factor exceeded 85%.

Based on the results obtained experimentally, the full treatment scheme of fl owback fl uid treat-ment was proposed (Fig. 2). After fi ltration of the fl owback fl uid by mechanical fi lters which remove solid particles from wastewater, the organic matter was removed. Organic compounds were then ad-sorbed in a column fi lled with modifi ed activated carbon (MAC). Organic compounds that were not adsorbed on MAC were partly destroyed in the ozonation process, where air was sucked by an oxygen concentrator and directed to the ozone generator followed by the ozonation chamber. The second MAC column after the ozonation process is an additional option if the fl uid consists of too much organic matter. Organic-free fl uid is then directed into a cascade of ion-exchangers. Anion and cation beds are used for the removal of se-

lected anions and cations. At this stage, some of the valuable compounds, e.g. Ba, Sr, U, and others could be recovered. The fi nal stage of fl owback purifi cation reduces the salinity, mainly coming from NaCl, by using reverse osmosis modules. After treatment, the permeated fl uid can then be reused as feed water for testing the next well or considered as sewage. If the purity is suffi ciently good, the obtained liquid could be discharged into the river. The retentate should be concentrated by evaporation or crystallization and passed on for fi nal disposal.

This research was supported by the research project titled “Conspan – BlueGas – technology of purifi cation of fl owback with recovery of water and valuable metals”.

References [1]. King, G.E. (2012). Hydraulic Fracturing 101: What

every representative, environmentalist, regulator, re-porter, investor, university researcher, neighbor and engineer should know about estimating frac risk and improving frac performance in unconventional gas and oils wells. SPE paper 152596. Society of Petro-leum Engineers. DOI: 10.2118/152596-MS.

[2]. Bem, H. (2005). Radioaktywność w środowisku na-turalnym. Łódź: PAN.

[3]. Babuponnusami, A., & Muthukumar, K. (2014). A review on Fenton and improvements to the Fenton process for wastewater treatment. J. Environ. Chem. Eng., 2 (1), 557-572. DOI: 10.1016/j.jece.2013.10.011.

[4]. Lin, S.H, & Lin, C.M. (1993). Treatment of textile waste effl uents by ozonation and chemical coagula-tion. Water Res., 27 (12), 1743-1748. DOI: 10.1016/ 0043-1354(93)90112-U.

Fig. 2. Technological scheme of purifi cation of fl owback fl uids from hydraulic fracturing.

AIR

INLET

FEED

SOLUTION

RETENTATE - CONDENSATED

SOLUTION

PERMEATE

PURIFIED SOLUTION

OUTLET

G O3

C O2

1 2 3 4

ANIONS AND CATIONS REMOVAL

ION-EXCHANGER REGENERATION

PA

1;2;3;4 - ion-exchangers mechanical filter MAC bed ozonation chamber

C O2 oxygen concentrator G O3 ozone generator

pump PremAir systemRO module PA

CENTRE FOR RADIOBIOLOGY CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRYAND BIOLOGICAL DOSIMETRY

Studies carried out in 2016 focused on the implementation of new biodosimetric tools that have been developed within the framework of the strategic research project “Technologies supporting development of safe nuclear power engineering” from the National Centre for Research and Development (SP/J/6/143 339/11). As a result of the project implementation, a new laboratory for biological dosimetry was established in the Centre and accredited by the Polish Centre for Accreditation. The participation of the Centre in the Coordination Action project RENEB founded within the 7th EU Framework Programme EURATOM – Fission, resulted in the creation of an operational network, based on the coordination of existing reli-able and proven methods in biological dosimetry. Accordingly, the Centre participated in the interlaboratory comparison organized in 2016. A further comparison exercise is expected in 2017. In addition, new, high throughput methods for biological dosimetry, based on gene ex-pression analysis, are being developed.

Two important research topics during the last few years have been the nanotoxicology and nanobiotechnology. A new scientifi c project was established, focused on the use of nanozeo-lites in prostate cancer treatment.

64 CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY

RECONSTRUCTION OF IONIZING RADIATION DOSE – A CASE STUDYTeresa Bartłomiejczyk1/, Iwona Buraczewska1/, Katarzyna Sikorska1/, Maria Kowalska2/,

Sylwester Sommer1/

1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland 2/ Central Laboratory for Radiological Protection, Warszawa, Poland

The Laboratory of Biological Dosimetry (PDB), Centre for Radiobiology and Biological Dosimetry, Institute of Nuclear Chemistry and Technology is accredited by the Polish Centre for Accreditation for the reconstruction of doses of 60Co gamma ra-diation and of X-rays (200 keV) on the basis of evaluation of the incidence of dicentric chromo-somes in peripheral blood lymphocytes. The PDB is one of the three laboratories in Poland that deal with biological dosimetry. The other two are the Henryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences (Kraków) and the Laboratory of Individual and Environmental Doses of the Central Laboratory for Radiological Protection (CLOR; Warszawa). Below, recent eva-luations of ionizing radiation doses are presented for three cases, where there was a considerable delay between exposure and dose reconstruction.

Case 1 was reported to the PDB for health rea-sons. The study was ordered because of malaise, health problems, strain, infl ammation of the sali-vary glands, and a dry mouth after 11 tooth radio- graphies, two pantomographies, and a CT of the chest and stomach. The received dose is hard to estimate, but counting 11 0.4, 2 1 and 2 30 mSv we get about 70 mSv on selected parts of the body. This should not cause any health effects. In 1200 cells examined, one dicentric chromosome was found, corresponding to 0.0014 Gy with a 95% confi dence interval of 0.000-0.0534. Further-more, 17 acentric fragments were present (which is higher than the control value). The dicentrics’ frequency was 0.83 per 1000 cells, while that of the acentric fragments was 14 per 1000 cells. Cells with two, or even four acentric fragments were found (e.g. Fig. 1). This is rather unusual even after low doses of ionizing radiation. In conclu-sion, the patient was not excessively irradiated, but the high number of acentric fragments may indicate an indeterminate genetic instability.

Case 2: According to the physical reconstruc-tion, the dose received on the head was in the range of several Sv of gamma radiation with a beta component. Biological dosimetry carried out joint-ly by the PDB and CLOR pointed to a low dose uniform irradiation of the body. Accordingly, the distribution of dicentrics between cells was con-

sistent with a Poisson distribution. When estimat-ing the dose (Table 1), it was taken into account that there was a half year delay in dose reconstruc-tion, associated with the loss of a number of di-centrics. The rate of lymphocyte loss in vivo nec-essary for the calculation was taken from [1-3]. In conclusion, biological dosimetry reconstruction did not confi rm the physical reconstruction of the dose.

Case 3 volunteered for examination at the PDB because of health ailments caused as a result of an X-ray scan of the whole body. Between the event and the reconstruction of the dose, fi ve years have passed. For this reason, in addition to the stand-ard dicentric test, an analysis of translocations was performed. It has been postulated that, unlike the frequency of dicentrics, the translocation rate does not change with the passage of time. The dose calculated from dicentric frequency was 0.021 Sv (0.000-0.080). In conclusion, the dose reconstruct-ed from translocation analysis was higher than that from the dicentric analysis. Reconstruction of the dose was based on the analysis of the data found in the IAEA’s Guide in Fig. 4.4 [4]. The es-

Fig. 1. Mitosis of patient case 1 with four acentric frag-ments (indicated by arrows), a feature that is unexpected in the case of an unirradiated individual.

Table 1. Data concerning dose reconstruction for case 2.

Number of scored

cells

Number of dicentrics

Dose and 95% confi dence

interval [Sv]

Days between exposure and dose

reconstruction

Half-life value of lymphocytes in blood taken for calculation

Corrected number

of dicentrics

Calculated dose and 95% confi dence

interval [Sv]

1790 5 0.067; 0.000-0.176 194

168 [1] 11 0.167; 0.077-0.272

800 [2] 6 0.086; 0.001-0.195

220 [3] 9 0.137; 0.048-0.244

65CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY

IMPACT OF NANOPARTICLES ON SURVIVAL OF HepG2 CELLS TREATED WITH TUMOUR NECROSIS FACTOR

Iwona Grądzka, Katarzyna Sikorska, Tomasz Stępkowski, Kamil Brzóska

timated dose based on analysis of the translocation frequency was 0.051 Sv (0.001-0.137). Interest-ingly, an error was found in the above-mentioned fi gure published in the IAEA’s Guide: the translo-cation frequency should have been expressed per 100 cells, according to [5]. The error is in the de-scription of the Y axis.

References[1]. Ramalho, A.T., Curado, M.P., & Natarajan, A.T. (1995).

Lifespan of human lymphocytes estimated during a six year cytogenetic follow-up of individuals accidentally exposed in the 1987 radiological accident in Brazil. Mutat. Res., 331 (1), 47-54.

[2]. Sreedevi, B., Rao, B.S., & Bhatt, B. (1993). Radiation--induced chromosome aberration yields following an accidental non-uniform exposure. Radiat. Prot. Dosim., 50 (1), 45-49.

[3]. Dolphin, G.W., Lloyd, D.C., & Purrott, R.J. (1973). Chromosome aberration analysis as a dosimetric tech-nique in radiological protection. Health Phys., 25 (1), 7-15.

[4]. IAEA (2011 ). Cytogenetic dosimetry: Applications in preparedness for and response to radiation emer-gencies. Vienna: IAEA.

[5]. Sigurdson, A.J., Ha, M., Hauptmann, M., Bhatti, P., Sram, R.J., Beskid, O., Tawn, E.J., Whitehouse, C.A., Lindholm, C., Nakano, M., Kodama, Y., Nakamura, N., Vorobtsova, I., Oestreicher, U., Stephan, G., Yong, L.C., Bauchinger, M., Schmid, E., Chung, H.W., Darroudi, F., Roy, L., Voisin, P., Barquinero, J.F., Livingston, G., Blakey, D., Hayata, I., Zhang, W., Wang, C., Bennett, L.M., Littlefi eld, L.G., Edwards, A.A., Kleinerman, R.A., & Tucker, J.D. (2008). International study of factors affecting human chromosome translocations. Mutat. Res., 652 (2), 112-121. DOI: 10.1016/j.mrgen-tox.2008.01.005.

Nanoparticles (NPs) and nanomaterials are de-fi ned as substances with at least one dimension less than 100 nm in size. The ever-increasing de-velopment of nanoparticles with various physico-chemical properties for different industrial appli-cations has greatly enhanced human exposure to nanomaterials. This exposure can be deliberate, e.g. in applications where nanoparticles are used as imaging agents or drug carriers; it also can be unintentional, e.g. due to the pollution of the en-vironment by the industrial production of nano-particles [1].

Our recent experiments showed that silver nanoparticles (Ag NPs) are able to activate the NF-B signalling pathway as well as the expres-sion of genes related to infl ammatory and stress response [2]. Similar transcriptional programmes can be activated in response to TNF (tumour ne-crosis factor) – a pleiotropic cytokine inducing a wide range of cellular responses that affect biologi-cal processes, such as lipid metabolism, coagula-tion, insulin resistance, and the function of en-dothelial cells. TNF is a major pro-infl ammatory cytokine, involved in the progression of diseases such as cancer, Alzheimer’s disease, diabetes type II, cardiovascular, pulmonary, or neurological dis-orders, and many autoimmune diseases. The cyto-toxic activity of TNF is of interest in the develop-ment of new antitumour strategies; however, the clinical use of TNF as an anticancer drug has been limited so far by its severe cardiovascular side effects. Therefore, TNF treatment is limited to regional and local administration of high doses of TNF, often in combination with chemotherapy, as accomplished in isolated limb and isolated he-patic perfusion [3].

The aim of the present study was to test the hypothesis that NPs widely used in medicine and industry may interfere with the cellular signalling activated by TNF. Such interference may change the fi nal cellular result of TNF action and disrupt

cellular homeostasis, thus contributing to the de-velopment of malignancy or autoimmune diseases.

We have tested three types of NPs (approxi-mately 20 nm in size) widely used in medicine and industry:• gold NPs (Au NPs) used for diagnostic and thera-

peutic purposes, including biosensor applica-tions, targeted delivery of anticancer drugs, bio-imaging of cells and tissues, photothermal agents, contrast agents, and radiosensitizers [4, 5].

• iron oxide NPs (Fe3O4 NPs) used for numerous in vivo applications, such as MRI (magnetic res-onance imaging) contrast enhancement, tissue repair, detoxifi cation of biological fl uids, drug delivery, and cell separation [6, 7].

• silver NPs (Ag NPs) widely used due to their antibacterial properties which makes them a de-sirable additive in many products such as tex-tiles, cosmetics, food packaging, surgical instru-ments, and wound dressings. Being present in so many consumer goods, Ag NPs are able to penetrate the human body via multiple paths (review in [8]).Experiments were performed on the human he-

patic cell line, HepG2, purchased from the Ame-rican Type Tissue Culture Collection (ATCC, Rock-ville, MD, USA). HepG2 cells were cultured in an EMEM medium supplemented with 10% fetal calf serum (FCS, Gibco ). The cells were incubated in a 5% CO2 atmosphere at 37oC.

To assess the effect of NPs on cell survival after TNF treatment, a clonogenic survival assay was used. The cells were seeded onto 60 mm Petri plates at a density of 700-1000 per plate in three repli-cates. Immediately afterwards, appropriate mix-tures of NP suspensions with TNF were added to the cell culture plates. The cells were grown in the presence of NPs until visible clones were formed (usually 8-14 days); they were then fi xed with formaldehyde and Giemsa stained. The clones in individual plates were counted and the cell sur-


vival was calculated as a percentage of clones in the untreated control. The results were shown as the means ± standard deviation (SD) of 3-5 inde-pendent experiments.

Different effects were observed for each of the NPs under study. Ag NPs signifi cantly sensitized HepG2 cells to TNF (Fig. 1A). A similar, but not statistically signifi cant, tendency was observed for Au NPs (Fig. 1B). In contrast, no impact of Fe3O4 NPs on the TNF action was observed (Fig. 1C). This result confi rms that nanoparticles may affect the cellular response to TNF. It also shows that this effect is related to the properties of the nano-materials. Therefore, a systematic study of the ef-fects of nanomaterials on cellular signal trans-duction networks is needed to provide more in-formation about the nature and specifi city of the functional interactions between nanomaterials and cells. Since these interactions may contribute to the development of diseases, but could also be of use to develop therapeutic strategies, such knowl-

edge will facilitate the purposeful design of nano-materials and lay the foundation for the controlled manipulation of biological systems through nano-technology.

References[1]. Sharifi , S., Behzadi, S., Laurent, S., Forrest, M.L.,

Stroeve, P., & Mahmoudi, M. (2012). Toxicity of nano-materials. Chem. Soc. Rev., 41 (6), 2323-2343. DOI: 10.1039/c1cs15188f.

[2]. Stępkowski, T.M., Brzóska, K., & Kruszewski, M. (2014). Silver nanoparticles induced changes in the ex-pression of NF-B related genes are cell type specifi c and related to the basal activity of NF-B. Toxicol. in Vitro, 28 (4), 473-478. DOI: 10.1016/j.tiv.2014.01.008.

[3]. Wajant, H., Gerspach, J., & Pfi zenmaier, K. (2005). Tumor therapeutics by design: targeting and activa-tion of death receptors. Cytokine Growth Factor Rev., 16 (1), 55-76.

[4]. Libutti, S.K., Paciotti, G.F., Byrnes, A.A., Alexander, Jr., H.R., Gannon, W.E., Walker, M., Seidel, G.D., Yulda-sheva, N., & Tamarkin, L. (2010). Phase I and pharma-

Fig. 1. Colony forming ability of HepG2 cells treated with TNF and NPs: Ag NPs (A), Au NPs (B), Fe3O4 NPs (C). Asterisks denote a statistically signifi cant difference between cells treated and not treated with NPs (t-test, p < 0.05).

A

B

C

67CENTRE FOR RADIOBIOLOGY AND BIOLOGICAL DOSIMETRY

FORMATION OF A DINITROSYL IRON COMPLEX WITH LOW-DENSITY LIPOPROTEIN AND ITS APPLICATION

AS IRON CARRIERHanna Lewandowska, Sylwia Męczyńska-Wielgosz, Katarzyna Sikorska, Grzegorz Wójciuk,

Jarosław Sadło, Jakub Dudek, Marcin Kruszewski

cokinetic studies of CYT-6091, a novel PEGylated col-loidal gold-rhTNF nanomedicine. Clin. Cancer Res., 16, 6139-6149. DOI: 10.1158/1078-0432.CCR-10-0978.

[5]. Weintraub, K. (2013). Biomedicine: the new gold stand-ard. Nature, 495, S14-S16.

[6]. Laurent, S., Forge, D., Port, M., Roch, A., Robic, C., Van der Elst, L., & Muller, R.N. (2008). Magnetic iron oxide nanoparticles: synthesis, stabilization, vectoriza-tion, physicochemical characterizations, and biologi-cal applications. Chem. Rev., 108 (6), 2064-2110. DOI: 10.1021/cr068445e.

[7]. Moghimi, S.M., Hunter, A.C., & Murray, J.C. (2005). Nanomedicine: current status and future prospects. FASEB J., 19 (3), 311-330.

[8]. Kruszewski, M., Brzoska, K., Brunborg, G., Asare, N., Dobrzynska, M., Dusinská, M., Fjellsbø, L., Georgant-zopoulou, A., Gromadzka-Ostrowska, J., Gutleb, A., Lankoff, A., Magdolenová, Z., Pran, E.R., Rinna, A., Instanes, C., Sandberg, W.J., Schwarze, P., Stępkowski, T., Wojewódzka, M., & Refsnes, M. (2011). Toxicity of silver nanomaterials in higher eukaryotes. Adv. Mol. Toxicol., 5, 179-218.

In view of the interrelations between NO, iron and low-density lipoprotein (LDL) in the cardio-vascular system (reviewed in [1]), it appeared in-teresting to fi nd out whether lipoprotein particles can undergo the process of iron-nitrosylation and

to characterize the properties of the DNIC-modi-fi ed LDL particles. An iron-nitrosylated LDL prep-aration containing the Fe(NO)2 motif (DNICLDL) was obtained and characterized for the fi rst time. Such a modifi cation of LDL transformed it into a carrier of two important biological agents, NO

and iron. The target of DNICLDL formation was the protein constituent of LDL, apolipoprotein B (ApoB100). The analysis of its iron contents gave an average of 73 iron atoms per molecule of pro-tein. Taking into account that there are 24 cys-

teines in ApoB100 and, according to our assump-tions, 13 cysteine moieties in hydrophilic regions, it can be clearly seen that not only –SH groups take part in DNICLDL formation with ApoB100.

DNICLDL particles were characterized in de-tail using physicochemical methods. Here, we

Fig. 1. Levels of total iron (measured by atomic absorption spectroscopy) in HepG2 and RAW 264.7 cells treated with native LDL or DNICLDL (M/g of protein).

Fig. 2. Metabolic activity (MTT assay) of HepG2 cells treated with different concentrations of LDL and its derivatives for 24 h. Data are expressed as a percentage of control, mean ± SD from three independent experiments. Asterisk de-notes statistically signifi cant difference from unexposed control, p < 0.05.

*

*

*

*

*

*


show their biological effects using HepG2 and RAW 264.7 cells in vitro. Evaluation of the uptake of the native and modifi ed lipoproteins by the HepG2 and RAW 264.7 cells was carried out us-ing a lipophilic fl uorescent dye (DiI stain, Mol-ecular Probes D282). In order to test its interac-tions with potential target cells, DNICLDL was administered to both the above-mentioned cell lines. The resulting effects were compared to those induced by the native LDL (nLDL) and oxidized LDL (oxLDL). Figure 1 shows that DNICLDL ad-ministration considerably increased the total iron content in the studied cell lines. These experi-mental results suggest that DNICLDL might be a potential transducer of iron.

Further, a genotoxicity test (not shown) reveal-ed that the chelation of iron in the form of DNIC strongly reduced the DNA damage induced by iron ions in the presence of H2O2-induced reac-tive oxygen species. This suggested a low availabil-ity of the DNICLDL-incorporated iron in Fenton--type reactions and hence a low toxicity. This con-clusion was also confi rmed by the results of the MTT assay (a colourimetric assay for assessing cell metabolic activity), which may, under defi ned conditions, refl ect the number of viable cells pre-sent. DNICLDL was found to be of low toxicity to mammalian cells in vitro (cf. Fig. 2).

In summary, we have elaborated a method of synthesis of a new kind of DNIC. Its structure is based on a natural carrier, the biological nanopar-ticle LDL. DNICLDL represents a completely new tool to supplement cells with nitric oxide and iron. Also, it seems to be a potent medium for the

delivery of iron and DNIC into mammalian cells. It should be stressed that despite several promis-ing trials to exploit lipoproteins as drug carriers [2-4], attempts to apply lipoprotein nanoparticles to carry nitric oxide and/or iron have not previ-ously been reported. The developed biocarriers showed an excellent bioavailability in vitro in model liver cells (HepG2) and macrophages (RAW 264.7) – representing two tissues in which both iron and nitric oxide metabolism play a crucial role.

This work was supported by the National Science Centre, Poland – grant No. 2012/07/D/ST4/02177.

R eferences[1]. Lewandowska, H., Kalinowska, M., Brzóska, K.,

Wójciuk, K., Wójciuk, G., & Kruszewski, M. (2011). Nitrosyl iron complexes—synthesis, structure and biol-ogy. Dalton Trans., 40, 8273-8289. DOI: 10.1039/C0DT01244K.

[2]. Chu, A.C., Tsang, S.Y., Lo, E.H., & Fung, K.P. (2001). Low density lipoprotein as a targeted carrier for doxo-rubicin in nude mice bearing human hepatoma HepG2 cells. Life Sci., 70 (5), 591-601.

[3]. Polo, L., Valduga, G., Jori, G., & Reddi, E. (2002). Low-density lipoprotein receptors in the uptake of tu-mour photosensitizers by human and rat transformed fi broblasts. Int. J. Biochem. Cell Biol., 34 (1), 10-23.

[4]. Huntosova, V., Buzova, D., Petrovajova, D., Kasak, P., Nadova, Z., Jancura, D., Sureau, F., & Miskovsky, P. (2012). Development of a new LDL-based trans-port system for hydrophobic/amphiphilic drug deliv-ery to cancer cells. Int. J. Pharm., 436 (1-2), 463-471. DOI: 10.1016/j.ijpharm.2012.07.005.

LABORATORY OF NUCLEAR LABORATORY OF NUCLEAR ANALYTICAL METHODSANALYTICAL METHODS

The research programme of the Laboratory of Nuclear Analytical Methods is focused on the development of nuclear and nuclear-related analytical methods for application in nuclear chemical engineering, radiobiological and environmental problems associated with the use of nuclear power and other specifi c fi elds of high technology. New procedures for the chemical analysis of various types of materials are also being developed. The main areas of activity of the Laboratory include inorganic trace analysis, and analytical and radiochemical separation methods. The Laboratory cooperates with the centres and laboratories of the INCT and pro-vides analytical services for them, as well as for other outside institutions. The Laboratory produces certifi ed reference materials (CRMs) for the purpose of inorganic trace analysis and provides profi ciency testing schemes on radionuclides and trace elements determination in food and environmental samples.

The main analytical techniques employed in the Laboratory include: 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, and gamma-ray spectrometry and alpha- and beta-ray counting.

In 2016, the Laboratory participated in the MODAS project from the National Centre for Research and Development (NCBR), Poland, being a member of the consortium of eight lead-ing Polish universities and scientifi c institutes. Within the scope of the MODAS project, the Laboratory was involved in the implementation of four new environmental CRMs certifi ed for the contents of trace elements in the practice of Polish and foreign analytical laboratories. The new CRMs are: Bottom Sediment (M-2 BotSed), Herring Tissue (M-3 HerTis), Cormorant Tissue (M-4 CormTis), and Cod Tissue (M-5 CodTis).

In 2016, the Laboratory of Nuclear Analytical Methods conducted a profi ciency test (PT) regarding the determination of Cs-137 and Sr-90 contents in waters and food samples. PT was provided at the request of the National Atomic Energy Agency (PAA), Poland. Eleven laboratories participated in the PT, including seven laboratories forming a radiation monitor-ing network in Poland (at the request of the PAA) and four other laboratories. The profi ciency testing scheme PLANTS has been provided in collaboration with the POLLAB-CHEM/EURACHEM-PL. Testing materials, namely a mix of powdered spices and herbs, were prepared to demonstrate the laboratories’ execution of determining the content of As, Cd, Cr, Cu, Fe, Hg, Mn, Mo, Pb, Se and Zn in food. In 2016, six laboratories partici-pated in the PT. The profi ciency tests were provided in accordance with the requirements of ISO/IEC 17043:2010, ISO 13528:2015 and the IUPAC International Harmonized Protocol (2006).

In 2016, the Food and Environmental Laboratory (FEL) was initiated within the Labora-tory of Nuclear Analytical Methods. The FEL provides services to municipal and private cus-tomers. The Laboratory specializes in the determination of radionuclides in waters and food-stuffs, as well as in environmental samples. Applied analysis methods have been approved by the State Sanitary Inspection.

70 LABORATORY OF NUCLEAR ANALYTICAL METHODS

MODIFICATION OF A POLYMER MONOLITHIC COLUMN WITH CROWN ETHER FOR SEQUENTIAL INJECTION CHROMATOGRAPHY

WITH ICP-MS DETECTIONKamila Kołacińska1/, Przemysław Koźmiński1/, Anna Bojanowska-Czajka1/, Marta Pyszynska1/,

Jakub Dudek1/, Ewelina Chajduk1/, Simona Prohazkova2/, Marek Trojanowicz1/

1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland2/ Comenius University, Faculty of Natural Sciences, Department of Analytical Chemistry, Bratislava,

Slovakia

An important developmental trend in the analysis of modern radioactivity is the mechanization and automation of analytical instrumentation, which is essential in multistep analytical procedures, which involve laborious separation and/or pre-concentration of analyte(s). Signifi cant attention in this aspect is focused on the development of fl ow analysis methods and instrumentation, also for the determination of radionuclides [1]. In the case of multicomponent analysis, a valuable vari-ant of fl ow methodologies is the so-called sequen-tial injection chromatography (SIC) [2]. A sche-matic diagram of a SIC system is shown in Fig. 1.

Generally, the SIC can be considered as a sim-plifi ed and less expensive system than high-perfor-mance liquid chromatography (HPLC) for liquid chromatography as it does not require a high-pres-sure pumping system. In this SIC system, high chromatographic effi ciency is provided by the use of monolithic columns or fused-core columns, in-stead of conventional packed columns with sta-tionary phase particles. Such low-pressure operat-ing systems exhibit the additional essential advan-tage of carrying out necessary sample processing operations in the mechanized mode, prior to the detection of analytes. For instance, it has been re-cently reported that in the SIC system, the priority pollutants were determined by exploiting an in--syringe dispersive liquid-liquid extraction, mono-lithic C18 column, and simultaneous UV detection at four wavelengths [4].

In chromatographic separation methods devel-oped for the determination of radionuclides, ex-traction chromatography plays a signifi cant role by using polymeric beads modifi ed with the fi lm

of the organic liquid phase which contains the ap-propriate extracting reagents. This technique was invented more than a half century ago [5], and very quickly found numerous routine applica-tions, described by Braun et al. [6]. In spite of huge progress in the development of separation methods in recent decades, extraction chromato-graphy methods are still commonly employed in analytical procedures for the separation and de-termination of numerous radionuclides for envi-ronmental and technological needs, as well as for food quality control. They are also employed in the development of radionuclide generator systems for nuclear medicine [7]. The advantage of such sorbents is the possibility of combining the selec-tivity of the liquid-liquid extraction system with a multistage chromatographic process. In the case of numerous commonly used extraction resins, the process of analyte distribution between the mobile phase and extractant, immobilized on an inert support, is associated with the conversion of a hydrated metal ion into a neutral, organophilic metal complex. A drawback of most extraction resins, especially in their applications in typical elution chromatography, is that the immobiliza-tion of an extractant on the support is a result of a purely physical entrapment, and not a chemical reaction. Hence, e.g. for commercially available Sr-resin® from Eichrom Technologies (USA), one can fi nd recommendations of reusing resin bed only once [8], or even to use a fresh resin bed for each sample [9]. This resin consists of 4,4’(5’)-di--t-butylcyclohexano 18-crown-6 (DBCC) in 1-oc-tanol (40%, this organic solution is loaded onto an inert chromatographic support). This ineffi -ciency can be due to both instability of two-phase sorption system and progressive contamination throughout the analysis of variable matrices of samples.

The properties of that resin in terms of its use in different confi gurations of fl ow analysis sys-tems for the determination of 90Sr or other radio-nuclides are being investigated by our research group. These studies are carried out by applying inductively coupled plasma-mass spectrometry (ICP-MS) detection, which is an especially favour-able technique in elemental isotopic analysis [10]. Because of its limited selectivity due to isobaric interferences, the past two decades brought a large number of works on measuring systems that combined ICP-MS with liquid chromatography systems, e.g., the application a system for the de-termination of fi ssion products and actinides in spent nuclear fuels [11, 12]. Several applications

Fig. 1. Scheme of the sequential injection chromatography system for use with different detectors (D) and with an optional pumping of reagent (- - -) for carrying out a post--column reaction [3].

71LABORATORY OF NUCLEAR ANALYTICAL METHODS

have also been reported for the determination of strontium isotopes [12-14]. In the aforemention-ed applications, the separation of analytes prior to ICP-MS detection was carried out using high--performance ion chromatography (HPIC).

The aim of the study reported herein was the application of Sr-resin in the isocratic chromato-graphy of Sr isotopes in the presence of other compounds in low-pressure liquid chromato-graphy with ICP-MS detection. The results of these studies can be potentially employed in the design of a SIC-ICP-MS setup for the analysis of radionuclide mixtures.

The experimental investigations were carried out with the following instrumentation. Flow measurements were performed with a commercial multisyringe system, equipped with a rotary multi-position valve lab-on-valve (MSFIA-LOV) from Crison Instruments (Bunyola, Spain). This setup consists of a multisyringe burette unit model BU4S, and is equipped with four 10 mL glass sy-ringes (Hamilton, Switzerland). The LOV was fab-ricated from methacrylate and incorporates 8 microchannels (1.5 mm I.D./16 mm length) dedi-cated to operation with the reagents. One of these microchannels functions as a sorbent microcol-umn (1.6 mm I.D./16 mm long) for preconcentra-tion and separation processes. The fl ow procedure was programmed and operated by the software AutoAnalysis 5.0 (Sciware, Spain). The ICP-MS instrument employed for off-line determinations was the Elan DRC II from Perkin Elmer (USA), which was equipped with a cross-fl ow nebulizer, Scott double-pass spray chamber, nickel cones, and with the ultrasonic nebulizer model U6000AT+. HPLC measurements were carried out with the Perkin Elmer Series 200 setup. The radiometric off-line measurements were carried out using the gamma spectrometer GENIE 2000 with an HPGe detector (Canberra Gamma Spectrometry, USA), whereas on-line gamma detection was carried out

with the laboratory-made fl ow spectrometer with Tl-doped NaI crystals (Institute of Nuclear Chem-istry and Technology, Poland).

Two examples of the application of isocratic chromatography using a column packed with Sr--resin, recorded in the HPLC-ICP-MS system, are shown in Fig. 2. In both cases, the deionized water was used as the eluent of the injected samples with a fl ow-rate of 1 mL/min. Parts A and B were both obtained by superimposing the individual chromatograms recorded for given m/z values. In similar measurements carried out using an HPLC system with an on-line pulse shape discrimination fl ow scintillation detector capable of analysing alpha- and beta-emitting radionuclides, the obtain-ed resolution of 90Y and 90Sr was much poorer [15]. In standard 90Sr solution, the content of 90Zr was below the limit of detection in the measure-ments, hence the absence of its signal in Fig. 2B.

As was expected from vast literature and our previous experiences, an important practical prob-

Fig. 2. Chromatograms recorded using the HPLC-ICP-MS system with a 1 mL Sr-resin column (5.0 mm I.D. and 50 mm length) for the separation of a mixture of Sr, Y and Zr (A), and a standard solution of 90Sr (B) with isocratic elution us-ing deionized water as the eluent. A – single isotope overlapped chromatograms recorded for m/z 88 (detection of 88Sr), 89 (detection of 89Y), and 90 (detection of 90Zr) from 50 L of an injected mixture containing 10 g/L each of Sr, Y and Zr. B – single isotope overlapped chromatograms recorded for m/z values from 84 to 90 for 50 l of a 90Sr standard solu-tion injected with an activity concentration 4.0 Bq/mL.

AB

Fig. 3. Breakthrough curves recorded in consecutive runs using columns with a 2 mL Sr-resin bed (100-150 m) by the gravitational fl ow of 0.5 mg/mL Sr solution in 3 M HNO3 solution. The Sr concentration was determined in each 1 mL fraction by ion chromatography. The retained Sr was eluted with 50 mM HNO3 and the column was re-generated with 3 M HNO3 solution between 1 to 4 con-secutive runs.


lem is the stability of the Sr-resin bed under the employed fl owing conditions. Breakthrough curves recorded in several consecutive measurements in preliminary studies for the characterization of Sr-resin indicated the deterioration of its chro-matographic effi ciency (Fig. 3). The column effi -ciency can be affected by several factors, includ-ing the mobile phase velocity, the stability of the liquid impregnating fi lm, the diffusion coeffi cients of analytes in the stationary and mobile phases, and the diameter of the support particles. Under fl owing conditions, the physical stability of the octanol layer on the hydrophobic particles can particularly be a crucial factor. In isocratic chro-matography, effi ciency deterioration is exhibited by a gradual decrease of the signal magnitude with multiple repetitions of measurements, which is de-monstrated by data shown in Fig. 4A.

In the chromatographic analysis of the mix-ture of Sr, Zr and Y at a content level of 10 g/L in the injected 50 l samples, a satisfactory repro-ducibility was obtained only in the fi rst two meas-urements. Additional confi rmation of such behav-iour was obtained in sequential injection analysis (SIA) measurements using Sr-resin for the sep-aration of Sr from other sample constituents in the fl ow system. As shown in Fig. 4B, for consecutive

repetitions of the three-stage analytical procedure, unfavourable changes were observed for the Sr eluted from the sorbent bed in the elution of in-terferences stage, and also in the last stage of the elution of retained Sr, which results in a signifi -cant drop of Sr determination recovery. Hence it was concluded that those properties might be im-proved by applying a different way to immobilize the Sr complexing ligand in the stationary phase.

The fi rst attempt at improving these properties utilized commercially available monolithic col-umns for the immobilization of the Sr-complex-ing ligand DBCC. The columns were invented in the early 1990s and are currently widely used in HPLC. Further, monolithic continuous beds are also employed in the sample pretreatment pro-cesses for the isolation and preconcentration of analytes [16, 17]. The most essential advantage of monolithic continuous beds is the possibility of their use in low-pressure systems with effi cient separation, which in some cases is evidently better than that obtained with sized particle-packed col-umns. This behaviour results from a much higher external porosity compared to particle-packed col-umns, which provides lower column backpressure, and allows for high fl ow rates. For reversed-phase separations, both silica-based monoliths and or-ganic polymer monoliths are commercially avail-able with different functional groups (C8, C18). The functionalization of monoliths can be carried out by the copolymerization of monomers con-taining the preferred monomers, or by post-poly-merization modifi cations using a variety of chemi-cal reactions. A simpler approach utilizes a dy-namic modifi cation of the monolithic polymer with appropriate components. While such a procedure is uncomplicated and inexpensive compared to the preparation of covalently bonded phases with particular functionalities, its success depends on careful optimization of the employed conditions, and primarily on the structure of the immobi-lized modifi er. Relatively often such methods are used for immobilization of chiral selectors for the chromatographic resolution of enantiomers, and successful stable modifi cations were reported for numerous selectors bearing hydrophobic chains on RP-18 monolithic columns, e.g. by pumping 0.025% of aqueous solution of the selector through the column [18]. The analytical litera-ture also provides examples of monolithic col-umns modifi cations for the chromatography of in-organic cations, including strontium. For instance, silica monolithic columns were chemically modi-fi ed with iminodiacetic acid following an earlier silanization step of the stationary phase [19]. The dynamic modifi cation with a 5% acetonitrile (ACN) solution of dioctylsulpho-succinate was employed for reversed-phase silica monolithic columns [20].

The functionalization of HPLC columns with different crown ethers is most often used to ob-tain a chiral resolution [21]. In one of pioneering works of this fi eld, the optical resolution of amine and amino ester salts was reported using dinaph-thyl substituted crown ether in the mobile phase compared to dinaphthyl substituted crown ether

Fig. 4. Illustration of the deterioration in the effi ciency of Sr-resin separation in chromatographic applications. A – Changes of the peak height for Sr in consecutive injec-tions of 50 L solution containing 10 g/L Sr, Zr and Y in 1 M HNO3 in HPLC-ICP-MS system. Conditions: 1 mL volume, column with 50-100 m Sr-resin beads, eluent – distilled water, fl ow rate – 1 mL/min. B – Changes of Sr recovery in determinations in SIA-LOV fl ow system with off-line ICP-MS detection using a Sr-resin microcolumn for the removal of interferences. Data were recorded for consecutive sorption/desorption processes for injections of 1.0 mL of 250 g/L Sr acidifi ed with 8 M HNO3, measured by recovery of Sr in injected solution after passing the sorbent bed (), in 1 mL 8 M solution of HNO3 used for the elution of interferences (), and in 10 mL deionized water used for the elution of retained Sr on Sr-resin micro-column ().

A

B


covalently attached to silica gel in the stationary phase [22]. Similarly, a successful dynamic coat-ing of reversed-phase C-18 column with crown ether was reported, which was made by pumping its methanol-water solution [23]. To achieve effec-tive coating, the ratio of methanol to water in the solution was decreased stepwise from 80 to 45%.

A similar modifi cation of reversed-phase mono-lithic columns with crown ether DBCC employed in commercial Sr-resin can be more diffi cult be-cause of the lack of structure of the long hydro-phobic alkyl chains, which are crucial for the suc-cessful and stable modifi cation of C18 stationary phase support [24]. The fi rst undertaken attempt was the modifi cation of a commercial monolithic column (Phenomenex Onyx™ Monolithic C18 Column 50 4.6 mm) with DBCC solution in 1-octanol, as it is employed for the fabrication of Sr-resin. In order to monitor the modifi cation progress, the complex with -emitting 85Sr was employed instead of pure ligand, which allows for radiometric gamma control of the retained crown ether at 514 keV. The 85Sr isotope was obtained by the irradiation of a solid sample of strontium salt in a nuclear reactor with a neutron stream of 1014 n·cm–2·s–1, cooling the activated sample for 7 days, and dissolution in 8 M HNO3. The 0.7 mL volume of aqueous solution of 85Sr was equili-brated overnight with a mixture of 0.47 g DBCC and 0.83 g octanol, and after complete separation (15 min at 30oC), the organic phase was used for the modifi cation of a column that was washed earlier with ACN. The modifi cation was carried out for 10 min with the fl ow rate 0.11 mL/min.

The effectiveness of monolith modifi cation with 85Sr-crown ether complex was examined by three different radiometric measurements. First, the gamma emission of octanol solution used for the modifi cation was examined, and it showed 5470 counts prior to the modifi cation and 40 counts after modifi cation, which evidently con-fi rms above 99% retention of the 85Sr complex. A similar test of off-line gamma spectrum was car-ried out for the monolithic column, and its results are shown in Fig. 5. Prior to the modifi cation, the number of counts at 514 keV was 8, whereas after modifi cation there were 740 counts, which also confi rms complex retention. The modifi ed col-

umn was then washed with 10 mL 8 M HNO3, and no measurable amount of 85Sr was detected in the eluate, however the complete elution of im-mobilized 85Sr was obtained in the fi rst two frac-tions of consecutive injections of 1 mL volumes of deionized water. This concluded the process of monolithic column modifi cation with DBCC li-gand.

For such a prepared monolithic column for ex-traction chromatography, the typical elution chro-matographic measurements were carried out using on-line gamma radiometric detection. Samples of a 400 L volume containing 85Sr in 1 or 3 M nitric acid were injected, followed by additional condi-tioning of the column with 1 mL of 1 or 3 M HNO3, and elution was carried out with deion-ized water at fl ow rate 0.2 mL/min. As is shown by the recorded chromatograms (Fig. 6), the con-centration of nitric acid in the injected sample in the range of 1 to 3 M does not affect the shape of

Fig. 5. Gamma spectra recorded off-line for the monolithic RP-18 column preconditioned with ACN: A – prior to its modifi cation with the octanol solution of DBCC complex with 85Sr, and B – after column modifi cation at a complex solution fl ow rate 0.11 mL/min. Signal characteristic for 85Sr at 514 keV.

A

B

Fig. 6. Chromatograms recorded for a monolithic RP-18 column modifi ed with DBCC in 1-octanol with -radiometric detection. The column was preconditioned by washing with 1 mL of 1 M (A) or 3 M (B) nitric acid solution. The column was then injected with 400 L 85Sr solution in 1 M (A) or 3 M (B) nitric acid, followed by injection of 1 mL of 1 M (A) or 3 M (B) nitric acid solution, and eluted with deionized water at fl ow rate 0.2 mL/min.


chromatographic peaks. The chromatographic ef-fi ciency for the Sr peak of the obtained modifi ed monolithic column for Sr determination (Fig. 6A) was compared with that of a column packed with Sr-resin (Fig. 2A), by evaluation of the theoreti-cal plate number, which was calculated according to the following commonly used formula:

N = 5.54 (tR/W1/2)2 where: tR – retention time, W1/2 – width of the peak in a half of its height. The value obtained for the modifi ed monolithic column (16 800 N·m–1), compared to that for the Sr-resin column (8970 N·m–1), shows an evident increase in the chroma-tographic effi ciency for the modifi ed monolithic column.

The prepared new stationary phase for extrac-tion chromatography, which employs silica mono-lith functionalized with C18 groups, in compari-son to commercial particle-based sorbent, results in an improvement of chromatographic effi ciency and stability of the extraction system. It also al-lows for the employment of modifi ed commercial monolithic columns in low-pressure SIC systems, which can carry out on-line sample processing for the isolation and/or preconcentration of analytes in addition to standard chromatographic separa-tion. Further improvement of the functional prop-erties of such systems can be expected with cova-lent attachment of affi nity ligands (e.g. DBCC) directly to the surface of the monolithic phase, or to the surface of the monolith after its modifi ca-tion with the appropriate nanoparticles, which has already been employed for different chroma-tographic applications [25].

References[1]. Kołacińska, K., & Trojanowicz, M. (2014). Applica-

tion of fl ow analysis in determination of selected radionuclides. Talanta, 125, 131-145.

[2]. Chocholous, P., Solich, P., & Satinsky, D. (2007). An overview of sequential injection chromatography. Anal. Chim. Acta, 600, 129-135.

[3]. Lähdesmäki, I., Chocholous, P., & Ruzicka, J. (2016), Sequential injection chromatrography. In Flow in-jection analysis. 2016 Edition. Tutorial & news on fl ow based micro analytical techniques. Retrieved December 28, 2016, from www.fl owinjectiontutori-al.com/Methods 4.0 SI Chromatography.html.

[4]. Gonzalez, A., Avivar, J., & Cerda, V. (2015). Determi-nation of priority phenolic pollutants exploiting an in-syringe dispersive liquid-liquid microextraction--multisyringe chromatography system. Anal. Bioanal. Chem., 407, 2013-2022.

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[6]. Braun, T., & Ghersini, G. (Eds.). (1975). Extraction chromatography. Amsterdam: Elsevier Publishing, 566 p.

[7]. Dietz, M.L., & Horwitz, E.P. (2000). Applications of extraction chromatography in the development of radionuclide generator systems for nuclear medicine. Ind. Eng. Chem. Res., 39, 3181-3188.

[8]. Kocadag, M., Musilek, A., & Steinhauser, G. (2013). On the interference of 210Pb in the determination of 90Sr using strontium specifi c resin. Nucl. Technol. Radiat. Protec., 28, 163-168.

[9]. Wall, A.J., Capo, R.C., Stewart, B.W., Phan, T.T., Jain, J.C., Hakala, J.A., & Guthrie, G.D. (2013). High throughput method for Sr extraction from variable matrix waters and Sr-87/Sr-86 isotope analysis by MC-ICP-MS. J. Anal. At. Spectrom., 28, 1338-1344.

[10]. Vanhaecke, F., & Degryse, P. (Eds.). (2012). Isotopic analysis. Fundamentals and applications using ICP-MS. Weinheim: Wiley-VCH, 529 p.

[11]. Alonso, J.I.G., Sena, F., Arbore, P., Betti, M., & Koch, L. (1995). Determination of fi ssion products and ac-tinides in spent nuclear fuels by isotope dilution ion chromatography inductively coupled plasma mass spectrometry. J. Anal. At. Spectrom., 10, 381-393.

[12]. Betti, M. (1997). Use of ion chromatography for the determination of fi ssion products and actinides in nuclear applications. J. Chromatogr. A, 789, 369-379.

[13]. Gracica-Ruiz, S., Moldovan, M., & Alonso, J.I.G. (2007). Large volume injection in ion chromato-graphy. Separation of rubidium and strontium for on-line inductively coupled plasma mass spectro-metry determination of strontium isotope ratios. J. Chromatogr. A, 1149, 274-281.

[14]. Plausinaitis, D., Naujalis, E., Prokopchik, A., & Bu-dreika, A. (2014). Method for detection of Cs and Sr isotopes avoiding interferences of Ba and Rb in ra-dioactive samples using ion chromatography coupled with ICP-MS. Curr. Anal. Chem., 10, 140-148.

[15]. Fjeld, R.A., DeVol, T.A., Leyba, J.D., & Paulenova, A. (2005). Measurement of radionuclides using ion chromatography and on-line radiation detection. J. Radioanal. Nucl. Chem., 263, 635-640.

[16]. Arrua, R.D., Causon, T.J., & Hilder, E.F. (2012). Re-cent developments and future possibilities in sep-aration science. Analyst, 137, 5179-5189.

[17]. Jandera, P. (2013). Advances in the development of organic polymer monolithic columns and their ap-plications in food analysis – A review. J. Chromatogr. A, 1313, 37-53.

[18]. Schmid, M.G., Schreiner, K., Reisinger, D., & Gübitz, G. (2006). Fast chiral separation by ligand-exchange HPLC using a dynamically coated monolithic col-umn. J. Sep. Sci., 29, 1470-1475.

[19]. Nesterenko, E.P., Nesterenko, P.N., Paull, B., Melen-dez, M., & Corredor, J.E. (2013). Fast direct determi-nation of strontium in seawater using high-perfor-mance chelation ion chromatography. Microchem. J., 111, 8-15.

[20]. Connolly, D., Victory, D., & Paull, B. (2004). Rapid, low pressure, and simultaneous ion chromatography of common inorganic anions and cations on short permanently coated monolithic columns. J. Sep. Sci., 27, 912-920.

[21]. Hyun, M.H. (2003). Characterization of liquid chro-matographic chiral separation on chiral crown ether stationary phases. J. Sep. Sci., 26, 242-250.

[22]. Sousa, L.R., Sogah, G.D.Y., Hoffman, D.H., & Cram, D.J. (1978). Host-guest complexation. 12. Total op-tical resolution of amine and amino ester salts by chromatography. J. Am. Chem. Soc., 100, 4569-4576.

[23]. Shinbo, T., Yamaguchi, T., Nishimura, K., & Sugiura, M. (1987). Chromatographic separation of racemic amino acids by use of chiral crown ether-coated reversed-phase packings. J. Chromatogr. A., 405, 145-153.

[24]. Shinbo, T., Yamaguchi, T., Yanagishita, H., Kitamoto, D., Sakaki, K., & Sugiura, M. (1992). Improved crown ether-based chiral stationary phase. J. Chromatogr. A, 625, 101-108.

[25]. Tang, S., Guo, Y., Xiong, C., Liu, S., Liu, X., & Jiang, S. (2014). Nanoparticle-based monoliths for chro-matographic separations. Analyst, 139, 4103-4117.


POSSIBILITY OF USING MODIFIED GRAPHENE O XIDE WITH MnO2 IN NEUTRON ACTIVATION ANALYSIS

AND INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRYEwelina Chajduk1/, Paweł Kalbarczyk1/, Halina Polkowska-Motrenko1/, Leszek Stobiński2/,

Ewelina Miśta3/

1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland2/ Warsaw University of Technology, Faculty of Chemical and Process Engineering,

Graphene Laboratory, Warszawa, Poland3/ National Centre for Nuclear Research, Otwock-Świerk, Poland

The discovery of graphene has caused a revolu-tion in the analytical community. However, the practical applications of graphene were greatly hampered by its preparation and dispersity in sol-vents. In comparison to graphene, graphene oxide (GO) has two important characteristics: (i) it can be produced by cost-effective chemical methods, and (ii) it is highly hydrophilic and can form stable aqueous colloids to facilitate the assembly of macroscopic structures by simple and cheap solution processes. Furthermore, GO has abun-dant oxygen-containing functional groups, such as hydroxyl, epoxy, carbonyl and carboxyl groups, which make it a good candidate for use in polymer composites, energy-related materials, sensors and “paper-like” materials (free-standing carbon-based membrane materials). The functionalization of GO using various chemical reactions allows for either covalent or non-covalent attachment to the result-ing chemically modifi ed GO. Such approaches, which add functionality to groups already present on the GO surfaces, make GO a more versatile precursor for a wide range of applications [1].

In this work, the possibility of using of gra-phene oxide modifi ed with MnO2 was examined. Sorbent GO-MnO2 was prepared by the Graphene Laboratory of the Warsaw University of Technol-ogy. The obtained material used in all experiments has the following parameters: 5% MnO2 in 0.5% GO in water solution. The synthesized MnO2-mo-difi ed graphene oxide was characterized by scan-ning electron microscopy (SEM). The morphol-ogy and microstructure of GO and the prepared GO-MnO2 nanocomposite are presented in Fig. 1. The elemental information of the graphene oxide and prepared sorbent was analysed by the energy-

-dispersive X-ray (EDX) spectroscopy; the obtain-ed results are presented in Table 1. As shown in Fig. 2, the EDX spectrum of the GO-MnO2 nano-composite shows the presence of C, O and Mn, indicating successful formation of the nanocom-posite with rather poor purity (the presence of Mg, Zn and Cl were also observed).

In order to fi nd potential separation possibil-ities of the prepared sorbent, its extraction behav-iour was investigated with a batch equilibration technique utilizing either radioactive tracers or multielemental standards in dependence on pH

Fig. 1. SEM image of GO (A) and GO-MnO2 (B).

BA

Table 1. Elemental composition of GO and GO-MnO2 in normalized atomic percentage content.

ElementNormalized atomic percentage content

GO GO-MnO2

C 48.95 39.18

O 48.45 49.91

S 0.69 0.45

Si 0.79 1.11

Ca 0.30 1.83

Na 0.38 2.44

K 0.17 0.60

Al 0.09 0.12

Mg 0.18 0.60

Mn 1.49

Cl 1.99

Zn 0.25

Ti 0.03


at room temperature. Known amounts of resin (ca. 1.2 mg) were brought in contact (for 24 h with occasional shaking) with 10 mL of a solu-

tion of appropriate composition, containing equal volumes (10-100 L) of radioactive tracers/multi-

elemental standards. After 24 h, the sorbent was fi ltered off and the individual tracer concentra-tion was determined in an aliquot of the solution by gamma-ray spectrometry/inductively coupled plasma-mass spectrometry (ICP-MS) and compar-ed with that of standard solution (without the resin). The percentages of retained amounts of total concentration are presented in Figs. 3-5. As can be seen, the sorption of individual elements strongly depends on the pH. In acidic solution, few elements show affi nity towards the prepared sorbent, including 233Pa, Au, Mo, Ni. Alkali metals are not retained on the resin under any pH condi-tions. From the obtained data, it seems to be that the prepared sorbent is appropriate for the selec-

tive separation of 233Pa and some noble metals. The dependence on the ionic strange was also

Fig. 2. EXD spectra of GO and GO-MnO2 sorbents.

Fig. 3. Percentage of adsorbed elements: Be, Cd, Co, Cr, Cu, Mo, Ni, Pb, Sr, Ti, Tl, V and Zn, in dependence of pH.

GOGO-MnO2

Inte

nsity

, cps

/a.u

.

Energy [keV]

Fig. 4. Percentage of adsorbed noble metals in dependence of pH.


checked and no infl uence on the sorption behav-iour was observed.

The obtained results have been verifi ed by col-umn experiments. Due to the small dimensions of nanoparticles, there are great diffi culties with col-umn preparation. The intermediate solution used in this work employed a 30 mm syringe fi lter with a pore size of 0.45 m to maintain the sorbent (ca. 2 mg). This method of operation is suffi cient – the dynamics of sorption on GO-MnO2 is very fast – after 5 min of contact between the aqueous phase and the sorbent, the maximum sorption has been achieved.

Thorium is an important alloying agent in mag-nesium, as it imparts greater strength and creep resistance at high temperatures. Thorium oxide is used as an industrial catalyst, and thorium itself can also be used as a source of nuclear power. Thorium is about three times as abundant as uranium and about as abundant as lead, however there is likely more energy available from thorium than from both uranium and fossil fuels. India and China are in the process of developing nu-clear power plants with thorium reactors, but this is still a very new technology. Thorium dioxide was formerly added to glass during manufacture to increase the refractive index, thus producing thoriated glass for use in high-quality camera lenses [2].

In the case of 233Pa (formed in nuclear reactors during the 232Th(n, )233Pa reaction), the mixture of radiotracers in H2O, acidifi ed with HNO3 to pH 1.5, was introduced on the fi lter with GO-MnO2. Next, 5 mL of 8 M HNO3 were passed through the column. Finally, adsorbed protactinium was recovered from the resin by eluting with 5 mL of concentrated H2O2 and the percentage of protac-tinium recovery was ca. 75%.

For the determination of radium in environ-mental samples, radiochemical procedures are typi-cally used, however these procedures are time--consuming. 226Ra emits mostly alpha radiation (E = 4.78 MeV), and gamma radiation (E = 186 keV) with a low abundance what limits the use of gamma-ray spectrometry without processing the sample. In the case of 226Ra, resins with MnO2 are used for its preconcentration [3]. Previous work of the Laboratory has shown that using commer-cially available MnO2 Resin (Eichrom) to the pre-concentration of 226Ra prior to analysis by ICP-MS is not possible. Eluents used for the recovery of retained radium (H2O2 and HCl mixture) also washed out manganese, which has a concentra-tion too high to determine Ra-226 in the eluted solution by ICP-MS. In this case, 226Ra can be ad-sorbed in solutions with a pH greater than 8 and removed from the sorbent using acidic solutions without destruction of its structure.

The preliminary results of work on the use of the GO-MnO2 sorbent in the NAA (neutron acti-vation analysis) and ICP-MS has been described. Further work will seek to optimize the separa-tion/preconcetration procedures and the analy sis of certifi ed reference materials.

References[1]. Yu, S., Wang, X., Tan, X., & Wang, X. (2015). Sorp-

tion of radionuclides from aqueous systems onto gra-phene oxide-based materials: a review. Inorg. Chem. Front., 2, 593-612.

[2]. Royal Society of Chemistry. (2016). Periodic Table – thorium. Retrieved December 28, 2016, from http://www.rsc.org/periodic-table/element/90/thorium.

[3]. Eichrom Technologies LLC. (2016). MnO2 Resin: An-other tool for radium separation & measurement. Retrieved December 28, 2016, from http://www.ei-chrom.com/products/info/mno2_resin.aspx.

Fig. 5. Percentage of adsorbed lanthanides, Sc, Y and Th, in dependence of pH.

LABORATORY LABORATORY OF MATERIAL RESEARCHOF MATERIAL RESEARCH

The activities of the Laboratory are concentrated on:• studies of coordination polymers built of s block metals and azine carboxylate ligands,• synthesis of nanoscale porous metal organic framework (nanoMOF) materials, • synthesis of functional materials – silver-modifi ed cotton and cellulose fibres using radia-

tion beam techniques,• improvement of the usable surface properties of special materials applied in nuclear energy

technologies (zirconium alloys, steels) using high intensity pulsed plasma beams (HIPPB),• characterization of art objects.

Porous coordination polymers, also called metal organic framework materials, have be-come a topical subject in recent years. They exhibit unique pore architecture and a broad range of potential applications. The latter include greenhouse gas removal, storage of gases and the selective separation of components of gaseous mixtures that are of interest for the development of modern energy technologies. In the case of MOFs, the pores’ structure and the host-guest molecules’ interaction can be tailored relatively easily for a potential applica-tion by carefully combining the ligand and the type of metal ion. At present, many potential applications of MOFs require them to be obtained at a nanometre scale. Nanoscopic dimen-sions are essential to provide MOFs with high surface areas, and for tuning their properties (catalytic, separation, sensing and sorption). One application requiring such dimensions is mixed matrix membrane synthesis, where MOF’s particles are used as fi llers in a polymer matrix. Others include MOFs with size-dependent properties (optical, electrical and mag-netic) and biocompatible materials for biomedical applications, e.g. encapsulation and trans-port of drugs. The integration of nanoscale MOFs onto porous supports would be advanta-geous for creating thin layer membranes. Studies performed recently in the Laboratory of Material Research concerning the synthesis of nanoscale MOFs are reported. The applied methods include template synthesis in the pores of track-etched membranes with well-de-fi ned cylindrical pores, synthesis in microfl uidic fl ow reactors and the synthesis of MOFs on the surface of porous alumina substrates and also on composites with graphene oxide.

Zirconium, due to its good water corrosion and radiation resistance at the normal working conditions of nuclear reactors, is commonly used as cladding material for fuel elements. However, in the case of LOCA (loss-of-coolant accident) conditions, the possible extremely fast oxidation of zirconium in a steam atmosphere, or in an air/steam mixture, at tempera-tures above 800oC results in intense hydrogen generation and a possible hydrogen-oxygen mixture explosion. These events, despite being very rare, negatively infl uence the public ac-ceptance for nuclear energy and result in high restoration costs for the accompanying dam-ages. The development of methods to minimize the risk in the case of design-basis and be-yond design-basis accidents is urgently needed. Materials with enhanced tolerance to high temperature oxidation have already been proposed for this purpose, such as silicon carbide, Mo-Zr, FeCrAl claddings, MAX phases and multilayer zirconium silicide coatings.

Zirconium silicide or zirconium silicate coatings are known for good resistance in high--temperature conditions and for that reason have been considered for application as environ-mental barrier coatings for high-temperature gas-turbine components. Up to now, their ap-plication as corrosion protective coatings for nuclear fuel pellets has been less explored. However, a review of the existing literature and an analysis of thermodynamic data indicate that silicon-based coatings may offer excellent prospects in this fi eld. In particular, they may provide a more protective barrier than the native ZrO2 fi lms formed on alloy cladding during routine nuclear reactor operation. Our work in the last year has focused on the development of silicon-based coatings on zirconium alloys claddings and the evaluation of their properties

during accident scenarios, as well as during the regular operation of reactors. Two processes have been considered for coating preparation. The fi rst one is based on the deposition of layers containing zirconium oxide and silicon oxide onto zirconium alloys tubes (and also onto fl at samples), followed by densifi cation of the deposited layers. The second one is based on the deposition of gradient layers of zirconium and silicon (and also possibly their oxides) by the physical vapour deposition (PVD) method.For the deposition of coatings precursors, three methods have been proposed: a dip coating method using mixed zirconium oxide and silicon oxide sols prepared by the sol-gel method, plasma electrolytic oxidation in silicate containing solutions, and electrophoretic deposition from zirconium oxide and silicon oxide containing suspensions, or directly from ZrSiO4 sus-pension.For the densifi cation of the prepared porous layers, the unique technique of high intensity pulsed plasma beams will be applied or, alternatively, electron beams operating in scanning mode. For modifi cation of the surface layer of zirconium, the tungsten inert gas (TIG) weld-ing method was used.

For the examination, characterization and analysis of cultural heritage artefacts or art objects and their component materials, a conservation scientist needs a palette of non-de-structive and non-invasive techniques, in order to improve our knowledge concerning their elaboration, their evolution and degradation during time, and to give a basis for their restora-tion and conservation. Among various methods used for the examination of art objects, nu-clear techniques are crucial due to their high sensitivity and reproducibility.

The objective of the current work was to research the history of mediaeval coinage in Poland during the reign of Władysław Jagiełło. The objects of the study were silver coins con-stituting an important element of the preserved heritage from the era of the multinational Polish Republic. The objective was to obtain information about the source of the raw materials and methods of their production. In total, 181 Władysław Jagiełło crown half-groschen were examined originating from the “Łódź” and “Biela” treasures. In addition, 15 Prague groschen were tested as reference: four coins minted during the reign of Carl I and 11 coins from that of Vaclav IV. The coins covered by our study originated from different archaeological fi nds made at different times, and had been hidden for different lengths of time. They displayed different states of advanced corrosion within each treasure, or even within individual coins. To sum up, it should be noted that the current study was the fi rst multidisciplinary research project on this scale concerning mediaeval coins performed in Poland. This vast body of ex-perimental material enabled the development of a database, which represents a signifi cant achievement and will facilitate continued work on coins from the relevant period.

The investigation into the chemical composition and manufacturing technology of his-torical glass was continued in 2016. Studies on historical glasses covered several issues, such as the structure and technology of early 20th century red stained glass, the chemical compo-sition of early-modern Dutch glass, the origin and technology of mediaeval stained glass, as well as the chemical composition, technology and durability of early-modern vessel glass. Within this last topic, almost 200 objects were analysed with the use of X-ray fl uorescence (XRF) in cooperation with the Corning Museum of Glass, NY, USA.

81LABORATORY OF MATERIAL RESEARCH

THE MODIFICATION OF ZIRCONIUM ALLOY SURFACE LAYER BY TIG METHODS

Wojciech Starosta1/, Marek Barlak2/, Paweł Kołodziejczak3/

1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland 2/ National Centre for Nuclear Research, Otwock-Świerk, Poland

3/ Warsaw University of Technology, Faculty of Production Engineering, Institute of Manufacturing Technologies, Warszawa, Poland

Zirconium alloys are widely applied in nuclear technologies. Long, cylindrical thin-walled tubes made of zirconium alloys are used in water reac-tors, where they serve as claddings for nuclear fuels. They play a very important role in enabling the hermetic enclosure of the nuclear fuel pellets loaded inside, and preventing nuclear fi ssion frag-ments escaping from the fuel into the coolant and contaminating it.

Zirconium alloys have been selected for use in nuclear reactors due to their unique properties, such as low thermal neutron absorption, suffi cient-ly good corrosion resistance in a high temperature water environment and suffi ciently good stability of their mechanical properties under the infl u-ence of neutron irradiation. At the regular operat-ing parameters of light water reactors (360oC, 195 bar), zirconium claddings slowly oxidize as a re-sult of their chemical interaction with cooling water. At high levels of oxidation, exceeding the permitted value of 16%, the nuclear fuels elements should be replaced.

Unfortunately, zirconium’s lack of resistance to high temperature oxidation in steam, or in a steam and hydrogen atmosphere, is completely unsatis-factory. Such conditions are expected in the case of nuclear accidents related to the abrupt interrupt of the main reactor cooling loop (loss-of-coolant accident, LOCA). At higher temperatures (exceed-ing 800oC), the rate of the zirconium oxidation reaction greatly increases, leading to the complete oxidation of the cladding within a short time and to the generation of a large volume of hydrogen generated from water decomposition. The accu-mulation of hydrogen is dangerous, due to the possibility of a chemical explosion of the oxygen--hydrogen mixture. Such events, although rare, negatively infl uence public acceptance of the de-velopment of nuclear energy. Moreover, the costs of the removal of the damaged reactor core and the restoration of the accompanying damage to the environment are extremely large.

Since the last nuclear accident in Japan (Fuku-shima 2014), research efforts in many nuclear re-search centres over the world have been directed at the development of alternatives to zirconium alloy-based claddings that offer much higher re-sistance to the severe conditions found during a LOCA. The concept of accident tolerant fuels (ATF) has been elaborated for this purpose, con-sisting of the development of materials resistant to high temperature oxidation in a water vapour (and a water vapour and hydrogen) environment [1-3]. The most revolutionary one consists in re-placing zirconium alloys with silicon carbide.

Others, which are feasible for implementation within a short time perspective, consist of the deposition of an external coating onto traditional zirconium alloy claddings. Such coatings should be made of material able to develop a protective layer in a high temperature water vapour environ-ment. Possible candidates include MAX ceramics, zirconium silicide or zirconium silicate. Both zir-conium silicide and zirconium silicate coatings are known for good oxidation resistance in high temperature conditions. A review of the existing literature and analysis of thermodynamic data in-dicate that zirconium silicide coatings may offer excellent prospects in this fi eld. In particular, they may provide a more protective barrier than the native ZrO2 fi lms formed on alloy cladding during routine nuclear plant operations, and provide an exceptional protective barrier during high tem-perature accident scenarios. The phase diagram for the zirconium-silicon system clearly shows the existence of intermetallic compounds with differ-ent Zr/Si ratios and stability regions. For example, ZrSi2 is stable up to 1620oC and ZrSi is stable up to 2210oC, etc. The stable temperature range for zircon (ZrSiO4) extends to 1673oC, where it thermally decomposes by a solid state reaction giving ZrO2 and SiO2. Both, Zr and Si readily form their respective oxides at high temperatures, and surface layers of ZrO2, SiO2 or even ZrSiO4 may form, depending on the stoichiometry of the Zr-silicide. Assuming that ZrO2 were formed above the Zr-silicide, the zirconium activity in the sili-cide would be reduced, favouring the oxidation of silicon to SiO2 under the ZrO2 layer. This inner layer of SiO2 can serve as a barrier layer to oxygen and moisture transport. The glassy properties of SiO2 at elevated temperatures can accommodate stresses from crystallographic transformations of the outer ZrO2 layer and incipiently seal any cracks that may form. Thus, in a high temperature oxi-dizing environment, multiple intermetallic com-pound layers can form with ZrO2 or SiO2 sand-wiched layers, in effect evolving naturally into a compositionally and functionally graded multi-layered system that is expected to provide the necessary protection under accident conditions.

We will summarize here the results of our re-cent research on silicon-based coating deposition using the tungsten inert gas (TIG) method.

Zirconium alloy samples with the composi-tion Zr – 98.29%, Sn – 0.26%, Fe – 0.21% and Hf – 1.01%, in the form of sheets with dimensions 20 mm 20 mm and a thickness of 1 mm were utilized. The samples were coated with a ZrSiO4 suspension (Zirconium S, PPH Kratos, Poland),

82 LABORATORY OF MATERIAL RESEARCH

or a suspension of Si powder in a 10% PVA (poly-vinyl alcohol) aqueous solution, applied by dip coating method. The thickness of the coating layer was up to about 60 m. The coated samples were remelted by the TIG method. The scheme of the TIG device is shown in Fig. 1.

Tungsten inert gas welding is an arc welding process that uses a non-consumable tungsten electrode. The weld area is protected from atmos-pheric contamination by an inert shielding gas. A constant current welding power supply produces electrical energy, which is conducted across the arc through a column of highly ionized gas and metal vapour plasma. The remelting process pa-rameters were as follows: electrode made from tungsten doped with thorium, angle – 40o; argon as the protective gas with 10 l/min fl ow; current in the range of 20-90 A; and an electrode feed in the range of 20-40 mm/min.

Samples of the initial and modifi ed materials were characterized using scanning electron micro-scopy – SEM (DSM 942 and EVO MA10, Zeiss,

Fig. 3. The general view of the surface of zirconium alloy samples coated with Zirconium S suspension and TIG treated at different currents. In the case of the 90 A cur-rent, cracks were observed (marked with arrows).

Fig. 2. The general view of the surface of zirconium alloy samples coated with ZrSiO4 (Zirconium S) suspension and TIG treated with currents of 70, 80 and 90 A.

Fig. 1. The scheme of the TIG welding process: 1 – tung-sten electrode, 2 – plasma gas, 3 – protective gas, 4 – powder suspension, 5 – plasma arc, 6 – coating, 7 – remelted base material.

2

31

5

6

7

4

–

+


Fig. 5. Scanning maps of zirconium and silicon distribu-tion on the surface of the modifi ed sample.

Fig. 4. Distribution of silicon content on the surfaces and on cross sections of modifi ed samples obtained at different magnifi cations – 1000 and 5000.

Germany), energy-dispersive X-ray spectrometry – EDS (Quantax 400, Bruker, Germany) and X-ray diffraction – XRD (Advance D8 diffractometer, Bruker, Germany). Microscopic observations were carried out for surface and an etched cross sec-tions with etchant composition of 10% HF + 65% HNO3 + H2O.

The general view of the surface coated with zirconium silicate (Zirconium S) and TIG remelt-ed with currents of 70, 80 and 90 A is shown in Fig. 2. The surface was shiny and continuous, without defects such as bubbles, voids or cracks.

In Fig. 3, SEM photos of the surface of raw and modifi ed samples made at different magnifi -cations are shown. In the case of the modifi ed samples, the SEM photos confi rm the remelting of the surface layer. The modifi ed surfaces were relatively smooth. However, at the highest cur-rent value, equal to 90 A, cracks were observed (marked with arrows).

The results for the silicon content on the sur-face and on cross sections of modifi ed samples taken at their central regions are shown in Fig. 4. No direct correlation between the silicon content and the current applied for the sample treatment was found. The observed discrepancies between the values of silicon content obtained under dif-ferent magnifi cations suggest an uneven silicon distribution.

Further studies of the distribution of zirconium and silicon on the surface of the sample (Fig. 5), and along the line crossing the boundary between the modifi ed and unmodifi ed regions (Fig. 6), re-vealed the peculiar distribution of silicon in the form of one-dimensional bands.

The results of the elements’ content distribu-tion are shown for a current of 30 A. However, the results for other currents were similar.

The XRD spectra for the samples coated with ZrSiO4 suspension (Zirconium S) showed the presence of refl ections for monoclinic zirconium oxide and zirconium alloy phases only. No silicon containing phases were found. However, in the case of samples coated with silicon powder sus-pended in PVA water solution and TIG treated, the presence of a zirconium silicide phase, ZrSi2, was revealed after treatment. The related XRD spectrum is shown in Fig. 7.

Fig. 6. The distribution of zirconium and silicon content along the line crossing the unmodifi ed (A) and modifi ed regions (B). The decrease in zirconium and increase in silicon content are clearly seen at the points marked by arrows.

A

B


COATINGS BASED ON SILICON COMPOUNDS ON ZIRCONIUM ALLOYS FOR HIGH TEMPERATURE CORROSION RESISTANCE IMPROVEMENT

Bożena Sartowska, Magdalena Miłkowska, Wojciech Starosta

Zirconium and zirconium alloys are commonly used as cladding material for fuel elements, due to their good water corrosion and radiation resist-ance at the normal working conditions of nuclear reactors. The concept of accident tolerant fuels (ATF) and accident tolerant materials (ATM), de-signating materials with increased accident toler-ance, has been developed recently [1, 2]. Notably, the zirconium silicide or zirconium silicate coat-ings are known for their good resistance in high temperature conditions. Thus, the aim of the cur-rent research was to identify the possibility of ex-tending the lifetime of zirconium claddings and

decreasing the hydrogen gas generation by apply-ing a zirconium silicide or/and zirconium silicate coating on zirconium claddings.

The sol-gel process is an effi cient method for obtaining a wide variety of ceramic materials such as monoliths, powders, fi bres, and thin fi lms [3-5]. Reports on the sol-gel coatings for corrosion pro-tection, which are an alternative to conventional highly toxic chromate coatings, are known [6, 7]. Mixed-metal oxide systems are of special interest for fabricating materials with properties that dif-fer from the corresponding independent material components. In recent years, SiO2-ZrO2 mixed

The following conclusions can be drawn:• The TIG treatment seems to be a simple, fast

and cheap method for the modifi cation of the material surface layer.

• The current value applied should be low enough to avoid the creation of cracks in the course of modifi cation or during corrosion tests in auto-claves. In the case of zirconium samples, the optimal value was determined to be 30 A.

• Silicon distribution studies show that silicon was introduced to a depth of up to 200 m. Due to such long range silicon redistribution, its concentration near the surface layer may be insuffi cient to provide the required corrosion protection of the zirconium alloy. Also, the pe-culiar silicon distribution in the form of bands seems to be unfavourable. Despite this, the for-mation of a zirconium disilicide phase has been observed after TIG treatment of silicon powder suspension deposited on zirconium alloy.These unfavourable tendencies may probably

be overcome by better selection of treatment con-

Fig.7. The result of Rietveld refi nement of XRD spectrum of the TIG treated zirconium alloy sample coated with silicon powder suspended in water PVA solutions, showing the presence of a synthesized zirconium silicide phase.

ditions, e.g. working in the pulsed current mode, and by proper selection of the heat source scan velocity.

References[1]. Zinkle, S.J., Terrani, K.A., Gehin, J.C., Ott, L.J., &

Snead, L.L. (2014). Accident tolerant fuels for LWRs: A perspective. J. Nucl. Mater., 448 (1-3), 374-379. DOI: 10.1016/j.jnucmat.2013.12.005.

[2]. Mariani, R.D., Medvedev, P., Porter, D.L., Hayes, S.L., Cole, J.I., & Bai, X.M. (2013). Novel accident-toler-ant fuel meat and cladding. LWR Fuel Performance Meeting TopFuel 2013, Charlotte, NC, USA, 15-19 September 2013. Retrieved December 28, 2016, from https://inldigitallibrary.inl.gov/sites/sti/sti/5868391.pdf.

[3]. AREVA Federal Services, LLC. (2015). Phase 1A fi nal report for the AREVA Team enhanced accident toler-ant fuels concepts. Retrieved December 28, 2016, from https://www.osti.gov/scitech/servlets/purl/1172983.


Fig. 2. Synthesis diagram of the preparation of silica-zirconia fi lms and powders.

oxides have attracted a great deal of attention for their physicochemical properties such as hardness, chemical resistance in basic conditions, and re-sistance to wear [8-10], as well as regarding the use of these fi lms as corrosion protective coatings for nuclear pellets.

For investigation zirconium alloy with the ele-mental composition: Zr – 98.29 wt%, Sn – 0.26 wt%, Fe – 0.21 wt%, Hf – 1.01 wt% (Firmetal, China), in the form of the fl at sheet with a thick-ness of 1 mm was employed. Silica and silica--zirconia fi lms were prepared by the sol-gel pro-cess using 99% tetraethylorthosilicate (TEOS; Si(OC2H5)4, produced by Aldrich) and zirconyl nitrate hydrate (ZrO(NO3)2·x H2O, produced by Aldrich) as precursors. Coatings were prepared by dipping into various sols which were prepared with different elemental composition and viscos-ity. The SiO2 sols were prepared according to the

procedures shown in Fig. 1. Obtained sols were deposited by dip coating over zirconium sub-strates. The fi lms were aged at RT for 24 h or were dried at 120oC for 24 h. SiO2-ZrO2 sols with zirconia content between 15 and 65 wt% were prepared with TEOS and zirconyl nitrate hydrate according to the procedure shown in Fig. 2. The obtained sol was aged at RT and applied to the zirconium plate by a dip coating process. In the other process, the sol was concentrated and the SiO2-ZrO2 gel powder was obtained. The powders were dried at 120oC for 24 h and subjected to successive thermal treatments at 800, 1000, and 1220oC.

Powders and fi lms were characterized using a variety of methods: optical microscopy (OM) and scanning electron microscopy (SEM) for surface morphology observations, X-ray diffraction (XRD) for phase analysis, energy dispersive spectroscopy

Fig. 1. Flowchart depicting the preparation of silica sols by two different methods: a) sol-gel synthesis via an aqueous route, and b) sol-gel synthesis without water.

A)

B)


Fig. 3. (A) SEM photographs of SiO2-ZrO2 calcined at 1220oC with 15% ZrO2 content. (B) XRD patterns of the SiO2-ZrO2 powders with different ZrO2 content calcined at 1000oC: 35, 50, 15 and 35% starting from the lowest line, respectively.

A

Fig. 4. Silicon-based compound layer on the zirconium sample (A) cross-section, (B) LSP elemental analysis across the modifi ed surface.

A

B

B

Lin

(C

ou

nts

)

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

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(EDS) for elemental analysis, differential scan-ning calorimetry coupled thermogravimetric ana-lysis (DSC/TGA) for thermal behaviour determi-nation, and Fourier transform infrared spectros-copy (FTIR) for changes of chemical bonding state of powders investigations.

Powders obtained using the described method resulted in grains of different sizes. The biggest grains were observed for the preparation with 15% ZrO2 content (Fig. 3A). Analysis of XRD patterns of the SiO2-ZrO2 powders confi rmed the presence of cubic zirconium oxide ZrO2 (Fig. 3B).

Coatings with a thickness of 0.3 m were ob-tained for one sol deposition (Fig. 4A). A line scan profi le (LSP) elemental analysis across the cross-section of the surface layer confi rmed the presence of silicon and zirconium in the area of the deposited layer. This result can be clearly seen between 4.0-6.5 m of the measured distance (Fig. 4B).

In addition, autoclave corrosion tests with the following parameters: water, temperature – 360oC and pressure – 195 bar (simulated parameters of reactor normal work conditions) are planned. Further, performing tests at different times: 7, 20, and 40 days will allow us to determine the kinetics of oxidation.

In conclusion, the deposition of thin silica and silica zirconia fi lm on the zirconia alloy has been demonstrated. Our results indicate that the sol-gel method seems to be promising for the fabrication corrosion protective coatings.

References[1]. Zinkle, S.J., Terrani, K.A., Gehin, J.C., Ott, L.J., &

Snead, L.L. (2014). Accident tolerant fuels for LWRs: A perspective. J. Nucl. Mater., 448 (1-3), 374-379. DOI: 10.1016/j.jnucmat.2013.12.005.

[2]. Mariani, R.D., Medvedev, P., Porter, D.L., Hayes, S.L., Cole, J.I., & Bai, X.M. (2013). Novel accident--tolerant fuel meat and cladding. In LWR Fuel Per-formance Meeting (Top Fuel 2013) Charlotte, North Carolina, United States, 15-19 September 2013 (pp. 763-770). Idaho Falls, Idaho: Idaho National Labora-tory.

[3]. Kamiya, K., Sakka, S., & Tatemichi, Y. (1980). Prep-aration of glass fi bres of the ZrO2-SiO2 and Na2O--ZrO2-SiO2 systems from metal alkoxides and their resistance to alkaline solution. J. Mater. Sci., 15 (7), 1765-1771. DOI: 10.1007/BF00550596.

[4]. Zhang, Y., Pan, L., Gao, Ch., & Zhao, Y. (2011). Syn-thesis of ZrO2-SiO2 mixed oxide by alcohol-aqueous heating method. J. Sol-Gel Sci. Technol., 58 (2), 572-579. DOI: 10.1007/s10971-011-2429-4.

[5]. Navio, J.A., Marchena, F.J., Macias, M., Colon, G., Lesand, M.A., & Sanchez-Soto, P.J. (1997). Prepara-tion and characterization of amorphous ZrO2-SiO2 composite powders processed by sol-gel chemistry. J. Sol-Gel Sci. Technol., 10 (2), 165-175. DOI: 10.1023/ A:1018399529744.

[6]. Dave, B.C., Hu, X., & Devaraj, Y. (2004). Sol-gel-de-rived corrosion-protection coatings. J. Sol-Gel Sci. Technol., 32 (1), 143-147. DOI: 10.1007/s10971-004--5779-3.

[7]. Zheludkevich, M.L., Miranda Salvado, I., & Ferreira, M.G.S. (2005). Sol-gel coatings for corrosion protec-tion of metals. J. Mater. Chem., 15 (48), 5099-5111. DOI: 10.1039/B419153F.

[8]. Dhere, S.L. (2015). Silica-zirconia alkali-resistant coat-ings by sol-gel route. Curr. Sci., 108 (9), 1647-1652.

[9]. Castro, Y., Aparicio, M., Moreno, R., & Duran, A. (2005). Silica-zirconia sol–gel coatings obtained by different synthesis routes. J. Sol-Gel Sci. Technol., 35 (1), 41-50. DOI: 10.1007/s10971-005-3213-0.

[10]. Rivero Garcia, R.B., da Silva, F.S., & Kawachi, E.Y. (2013). New sol-gel route for SiO2/ZrO2 fi lm prepa-ration. Colloids Surf. A Physicochem. Eng. Asp., 436, 484-488. DOI: 10.1016/j.colsurfa.2013.07.016.

CHARACTERIZATION OF SILVER WŁADYSŁAW JAGIEŁŁO CROWN HALF-GROSCHEN

MADE BY THE POLISH MINT IN KRAKÓW IN 1394-1434 BY THE X-RAY FLUORESCENCE METHOD

Ewa Pańczyk1/, Joachim Kierzek1/, Lech Waliś1/, Michał Zawadzki2/, Maciej Widawski3/, Władysław Weker3/

1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland2/ Royal Castle in Warsaw, Poland

3/ National Archaeological Museum, Warszawa, Poland

The objective of the current work was to research the history of mediaeval coinage in Poland during the reign of Władysław Jagiełło. The object of the study was silver coins constituting an important element of the preserved heritage from the era of the multinational Polish Republic. The intention of the work was to obtain information regarding the source of the raw materials and methods used in their production.

Due to the needs for nondestructive research procedures or to keep the sample mass to a mini-mum, X-ray fl uorescence (XRF) is particularly use-ful in the determination of the elemental compo-

sition of historical objects. In fact, this method has been used for this purpose for almost half a century [1-3]. With all its variations, XRF is among the most fl exible methods of works of art and archaeological artefact study.

Multivariate statistical methods which are re-cently fi nding their way into archaeometry are very useful in analysing the results of tests per-formed on large sets of objects [3]. The methods of multivariate statistical analysis used most fre-quently for the classifi cation and categorization of artefacts include: cluster analysis, factor analysis, principal component analysis, and discriminant


Władysław Jagiełło crown half-groschen, “Łódź” treasure

Prague groschen Carl I

Fig.1. Examples of investigated coins.

analysis. Cluster and principal component analyses are used to verify attribution fi ndings of technol-ogy, historical, and stylistic research. Discrimi-nant analysis helps to verify the allocation of ar-chaeological artefacts to different groups defi ning the origin of objects, dating object production, and the origin of raw materials [1-3].

The study covered Władysław Jagiełło crown half-groschen made by the mint in Kraków in 1394-1434. According to the sole existing mono-graph of these coins, published in 1970, they have been divided into thirteen types (I-XIII) based on distinguishing mint marks placed on their reverse. According to the monograph’s author, Stanisław Kubiak, this typology should also refl ect the chro-nology of the individual issues [4]. However, the typology criteria and chronology of the relevant types are seriously questioned by numismatists pointing to signifi cant stylistic differences between coins of the same type, thus suggesting that they might have been made at different time.

It seems likely that the stylistic analysis is not capable of a precise classifi cation, unless there are some characteristics of the die constituting ade-quate differentiating features.

The use of trace elements alloy analysis will shed new light on the origins of the silver used in Jagiełło’s coins. Currently available literature pro-vides no accurate answer regarding the origin, spe-cifying two likely sources of the metal: purchase in Hungary or reprocessing of Prague groschen. There is no information about local deposits of silver being operated at that time.

In total, 183 Władysław Jagiełło crown half--groschen were examined originating from the “Łódź” and “Biela” treasures. In addition, 15 Prague groschen were tested as a reference, in-cluding 4 coins minted during Carl I and 11 coins minted during Vaclav IV.

Photographs of representative sample coins involved in the study can be found in Fig. 1.

The composition of the coins was analysed us-ing X-ray fl uorescence. This method meets all basic requirements of historical artefact analysis: it is non-destructive, does not require samples to be taken, and does not permanently change the sur-face of the tested objects.

The studies were performed using an X-ray spectrometer with a Si(Li) detector with an ac-tive area of 80 mm2, thickness of 5 mm, and a resolution of 180 eV for a Mn K line of 5.9 keV. Amplifi ed signals from the detector were record-ed using a computer-controlled multichannel am-plitude analyser from ORTEC.

A single measurement period was 1000 s in length. Each coin was measured twice, once on each side – the obverse and reverse.

Analysis of the spectrum of secondary X-ray ra-diation recorded was performed using AXIL-QXAS software developed and distributed by the Inter-national Atomic Energy Agency (IAEA). The out-come of this analysis was the number of lines of radiation characteristic of the elements under con-sideration.

For the purpose of the current study, a ring--shaped 238Pu source of radiation was used. For uranium, this source emits L1 radiation with an energy of 11.6-20.7 keV (emission effi ciency –

Prague groschen Vaclav IV

Władysław Jagiełło crown half-groschen, “Biela” treasure


Ag vs Cuhalf-groschen_ XRF 15v*198c

0 10 20 30 40 50 60 70 80

Cu%

10

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30

40

50

60

70

80

90

Ag%

half-groschen-Biela

Prague groschen

half-groschen- Łódź

half-groschen counterfeit

Fig. 2. Ag vs. Cu. Władysław Jagiełło crown half-groschen (“Biela” and “Łódź” treasures), Prague groschen Carl I and Vaclav IV – 198 coins tested.

10.6%) and gamma radiation with energies of 43.5, 99.9 and 152.7 keV and effi ciencies of 0.04, 0.007 and 0.001%, respectively.

The measuring setup with a 238Pu source en-sures analysis of the relevant elements present in silver coins: primary – Ag and Cu, secondary – Zn and Pb, and trace – Au, Hg, and Bi. The con-tent of Cu, Zn and Ag is defi ned based on the K-line, while the L-line is used for the remaining elements. K-lines of Cu and Zn, and L-lines of Au, Hg, Pb, and Bi, are excited by L-lines of U and K-lines of Ag by gamma radiation of the 238Pu source. As the tests were performed without the use of a vacuum chamber, no light elements were included in the analysis.

The XRF method provides information about the elemental composition of the surface area of the specimen. In the case of Cu determination based on the K-line, the obtained information re-lates to a layer with a thickness of 20-50 m thick. A similar thickness is accessible in case of Zn, Au, Hg, and Pb contents determined using the L-line, whereas Ag contents based on the K-line

are determined for a thickness of approximately 300 m [3].

The elemental composition of Władysław Ja-giełło crown half-groschen and Prague groschen determined by the XRF method is presented in Figs. 2-6.

Figure 2 presents the correlation of silver and copper for Władysław Jagiełło crown half-gro-

schen “Biela” and “Łódź” treasures) and Prague groschen.

Figures 3-6 contain graphs of Zn/Ag, Pb/Ag, and Bi/Ag standardized variables ratio to Cu/Ag for the Władysław Jagiełło crown half-groschen from the “Biela” and “Łódź” treasures, and the Prague groschen of Carl I and Vaclav IV (198 coins).

Within the analysed crown half-groschen and the Prague groschen, it is possible to specify three well-defi ned groups of coins differing in their ana-lysed elements content.

The value of the Prague groschen and Włady-sław Jagiełło crown half-groschen has been dimi-nished over time. Initially, in 1300-1305 (Vaclav II reign), the coins were made of almost pure sil-ver (15 parts of silver, 1 part of copper). However, over time the fi neness of the coins was reduced to a point in the 16th century, when it reached just 44% of silver. The coins covered by the analysis originate from the reigns of Carl I (1346-1378) and Vaclav IV (1378-1419). The Carl groschen have a signifi cantly higher silver contents ranging

from 77 to 83% with the exception of one coin. The Vaclav groschen were made of alloys contain-ing between 64 and 74% silver (Fig. 2).

The Władysław Jagiełło crown half-groschen were made in Kraków according to other weight and quality standards than in Prague.

Five coins with a signifi cantly lower silver con-tent (ranging between 17 and 22%) are particu-


Fig. 3. Zn/Ag vs. Cu/Ag. Władysław Jagiełło crown half-groschen (“Biela” and “Łódź” treasures), Prague groschen Carl I and Vaclav IV – 198 coins tested.

Zn/Ag vs Cu/Aghalf-groschen_XRF 15v*198c

-1 0 1 2 3 4 5Cu/Ag

0,000

0,002

0,004

0,006

0,008

0,010

0,012

0,014

0,016

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/Ag

half-groschen-Biela

Prague groschen



Fig. 4. Au/Ag vs. Cu/Ag. Władysław Jagiełło crown half-groschen (“Biela” and “Łódź” treasures), Prague groschen Carl I and Vaclav IV – 198 coins tested.

Au/Ag vs Cu/Aghalf-groschen_XRF 15v*198c

-1 0 1 2 3 4 5Cu/Ag

-0,001

0,000

0,001

0,002

0,003

0,004

0,005

0,006

Au/A

g

g147

g180

half-groschen-Biela

Prague groschen




Fig. 6. Bi/Ag vs. Cu/Ag. Władysław Jagiełło crown half-groschen (“Biela” and “Łódź” treasures), Prague groschen Carl I and Vaclav IV – 198 coins tested.

Fig. 5. Pb/Ag vs. Cu/Ag. Władysław Jagiełło crown half-groschen (“Biela” and “Łódź” treasures), Prague groschen Carl I and Vaclav IV – 198 coins tested.

Pb/Ag vs Cu/Aghalf-groschen_XRF 15v*198c

-1 0 1 2 3 4 5

Cu/Ag

0,000

0,005

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0,015

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0,025

0,030

0,035

0,040Pb

/Ag

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g180

half-groschen-Biela

Prague groschen



Bi/Ag vs Cu/Aghalf-groschen_XRF 15v*198c

-1 0 1 2 3 4 5

Cu/Ag

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Prague groschen




Fig. 7. Cluster analysis of studied Władysław Jagiełło crown half-groschen (“Biela” and “Łódź” treasures), Prague groschen Carl I and Vaclav IV – 196 items. Analysis was carried out for trace elements (Zn, Au, Hg, Pb, Bi) determined by XRF. Feature number represents the determined element number.

larly interesting. Three of them (catalogue num-bers: Łódź 1099, Łódź 1103, Łódź 1106) had been previously deemed counterfeit due to certain properties of the die. The other two, bearing cata-logue numbers Łódź 604 (type XI/9) and Łódź 944 (type VI/7), were made using good quality dies, identical to those used at the mint. Therefore, in this case we are facing either a case of abuse by

the mint staff, or dealing with the product of a very skilled adulterator using good quality dies that were probably taken from the mint illegally.

Assuming that the content of Au is an indica-tion of the source of silver, and that lead content corresponds to the technology applied for its pro-duction, we may observe a gradual increase in gold contents over time. This change may refl ect a change of the source of silver, but a further con-fi rmation would require more unambigous his-torical and analytical evidence. A high gold con-tent may also indicate that coins were made from a reprocessed material.

A summary analysis of data was performed us-ing cluster analysis – a multivariate statistical analysis method. This analysis included all tested coins. The synthesized dataset included all sec-ondary elements measured with the XRF method, including: Zn, Au, Hg, Pb, and Bi. Figure 7 repre-sents fi ndings of multivariate analysis of Włady-sław Jagiełło crown half-groschen and Prague gro-schen. There is a precisely identifi ed division into

three well-defi ned groups separately containing half-groschen from the “Biela” treasure, half-gro-schen from the “Łódź” treasure, and Prague gro-schen. The group of crown half-groschen from the “Biela” treasure include 8 coins of the newer va-riety of half-groschen from “Łódź” treasure (type I, III, IV and V; catalogue numbers: 1, 5, 19, 104, 108, 141, 163 and 171). This fact was also noted

during detailed analysis of the XRF results (Figs. 2-6).

In summary, it should be noted that the cur-rent study was the fi rst multidisciplinary research study of mediaeval coins of this scale performed in Poland. This vast body of experimental mate-rial enabled development of a database which represents a signifi cant achievement and will fa-cilitate continued work on coins from the relevant period. It also demonstrates how diffi cult it is to analyse coins discovered after centuries maintain-ed in an uncontrolled environment.

References

[1]. Pańczyk, E., Sartowska, B., Waliś, L., Dudek, J., Weker, W., & Widawski, M. (2015). The origin and chronol-ogy of medieval silver coins based on the analysis of chemical composition. Nukleonika, 60, 3, 657-663.

[2]. Rehren, T., Belgya, T., Jambon, A., Káli, G., Kasztovsz-ky, Zs., Kis, Z., Kovács, I., Maróti, B., Martinón-Torres, M., Miniaci, G., Pigott, V.C., Radivojević, M., Rosta, L., Szentmiklósi, L., & Szökefalvi-Nagy, Z. (2013). 5000

tree diagrams for 196 casesWard's method

Euclidean distance

J124

J125

J126

J110 J7

7J1

06 J82

J71

J68

J67

J81

J79

J89

J88

J85

J74

J87

J59

J97

J98

J45

J40

J31

J117

J113

J115 J5

8J4

7J9

5J7

0J4

8J4

2J6

3J4

6J6

5J9

4J9

3J3

6J1

22J1

08 J39

J75

J37

J123 J8

4J4

4J6

9J3

5J2

9J5

4J5

3J1

18 J61

J100 J3

8J2

8J8

0J7

3J7

2J5

7J5

5J1

11J1

12 J76

J114

J104 J5

6J1

09J1

05 J52

J66

J64

J119 J5

1J6

0J9

6J1

0J1

21J1

20J1

07 J92

J101 J5

0J1

02J1

03 J99

J43

J41

J91

J83

J78

J34

J86

J116 J9

0J4

9J3

0J2

7J6

2J1

1 J8 J24

J18

J13

J12 J5 J32

J22

J16

J26

J17 J7 J33 J9 J19

J21 J6 J2

B19 g1

2g1

5g1

1 g8 g13 g4 g3 g2 g1 g9 g5 g14

g10 g7 g6

B20

B24

B46

B49

B40

B34

B11

B10

B28

B26

B13 B

8J2

0B

41 J4 J1 J3 B5

B47 J1

5B

18 J14

B16 J2

3B

39B

33B

15B

51B

45 J25

B50 B

4B

17 B3

B25 B

6B

22 B2

B44

B23

B43

B35

B30 B

9B

32B

27B

48B

21B

29B

12 B7

B36

B38

B37

B14

B31

B42 B

1

0

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100

Link

age

dist

ance

Właysław Jagiełło crown half-groschen (Łódź)

Prague groschen

Władysłąw Jagiełło crown half-groschen(Biela)

half-groschen , Łódź, number 1, 5, 19, 104,108,141,163, 171


INVESTIGATION OF THE RELATIONSHIP BETWEEN ORIGIN, TECHNOLOGY AND DURABILITY OF GLASS, WITH A SPECIAL FOCUS

ON LATE 17th AND 18th CENTURY GLASSJerzy J. Kunicki-Goldfi nger1/, Stephen P. Koob2/

1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland1/ The Corning Museum of Glass, Corning, N.Y., USA

The project aimed to investigate the relationship between origin, technology and durability of glass, and was focused on a group of unstable glasses that underwent a continuous and irretriev-able decomposition irrespective of the storage con-ditions [1-3]. One of the largest groups of such glasses originates from post-mediaeval Europe. As most of the studies on such phenomenon have been concerned with soda glasses, this pro-ject was especially focused on potassium glasses.

The Corning Museum of Glass collection, which is the most comprehensive collection of glass in the world, was examined to select the objects best fi tting the target of late 17th and 18th century po-tassium glasses. Almost 200 pieces were eventual-ly selected for further detailed examination. These were colourless glass vessels, such as goblets, beakers, jugs and other types of tableware.

The examination consisted of three main steps. First, naked eye inspection and an optical micros-copy survey of the condition of the glass surface

were performed to identify even the very fi rst stages of crizzling or other glass instability symp-toms. Second, a naked eye inspection of glass fl u-

Fig. 1. The analysis of baroque goblet with the use of the Bruker TRACER III-V Portable XRF analyser.

Fig. 2. Spectrum of excited radiation in a colourless glass vessel. The Bruker TRACER III-V Portable XRF analyser equipped with an X-ray tube with Rh target. Cu-Ti-Al fi lter applied to analyse the elements from Fe to Mo.

years old Egyptian iron beads made from hammered meteoritic iron. J. Archaeol. Sci., 40, 4785-4792.

[3]. Kierzek, J., Kunicki-Goldfi nger, J., & Małożewska-Buć-ko, B. (2000). Rentgenowska analiza fl uorescencyjna

w badaniu dzieł sztuki. Wybrane zagadnienia. Ochro-na Zabytków, 2, 166-181.

[4]. Kubiak, S. (1970). Monety pierwszych Jagiellonów (1386-1444). Wrocław-Warszawa-Kraków.

0

1000

2000

3000

4000

5000

6000

7000

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9000

10000

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40

Coun

ts

Energy (keV)


orescence under the long- and short-wave ultra-violet radiation (so-called UV-A and UV-C, respec-tively) was performed in order to correlate the presence or absence of some chemical constitu-ents of glass and the colour of the fl uorescence. Third, X-ray fl uorescence analysis (XRF) of glass was performed using a portable analyser (Fig. 1), with the goal of identifying the selected glass con-stituents and characterizing, as far as possible, the chemical and technological type of glass. For this goal, the Bruker TRACER III-V Portable XRF ana-lyser equipped with an X-ray tube with rhodium (Rh) target and a high-resolution, Peltier cooled, Silicon PIN (Si-PIN) diode detector was employ-ed. The experimental conditions for low-energy runs were 15 kV and 14.50 A, and for high--energy runs – 40 kV and 6 A. A Ti fi lter was used for low-energy runs and a Cu-Ti-Al fi lter for high-energy runs. All glasses were measured for 600 s separately for low-energy and high-energy runs. An internal instrumental vacuum was used for the low-energy runs. The X-ray spectra were evaluated using the Interactive Least-squares Fit-ting (AXIL) software.

The gathered X-ray spectra (Fig. 2) and the fi -nal results are still being processed. However, the preliminary results provided us with a tentative grouping of glass objects with respect to some characteristic glass constituents and the identi-fi ed raw materials used. The most important vari-ables that allow us to group the glasses are As, Pb, Zr, Rb, Sr, Y, Sb, Ca, Fe and Mn. The fi nal results will be compared with the results obtain-ed from our previous similar projects [4-6].

The results broaden our knowledge regarding the historical glass technologies, the raw materials used, the glass formulations, the glass chemical composition, and the glass durability. They also allow us to correlate the chemical and techno-

logical characteristics of the glasses with their origin and in some cases even with specifi c glass-houses.

The project has been supported by the Kosciu-szko Foundation fellowship to carry out, among others, the XRF analyses at the Corning Museum of Glass in Corning, N.Y., USA.

References[1]. Brill, R.H. (1975). Crizzling: a problem in glass con-

servation. In N.S. Brommelle & P. Smith (Eds.), Con-servation in archaeology and the applied arts. Pre-prints of the contributions to the IIC Stockholm Congress, 2-6 June 1975 (pp. 121-134). London: In-ternational Institute for Conservation of Historic and Artistic Works.

[2]. Koob, S.P. (2006). Conservation and care of glass ob-jects. London and Corning, N.Y.: Archetype Publica-tions in association with the Corning Museum of Glass, 158 p.

[3]. Kunicki-Goldfi nger, J.J. (2008). Unstable historic glass: symptoms, causes, mechanisms and conservation. Rev. Conserv., 9, 47-60.

[4]. Kunicki-Goldfi nger J.J., Kierzek, J., Kasprzak, A.J., & Małożewska-Bućko, B. (2000). A study of 18th cen-tury glass vessels from central Europe by X-ray fl uo-rescence analysis. X-Ray Spectrom., 29 (4), 310-316.

[5]. Kunicki-Goldfi nger, J.J., Kierzek, J., Kasprzak, A.J., & Małożewska-Bućko, B. (2003). Analyses of 18th cen-tury central European colourless glass vessels. In An-nales du 15e Congrès de l’Association Internationale pour l’Histoire du Verre, New York – Corning 2001 (pp. 224-229). Nottingham: Association Internationale pour l’Histoire du Verre.

[6]. Kunicki-Goldfi nger, J.J., Kierzek, J., Dzierżanowski, P., & Kasprzak, A.J. (2005). Central European crystal glass of the fi rst half of the eighteenth century. In Annales du 16e Congrès de l’Association Internationale pour l’Histoire du Verre, London 2003 (pp. 258-262). Not-tingham: Association Internationale pour l’Histoire du Verre.

POLLUTION CONTROL POLLUTION CONTROL TECHNOLOGIES LABORATORYTECHNOLOGIES LABORATORY

The research activities of the Pollution Control Technologies Laboratory concern the con-cepts and methods of process engineering applicable to the environmental area. In particular, we participate in research on the application of electron accelerators to such environmental technologies as fl ue gas and water treatment, wastewater purifi cation, the processing of vari-ous types of industrial waste, etc.

The main aims of the Laboratory's activity are:• development of new processes and technologies of environmental engineering,• development of environmental applications of radiation technologies,• promotion of nuclear methods in the fi eld of environmental applications.

The activities of our group cover both basic and applied research. Among others, the most important research fi elds are:• development of electron beam fl ue gas treatment (EBFGT) technology,• support for the industrial implementation of the EBFGT process,• investigation of chemical reaction mechanisms and kinetics in gas phases and aqueous

solutions irradiated by electron beams, • study of the mechanism of removal of volatile organic compounds (VOCs) and other pol-

lutants from fl ue gas by electron beam irradiation,• process modelling.

The Laboratory is equipped with research tools such as:• a laboratory installation for electron beam fl ue gas treatment;• Model 40 UV pulsed fl uorescent SO2 analysers and Model 10 A/R chemiluminescent

NO/NOx analysers with molybdenum converters, manufactured by Thermo Electron Cor-poration (USA);

• GC-17A gas chromatograph with a GCMS-QP5050 mass spectrometer, manufactured by Shimadzu Corporation (Japan);

• Lancom II portable gas analyser type, manufactured by Land Combustion (UK) (NOx, SO2, CO, O2, etc.). The Laboratory is open for any form of cooperation. In particular, we offer such activities

as:• laboratory research on environmental applications of electron accelerators,• theoretical modelling of chemical processes under electron beam irradiation,• concept design of electron beam technology implementation,• process equipment design with the 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 (Den-

mark);• 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);

• National Centre for Nuclear Research, Otwock-Świerk (Poland);• Ukrainian Engineering Pedagogics Academy (Ukraine);• Tsinghua University (China);• Xi’an Jiaotong University (China);• Joint Institute for Power and Nuclear Research – Sosny, National Academy of Sciences of

Belarus (Belarus);• 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).

97POLLUTION CONTROL TECHNOLOGIES LABORATORY

NUMERICAL SIMULATION OF PERFLUOROOCTANOIC ACID DEGRADATION

IN WATER UNDER IONIZATION RADIATIONHenrietta Nichipor1/, Yongxia Sun2/, Andrzej G. Chmielewski2/

1/ Joint Institute for Power and Nuclear Research – Sosny, National Academy of Sciences of Belarus, Minsk, Belarus

2/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland

IntroductionPerfl uoroalkyl compounds are widely used in

consumer products, such as textiles, carpets, pack-aging, cleaning products, etc. Perfl uorooctane sul-fonate (PFOS) and perfl uorooctanoic acid (PFOA) resist photolysis, hydrolysis, or biodegradation under environmental conditions. They have po-tential to bioaccumulate and biomagnify in wild-life and human beings. Kannan K. et al. [1] report-ed that PFOS and PFOA were detected in human blood samples from the United States, Europe, and some Asian countries. Relatively high concen-trations of PFOS and PFOA were detected in hu-man blood from Poland: 42.1 ng/mL PFOS and 21.3 ng/mL PFOA. PFOS and PFOA were labeled as “emerging contaminants” by the United States Environmental Protection Agency (US EPA) in May 2012 and were listed as persistent organic pollutants (POPs) under the Stockholm Conven-tion.

PFOS and PFOA are not only persistent, but are also found in very low concentrations that are diffi cult to detect. Conventional technologies used to treat normal wastewater are not applicable. Advanced oxidation ionization technology is one of the most promising technologies for the remov-al of organic pollutants from water and waste.

This paper is devoted to a simulation of PFOA transformation in water containing O2 or Ar with t-butanol in order to get a better understanding of the mechanism of PFOA degradation under ion-ization radiation. Model calculationsPrimary radiation-chemical processes

The total concentration of PFOA in the water did not exceed 0.3% (w/w). Therefore, the direct action of ionizing radiation on these compounds may be neglected, i.e. more than 99.7% of accel-erated electrons, as well as secondary electrons arising in the medium, interact with water mol-ecules producing chemically active short-lived par-ticles: hydrated electrons (e–

aq), H atoms, and OH radicals. Their initial radiation-chemical yields, Ge–

aq, GH, and GOH are equal to 2.7, 0.61 and 2.71 molecules/100 eV, respectively [2]. Also, hydrogen peroxide, which can take part in some reactions with the solute, is produced as a primary product of water radiolysis, with a yield GH2O2 = 0.7 mol-ecules/100 eV.

It is known that so-called “spur” or “track” re-actions play a minor role at pollutant concentra-tions near or less than 10–3 mol/L, even if their rate constants with primary water radiolysis prod-ucts are high enough. Any increase in the G-value of the primary products of radiolysis due to pen-

etration of pollutant molecules into “spurs” would not exceed 10% [3]. Model of water radiolysis

The main reactions of water radiolysis in the model are presented in Table 1. The rate con-stants of these reactions were taken from the lit-erature [4].

The rate constants for reactions of hydrated electrons, H atoms, and OH radicals with PFOA are high enough (Table 2) to prevent reactions be-tween short-lived particles. Also, it should be taken into account that both types of reducing particles, i.e. hydrated electrons and H atoms, re-act rapidly with dissolved oxygen producing per-oxide radicals. Because the concentration of dis-solved oxygen is 1 10–4 mol/L and the rate con-stants of its reactions with hydrated electrons and H atoms are near 2 1010 dm3·mol–1·s–1 [4], these reactions are competitive with the reactions of hydrated electrons and H atoms with dissolved PFOA.Numerical simulation of PFOA decomposition in aqueous solution

The chemical model for the decomposition of PFOA in aqueous solution under ionization radia-tion includes 58 reactions involving 19 species. The integration of the complete system of fi rst order ordinary differential equations was perform-ed by the use of the KINETIC computer code [7], employing a Gear algorithm especially suited for stiff systems. Care was taken to ensure charge and mass conservation. The input values for the numerical simulation were the same as those given in experimental work [8]. The temperature, pressure, and water concentration were 298 K, 1 atm., and 55.35 mol/L, respectively. Results and discussion

The fi rst step was the calculation of PFOA decomposition in an aerated solution of pH 7.0 under gamma irradiation. The dose rate of the gamma irradiation was 4.8 kGy/h, while the O2 concentration was 1.0 10–4 mol/L. The calcu-lated results are presented in Fig. 1 and compared with experimental results [8].

PFOA decomposition is caused by reactions with OH radicals, hydrated electrons, and H atoms. The best agreement of the calculation results with experimental data was obtained when the reac-tion of PFOA with OH radicals had a rate con-stant of 1.0 105 dm3·mol–1·s–1. OH radicals play an important role in PFOA decomposition.

The second step was the calculation of PFOA decomposition in an Ar-saturated solution of pH 7 with 20 mg/L of t-butanol under EB or gamma irradiation. For the EB irradiation, a pulse 10 MeV

98 POLLUTION CONTROL TECHNOLOGIES LABORATORY

Table 1. Chemical model of water (containing O2) radiolysis under the action of radiation.

No. Reactions k [dm3·mol–1·s–1]1 2e–

aq H2 + 2OH– k1 = 4.97 109 2 e–

aq + H H2 + OH– k2 = 1.89 1010 3 e–

aq + OH OH– k3 = 3.00 1010

4 e–aq + O– 2OH– k4 = 2.20 1010

5 e–aq + HO2 HO2

– k5 = 2.00 1010 6 e–

aq + O2– OH– + HO2

– k6 = 1.30 1010 7 e–

aq + H2O2 OH– + OH k7 = 1.20 1010 8 e–

aq + HO2– OH– + O– k8 = 3.50 109

9 e–aq + O2 O2

– k9 = 1.80 1010 10 e–

aq + H+ H k10 = 2.30 1010 11 e–

aq + H2O OH– + H k11 = 1.90 101 12 2H H2 k12 = 7.80 109 13 H + OH H2O k13 = 2.50 1010 14 H + HO2 H2O2 k14 = 2.00 1010 15 H + O2

– HO2– k15 = 2.00 1010

16 H2O2 + H OH + H2O k16 = 8.42 106 17 O2 + H HO2 k17 = 2.10 1010 18 OH– + H e–

aq + H2O k18 = 2.20 107

19 2OH H2O2k19 = 5.50 109

k-19 = 3.184 10–7 20 OH + O– HO2

– k20 = 2.00 1010 21 OH + HO2 O2 + H2O k21 = 6.30 109 22 OH + O2

– O2 + OH– k22 = 8.20 109 23 H2O2 + OH HO2 + H2O k23 = 4.06 107 24 OH + HO2

– OH– + HO2 k24 = 7.50 107 25 H2 + OH H + H2O k25 = 3.81 107 26 OH– + OH O– + H2O k26 = 1.20 1010 27 2O– OH– + HO2

– k27 = 1.00 109 28 O2

– + O– O2 + 2OH– k28 = 6.00 108 29 H2O2 + O– O2

– + H2O k29 = 5.00 108

30 O– + HO2– OH– + O2

– k30 = 4.00 108 31 H2 + O– OH– + H k31 = 8.00 107 32 O– + H2O OH– + OH k32 = 1.75 106 33 2HO2 H2O2 + O2 k33 = 8.30 105 34 H2O2 + HO2 O2 + OH + H2O k34 = 2.00 10–1 35 O2

– + HO2 O2 + HO2– k35 = 9.70 107

36 HO2 H+ + O2– k36 = 7.50 105

37 2O2– H2O2 + O2 + 2OH– k37 = 3.00 10–1

38 H2O2 + O2– O2 + OH– + OH k38 = 1.30 10–1

39 O2– + HO2

– O2 + OH– + O– k39 = 1.30 10–1 40 H+ + O2

– HO2 k40 = 5.10 1010

41 H2O2 + OH– HO2– + H2O

k41 = 1.00 1010 k-41 =1.13 106

42 H+ + HO2– H2O2 k42 = 2.00 1010

43 H+ + OH– H2Ok43 = 1.40 1011 k-43 = 2.52 10–5

44 O2 + O– O3– k44 = 3.00 109

45 O– + O3– 2O2

– k45 = 7.00 109 46 H2O2 + O3

– O2 + O2– + H2O k46 = 1.60 106

47 HO2– + O3 O2 + OH– + O2

– k47 = 8.90 105 48 O3

– O2 + O– k48 = 3.00 102 49 H2 + O3

– O2 + OH– + H k49 = 2.50 105 50 H+ + O– OH k50 = 1.00 1010 51 OH– + HO2 O2

– + H2O k51 = 1.00 1010


electron accelerator with a mean beam power of 10 kW was used; the pulse duration was 6 s, the pulse repetition rate was 300 per second, and the dose rate was about 4 Gy/per cycle. The relevant calculated results are presented in Fig. 2 and com-pared with experimental results [8].

From Fig. 2, it can be seen that PFOA decom-position under gamma irradiation is faster than that under EB irradiation. Based on the calculat-ed results, 77% of the PFOA reacted with H, 16% of the PFOA reacted with OH, and 7% of the PFOA reacted with hydrated electrons under gamma ir-radiation; while under EB irradiation, 96% of the PFOA reacted with H and 4% of the PFOA react-ed with OH.

The reaction of hydrated electrons with PFOA takes place during PFOA decomposition in water only at pH 7 or more. The best agreement between the calculated and experimental results was ob-tained at the following reaction rate constants of

Table 2. Reaction rate constant of species with PFOA.

Species Rate constant [dm3·mol–1·s–1] Ref.

OH3.0 107 [5]

1.0 105 [6]

H 9.0 107 [6]

Hydrated electrons (1.3-5.1) 107 [6]

PFOA: PFOA with H being 6.0 104 dm3·mol–1·s–1 and PFOA with hydrated electrons being 1.0 106

dm3·mol–1·s–1. PFOA decomposition in acid solution (pH = 2)

in an Ar-saturated solution with 20 mg/L of t-bu-tanol presence under EB or gamma irradiation was investigated; the calculated results are pre-sented in Fig. 3 and compared with experimental results [8]. It can be seen that PFOA decomposi-tion under gamma irradiation is faster than that under EB irradiation in acid solution; this phe-nomenon is the similar to that obtained in neutral solution. H atoms are main species contributing to PFOA decomposition.

From Figs. 1-3, it can be seen that the calcu-lated results of PFOA degradation under gamma irradiation show faster degradation than the ex-perimental results. Under gamma irradiation, in aerated solution, OH radicals play an important role, while in Ar-saturated solutions with t-bu-tanol presence, both H atoms and OH radicals play an important role. Solvated electrons take part in PFOA degradation when the pH is 7 or even higher. The reaction rate constants of the species OH, H and hydrated electrons with PFOA were as follows: 3.0 107, 9.0 107, and (1.3-5.1) 107 dm3·mol–1·s–1, respectively. The reaction rate constant of H radicals with PFOA is the highest. In acid solution, the H radicals' concentration was high, and the H radical reaction with PFOA was a main reaction for PFOA degradation.Conclusions

PFOA can be decomposed under EB or gamma irradiation. Although the decomposition effi ciency of PFOA under gamma irradiation is higher than that using EB, EB is a more promising technology for the removal of organic pollutants from the ef-fl uent of wastewater treatment plants. Based on the modelling calculation results, H and OH radi-cals play the most important role for PFOA deg-radation in solution. In acid solution, H radicals play the dominant role. However, the mechanism of PFOA removal needs to be further investigat-ed, especially the radiolysis products of the irradi-ated solution.

0

20

40

60

80

100

0 10 20 30 40 50 60

Dose (kGy)

PFO

A c

oncn

. in

solu

tion

(%) exp. cal.

Fig. 1. PFOA decomposition in aerated solution of pH 7.0 under gamma irradiation (initial concentration = 1 mg/L).

Fig. 2. PFOA decomposition in Ar-saturated solution of pH 7 with 20 mg/L of t-butanol.

0

20

40

60

80

100

0 20 40 60 80 100 120

Dose (kGy)

PFO

A c

oncn

. In

solu

tion

(%)

exp.( gamma)cal.(gamma)exp.(EB)cal.(EB)

Fig. 3. PFOA decomposition in Ar-saturated solution of pH 2 with 20 mg/L of t-butanol.

0

20

40

60

80

100

0 20 40 60 80 100Dose (kGy)

PFO

A c

oncn

. in

solu

tion

(%)

exp.(gamma)cal.(gamma)exp.(EB)cal.(EB)


References

[1]. Kannan, K., Corsolini, S., Falandysz, J., Fillmann, G., Kumar, K.S., Loganathan, B.G., Mohd, M.A., Olivero, J., Van Wouwe, N., Yang, J.H., & Aldous, K.M. (2004). Perfl uorooctanesulfonate and related fl uorochemicals in human blood from several countries. Environ. Sci. Technol., 38 (17), 4489-4495. DOI: 10.1021/es0493446.

[2]. Pikaev, A.K. (1986). Sovremennaya radiatsionnaya khimiya. Radioliz gasov i zhidkostei (Modern radia-tion chemistry. Radiolysis of gases and liquids). Mos-cow: Nauka.

[3]. Makarov, L.E., Ponomarev, A.V., & Han, B. (2004). Demonstration plant for electron-beam treatment of Taegu Dye Industry Complex wastewater. In Emerg-ing applications of radiation processing. Proceedings of a technical meeting held in Vienna, Austria, 28-30 April 2003 (pp. 138-152). Vienna: IAEA. (IAEA-TEC--DOC-1386).

[4]. Buxton, G.V., Greenstock, C.L., Helman, W.P., & Ross, A.B. (1988). Critical review of rate constants for reac-

tions of hydrated electrons, hydrogen atoms and hy-droxyl radicals (OH/O–) in aqueous solutions. J. Phys. Chem. Ref. Data, 17, 513-886.

[5]. Szajdzińska-Pietek, E., & Gębicki, J.L. (2000). Pulse radiolytic investigation of perfl uorinated surfactants in aqueous solutions. Res. Chem. Intermediat., 26 (9), 897-912.

[6]. Vecitis, C.D., Park, H., Cheng, J., Mader, B.T., & Hoff-mann, M.R. (2009). Treatment technologies for aque-ous perfl uorooctanesulfonate (PFOS) and perfl uorooc-tanoate (PFOA). Front. Environ. Sci. Eng. China, 3 (2), 129-151. DOI: 10.1007/s11783-009-0022-7.

[7]. Bubnov, V.P., Bugaenko, V.I., Grishkin, V.L., Koroza, G.A., & Nichipor, G.V. (1993). The radiolysis model of fl ue gases. Therm. Eng., 1, 42-45 (in Russian).

[8]. Bojanowska-Czajka, A., Moskal, J., Kulisa, K., Łycz-ko, M., Kciuk, G., & Trojanowicz. M. (2015). Appli-cation of ionizing radiation for decomposition of per-fl uorinated surfactants. In INCT Annual Report 2014 (pp. 66-70). Warszawa: Institute of Nuclear Chemistry and Technology.

NUMERICAL SIMULATION OF NOx AND SO2 REMOVAL UNDER ELECTRON BEAM IRRADIATION

WITH TWO COMPUTER PROGRAMS: KINETIC AND MATLABEwa Zwolińska1/, Yongxia Sun1/, Henrietta Nichipor2/

1/ Institute of Nuclear Chemistry and Technology, Warszawa, Poland 2/ Joint Institute for Power and Nuclear Research – Sosny, National Academy of Sciences of Belarus,

Minsk, Belarus

The emission of SO2 and NOx from diesel oil fl ue gases is an emerging problem, which needs urgent resolution. During the burning of diesel oils, high concentrations of both pollutants are created in the exhaust gases. However, none of the commer-cially available methods are able to remove high concentrations of SO2 and NOx with acceptable effi ciency to fulfi l new restrictions. One of the de-veloping methods used to remove both pollutants is electron beam fl ue gas treatment technology (EBFGT). Between 1999 and 2003 the technology was successfully implemented in the Electropower Station “Pomorzany” and has been working since then [1]. Although NOx reduction from coal com-bustion fl ue gas is carried out easily, with high ef-fi ciency, due to its low concentration, the removal of high concentrations of NOx requires a high en-ergy input and is not very effi cient [2]. That is the reason why the optimization of the process is need-ed. Furthermore, the mechanism of the process is still not fully known. When the composition of the fl ue gas changes, the mechanism of the process can also change correspondingly. With the aid of a computer simulation of the process, it is possible to discover the mechanism of the reactions re-sponsible for the NOx and SO2 removal as well as the major and minor products, and estimate their removal effi ciency, which is crucial to allow for the development and improvement of the process.

The modelling was performed with two com-puter programs: Matlab and Kinetic. In both pro-grams the designed models included the same re-actions; they contained 282 reactions and 44 species. The models were based on stiff systems

of ordinary differential equations. The aim of our work was to compare the calculated results ob-tained from both programs using a single chemi-cal model, as well as comparing these results with the ones obtained experimentally. These steps en-abled us to fi nd the most important reactions and the major species taking part in the process.

The composition of the gas for modelling was the same as in the experiments. The concentra-tion of N2, CO2, H2O, O2, NO and SO2 (v/v) were as follows: 70.6%, 15.6%, 8.2%, 5.6%, 200-1700 ppmv and 500-2000 ppmv. The reactions were chosen based on previous models [3, 4] and the literature [5].

Figures 1 and 2 show the comparison between results obtained from experimental work and nu-merical simulation (Kinetic and Matlab). The re-sults show that an increasing inlet concentration of SO2 and NOx decreases the effi ciency of their removal. The dependencies are qualitatively con-sistent with experimental results, both for low and high inlet concentrations of pollutants. There is a tendency for the results from the Kinetic model-ling to be closer to the experimental trends. This might be explained by the fact that the Kinetic program takes into consideration a pulsed irra-diation mode, which was used in the experiments, whereas Matlab modelling includes only a con-tinuous irradiation mode.

In order to check the response of the model to the parameters infl uencing the process of remov-al, a sensitivity analysis concerning the inlet con-centrations of the pollutants and temperature was carried out.


Fig. 1. The comparison of the results obtained from Matlab simulation and experimental work. Initial concentration of SO2 – 700 ppm, temperature – 90oC.

The infl uence of the inlet concentration of SO2 on the removal effi ciency of NOx and vice versa were checked experimentally and with both com-puter programs (Figs. 3 and 4). The calculation results obtained from both programs show the same dependence as the experiments, and con-fi rm that a higher concentration of SO2 has a posi-tive impact on NO removal effi ciency, whereas a higher concentration of NO has a negative im-pact on SO2 removal effi ciency.

Furthermore, the impact of the temperature on removal effi ciency of SO2 and NOx was examined (Figs. 5 and 6). The modelling simulation indicat-ed that temperature had barely any impact on the NOx removal effi ciency, while experiments showed

that higher temperatures had a positive impact on NOx removal effi ciency. The infl uence of the tem-perature on the SO2 removal effi ciency was also examined. Experiments and Matlab simulation showed that lower temperature had a positive im-pact, whereas Kinetic simulation showed almost no difference. The lack of sensitivity of the models with regard to the temperature is connected with the fact that probably not all of the reaction rates, which are included in the models, have their tem-perature dependent formulae in the model.

The analysis of both models makes it possible to highlight the most important reactions occur-ring during the process of NOx and SO2 removal:

HO2 + NO NO2 + OH

Fig. 2. The comparison of the results obtained from Kinetic simulation and experimental work. Initial concentration of SO2 – 700 ppm, temperature – 90oC.


OH + NO2 + M HNO3 + MSO2 + OH + M HSO3 + M

HSO3 + O2 SO3 + HO2

SO3 + H2O H2SO4NO2 + O3 O2 + NO3

O + NO + M NO2 + MBased on the calcuation results, we can draw

the following conclusions:• The results obtained using both models agree

qualitatively with the experimental results. • A high dose has a positive impact on NOx and

SO2 removal effi ciencies.• Numerical simulation predicted that a higher

inlet concentration of pollutants has a negative impact on its removal effi ciency. The effect is stronger for high inlet concentrations of SO2 and NOx.

• The effectivenes of the NO removal is infl u-enced by the SO2 initial concentration, which is proved both experimentally and by modelling. This synergistic effect is caused by the produc-tion of HO2

radicals during SO2 removal, which are later used during NOx removal.

• The infl uence of the NO inlet concentration on SO2 removal effi ciency is the opposite. This is

caused by the competition between the NOx and SO2 removal reactions.

• The infl uence of the temperature on the remov-al effi ciencies of the pollutants are better shown by experiments than by modelling.

• OH and HO2 radicals are main reactive spe-

cies for the reduction of NOx and SO2 from fl ue gases.

References[1]. Chmielewski, A.G., Licki, J., Pawelec, A., Tymiński, B.,

& Zimek, Z. (2004). Operational experience of the in-dustrial plant for electron beam fl ue gas treatment. Radiat. Phys. Chem., 71, 441-444. DOI: 10.1016/j.rad-physchem.2004.03.020.

[2]. Chmielewski, A.G., Sun, Y., Licki, J., Pawelec, A., Witman, S., & Zimek, Z. (2012). Electron beam treat-ment of high NOx concentration off-gases. Radiat. Phys. Chem., 81, 1036-1039. DOI: 10.1016/j.radphys-chem.2011.12.012.

[3]. Zwolinska, E., Sun, Y., Chmielewski, A.G., Nichipor, H., & Bulka, S. (2015). Modelling study of NOx re-moval in oil-fi red waste off-gases under electron beam irradiation. Radiat. Phys. Chem., 113, 20-23. DOI: 10.1016/j.radphyschem.2015.04.008.

[4]. Zwolińska, E., Gogulancea, V., Lavric, V., Sun, Y., & Chmielewski, A.G. (2015). Optimization of the process

Fig. 5. The infl uence of the temperature on the NOx remov-al effi ciency results obtained experimentally and by both computer programs. NO initial concentration – 200 ppm, SO2 initial concentration – 700 ppm, dose – 32.7 kGy.

Fig. 6. The infl uence of the temperature on the SO2 removal effi ciency results obtained experimentally and by both computer programs. NO initial concentration – 200 ppm, SO2 initial concentration – 700 ppm, dose – 32.7 kGy.

Fig. 3. The infl uence of the change in SO2 initial concen-tration on the NOx removal effi ciency results obtained ex-perimentally and by modelling. NOx initial concentration – 200 ppm, temperature – 90oC, dose – 21.8 kGy.

Fig. 4. The infl uence of the change in NO initial concen-tration on the SO2 removal effi ciency results obtained ex-perimentally and by modelling. SO2 initial concentration – 700 ppm, temperature – 90oC, dose – 21.8 kGy.


parameters infl uencing the removal of SO2 and NOx during electron beam fl ue gas treatment process by mathematical modeling in Matlab. In INCT Annual Report 2015 (pp. 85-87). Warszawa: Institute of Nu-clear Chemistry and Technology 2015,

[5]. NIST. (2013). NIST Chemical Kinetics Database. Re-trieved December 16, 2016, from http://kinetics.nist.gov/kinetics/index.jsp.

STABLE ISOTOPE LABORATORYSTABLE ISOTOPE LABORATORY

Basic activities 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 also concerns the application of IRMS to the environmental area, including determination of the stable isotope composition of hydrogeological, environmental, and food samples.

The main aims of the activity of the Laboratory are:• preparation and measurement of the stable isotope composition of food and environmental

samples;• establishing new areas of the application of stable isotope compositions for food authen-

ticity control, environmental protection, and origin identifi cation.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).

The Laboratory research staff is involved in the following projects:• “The study of the infl uence of the environmental factors on the isotopic compositions of

dairy products”,• accreditation process (isotopic method for food authenticity control),• interlaboratory profi ciency 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 prepared to

undertake any research and development task within the scope of our activity. In particular, we offer our measurement experience, precision, and profi ciency in the fi eld of stable isotope composition to aid the research of others. In addition, we are open to perform any service regarding the control of food authenticity by stable isotope methods supported by gas chro-matography (GC) and gas chromatography-mass spectrometry (GC-MS) methods.

Our Laboratory cooperates with the following national partners:• Agricultural and Food Quality Inspection,• Polish Association of Juice Producers,• customs inspections,• food export-import company,• food control laboratories,• private customersand foreign partners:• Eurofi ns Scientifi c Analytics (France),• International Atomic Energy Agency (IAEA),• Joint Research Centre (Ispra, Italy).

106 STABLE ISOTOPE LABORATORY

STUDY OF STABLE ISOTOPE COMPOSITION OF POLISH CIDERSRyszard Wierzchnicki, Renata Adamska

Stable isotope analyses have been useful tool for food authenticity control. An important limitation of applying the isotopic method for food authen-ticity control is a lack of a database comprising the stable isotope compositions of different origin foods. For many years, the Stable Isotope Labora-tory of the Institute of Nuclear Chemistry and Technology (INCT) has carried out studies on the isotopic composition of food for elaboration and implementation in new isotope ratio mass spectro-metry (IRMS) methods, and also creates a data-base of some foods from the Polish market. Our recent studies concerned the intramolecular iso-topic distribution pattern between the compo-nents of ciders.

Cider is the popular drink produced by apple juice fermentation. The main chemical compo-nents of cider are: water, ethanol, sugars and CO2. The subject of the study is the stable isotope com-position of water, ethanol, and CO2 included in ciders. Accordingly, the study aim is to investigate the stable isotope compositions of these compo-nents, as well as indentifying their source, in an effort to control the authenticity of the drinks.

The addition of sugar to the production of ci-ders is allowed in some countries but forbidden in the others (e.g. France). During the fermentation of sugars in juice, ethanol and CO2 are produced. The addition of beet sugar (C3 plants – Calvin cycle) or cane sugar and corn syrup (C4 plans – Hatch-Slack pathway) results in different isotopic composition of CO2 and ethanol. Artifi cial car-bonated ciders typically using CO2 from an indus-trial source result in a 13C value lower than -40‰.

Our method is to look for the range of values of the isotopic compositions of authentic ciders. In the study, the stable isotope method for meas-urement of ethanol and CO2 bubbles (natural or exogenous carbonation) will be elaborated to con-trol the quality of ciders and their compliance with labelling (authenticity). The basic problem sorrounding CO2 is: Is the CO2 gas in ciders from a natural source (natural fermentation) or from an industrial (technical) source? For control of cider authenticity, the basic information is the compliance oxygen isotopic composition in cider (water) with the corresponding composition for apple juices from the same geographical region.

Samples of commercial ciders were purchased from a Polish market. We examined their isotopic composition using IRMS methods. Spcecially, our study concerned the isotopic composition of car-bon 13C ‰ in ethanol, oxygen 18O in water, and carbon 13C in CO2 [1, 2].

The isotopic compositions of water and CO2 [1, 3-5] were determined using GasBench (Thermo-Quest) connected in the continuous fl ow mode to a DELTAplus (FinniganMat) mass spectrometer. The isotopic composition 13C of ethanol was measured using the same mass spectrometer with the elemental analyser Flash EA1112 (Thermo-Quest). Every sample was measured six times for both the carbon and oxygen isotopic composition. The standard deviation of the values obtained from measurements was 0.2‰ for 13C (ethanol and CO2) and 0.15‰ for 18O (water).

The isotopic composition of 13C in CO2 and ethanol is fi nally expressed by the following equa-tion:

The examples of measured isotopic composi-tion values of cider components are presented in Figs. 1-3.

13 13

12 1213 SAMPLE STANDARD 0

00vsPDB 13

12STANDARD

C CC C

C 1000CC

Fig. 1. The measured 13C values of ethanol for ciders.

Fig. 2. The measured 18O values for ciders (water).

Fig. 3. The measured 13C values of CO2 included in the tested ciders.

107STABLE ISOTOPE LABORATORY

In conclusion, the work will be continued to characterize components from the bigger popula-tion of commercial products (ciders). The main result of the studies will be the formation of a database containing the stable isotopic composi-tions for all of the basic components of ciders from different origins. By utilizing the database, employing the isotopic method for the origin con-trol of ciders can be implemented in everyday practice.

Finally, on the basis of the study the correla-tions between a carbon isotopic composition 13C in CO2 and C2H5OH and 18O in water will be elaborated on.

References[1]. Gaillard, L., Guyon, F., Salagoity, M.-H., & Medina, B.

(2013). Authenticity of carbon dioxide bubbles in French ciders through multifl ow-isotope ratio mass spectro-metry measurements. Food Chem., 141, 2103-2107.

[2]. Carter, J.F., Yates, H.S.A., & Tinngi, U. (2015). Stable isotope and chemical compositions of European and Australasian ciders as a guide to authenticity. J. Agric. Food Chem., 63, 975-982.

[3]. Gonzalez-Martin, I., Gonzalez-Perez, C., & Marques--Macias, E. (1997). Contribution to the study of the origin of CO2 in Spanish sparkling wines by determi-nation of the 13C/12C isotope ratio. J. Agric. Food Chem., 45, 1149-1151.

[4]. Martinelli, L.A., Moreira, M.Z., Ometto, J.P.H.B., Al-carde, A.R., Rizzon, L.A., Stange, E., & Ehleringer, J.R. (2003). Stable carbon isotopic composition of the wine and CO2 bubbles of sparkling wines: Detecting C4 Sugar additions. J. Agric. Food Chem., 51, 2625-2631.

[5]. Cabañero, A.I., San-Hipólito, T., & Rupérez, M. (2007). GasBench/isotope ratio mass spectrometry: a carbon isotope approach to detect exogenous CO2 in sparkling drinks. Rapid Commun. Mass Spectrom., 21 (20), 3323-3328.

LABORATORY LABORATORY FOR MEASUREMENTS FOR MEASUREMENTS

OF TECHNOLOGICAL DOSESOF TECHNOLOGICAL DOSES

The Laboratory for Measurements of Technological Doses (LMTD) was created in 1998 and accredited as a testing laboratory in February 2004 (Polish Centre of Accreditation, accredi-tation 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 fi lm dosimeter (10-80 kGy),• electron radiation dose measurement by means of a CTA fi lm 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 60Co gamma radiation to strictly de-

fi ne doses,• irradiation of dosimeters or other small objects with 10 MeV electron beams to strictly

defi ne doses.The secondary standard of the dose rate utilized by the LMTD is a 60Co gamma source

Issledovatel and a Gamma Chamber 5000. The sources were calibrated in January 2016 and in March 2012, respectively, according to the NPL (National Physical Laboratory, Teddington, UK) primary standard. The uncertainty of the dose rate was estimated to be 3.0 and 3.1% (U, k = 2).

110 LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES

MEASUREMENT TRACEABILITY OF 60Co GAMMA SOURCE ISSLEDOVATELAnna Korzeniowska-Sobczuk, Magdalena Karlińska

Table 1. Summary of the results of the calibration for all measuring positions of the LMTD tripod.

In accordance with the recommendations of the standard PN-EN ISO/IAC 17025:2005 [1] a lab-oratory establishes traceability of its own meas-urement standards and measuring instruments to the SI by means of an unbroken chain of calibra-tions or comparisons that links them to the rele-vant primary standards of the SI units of meas-urement. The link to SI units may be achieved by referencing to the national measurement stand-ards. These may be primary standards, which are primary realizations of the SI units or agreed rep-resentations of SI units based on fundamental physical constants, or they may be secondary standards calibrated by another national metrol-ogy institute. Calibration of all types of dosimeter systems used routinely should be checked by com-parison with a reference standard or a transfer standard dosimeter. Detailed guidance regarding the experiment is shown in the standard ISO/ASTM 51400:2003(E) [2].

A 60Co gamma source Issledovatel is similar in its construction to the well-known Gammacell 220 (Nordion, Canada). Here, individual 60Co sources are placed at fi xed positions around the cylindri-cal working area having dimensions: h = 20 cm, Ø = 14 cm. There are actually 36 gamma sources

and a place for an additional 12 sources. The use of biological shields enables one to work in the vicinity of the source at all times without over-crossing the permissible doses. The irradiated samples are lifted automatically via an electric motor into the working area. The dose absorbed by the sample consists of two parts: • dose obtained by the sample at a stationary,

immobile position; • dose obtained during sample movement into

and out of the radiation fi eld, known as the throw-out or down-up dose.The Laboratory for Measurements of Tech-

nological Doses (LMTD) uses two 60Co gamma sources: Issledovatel and Gamma Chamber 5000. In accordance with the requirements of the man-agement system, large sources of radiation must be calibrated every 5 years regarding accurate control of doses. By using dosimeters, the LMTD has a reference traceable to a primary standard

maintained by the National Metrology Institute. To ensure the traceability of gamma source meas-urement, the LMTD is required to purchase ser-vices from the National Physical Laboratory (NPL, Teddington, United Kingdom). The fi rst offi cial measurement of the traceability of the 60Co gamma source Issledovatel was carried out in December 2003, and subsequent measure-ments were carried out in April 2009 and January 2016.

Calibration measurements for the gamma ra-diation source Issledovatel were performed by the following steps:• irradiation transfer of alanine dosimeters in the

six working slots of the standard polystyrene tripod used by the LMTD for irradiation;

• accurate measurement of irradiation time us-ing two independent, calibrated timers;

• reading the dose by NPL;• calculation of the dose rate in SI units (kGy/h);• creation of a balance of uncertainty for the ir-

radiation.The NPL results of dose measurements for ala-

nine and the LMTD calculated dose after the sec-ond traceability measurements are given in Table 1. The results show agreement between doses meas-

ured with alanine reference dosimeters and the calculated dose with a maximum difference of 1.1%. The calibration verifi cation result is accept-ed and importantly meets the requirements of ASTM. The balance that was developed takes into account the uncertainty of such cases as mention-ed above, and sources of uncertainity and their corresponding values are shown in Table 2. The expanded uncertainty surrounding dose rate meas-urement in the 60Co gamma source Issledovatel are estimated to be 2.97% (k = 2).

The current values of the dose rate 60Co gamma source Issledovatel in reference points are calcu-lated by taking into account the absorbed dose specifi ed in the NPL protocol “Certifi cate of cali-bration” No. 2015110464/1 dated 16.02.2016, the value of a constant rate of decay of 60Co, and the temporal distance calibration date (12.01.2016) from the date of irradiation, assuming an expo-nential nature of the activity decay curve.

No.position

Calculated dose rate at the source on 12.01.2016

[kGy/h]

The dose rate measured alanine NPL

[kGy/h]

Difference in the dose rate

[%]

The dose moving down the mountain

[kGy]

1 0.366 0.365 -0.27

0.002

2 0.368 0.365 -0.82

3 0.375 0.371 -1.08

4 0.378 0.375 -0.80

5 0.372 0.371 -0.27

6 0.365 0.365 0.00

111LABORATORY FOR MEASUREMENTS OF TECHNOLOGICAL DOSES

References[1]. Polski Komitet Normalizacyjny. (2005). Ogólne wyma-

gania dotyczące kompetencji laboratoriów badawczych i wzorcujących (General requirements for the compe-tence of testing and calibration laboratories). PN-EN ISO/IAC 17025:2005.

[2]. International Organization for Standardization/ASTM International. (2003). Standard practice for character-ization and performance of a high-dose radiation dosimetry calibration laboratory. ISO/ASTM 51400:2003(E).

Table 2. Measurement uncertainties for 60Co gamma source Issledovatel.

Sources of uncertainty of irradiation in 60Co gamma source Issledovatel

Uncertainty associated with calibration of this batch of alanine dosimeters 2.4%

Uncertainty associated with variation between individual dosimeters within this batch 1.0%

Variability in tripod positioning 0.02%

The non-uniformity of the dose in the cavity tripod 0.9%

Uncertainty associated with a dose moving down the mountain 0.01%

Uncertainty associated with the rate constant decay of cobalt 0.5%

The expanded uncertainty U (k = 2) 2.97%

LABORATORY FOR DETECTION LABORATORY FOR DETECTION OF IRRADIATED FOODOF IRRADIATED FOOD

The Laboratory for Detection of Irradiated Food was created at the Institute of Nuclear Chemistry and Technology in 1994. The adoption of the quality assurance system resulted in accreditation of the Laboratory in 1999 by the Polish Centre for Accreditation (PCA). Since that time, the Laboratory for Detection of Irradiated Food has constantly maintained the status of an accredited R&D unit and is authorized to examine food samples to classify them as being either irradiated or not irradiated. Every four years, the Laboratory accreditation certifi cate must to be renewed after succesfully passing the PCA expert audit. The current certifi cate, which is the 5th, was received on 30th September 2014 and is valid until 24th October 2018.

Professional and well-experienced staff members are working to improve irradiation de-tection methods adapted in the Laboratory to make them more sensitive and reliable for an extended group of food articles. The Laboratory offers analytical services for this application to domestic and foreign customers for an extended assortment of food articles via the use of fi ve appropriate and normalized analytical methods. The Scope of Accreditation – an integral part of the accreditation certifi cate, offers customers fi ve methods suitable to detect radiation treatment in almost all foodstuffs available in the open market. During the last 17 years of analytical activity, nearly 4000 food samples were successfully examined and classifi ed.Nowadays, many food items such as herbal pharmaceuticals, diet supplements, and food extracts are received by the Laboratory for examination of irradiation from our domestic and foreign customers.

The Laboratory implemented the following detection methods:• A method for the detection of irradiated food from which silicate minerals can be isolated

using a thermoluminescence (TL) reader, this method is based on analytical procedures recommended by the CEN European standard EN 1788.

• A method for the detection of irradiated food containing bone via use of electron para-magnetic spectroscopy (EPR/ESR) based on an analytical procedure described by the CEN European standard EN 1786.

• A method for the detection of irradiated food containing cellulose via use of EPR spec-troscopy based on an analytical procedure described by the CEN European standard EN 1787.

• A method for the detection of irradiated food containing crystalline sugars with EPR spec-troscopy based on analytical procedures described by the CEN European standard EN 13708.

• A method for the detection of irradiated food using a photostimulated luminescence (PSL) reader; this method is based on analytical procedures recommended by the CEN European standard EN 13751.

The application of the aforementioned fi ve standardized detection methods to specifi ed groups of foods that have been validated in the Laboratory guarantees the accurate analysis and re-liable classifi cation of food samples delivered to the Laboratory for testing.

The Laboratory is actively implementing improved analytical and measurement proce-dures that are suitable for irradiation detection in complex food articles containing low or very low concentrations of irradiated ingredients. These are typically aromatic herbs and spices admixed to the product.It has been experimentally proven that modifi cation of the mineral isolation procedure, the determination of isolated mineral content, and the effectiveness of mineral thermolumines-cence are the important factors that infl uence the detection ability of the employed analytical method.

In 2016, the Laboratory reported a large increase in the number of samples delivered by domestic customers to by analysed; samples were also delivered by foreign customers in Ger-many, Italy, Denmark, Latvia, Hungary, and Spain. The assortment of samples received com-prised food extracts, herbal pharmaceuticals, diet supplements, spices, dried vegetables, and red fermented rice. In total, 765 samples were examined. Of these, 760 samples were examined by the TL method, while the EPR based analytical procedures were applied only fi ve times.

From 19th June 2012, the Laboratory has held the status of the primary reference labora-tory in the fi eld 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 respon-sible for managing and monitoring irradiated food around the country.

In October 2016, the Laboratory organized the “Intercomparative exercise for quality as-surance on TL irradiated food detection method” with the participation of specialized ana-lytical laboratories from Poland.

115LABORATORY FOR DETECTION OF IRRADIATED FOOD

INVESTIGATION OF THE THERMOLUMINESCENCE METHOD OF LOW DOSE IRRADIATED DRIED FRUITS

Magdalena W. Sadowska, Grażyna Liśkiewicz

Dried fruits are a commercial product for home use and are also used industrially as active ingre-dients in plant pharmaceuticals, namely diet sup-plements, as well as teas and herbal infusions. These products are available in shops and are also sold in pharmacies and drugstores without medi-cal prescriptions. In addition to herbs and spices, dried fruits are included in a group of products that are subject to ionizing radiation. The safe dose of ionizing recommended by FAO/WHO [1] is 7-10 kGy. However, recently for the decontami-nation of these products thermal methods are ap-plied in combination with irradiation. It is known that markedly lower doses of ionizing radiation are applied in the combined disinfection processes.

The aim of the present study was to determine the possibility and reliability of detecting of irra-diation in dried fruits irradiated with low doses of ionizing radiation. The analytical procedure ap-plied is based on the CEN European standard EN 1788 regarding the detection of irradiated food

from which silicate minerals can be isolated based on the thermoluminescence method (TL) [2]. The subjects of the investigation were 10 varieties of dried fruit used in the pharmaceutical industry for the production of phytopreparation, mainly food supplements. The following fruits were studied: dried strawberries, dried cherries, dried black cur-rants, dried raisins of two types, dried mulberries, dried apricots, dried fi gs, dried dates and prunes. Taking into account the results of the previous re-search carried out on plant material, the radiation doses used were: 0.1, 0.3, and 0.5 kGy. For com-parison non-irradiated samples of all tested prod-ucts were also investigated.

The fruit samples were washed with deminer-alized water and subsequently endured ultrasound treatment for at least 20 min. The following den-sity separation was then carried out in compliance with the procedure given in the EN 1788 stand-ard. All samples were sieved on 250 m nylon

sieves. Silicate minerals isolated from the samples were placed in stainless steel TL measuring cups and heated overnight at 50oC. Thermolumines-cence measurements were carried out using a RISOE TL/OSL DA 20 reader. The instrument adjustments were as follows: initial temperature – 50oC, fi nal temperature – 450oC, speed of the heating – 6oC/s.

Two subsequent TL measurements were con-ducted with each of samples. These were: a preli-minary measure (glow 1) and a calibrated measure (glow 2) which was performed after the calibrat-ed irradiation of TL measuring cups containing the minerals with radiation via a dose of 1 kGy of the 60Co gamma rays from Gamma Chamber 5000.

Table 1 comprises the representative results ob-tained with dried fruits. The TL intensities attrib-uted to glow 1 and glow 2 represent the integrated area under the TL time dependent curve within the range of 150-250oC.

The recorded TL glow 1 curves of all irradiat-ed samples show the maxima of the TL intensity in the range of temperatures between 170 and 210oC, which is typical for irradiated silicate min-erals isolated from food. However, the glow 1/glow 2 ratio calculated for all samples irradiated with 0.3 and 0.5 kGy was higher than 0.1 proving the irradiation guidlines according to EN 1788.

Ambiguous results were obtained from the samples irradiated with the lowest dose of 0.1 kGy. The glow 1/glow 2 ratio for these samples decreased below 0.1 and was slightly lower than the others within the limits of 0.048-0.094. On the other hand, the glow curves of these samples in the range of 150-250oC have well distinguished peaks from 184 to 208oC (Fig. 1) which is typical for irradiated samples.

The standard that EN 1788:2001 provides for such cases is true promarily with respect to mix-ed products, with an emphasis on the presence

Table 1. Representative results of applied dose, temperature, and glow ratios of minerals isolated from dried fruits.

Type of fruit (country of origin)

Radiation dose

[kGy]

Intensity glow 1 (150-250oC)

Intensity glow 2 (150-250oC)

Glow 1/glow 2 ratio

TL max. glow 1 [oC]

TL max. glow 2 [oC]

1 2 3 4 5 6 7

Dried strawberry (Thailand)

0 198 506 70 836 640 0.003 274 184

0.1 4 523 523 65 911 546 0.069 189 185

0.3 17 255 429 60 080 576 0.287 187 184

0.5 12 389 562 25 769 557 0.481 184 185

Sultana raisins (India)

0 10 854 7 716 995 0.001 > 300 193

0.1 626 748 13 023 415 0.048 202 195

0.3 2 097 384 13 172 576 0.159 204 193

0.5 3 007 242 8 762 420 0.343 202 189

116 LABORATORY FOR DETECTION OF IRRADIATED FOOD

and shape of the glow maxima in the range of 250-150oC. The European standard says that suf-fi ciently reliable evidence of sample irradiation in-cludes a glow 1/glow 2 ratio that is slightly lower than the value of 0.1, as in the case of the examin-ed samples, and well distinguished maximum ob-served in the range of 150-250oC. All investigated samples have glow 2 curves with maximum in the

range 170-200oC (Fig. 2). It proofs the presents of silicate minerals in all samples.

The investigation of 10 dried fruits showed that this group of products can be investigated ef-fectively independent of irradiation by the thermo-luminescence method.

The important achievement of the present study was that it was ascertained that the TL

Fig. 1. Glow 1 curve of dried dates irradiated with 0.1 kGy gamma rays.

Fig. 2. Glow 2 curve of dried dates after calibrated irradiation with a dose of 1 kGy.

117LABORATORY FOR DETECTION OF IRRADIATED FOOD

method is suitable for the identifi cation of food irradiated with low doses of ionizing radiation (0.5 kGy and lower). Thus, this method is suitable and effective for the control of food articles irra-diated with low doses. These kinds of food prod-ucts are likely present in the food market as a con-sequence of the development and implementation of combined microbial decontamination methods as thermal/radiation treatment.

References[1]. FAO/WHO. General Standard for Irradiated Foods.

Codex Stan. 106-1983, Rev.1-2003.[2]. European Committee for Standardization. Foodstuffs

– Thermoluminescence detection of irradiated food from which silicate minerals can be isolated. EN 1788:2001.

ADVANTAGE OF NEW THERMOLUMINESCENCE READER-ANALYSER INSTALLED IN THE LABORATORY FOR DETECTION

OF IRRADIATED FOODGrzegorz Guzik

Thermoluminescence (TL) measurement is an es-sential analytical method that enables the detec-tion of irradiated food. Although the method is rather time-consuming due to the necessity of special sample preparation, it provides highly ac-curate and reliable results. The method is appli-cable to a wide assortment of foodstuffs.

The method has only been validated for use with simple uniform food samples (spices, fruits, etc.), but has not yet been validated for use with widely distributed blends of products or food samples containing admixtures of irradiated prod-uct only. To validate TL measurement for this ap-plication, samples were irradiated with doses of ionizing radiation equal to or lower than 10 kGy, as recommended by FAO/WHO in Codex Ali-mentarius [1].

The accredited Laboratory for Detection of Ir-radiated Food of the Institute of Nuclear Chem-istry and Technology (INCT) received its present Accreditation Certifi cate of Testing Laboratory number AB 262 dated 25 October 1999 from the Polish Centre of Accreditation, which has been ex-tended until 24 October 2018. The accreditation range is defi ned in the appendix to this document, titled “Scope of Accreditation”, with the list of standard methods for the detection of irradiation for different groups of food which are recommend-ed by the European Committee for Standardiza-tion (CEN), including thermoluminescence.

Until now, the Laboratory for Identifi cation of Irradiated Food executed the TL measure-ment via a single Risoe National Laboratory type TL/OSL-DA-20 reader. In the event of unexpect-ed instrument failure, followed by a deterioration of the instruments operational ability, the Labora-

tory was unable to fulfi l its analytical obligations to domestic and foreign customers on time. Such situations also negatively infl uenced the analyti-cal obligations of the Laboratory as the Reference Laboratory of the Ministry of Health. Recently, the Laboratory was equipped with a new TL device – Laboratory Reader-Analyser RA04, produced by MIKROLAB s.c. (Kraków, Poland). Technical specifi cation of the instrument meets all relevant requirements of European Directives 72/23/EEC and 93/68/EEC as well as the European standard (Polish version) PN-EN 61010-1:2004. The ad-vantage of a new TL reader is that the installation of luminescence diodes allow for quick measure-ment of light count, which is not possible with the TL/OSL-DA-20 reader.

In order to test the ability of the new instru-ment to be employed as a tool to fulfi l the analy-tical duties of the Laboratory (TL measurements), a comparative study was arranged with the use of the TL/OSL-DA-20 reader as a reference. All test TL measurements were performed using the two instruments in parallel under the same measuring conditions and adjustments.

The samples used in the comparative study to test new TL reader were selected herbs, season-ings, mushrooms, and dietary supplements, all of which are commercially available. The samples were coded and numbered from 1 to 6 (Table 1).

The sample preparation procedure was consist-ent with the methodology described in the PN-EN 1788:2002 standard [2]. The mineral fraction iso-lated from test samples by the density separation method was TL analysed in two repetitions, while three repetitions of blind tests were carried out. The thermoluminescence measurements were con-

Code number Name of product Form of product

T1/A/16 L-arginini-yrtti-sinkkivalmiste diet supplement

T2/A/16 dried button mushroom crumbled dried fungi

T3/A/16 mushroom soup instant powder

T4/A/16 green barley ground powder

T5/A/16 savoury ground seasoning

T6/A/16 broken pepper broken, crumbled seasoning

Table 1. Samples used in the comparative study.

118 LABORATORY FOR DETECTION OF IRRADIATED FOOD

ducted in accordance with the PN-EN 1788:2002 standard and user instructions “Manual of the Thermoluminescence Laboratory Analyser RA04” and “Manual of the Thermoluminescence Lab-oratory Reader RISØ National Laboratory reader TL/OSL-DA-20”.

The results of the TL analyses obtained with two different thermoluminescence readers and the classifi cation of tested samples are presented in Table 2.

The classifi cation of samples obtained inde-pendently from the two instruments was fully con-sistent. No problems appeared by the detection of radiation treatment in samples exposed to ioniz-ing radiation. It is concluded, therefore, that Lab-oratory Reader-Analyser RA04 installed in the Laboratory is suitable to be successfully used for the TL analysis of representative groups of food products tested in the present study to determine whether or not they have been irradiated. The specifi city of the TL analysis of the mineral frac-tion of the investigated food samples is demon-strated by the relatively high dispersion of experi-mental results (count numbers). This is typical for the TL method thus making it diffi cult to de-termine, even roughly, the dose applied to irradi-ate the investigated sample. The decisive para-meters necessary to evaluate new instruments remain the maxima of TL luminescence in glow curves (glow 1) recorded within the temperature range of 150-250oC, as well as the glow 1/glow 2 ratios. Both parameters are simultaneously the basic criterions for food sample classifi cation. The spread of TL maxima as estimated in the glow 1 curves recorded with the Laboratory Reader-Analyser RA04 are from 189 to 232oC, which is not worse than the data recorded with the TL/OSL-DA-20 reader. All maxima fall within

the range of 150-250oC. The criterion decisive to distinguish whether or not a food sample has been irradiated is a critical value of glow 1/glow 2 equal to 0.1. A glow 1/glow 2 ratio lower than 0.1 denotes that the sample was not irradiated, while a higher value indicates that the sample was irradiated. The lowest glow 1/glow 2 value obtained from an irradiated sample using the Laboratory Reader-Analyser RA04 was 0.2241, while the corresponding value obtained with the TL/OSL-DA-20 reader was 0.2382. The results are comparable. Importantly, it should be noted that the obtained results are in accordance with the declarations given by the producers of the in-vestigated samples.

Therefore, it is concluded that the Laboratory Reader-Analyser RA04 is considered to be posi-tively verifi ed in compliance with the require-ments of the PN-EN 1788:2002 standard. It also works equally as quick and precisely as the TL/OSL-DA-20 reader. The instrument can be now successfully used for testing food samples delivered to the Laboratory to determine whether or not they have been irradiated. The newly adapt-ed TL reader enlarges the analytical ability of the Laboratory to control the increasing number of food samples delivered from domestic fi rms and from abroad.

References[1]. FAO/WHO Codex Alimentarius Commission. (1984).

Codex Alimentarius. Vol. XV. Codex general standard for irradiated foods and recommended international code of practice for the operation of radiation facili-ties used for the treatment of foods. FAO.

[2]. European Committee for Standardization. (2002). Foodstuffs – Thermoluminescence detection of irradi-ated food from which silicate minerals can be isolat-ed. PN-EN 1788:2002.

Code number

Laboratory Reader-Analyser RA04 Risoe National Laboratory TL/OSL-DA-20 rea der

evaluation glow 1/glow 2* glow 1/glow 2* evaluation

T1/A/16 irradiated 0.2241 0.4863 irradiated








T5/A/16 non-irradiated 0.0813 0.0011 non-irradiated




Table 2. Results obtained for both apparatuses.

* Glow 1 – the TL glow curve registered (count number vs. temperature) with mineral fraction isolated from raw sample within the temperature range of 150-250oC; glow 2 – the TL glow curve registered with the same mineral fraction ir-radiated with the calibration dose 1 kGy within the temperature range of 150-250oC; glow 1/glow 2 – the ratio of the integrated areas below the glow curves glow 1 and glow 2.

LABORATORY LABORATORY OF NUCLEAR CONTROL SYSTEMSOF NUCLEAR CONTROL SYSTEMS

AND METHODSAND METHODS

The primary focus of the Laboratory activity in 2016 was the development of methods and equipment, based generally on the applications of ionizing radiation and process engineering for both measurements and diagnostic purposes. The research programme of the Laboratory focused on the following topics:• development of measuring devices and systems for industry and for protection of the en-

vironment;• development of measuring equipment for other Institute laboratories and centres;• development of a new leakage control method for testing industrial installations during

their operation;• identifi cation and optimization of industrial processes using the tracer and radiotracer

methods;• application of membrane processes of biogas separation and their enrichment in methane;• elaboration and industrial scale implementation of new methods and technology for biogas

production by fermentation of agriculture substrates and by-products such as wastewater sediments obtained during wastewater clarifi cation.In the fi eld of elaboration and construction of nuclear instrumentation, these works were

directed towards the detection of radioactive contamination and measurements of the con-centration of radon daughters in air.

In collaboration with the International Atomic Energy Agency (IAEA), we carried out the works concerning the development of radiometric methods for optimization of mining and metallurgical processes, including the elaboration of new nano-radiotracers with magnetic and fl uorescence properties.

120 LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS

RADIOMETRIC METHOD FOR MEASURING AND MODELLING MULTIPHASE SYSTEMS TOWARDS PROCESS MANAGEMENT

Jacek Palige, Otton Roubinek, Andrzej Dobrowolski, Wojciech Sołtyk

The legal requirement and steady increase in en-ergy demand means that there is a need to develop alternative energy technologies, such as nuclear power and biotechnology that do not lead to an increase of CO2 emission. These will replace exist-ing energy sources based on the combustion of coal, oil, and natural gas. Energy production us-ing biogas obtained from the anaerobic digestion of selected agricultural products, as well as from agricultural and food wastes, is extremely impor-tant due to the large Polish agricultural potential. This biotechnology also provides the possibility to use the sediment from the wastewater treatment station as a source of biogas production. Currently in Poland, there are about thirty large functional biogas plants with a capacity of 1 MW each. One of the employed technologies is the following

Polish solution based on the Polish patent No. 197595.

Here, the fermentation process is carried out in several stages:• biomass preparation (fragmentation, mixing with

process water and liquid digestate to obtain a suspension with 5-8% of dry weigh content);

• production of biogas in a cascade of hydrolyser and fermenter which introduces signifi cant sep-aration of the biomass hydrolysis from basic methane fermentation;

• recycling to the process effl uent with required cultures of microorganisms;

• mixing of suspension in the fermenter by liquid feed streams and streams of circulation forced by periodically pumping the slurry from the out-let to the inlet of the fermenter and from the bottom of the fermenter to the surface of the liquid phase which leads to homogenization of the composition of the slurry and partly pre-vents the formation of fl oating sludge.From the process engineering point of view, it

was very important to investigate the effi ciency of methane production process (gas composition and quantity of gas obtained from 1 kg of dry mass) and to also optimize the geometry of tanks, the mixing effi ciency, and check the liquid phase residence time distribution (RTD) function. For these pur-poses and to scale up installations, the following three types of digestion systems were investigated:• the laboratory system consisting of a hydrolyser

with 2 dm3 volume and a fermenter with a 42 dm3 volume,

• the laboratory system consisting of a 42 dm3 hydrolyser and 400 dm3 fermenter,

• pilot plant with a 1 m3 hydrolyser and 8 m3 fer-menter.

In all cases, the hydrolysers and fermenters pre-sent the horizontal, steel or plastic cylinders equip-ped in hydraulic systems for feed and mixing of the biomass.

The fi rst installation with a hydrolyser of 2 dm3 volume (length – 27 cm, diameter – 13 cm) and fermenter of 42 dm3 volume (length – 60 cm, dia-meter – 30.5 cm) was investigated.

The system is working quasi-continuously. The materials i.e. 1 dm3 of raw biomass plus 1 dm3 of recirculating liquid from the fermenter is charged to the hydrolyser, and each is pumped to the fer-menter for 2 days.

Every 2-3 days, a volume of 2 dm3 of liquid is removed from the fermenter (1 dm3 of recirculat-ed). A scheme of the fl ow is presented in Fig 1.

The general view of the installation under in-vestigation is presented in Fig. 2. The consistency of the liquid phase in the fermenter – mixture of solid particles, water, suspensions etc., were taken into account, and only a radioactive tracer was used for RTD function determination. Accord-

Fi g. 2. View of installation (plus scanner).

Fig. 1. Scheme of the material fl ow in installation.

121LABORATORY OF NUCLEAR CONTROL SYSTEMS AND METHODS

ingly, a tracer was applied the hydrogen isotope – tritium (T) in the form of tritium water (half--time of tritium is T1/2 4510 days, emission of soft beta radiation – 0.018 MeV). The tracer was injected instantaneously to the input of fermenter during charging. The samples of materials were taken from the output of the fermenter during the periodic discharge. The sample activity was meas-ured with a liquid scintillator Wallac-Guardian application so samples were distillated before the measuring procedure.

The mean fl ow rate during the experiment was Q = 0.60 dm3/day. The results of the measure-ment with data extrapolation are presented in Fig. 3.

The measured curve (tracer concentration vs. time of experiment) represents the experimental RTD curve. The scheme of fl ow in the fermenter was simulated using a simple model consisting of plug fl ow and two units of perfect mixing. The result of fi tting the experimental data with the theoretical RTD curve is presented in Fig. 4.

The model parameters are:• plug fl ow units – T1 = 2 days;• perfect mixers – T2 = 24 days, T3 = 26 days.

The obtained results indicate that in fermenter, the dead volume does not exist and there are two

Fig. 3. Experimental curve RTD.

regions with perfect mixing of the liquid phase. The obtained fl ow structure is profi table based on how the fermenter works.

The fermenter presents the close, steel cylin-drical container so that it is diffi cult to check the volume of liquid phase inside. To determine the liquid volume and presents of foam inside the fer-menter, measurements were carried out that ap-plied the gamma scanner technology elaborated by the Institute of Nuclear Chemistry and Technol-ogy (INCT) in the frame of IAEA TC project Pol 0/010. The sealed sources of Co-60 and Cs-137 with an activity of 550 MBq were used. During the measurements, the collimated source and de-tector moved along the height of the fermenter with the space step of discretization 1 cm. Figure 5 shows the scan of a fermenter obtained in the centre cross-section. Analysis of the density dis-tribution inside the reactor indicated that the height of the liquid phase is about 20 cm includ-ing about 3 cm of foam. The calculated volume of the liquid phase is about 30 dm3, so the theoreti-

cal mean residence time (MRT) during the experi-ment was 51 days. This value confi rms, that the inside of the fermenter is not observed the pres-ence of dead volume.

Fig. 4. Comparison of experimental and model RTD func-tion.

Fig. 5. Scheme of scanning measurement and distribution of the density inside the fermentor.

122 PUBLICATIONS IN 2016

PUBLICATIONS IN 2016

ARTICLES

Journals from Thomson Reuters database JCR1. Arabski M., Barabanova A., Gałczyńska K., Węgierek-Ciuk A., Dzidowska K., Augustyniak D., Dru-

lis-Kawa Z., Lankoff A., Yermak I., Molinaro A., Kaca W. Modifi cation biological activity of S and R forms of Proteus mirabilis and Burkholderia cepacia lipo-polysaccharides by carrageenans. Carbohydrate Polymers, 149, 408-414 (2016).

2. Asare N., Dueale N., Slagsvold H.H., Lindeman B., Olsen A.K., Gromadzka-Ostrowska J., Męczyń-ska-Wielgosz S., Kruszewski M., Brunborg G., Instanes Ch. Genotoxicity and gene expression modulation of silver and titanium dioxide nanoparticles in mice. Nanotoxicology, 10, 3, 312-321 (2016).

3. Bobrowski K., Skotnicki K., Szreder T. Application of radiation chemistry to some selected technological issues related to the development of nuclear energy. Topics in Current Chemistry, 374, 5, 60(48 p.) (2016). DOI: 10.1007/s41061-016-0058-7.

4. Boguski J., Przybytniak G. Benefi ts and drawbacks of selected condition monitoring methods applied to accelerated radiation aged cable. Polymer Testing, 53, 197-203 (2016).

5. Brykała M., Rogowski M. Preparation of microspheres of carbon black dispersion in uranyl-ascorbate gels as precursors for uranium carbide. Progress in Nuclear Energy, 89, 132-139 (2016).

6. Brykała M., Rogowski M. The complex sol-gel process for producing small ThO2 microspheres. Journal of Nuclear Materials, 473, 249-255 (2016).

7. Chajduk E., Bojanowska-Czajka A. Corrosion mitigation in coolant systems in nuclear power plants. Progress in Nuclear Energy, 88, 1-9 (2016).

8. Chajduk E., Kulisa K., Samczyński Z. Oznaczanie wybranych zanieczyszczeń obecnych w wodach obiegu pierwotnego podczas normalnej eksploatacji elektrowni jądrowej (Determination of selected impurities in primary circuit waters during normal operation of nuclear power plants). Przemysł Chemiczny, 5, 934-937 (2016).

9. Chmielewska D., Stachurska L. Studies on the potassium-nickel hexacyanoferrate/ethanolamine/silica ion exchanger for 60Co removal from spent fuel storage basins and the primary water circuit of nuclear reactors. Journal o Radioanalytical and Nuclear Chemistry, 307, 1295-1301 (2016).

10. Chmielewski A.G., Han B. Electron beam technology for environmental pollution control. Topics in Current Chemistry (Z), 374, 68, 30 p. (2016). DOI: 10.1007/s41061-016-0069-4.

11. Chmielewski A.G., Szołucha M.M.Radiation chemistry for modern nuclear energy developments. Radiation Physics and Chemistry, 124, 235-240 (2016).

123PUBLICATIONS IN 2016

12. Chmielewski A.G., Wawszczak D., Brykała M.Possibility of uranium and rare metal recovery in the Polish copper.Hydrometallurgy, 159, 12-18 (2016).

13. Chróścicka A., Jaegermann Z., Wychowański P., Ratajska A., Sadło J., Hoser G., Michałowski S., Lewandowska-Szumiel M. Synthetic calcite as a scaffold for osteoinductive bone substitutes. Annals of Biomedical Engineering, 44, 7, 2145-2157 (2016).

14. Cieśla K., Sartowska B. Modifi cation of the microstructure of the fi lms formed by gamma irradiated starch examined by SEM. Radiation Physics and Chemistry, 118, 87-95 (2016).

15. Clementi C., Nowik W., Romani A., Cardon D., Trojanowicz M., Davantes A., Chaminade P. Towards a semiquantitative non invasive characterisation of Tyrian purple dye composition: Conver-gence of UV-Visible refl ectance spectroscopy and fast-high temperature-high performance liquid chro-matography with photodiode array detection. Analytica Chimica Acta, 926, 17-27 (2016).

16. Dispenza C., Sabatino M.A., Grimaldi N., Mangione M.R., Walo M., Murugan E., Jonsson M. On the origin of functionalization in one-pot radiation synthesis of nanogels from polymer solutions. RSC Advances, 6, 2582-2591 (2016).

17. Dobrowolski J.Cz., Jamróz M.H., Lipiński P.F.J. On chiral graph topological indices of -amino acids. MATCH Communications in Mathematical and in Computer Chemistry, 76, 2, 401-418 (2016).

18. Dobrowolski J.Cz., Lipiński P.F. On splitting of the NICS(1) magnetic aromaticity index. RSC Advances, 6, 23900-23904 (2016).

19. Dziendzikowska K., Krawczyńska A., Królikowski T., Brzóska K., Lankoff A., Dziendzikowski M., Stępkowski T., Kruszewski M., Gromadzka-Ostrowska J. Progressive effects of silver nanoparticles on hormonal regulation of reproduction in male rats. Toxicology and Applied Pharmacology, 313, 35-46 (2016).

20. Fernandes Â., Barreira J.C.M., Antonio A.L., Rafalski A., Morales P., Férnandez-Ruiz V., Oliveira M.B.P.P., Martins A., Ferreira I.C.F.R. Gamma and electron-beam irradiation as viable technologies for wild mushrooms conservation: effects on macro- and micro-elements. European Food Research and Technology, 242, 1169-1175 (2016).

21. Filipiak P., Bobrowski K., Hug G.L., Pogocki D., Schöneich C., Marciniak B. Formation of a three-electron sulfur-sulfur bond as a probe for interaction between side chains of me-thionine residues. The Journal of Physical Chemistry B, 120, 9732-9744 (2016).

22. Fuks L., Oszczak A., Dudek J., Majdan M., Trytek M. Removal of the radionuclides from aqueous solutions by biosorption on the roots of the dandelion (Taraxacum offi ciale). International Journal of Environmental Science and Technology, 13, 2339-2352 (2016).

23. Gach K., Grądzka I., Wasyk I., Męczyńska-Wielgosz S., Iwaneńko T., Szymański J., Koszuk J., Ja-necki T., Kruszewski M., Janecka A. Anticancer activity and radiosensitization effect of methyleneisoxazolidin-5-ones in hepatocellular car-cinoma HepG2 cells. Chemico-Biological Interactions, 248, 68-73 (2016).

24. Gładysz-Płaska A., Oszczak A., Fuks L., Majdan M. New effective sorbents for removal of Am-241 from drinking water. Polish Journal of Environmental Studies, 25, 6, 2401-2410 (2016).

25. Gumiela M., Dudek J., Bilewicz A. New precipitation method for isolation of 99mTc from irradiated 100Mo target. Journal of Radioanalytical and Nuclear Chemistry, 310, 1061-1067 (2016). DOI: 10.1007/s10967-016--4967-2.


26. Guzik G.P., Stachowicz W. Study on radiation-induced radicals giving rise to stable EPR signal suitable for the detection of irradia-tion in L-sorbose-containing fruits. Nukleonika, 61, 4, 461-465 (2016).

27. Klionsky D., J., Abdelmohsen K., Abe A., …, Stępkowski T., … (and others). Guidelines for the use and interpretation of assays for monitoring autophagy (3rd edition). Autophagy, 12, 1, 1-222 (2016).

28. Kużelewska I., Polkowska-Motrenko H., Danko B.Determination of chromium in biological materials by radiochemical neutron activation analysis (RNAA) using manganese dioxide. Journal of Radioanalytical and Nuclear Chemistry, 310, 559-564 (2016).

29. Lazurik V.M., Lazurik V.T., Popov G., Zimek Z.Two-parametric model of electron beam in computational dosimetry for radiation processing. Radiation Physics and Chemistry, 124, 230-234 (2016).

30. Lewandowska H., Kalinowska M., Lewandowski W., Stępkowski T.M., Brzóska K. The role of natural polyphenols in cell signaling and cytoprotection against cancer development. Journal of Nutritional Biochemistry, 32, 6, 1-19 (2016).

31. Lipiński P.F.J., Dobrowolski J.Cz.Substituent effect in theoretical ROA spectra. RSC Advances, 6, 40760-40764 (2016).

32. Lipiński P.F.J., Jarończyk M., Ostrowski S., Dobrowolski J.Cz., Sadlej J. Conformation of six fentanyls revisited. Computational and Theoretical Chemistry, 1086, 18-24 (2016).

33. Łada W., Iller E., Wawszczak D., Komor M., Dziel T. 90Y microspheres prepared by sol-gel method, promising medical material for radioembolization of liver malignancies. Materials Science and Engineering C, 67, 629-635 (2016).

34. Łuczyńska K., Drużbicki K., Łyczko K., Dobrowolski J.Cz. Structure-spectra correlations in anilate complexes with picolines. Crystal Growth & Design, 16, 6069-6083 (2016).

35. Matysiak M., Kapka-Skrzypczak L., Brzóska K., Gutleb A.C., Kruszewski M. Proteomic approach to nanotoxicity.Journal of Proteomics, 137, 35-44 (2016).

36. Mays C., Valůch J., Perko T., Daris I., Condi C., Miśkiewicz A., Zakrzewska G., Constantin M., Diaconu D., Kralj M., Železnik N. Looking for citizen-centered communication: dialogues or nuclear safety specialists and media professionals. Journal of Radiological Protection, 36, S143-S159 (2016).

37. Męczyńska-Wielgosz S., Piotrowska A., Majkowska-Pilip A., Bilewicz A., Kruszewski M. Effect of surface functionalization on the cellular uptake and toxicity of nanozeolite A. Nanoscale Research Letters, 11, 123 (14 p.). DOI: 10.1186/s11671-016-1334-8.

38. Miśkiewicz A., Zakrzewska-Kołtuniewicz G., Dłuska E., Walo P.F. Application of membrane contractor with helical fl ow for processing uranium ores. Hydrometallurgy, 163, 108-114 (2016).

39. Pawelec A., Chmielewski A.G., Licki J., Bumsoo Han, Jinkyu Kim, Kunnummal N., Fageeha O.I. Pilot plant for electron beam treatment of fl ue gases from heavy fuel oil fi red boiler. Fuel Processing Technology, 145, 123-129 (2016).

40. Pawlukojć A., Hetmańczyk Ł. INS, DFT and temperature dependent IR studies on dynamical properties of acetylcholine chloride. Vibrational Spectroscopy, 82, 37-43 (2016).

41. Perez-Ortega P., Lara-Ortega F.J., García-Reyes J.F., Gilbert-López B., Trojanowicz M., Molina-Diaz A. A feasibility study of UHPLC-HRMS accurate-mass screening methods for multiclass testing of organic contaminants in food. Talanta, 160, 704-712 (2016).


42. Przybytniak G., Nowicki A., Mirkowski K., Stobiński L. Gamma-rays initiated cationic polymerization of epoxy resins and their carbon nanotubes composites. Radiation Physics and Chemistry, 121, 16-22 (2016).

43. Rode J.E., Narbutt J., Dudek M.K., Kaźmierski S., Dobrowolski J.Cz. On the conformation of the actinide-selective hydrophilic SO3-Ph-BTP ligand in aqueous solution. A com-putational study. Journal of Molecular Liquids, 219, 224-231 (2016).

44. Skotnicki K., De la Fuente J., Cañete A., Bobrowski K. Radiation-induced reduction of quinoxalin-2 derivatives in aqueous solutions. Radiation Physics and Chemistry, 124, 91-98 (2016).

45. Stasiulaitiene I., Martuzavicius D., Abromaitis V., Tichonovas M., Baltrusaitis J., Brandenburg R., Pawelec A. Comparative life cycle assessment of plasma-based and traditional exhaust gas treatment technologies. Journal of Cleaner Production, 112, 1804-1812 (2016).

46. Steczek Ł., Rejnis M., Narbutt J., Charbonnel M.C., Moisy P. On the stoichiometry and stability of americium(III) complexes with a hydrophilic So3-Ph-BTP ligand, studies by liquid-liquid extraction. Journal of Radioanalytical and Nuclear Chemistry, 309, 891-897 (2016).

47. Sun Y., Zwolińska E., Chmielewski A.G. Abatement technologies for high concentrations of NOx and SO2 removal from exhaust gases: A re-view. Critical Reviews in Environmental Science and Technology, 46, 2, 119-142 (2016).

48. Szkliniarz K., Sitarz M., Walczak R., Jastrzębski J., Bilewicz A., Choiński J., Jakubowski A., Majko-wska A., Stolarz A., Trzcińska A., Zipper W.Production of medical Sc radioisotopes with an alpha particle beam.Applied Radiation and Isotopes, 118, 182-189 (2016).

49. Szreder T., Skrzypczak A. Infl uence of the benzyl substituent on radiation chemistry of selected ionic liquids: gaseous products analysis. Journal of Radioanalytical and Nuclear Chemistry, 307, 195-202 (2016).

50. Święch O., Majdecki M., Dębiński A., Krzak A., Stępkowski T.M., Wójciuk G., Kruszewski M., Bile-wicz R. Competition between self-inclusion and drug binding explains the pH dependence of the cyclodextrin drug carrier – molecular modelling and electrochemistry studies. Nanoscale, 8, 16733-16742 (2016).

51. Święch O.A., Opuchlik L.J., Wójciuk G., Stępkowski T.M., Kruszewski M., Bilewicz R. Doxorubicin carriers based on Au nanoparticles – effect of shape and gold-drug linker on the carrier toxicity and therapeutic performance. RSC Advances, 6, 31960-31967 (2016).

52. Trojanowicz M. Flow chemistry vs. fl ow analysis. Talanta, 146, 621-650 (2016).

53. Trojanowicz M. Impact of nanotechnology on design of advanced screen-printed electrodes for different analytical ap-plications. Trends in Analytical Chemistry, 84, 22-47 (2016).

54. Trojanowicz M., Kołacińska K. Recent advanced in fl ow injection analysis. Analyst, 141, 2085-2139 (2016).

55. Walo M., Przybytniak G., Barsbay M., Güven O. Functionalization of poly(ester-urethane) surface by radiation-induced grafting of N-isopropylacrylamide using conventional and reversible addition – fragmentation chain transfer-mediated methods. Polymer International, 65, 192-199 (2016).


56. Westphal K., Skotnicki K., Bobrowski K., Rak J. Radiation damage to single stranded oligonucleotide trimers labelled with 5-iodopyrimidines. Organic & Biomolecular Chemistry, 14, 9331-9337 (2016).

57. Zeleznik N., Constantin M., Schneider N., Mays C., Zakrzewska G., Diaconu D. Radiation perception in Europe. Nuclear Engineering International, 1, 40-41 (2016).

Scientifi c journals (without IF) evaluated by the Ministry of Science and Higher Education (List B)

58. Furman-Toczek D., Zagórska-Dziok M., Dudra-Jastrzębska M., Kruszewski M., Kapka-Skrzypczak L. A review of selected natural phytochemicals in preventing and treting malignant skin neoplasms. Journal of Pre-Clinical and Clinical Research, 10, 2, 127-130 (2016).

59. Furman-Toczek D., Zagórska-Dziok M., Kruszewski M., Kapka-Skrzypczak L. Tlenek węgla – trucizna czy potencjalny terapeutyk? (Carbon monoxide – poison or potential thera-peutic agent?). Medycyna Środowiskowa – Environmental Medicine, 19, 4, 59-69 (2016).

60. Kołacińska K., Sasin R. Analiza kosztów i korzyści wdrożenia energetyki jądrowej w Polsce (Cost and benefi t analysis of Polish nuclear power programme). Rynek Energii, 3, 43-56 (2016).

61. Palige J., Roubinek O., Ciężkowska M., Pyzik A., Dobrowolski A., Chmielewski A.G. Badania wytwarzania biogazu z kiszonki kukurydzy w reaktorze okresowym z hydromieszaniem (Re-search into production of biogas from maize silage in a batch reactor with hydromixing). Inżynieria i Aparatura Chemiczna, 55, 1, 32-33 (2016).

62. Sartowska B., Starosta W., Barlak M., Waliś L. Modifi cation of zirconium alloys surface using high intensity pulsed plasma beams. Archives of Materials Sciences and Engineering, 77, 2, 53-57 (2016).

63. Zagórska-Dziok M., Furman-Toczek D., Kruszewski M., Kapka-Skrzypczak L. Resweratrol jako związek chemoprewencyjny w terapii nowotworów (Resveratrol as a chemopreven-tive compound in cancer therapy). Problemy Higieny i Epidemiologii, 97, 4, 308-317 (2016).

Other journals64. Engelman H.-J., Głuszewski W.

Kompozyty polimer-metal w ochronie radiologicznej (Polymer-metal composites in radiological protec-tion). Tworzywa Sztuczne w Przemyśle, 4, 56-57 (2016).

65. Głuszewski W. Bezpieczeństwo instalacji radiacyjnych (Safety of the radiation installation). Bezpieczeństwo Jądrowe i Ochrona Radiologiczna, 3, 9 (2016).

66. Głuszewski W. Nowe czasy – nowe wyzwania dla IOR (New times – new challenges for IOR). Bezpieczeństwo Jądrowe i Ochrona Radiologiczna, 3, 10-12 (2016).

67. Głuszewski W. Polimerowe kompozyty w ochronie radiologicznej (Polymer materials in radiological protection). Bezpieczeństwo Jądrowe i Ochrona Radiologiczna, 3, 5-8 (2016).

68. Głuszewski W. Polskie Towarzystwo Nukleoniczne (Polish Nuclear Society). Orbital, 2, 57-60 (2016).

69. Głuszewski W., Rajkiewicz M., Przybytniak G., Boguski J. Tworzywa polimerowe w atomistyce (Polymer materials in nuclear industry). Tworzywa Sztuczne w Przemyśle, 1, 28-29 (2016).


70. Głuszewski W., Tran K., Cortella L., Abbasova D. Radiacyjna modyfi kacja celulozy i konsolidacja radiacyjna (Radiation modifi cation of cellulose and radiation consolidation). Tworzywa Sztuczne w Przemyśle, 3, 98-99 (2016).

71. Kornacka E.M. Opakowania stosowane w sterylizacji radiacyjnej (Packaging used in radiation sterilization). Postępy Techniki Jądrowej, 59, 3, 28-32 (2016).

72. Krajewski P., Sommer S. Koncepcja organizacyjna Organizacji Wsparcia Technicznego w Polsce (Organisational concept of Technical Support Organization in Poland). Postępy Techniki Jądrowej, 59, 4, 12-14 (2016).

73. Kunicki-Goldfinger J.J., Pańczyk E. Badania historycznych szkieł przy użyciu metod jądrowych (Studies of historical glass with the use of nuclear methods). Postępy Techniki Jądrowej, 59, 4, 30-33 (2016).

74. Latek S. Społeczno-techniczne zarządzanie dużymi wypadkami jądrowymi (Socio-technical management of big nuclear accidents). Postępy Techniki Jądrowej, 59, 3, 33-37 (2016).

75. Latek S., Chmielowski W.Wywiad z prof. Jurijem Cołakowiczem Oganesjanem, kierownikiem naukowym Laboratorium Reakcji Jądrowych Zjednoczonego Instytutu Badań Jądrowych (Interview with Prof. Yuri Tsolakovich Oganes-sian, scientifi c director of the Flerov Laboratory of Nuclear Reactions). Postępy Techniki Jądrowej, 59, 2, 15-17 (2016).

76. Latek S., Zalewska E. Jubileusz sześćdziesięciolecia Międzynarodowej Agencji Energii Atomowej (Sixtieth anniversary of the International Atomic Energy Agency). Postępy Techniki Jądrowej, 59, 4, 2-6 (2016).

77. Lazurik V.T., Popov G.F., Salah S., Zimek Z.Approbation methods of numerical differentiation the depth dose distribution measured with applica-tion dosimetry wedge method. Visnyk of Kherson National Technical University, 3(58), 357-360 (2016).

78. Lazurik V.T., Popov G.F., Salah S., Zimek Z. Methods of calculating the partial derivatives of the electron radiation dose which is measured with dosimetric wedge.Visnik Kharkivskogo Nacional’nogo Universitetu im. V. H. Karazina. Seria: Matematichne Modelju-vannya Informacijni Technologii. Avtomatizovani Sistemi Upravlinnya, 29, 1-10 (2016).

79. Łyczko K. Crystal structure of a second polymorph of tricarbonyl(N-methylpyridine-2-carboxamide-2N1,O)(thio-cyanato-N)rhenium(I). Acta Crystallographica Section E: Crystallographic Communications, 72, 1386-1389 + [4] p. (2016).

80. Mikulski A., Latek S. Rozmowa z mgr. inż. Andrzejem Szozdą, byłym Ministrem Energetyki i Energii Atomowej (Interview with Andrzej Szozda, former Minister of Power Industry and Nuclear Energy (1976-1979)). Postępy Techniki Jądrowej, 59, 2, 31-33 (2016).

81. Narbutt J. New trends in the reprocessing of spent nuclear fuel. Separation of minor actinides by solvent extraction. Annales Universitatis Mariae Curie-Skłodowska Sectio AA, LXXI, 1, 123-140 (2016).

82. Roszkowska-Kaczor A., Głuszewski W., Stasiek A. Zastosowanie radiacyjnego sieciowania w produkcji polietylenowych pianek (Application of radiation crosslinking in the production of polyethylene foam). Tworzywa Sztuczne w Przemyśle, 5, 47-48 (2016).

83. Sartowska B., Barlak M., Starosta W., Waliś L., Senatorski J. Re-melting technique with high intense pulsed plasma beams applied for surface modifi cation of steel. Own investigations. Materials Science Forum, 879, 1668-1673 (2016). DOI: 10.4028/www.scientifi c.net/MSF.879.1668.


CHAPTERS IN BOOKS

1. Chmielewski A.G.Rola energetyki jądrowej w ochronie środowiska naturalnego i zdrowia człowieka (The role of nuclear energy in the protection of the environment and human health).In: Monografi a II Kongresu Elektryki Polskiej. Tom II. Praca zbiorowa pod redakcją kolegium w składzie: S. Wincenciak, P. Szymczak, A. Kopycińska, M. Bartosik, M. Kaźmierkowski, K. Perlicki, A. Strupcze-wski, K. Woliński, A.M. Wilk, J. Szczurowski. Rozdział 8. Energetyka jądrowa. Red. nauk. A. Strupcze-wski (pp. 752-764). Stowarzyszenie Elektryków Polskich, Warszawa 2016.

2. Chmielewski A.G., Palige J., Kryłowicz A., Usidus J., Chrzanowski K.Polska myśl techniczna w wytwarzaniu i użytkowaniu biometanu w energetyce, w przemyśle i w trans-porcie (Polish engineering achievements in the production and use of biomethane in the energy sector, industry and transport). In: Monografi a II Kongresu Elektryki Polskiej. Tom II. Praca zbiorowa pod redakcją kolegium w składzie: S. Wincenciak, P. Szymczak, A. Kopycińska, M. Bartosik, M. Kaźmierkowski, K. Perlicki, A. Strupcze-wski, K. Woliński, A.M. Wilk, J. Szczurowski. Rozdział 3. Energetyka rozproszona i odnawialne źródła energii. Red. nauk. A.G. Chmielewski (pp. 259-285). Stowarzyszenie Elektryków Polskich, Warszawa 2016.

3. Cieśla K.A., Drewnik J., Abramowska A., Buczkowski M.J., Głuszewski W., Nowicki A., Boguski J., Strzelczak G., Sartowska B. Based on starch – PVA system and cellulose reinforced packaging materials. The effects of ionizing radia-tion. (Chapter 14). In: Report of the 3rd RCM of the CRP on Application of Radiation Technology in the Development of Advanced Packaging Materials for Food Products, 11-15 July 2016, Vienna, Austria. IAEA, Vienna 2016, pp. 232-248, http://www-naweb.iaea.org/napc/iachem/working_materials/F22063%20APA416.pdf.

4. Dybczyński R.S., Polkowska-Motrenko H. Certifi ed reference materials in inorganic trace analysis. (Chapter 4). In: Handbook of trace analysis. Fundamentals and applications. I. Baranowska (Ed.). Springer, Switzer-land 2016, pp. 49-73.

5. Koc M., Chorąży K., Trojanowicz M. Chromatographic determination of PFOA, other selected perfl uorinated organic compounds, and total organic fl uorine in natural waters and milk samples. (Chapter 4). In: Perfl uorooctanoic acid (PFOA). Global occurrence, exposure and health effects. E. Hampton (Ed.). Biochemistry Research Trends. Nova Publishers, New York 2016, pp. 89-114.

6. Sun Y., Chmielewski A.G.Evaluation of eb technology for gas pollutants emission control for different emission sources. (Chapter 13). In: Radiation technology for cleaner products and processes. Proceedings of the Technical Meeting on De-ployment of Clean (Green) Radiation Technology for Environmental Remediation. IAEA-TECDOC-1786. IAEA, Vienna 2016, pp. 140-150.

7. Trojanowicz M. Flow injection analysis. Origin and development. (Chapter 1). In: Flow injection analysis of food additives. C. Ruiz-Capillas, L.M.L. Nollet (Eds.). CRC Press Taylor & Francis Group, 2016, pp. 3-34.

8. Zimek Z.Bezpieczeństwo czy ryzyko jądrowe – społeczne aspekty wdrożenia energetyki jądrowej (Nuclear safety or risk – social aspects of the implementation of nuclear power).In: Monografi a II Kongresu Elektryki Polskiej. Tom II. Praca zbiorowa pod redakcją kolegium w składzie: S. Wincenciak, P. Szymczak, A. Kopycińska, M. Bartosik, M. Kaźmierkowski, K. Perlicki, A. Strupcze-wski, K. Woliński, A. M. Wilk, J. Szczurowski. Rozdział 8. Energetyka jądrowa. Red. nauk. A. Strupcze-wski (pp. 780-784). Stowarzyszenie Elektryków Polskich, Warszawa 2016.

84. Sommer S., Wojsa T. Gospodarka odpadami promieniotwórczymi w Hiszpanii (Radiation waste management in Spain). Bezpieczeństwo Jądrowe i Ochrona Radiologiczna, 3, 26-30 (2016).

85. Usidus J., Chmielewski A.G., Palige J., Kryłowicz A. Uzupełnianie mocy wytwórczych w krajowym systemie elektroenergetycznym (Supplement of the power in national electroenergetic system). Energia Elektryczna, 10, 15-17 (2016).


1. Chmielewski A.G. Elektronno-luchevaya ochistka dymovykh gazov. ERTYS INVEST 2016 International Investment Forum, Pavlodar, Kazakhstan, 2.11.2016, [10] p.

2. Chmielewski A.G., Smoliński T., Pyszynska M. Zastosowanie radioznaczników w rozwoju technologii hydrometalurgicznych (Radiotracers applications in hydrometallurgical technologies development). 4. Konferencja międzynarodowa: Metale towarzyszące w przemyśle metali nieżelaznych, Wrocław, Poland, 15-17.06.2016, [10] p.

3. Kiegiel K., Zakrzewska-Kołtuniewicz G., Wołoszczuk K., Krajewski P., Poumandere M., Mays C., Diaconu D. Assessment of regional capabilities for new reactors development through an integrated approach – evaluation of Polish contribution to ALFRED demonstrator. ENC 2016 European Nuclear Conference, Warsaw, Poland, 9-13.10.2016. Conference proceedings, pp. 408-414.

4. Miśta E.A., Gójska A.M., Kalbarczyk P. Badania proweniencyjne oraz technologiczne obiektów archeologicznych wykonanych ze stopów srebra i miedzi (Provenance studies of archaeological objects made from silver and copper alloys). Nauki ścisłe i zabytki. Materiały z konferencji, Kraków, 25.09.2015. Pod red. T. Łojewskiego i B. Krajew-skiej. Wydział Chemii Uniwersytetu Jagiellońskiego, Kraków 2016, pp. 91-99.

5. Smoliński T., Rogowski M., Pyszynska M., Chmielewski A.G. Eksperymentalne metody hydrometalurgiczne do odzysku metali optymalizowane metodami radioizo-topowymi (Experimental methods for hydrometallurgical recovery of metals optimized by radiotracers methods). XII Konferencja Dla Miasta i Środowiska – Problemy Unieszkodliwiania Odpadów, Warszawa, Poland, Poland, 28.11.2016, [6] p.

6. Trojanowicz M., Bojanowska-Czajka A., Borowiecka S. Application of ionizing radiation for wastewater treatment for radiolytic removal of selected organic pollutants. Proceedings CRETE 2016, Fifth International Conference on Industrial & Hazardous Waste Manage-ment, Chania, Crete, Greece, 27-30.09.2016, [7] p.

7. Włodarczyk D., Miśta E.A., Żmuda-Trzebiatowska I., Kalbarczyk P., Kolbadinejad M., Lashkari A. Analiza archeometryczna dekoracyjnych kafl i naściennych z Iranu (Archaeometric analysis of decora-tive wall tiles from Iran). Nauki ścisłe i zabytki. Materiały z konferencji, Kraków, 25.09.2015. Pod red. T. Łojewskiego i B. Krajew-skiej. Wydział Chemii Uniwersytetu Jagiellońskiego, Kraków 2016, pp. 101-110.

CONFERENCE ABSTRACTS

1. Abramowska A., Gajda D.K., Kiegiel K., Miśkiewicz A., Drzewicz P., Zakrzewska-Kołtuniewicz G. Purifi cation of fl owback fl uids after hydraulic fracturing of Polish gas shales by hybrid methods. Proceedings of the IVth International Conference on Methods and Materials for Separation Processes “Separation science – theory and practice 2016”, Brunów (Lwówek Śląski), Poland, 4-8.09.2016. Ofi -cyna Wydawnicza Politechnika Wrocławskiej, Wrocław 2016, p. 105.

CONFERENCE PROCEEDINGS

1. INCT Annual Report 2015.Institute of Nuclear Chemistry and Technology, Warszawa 2016, 171 p.

2. Zimek Z., Roman K., Długoń S. Laboratoryjna instalacja do ciągłej obróbki radiacyjnej ciekłych zanieczyszczeń przemysłowych (Labo-ratory installation for continuous irradiation process of liquid industrial waste). Instytut Chemii i Techniki Jądrowej, Warszawa 2016. Raporty IChTJ. Seria B nr 1/2016, 26 p.

THE INCT PUBLICATIONS


2. Abramowska A., Gajda D.K., Kiegiel K., Miśkiewicz A., Zakrzewska-Kołtuniewicz G. Treatment of radioactive wastewater by hybrid methods. ENC 2016 European Nuclear Conference, Warsaw, Poland, 9-13.10.2016. Book of abstracts, pp. 94-95.

3. Bartłomiejczyk T., Buraczewska I., Sikorska K., Kowalska M., Sommer S. Akredytowana Pracownia Dozymetrii Biologicznej ZN-CRDB IChTJ w Warszawie: interesujące przy-padki szacowania dawki pochłoniętej (case study) (Accredited Laboratory of Radiation Dosimetry, Centre for Radiobiology and Biological Dosimetry, Institute of Nuclear Chemistry and Technology in Warsaw: interesting cases of assessment of the radiation dose received (case study)). XVII Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Siedlce, Poland, 27-30.09.2016. Materiały konferencyjne, p. 90.

4. Bilewicz A., Dziawer Ł., Koźmiński P., Pruszyński M., Majkowska-Pilip A., Stolarz A., Szkliniarz K., Jastrzębski J., Celichowski G., Grobelny J., Tomaszewska E. Gold nanoparticles labelled with 211At conjugated to substance P and trastuzumab – new radiophar-maceuticals for alpha particle therapy. EANN’16. Annual Congress of the European Association of Nuclear Medicine, Barcelona, Spain, 15-19.10.2016. European Journal of Nuclear Medicine and Molecular Imaging, 43, Suppl. 1, S198-S199.

5. Bilewicz A., Walczak R., Majkowska A., Misiak R., Choiński J., Sitarz M., Stolarz A., Jastrzębski J. Cyclotron production of theranostic pair 43Sc-47Sc on calcium targets. EANN’16. Annual Congress of the European Association of Nuclear Medicine, Barcelona, Spain, 15-19.10.2016. European Journal of Nuclear Medicine and Molecular Imaging, 43, Suppl. 1, S135-S136.

6. Bobrowski K., Filipiak P., Hug G.L., Pogocki D., Schöneich C., Marciniak B. Formation of three-electron sulfur-sulfur bond as a probe for interaction between side chains of methio-nine residues. ICIP 2016. International Conference on Ionizing Processes, Brookhaven, USA, 10-14.10.2016, p. 58.

7. Brzóska K. Mechanizmy toksyczności nanocząsteczek srebra (Mechanisms of silver nanoparticles toxicity). NanoBioMateriały – teoria i praktyka, Toruń, Poland, 2-3.06.2016. Materiały konferencyjne, p. 16.

8. Buraczewska I., Kulka U., Abend M., Ainsbury E., Badie C., Barquinero J.F., Barrios L., Beinke C., Bortolin E., Cucu A., De Amicis A., Dominiquez I., Fattibene P., Frovig A.M., Gregoire E., Guogyte K., Hadjidekova V., Jaworska A., Kriehuber R., Lloyd D., Lumniczky K., Lyng F., Meschini R., Della Monaca S., Monteiro Gil O., Montoro A., Moquet J., Moreno M., Oestreicher U., Palitti F., Pantelias R., Patrono C., Piquret-Stephan L., Port M., Prieto M.J., Quintens R., Ricoul M., Roy L., Sáfrány G., Sabatier L., Sebastià N., Sommer S., Terzoudi G., Testa A., Theirens H., Turai I., Trompier F., Valente M., Vaz P., Voisin P., Vral A., Woda C., Zafi ropoulos D., Wójcik A. Running the European network of biological dosimetry and physical retrospective dosimetry. XVII Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Siedlce, Poland, 27-30.09.2016. Materiały konferencyjne, p. 91.

9. Cędrowska E., Bilewicz A., Morgenstern A., Bruchertseifer F. Magnetyczne nanocząstki jako nośniki dla 225Ac w celowanej terapii radionuklidowej i diagnostyce MRI (Magnetic nanoparticles as carriers for 225Ac for targeted radionuclide therapy and MRI). ChemSession’16. XIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 10.06.2016. Streszczenia, p. 61.

10. Chajduk E., Pyszynska M., Polkowska-Motrenko H. Elemental analysis of infant formulas by INAA and ICP-MS. Comparison of estimated intakes with the safety limits for trace elements. RANC-2016. International Conference on Radioanalytical and Nuclear Chemistry, Budapest, Hungary, 10-15.04.2016. Book of abstracts, pp. 60-61.

11. Chmielewska D., Henczka M. Studies of different radionuclides sorption from liquid radioactive waste onto SiEA-KNiFe ion exchanger. 22nd Polish Conference of Chemical and Process Engineering, Spała, Poland, 5-9.09.09.2016. Book of abstracts, p. 58.

12. Chmielewska-Śmietanko D., Gryczka U., Migdał W., Kopeć K. Electron beam for preservation of biodeteriorated cultural heritage paper-based objects. IMRP2016 – 18th International Meeting on Radiation Processing, Vancouver, Canada, 7-11.11.2016, [2] p. https://cm.imrp-iia.com/mobis/lecture/146.

13. Chmielewski A.G. ENERGIEWENDE – an example for the other countries or Wagner’s legend of 21st century? ECOpole’16 Conference, Opole, Poland, 5-7.10.2016, [2] p.


14. Cieśla K., Abramowska A., Boguski J., Drewnik J. The effect of PVA type and radiation treatment on the properties of starch-PVA fi lms. IRaP 2016. 12th International Symposium on Ionizing Radiation and Polymers, Presquîle de Giens, France, 25-30.09.2016, p. 106.

15. Cieśla K., Abramowska A., Drewnik J., Buczkowski M. The effect of some compositional factors and ionizing radiation on the properties of starch-PVA-nano-cellulose fi lms. IRaP 2016. 12th International Symposium on Ionizing Radiation and Polymers, Presquîle de Giens, France, 25-30.09.2016, p. 61.

16. Cieśla K., Mirkowski K., Ludwicka K. The effect of gamma radiation on interaction of bionanocellulose with water. Workshop “Cellulosic material properties and industrial potential” (COST Action FP1205 “Innova-tive applications of regenerated wood cellulose fi bres”), Boras, Sweden, 13-14.04.2016. D. Jones, N. Johansson & M. Henriksson (Eds.), [2] p.

17. Czub J., Banaś D., Braziewicz J., Kubala-Kukuś A., Lankoff A., Stabrawa I. Total refl ection X-ray fl uorescence – a valuable tool for quantifi cation of selected elements in human lymphocytes. ERR 2016. 42nd Conference of the European Radiation Research Society, Amsterdam, Holland, 4-8.09.2016, p. 253.

18. Diaconu D., Constantin M., Perko T., Turcanu C., Mays C., Baumont G., Železnik N., Zakrzewska-Koł-tuniewicz G. Good practices for public communication, education, training and information about ionizing radiation. RICOMET 2016. International Conference: Risk perception, communication and ethics of exposures to ionizing radiation, Bucharest, Romania, 1-3.06.2016. Book of abstracts, p. 29.

19. Diaconu D., Mays C., Železnik N., Constantin M., Perko T., Turcanu C., Baumont G., Zakrzewska-Koł-tuniewicz G. Developing good practices for a better communication of ionizing radiation risks to the population. NUCLEAR 2016. 9th Annual International Conference on Sustainable Development through Nuclear Research and Education, Pitesti, Romania, 18-20 May 2016, [2] p.

20. Dobrowolski J.Cz., Jamróz M.H., Lipiński P.F.J. On chiral graph topological indices of -amino acids. 88. Sjezd Ceskych a Slovenskych Chemickych Spolecnosti, Praque, Czech Republic, 4-7.09.2016. Czech Chemical Society Symposium Series, 14, 5, 258 (2016).

21. Dobrowolski J.Cz., Lipiński P.F.J., Jamróz M.H., Rode J.Calculations of VCD spectra of methylthiirane revisited. 5th International Conference on Vibrational Optical Activity, Antwerp, Belgium, 11-16.09.2016. Book of abstracts, [1] p.

22. Drewnik J., Cieśla K. The effect of composition and ionizing radiation on the migration phenomena in starch-PVA fi lms placed in isooctane. MoDeST 2016. 9th International Conference on Modifi cation, Degradation and Stabilization of Poly-mers, Kraków, Poland, 4-8.09.2016. Book of abstracts, p. 216.

23. Drewnik J., Cieśla K., Buczkowski M., Boguski J., Głuszewski W. Effect of ionizing radiation on the properties of starch-poly(vinyl alcohol) fi lms containing nanocellulose. Workshop “Cellulosic material properties and industrial potential” (COST Action FP1205 “Innova-tive applications of regenerated wood cellulose fi bres”), Boras, Sweden, 13-14.04.2016. D. Jones, N. Johansson & M. Henriksson (Eds.), [2] p.

24. Dziawer Ł. Koniugaty nanocząstek złota i substancji P jako nośniki 211At w alfa terapii (Gold nanoparticles con-jugated with substance P as carriers for 211At for alpha therapy). ChemSession’16. XIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 10.06.2016. Streszczenia, p. 80.

25. Dziawer Ł., Bilewicz A. Conjugate of gold nanoparticle – substance P(5-11) as 211At carriers for alpha. 10th International Summer Schools on Nanosciences & Nanotechnologies, Organic Electronics & Nanomedicine, Thessaloniki, Greece, 2-9.07.2016. Book of abstracts, [1] p.


26. Dziendzikowska K., Oczkowski M., Stachoń M., Gromadzka-Ostrowska J., Madej D., Wilczak J., Królikowski T., Mruk R., Królikowski T., Øvrevik J., Myhre O., Magnusson P., Kowalska M., Krusze-wski M., Lankoff A. The effect of diesel exhaust from combustion of 1st generation biodiesel fuels (B7) on sex steroid hor-mones concentration and sperm count in male Fischer 344 rats. 4th Winter Workshop of the Society for Biology and Reproduction “Central and local regulations of reproductive processes”, Zakopane, Poland, 3-5.02.2016, pp. 64-65.

27. Dziendzikowska K., Oczkowski M., Stachoń M., Wilczak J., Królikowski T., Mruk R., Gromadzka-Os-trowska J., Øvrevik J., Kowalska M., Węgierek-Ciuk A., Lisowska H., Kruszewski M., Lankoff A. Inhalation of diesel engine exhaust from combustion of 1st generation biodiesel fuel (B20) affects endocrine regulation of reproduction in male rats. Abstracts of the 52nd Congress of the European Societies of Toxicology (EUROTOX). Toxicology Letters, 258S, S182 (2016).

28. Fuks L., Oszczak A. Naturalne sorbenty pochodzenia biologicznego do usuwania radioizotopów z roztworów wodnych (Natural sorbents of biological origin for removal of the radionuclides from aqueous solutions). VII Krajowa Konferencja Radiochemii i Chemii Jądrowej, Lublin, Poland, 17-20.04.2016. Streszczenia, p. 24.

29. Gajda D., Kiegiel K., Miśkiewicz A., Abramowska A., Chajduk E., Wołkowicz S., Konieczyńska M., Zakrzewska-Kołtuniewicz G. Possibility of uranium recovery from Polish unconventional resources. ENC 2016 European Nuclear Conference, Warsaw, Poland, 9-13.10.2016. Book of abstracts, p. 97.

30. Głuszewski W., Cortella L. Radiacyjna odporność materiałów w konserwacji obiektów o znaczeniu historycznym (Radiation re-sistant of materials in the preservation of objects with historical importance). XVI Konferencja „Analiza chemiczna w ochronie zabytków”, Warszawa, Poland, 1-2.12.2016, p. 32.

31. Grądzka I., Gach K., Janecka A., Wasyk I., Iwaneńko T., Męczyńska-Wielgosz S., Szymański J., Ko-szuk J., Janecki T., Kruszewski M. Promieniouczulające działanie partenolidu – naturalnego składnika roślin – oraz jego pochodnych na komórki raka wątroby HepG2 (Radiosensitization properties of natural plant component – parthe-nolide and its derivatives on human hepatoma cells HepG2). XVII Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Siedlce, Poland, 27-30.09.2016. Materiały konferencyjne, p. 49.

32. Gryczka U., Migdał W., Bułka S. Effectiveness of radiation microbiological decontamination process of agricultural products with use of low energy electron beam. IMRP2016 – 18th International Meeting on Radiation Processing, Vancouver, Canada, 7-11.11.2016, [2] p. https://cm.imrp-iia.com/mobis/lecture/175.

33. Gryczka U., Migdał W., Bułka S., Sadło J., Zimek Z. Dose distribution in food products irradiated with low energy electron beam. IMRP2016 – 18th International Meeting on Radiation Processing, Vancouver, Canada, 7-11.11.2016, [2] p. https://cm.imrp-iia.com/mobis/lecture/200.

34. Gryczka U., Migdał W., Orlikowski L., Bułka S., Ptaszek M., Błaszak M. Zastosowanie niskoenergetycznych akceleratorów elektronów do zwalczania patogenów ziarna i na-sion (Use of low energy electron beam for elimination of pathogens in seeds and grains). V Konferencja naukowa „Nowe patogeny i choroby roślin”, Skierniewice, Poland, 6.04.2016. Streszcze-nia. Oprac. L.B. Orlikowski, A. Jarecka-Boncela, M. Ptaszek. Instytut Ogrodnictwa InHort, Skiernie-wice 2016, p. 19.

35. Gumiela M., Gniazdowska E., Bilewicz A. Znakowanie radiofarmaceutyków technetem-99m otrzymywanym w cyklotronie (Labelling of radio-pharmaceuticals with technetium-99m obtained in the cyclotron). ChemSession’16. XIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 10.06.2016. Streszczenia, p. 99.

36. Herdzik-Koniecko I., Wagner C., Geist A., Panak P.J., Rejnis-Strzelak M., Steczek Ł., Łyczko M., Narbutt J. Use of TRLFS and ESI-MS methods for search and characterization of Cm(III) and Eu(III) complexes with SO 3– Ph-BTP and TODGA ligands in solvent extraction systems.


ATALANTE 2016 – Nuclear Chemistry for Sustainable Fuel Cycles, Le Corum, Montpellier, France, 5-10.06.2016, [1] p.

37. Hęclik K.I., Hęclik K., Lankoff A., Pogocki D. Oznaczanie toksyczności nanocząstek metali syntezowanych w torfi e (Determination of toxicity of metal nanoparticles synthetized in peat soil). NanoBioMateriały – teoria i praktyka, Toruń, Poland, 2-3.06.2016. Materiały konferencyjne, p. 77.

38. Kiegiel K., Zakrzewska-Kołtuniewicz G., Wołoszczuk K., Krajewski P., Diaconu D., Poumandere M., Mays C. Assessment of regional capabilities for new reactors development through an integrated approach – evaluation of Polish contribution to ALFRED demonstrator. ENC 2016 European Nuclear Conference, Warsaw, Poland, 9-13.10.2016. Book of abstracts, p. 102.

39. Kodziszewska K., Leszek P., Sochanowicz B., Brzóska K., Piotrowski W., Zieliński T. Why treatment with natriuretic peptide analogs failed to fulfi ll our expectations? – receptor expression and function in a failing heart. Heart Failure 2016 and the 3rd World Congress on Acute Heart Failure, Florence, Italy, 21-24.05.2016. European Journal of Heart Failure, 18, Suppl. 1, 8-9 (2016).

40. Kołacińska K., Chajduk E., Dudek J., Samczyński Z., Łokas E., Bojanowska-Czajka A. Optymalizacja zautomatyzowanych oznaczeń 90Sr i 99Tc metodami analizy przepływowej z detekcją ICP-MS (Optimization of fully automated fl ow injection systems dedicated for determinations of 90Sr and 99Tc with ICP-MS detection). VII Krajowa Konferencja Radiochemii i Chemii Jądrowej, Lublin, Poland, 17-20.04.2016. Streszcze-nia, p. 28.

41. Kowalska M., Węgierek-Ciuk A., Czarnocka J., Odziemkowska M., Kruszewski M., Lisowska H., Mruk R., Oczkowski M., Dziendzikowska K., Oddvar M., Magnusson P., Gromadzka-Ostrowska J., Ovrevik J., Wojewódzka M., Lankoff A. The uptake kinetics and genotoxicity effects of diesel exhaust particles from the combustion of 1st and 2nd generation biodiesel fuels in BEAS-2B cells. NanoBioMateriały – teoria i praktyka, Toruń, Poland, 2-3.06.2016. Materiały konferencyjne, p. 79.

42. Kowalska M., Węgierek-Ciuk A., Iwaneńko T., Kruszewski M., Lisowska H., Męczyńska-Wielgosz S., Wojewódzka M., Lankoff A. Efekty skojarzonego działania nanorurek węglowych oraz promieniowania jonizującego na powsta-wanie uszkodzeń DNA w komórkach A549 in vitro (The effects of the associated activity of carbon nanotubes and ionizing radiation on the formation of DNA damage in A549 cells in vitro). XVII Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Siedlce, Poland, 27-30.09.2016. Materiały konferencyjne, p. 70.

43. Kralj M., Daris I., Železnik N., Marega M., Istenic R., Diaconu D., Zakrzewska G., Mays C. Guidelines for information sources for improvement of solutions for information materials and activities about ionizing radiation. RICOMET 2016. International Conference: Risk perception, communication and ethics of exposures to ionizing radiation, Bucharest, Romania, 1-3.06.2016. Book of abstracts, p. 27.

44. Kruszewski M., Matysiak M., Wojewódzka M., Męczyńska-Wielgosz S., Kapka-Skrzypczak L. Cyto- and genotoxicity of nanoparticle binary mixtures on two human cell lines. XIV International Congress of Toxicology in conjunction with the X Mexican Congress of Toxicology, Merida, Mexico, 2-6.10.2016. Toxicology Letters, 259S, S188-S189 (2016).

45. Krzak A., Święch O., Majdecki M., Stępkowski T., Kruszewski M., Bilewicz R. Pochodna -cyklodekstryny o właściwościach antyoksydacyjnych jako nośnik leku w terapii przeciw-nowotworowej (-cyclodextrin derivative with antioxidant properties as a potential drug carrier in anti-cancer therapy). NanoBioMateriały – teoria i praktyka, Toruń, Poland, 2-3.06.2016. Materiały konferencyjne, p. 91.

46. Kulka U., Abend M., Ainsbury E., Badie C., Barquinero J.F., Barrios L., Beinke C., Bortolin E., Cucu A., De Amicis A., Domínguez I., Fattibene P., Frovig A.M., Gregoire E., Guogyte K., Hadjidekova V., Jaworska A., Kriehuber R., Lloyd D., Lumniczky K., Lyng F., Meschini R., Della Monaca J., Monteiro Gil O., Montoro A., Moquet J., Moreno M., Oestreicher U., Pantelias G., Patrono C., Piqueret-Ste-phan L., Port M., Prieto M.J., Quintens R., Ricoul M., Roy L., Sáfrány G., Sabatier L., Sebastià N., Sommer S., Terzoudi G., Testa A., Thierens H., Trompier F., Valente M., Vaz P., Vral A., Woda C., Zafi ropoulos D., Wójcik A. RENEB – Running and European Network of biological dosimetry and physical-retrospective dosimetry. RPW Radiation Protection Week, 2016, Oxford, UK, 19-23.09.2016. Abstracts eBook, pp. 103-104.


47. Kużelewska I., Polkowska-Motrenko H. Opracowanie procedury oznaczania chromu w próbkach środowiskowych metodą neutronowej ana-lizy aktywacyjnej (NAA) (Development of the procedure for the determination of chromium in envi-ronmental samples by neutron activation analysis (NAA)). VII Krajowa Konferencja Radiochemii i Chemii Jądrowej, Lublin, Poland, 17-20.04.2016. Streszcze-nia, p. 30.

48. Lankoff A., Kowalska M., Węgierek-Ciuk A., Lisowska H., Czarnocka J., Odziemkowska M., Mruk R., Gromadzka-Ostrowska J., Dziendzikowska K., Oczkowski M., Męczyńska-Wielgosz S., Wojewódzka M., Ovrevik J., Oddvar M., Magnusson P., Kruszewski M. Comparative analysis of toxicology of diesel engine particles generated from the combustion of 1st and 2nd generation biodiesel fuels in vitro. Cyto- and genotoxicity of nanoparticle binary mixtures on two human cell lines. XIV International Congress of Toxicology in conjunction with the X Mexican Congress of Toxicology, Merida, Mexico, 2-6.10.2016. Toxicology Letters, 259S, S73 (2016).

49. Latek S., Sommer S., Zakrzewska-Kołtuniewicz G. The utility of the concept of mental models related to ionizing radiation in the process of the Polish nuclear power program (PNPP) development. RICOMET 2016. International Conference: Risk perception, communication and ethics of exposures to ionizing radiation, Bucharest, Romania, 1-3.06.2016. Book of abstracts, p. 33.

50. Lisowska H., Cheng L., Lundholm L., Węgierek-Ciuk A., Lankoff A., Kowalska M., Kuszewski T., Sommer S., Haghdoost S., Sollazzo A., Wójcik A.Wpływ hipotermii na kinetykę powstawania popromiennych aberracji chromosomowych w limfocy-tach krwi obwodowej in vitro (Hypothermia modulates the DNA damage response to ionising radia-tion (in terms of chromosomal aberrations) in human peripheral blood lymphocytes). XVII Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Siedlce, Poland, 27-30.09.2016. Materiały konferencyjne, p. 72.

51. Lisowska H., Cheng L., Lundholm L., Węgierek-Ciuk A., Lankoff A., Kowalska M., Sommer S., Haghdoost S., Sollazzo A., Kuszewski T., Wójcik A. Mechanisms of the radioprotective effect of hypothermia in human peripheral blood lymphocytes. ERR 2016. 42nd Conference of the European Radiation Research Society, Amsterdam, Holland, 4-8.09.2016, p. 202.

52. Łada W., Wawszczak D., Deptuła A., Ostyk-Narbutt J., Iller E., Królicki L. Nowa technologia otrzymywania mikrosfer trójtlenku itru do zastosowania w terapii raka wątroby (Production of yttrium trioxide microspheres for reduced tumor liver by new technology). Innowacyjni Naukowcy, Wrocław, Poland, 30.05.2016. Materiały konferencyjne, [1] p.

53. Łuczyńska K., Drużbicki K., Łyczko K., Dobrowolski J.Cz. Structure-spectra correlations in hydrogen-bonded complex of chloranilic acid with -picoline. EUCMOS 2016. 33rd European Congress on Molecular Spectroscopy, Szeged, Hungary, 30.07.-4.08.2016, p. 154.

54. Majkowska-Pilip A., Gniazdowska E., Rawicz-Galińska A., Bednarczyk M., Koźmiński P., Budle-wski T., Bilewicz A. Physicochemical and biological characterization of Substance P fragments labeled with 177Lu. EANN’16. Annual Congress of the European Association of Nuclear Medicine, Barcelona, Spain,15-19.10.2016. European Journal of Nuclear Medicine and Molecular Imaging, 43, Suppl. 1, S430 (2016).

55. Matysiak M., Męczyńska-Wielgosz S., Kruszewski M., Kapka-Skrzypczak L. Ocena cytotoksycznego działania mieszanin nanocząstek (Assessment of cytotoxic effects of mixed nanoparticles). NanoBioMateriały – teoria i praktyka, Toruń, Poland, 2-3.06.2016. Materiały konferencyjne, p. 43.

56. Misiak R., Bartyzel M., Wąs B., Mietelski J.W., Bilewicz A. Evaluation a radionuclide purity of 226Th formed from the decay of 230U for targeted alpha therapy. 9th International Conference on Nuclear and Radiochemistry NRC9, Helsinki, Finland, 29.08.-2.09.2016. Abstracts, pp. 487-488.

57. Miśkiewicz A., Iwińska K. Socio-economic impact and perception analysis of the Nuclear Power Plant Programme in Poland. RICOMET 2016: International Conference: Risk perception, communication and ethics of exposures to ionising radiation, Bucharest, Romania, 1-3.06.2016, [1] p.

58. Miśkiewicz A., Zakrzewska-Kołtuniewicz G., Abramowska A., Pasieczna-Patkowska S. Membrane fouling investigation – a comparison of different techniques.


Proceedings of the IVth International Conference on Methods and Materials for Separation Processes “Separation science – theory and practice 2016”, Brunów (Lwówek Śląski), Poland, 4-8.09.2016. Ofi -cyna Wydawnicza Politechnika Wrocławskiej, Wrocław 2016, p. 104.

59. Miśkiewicz A., Zakrzewska-Kołtuniewicz G., Pasieczna-Patkowska S. A photoacoustic spectroscopy as a potential method for the membranę fouling investigation. PERMA 2016: Membrane Science and Technology Conference of Visegrad Countries, Prague, Czech Republic, 15-19.05.2016. Book of abstracts, p. 164.

60. Narbutt J. Oddzielanie ameryku(III) od lantanowcowych produktów rozszczepienia metodą reekstrakcji selek-tywnymi hydrofi lowymi ligandami poli-N-dentnymi (Separation of americium(III) from lanthanide fi ssion products by re-extraction with selective hydrophilic poly-N-dentate ligands). VII Krajowa Konferencja Radiochemii i Chemii Jądrowej, Lublin, Poland, 17-20.04.2016. Streszcze-nia, p. 14.

61. Narbutt J., Fuks L. Fizykochemiczne metody rozdzielania jonów metali oraz specyfi czności chemii pierwiastków f-elek-tronowych. W 90-lecie urodzin Profesora Sławomira Siekierskiego (Physicochemical methods of sep-arating metal ions and the specifi city of chemistry of f-electron elements. In the 90 anniversary of the birth of Professor Sławomir Siekierski). VII Krajowa Konferencja Radiochemii i Chemii Jądrowej, Lublin, Poland, 17-20.04.2016. Streszcze-nia, p. 32.

62. Oczkowski M., Dziendzikowska K., Gromadzka-Ostrowska J., Stachoń M., Wilczak J., Królikowski T., Mruk R., Øvrevik J., Kowalska M., Kruszewski M., Lankoff A. Infl uence of diesel engine exhaust from combustion of second generation biodiesel fuels on selected parameters of hormonal regulation of reproduction in animal model. Konferencja Polskiego Towarzystwa Andrologicznego, Gdańsk, Poland, 30.09.-01.10.2016. Streszcze-nia, p. 55.

63. Oczkowski M., Dziendzikowska K., Gromadzka-Ostrowska J., Stachoń M., Wilczak J., Królikowski T., Mruk R., Øvrevik J., Kowalska M., Kruszewski M., Lankoff A. Wpływ spalin biopaliw drugiej generacji na wybrane parametry hormonalnej regulacji rozrodu u zwie-rząt modelowych (Infl uence of diesel engine exhaust from combustion of second generation biodiesel fuels on selected parameters of hormonal regulation of reproduction in animal model). Konferencja Polskiego Towarzystwa Andrologicznego, Gdańsk, Poland, 30.09.-01.10.2016. Streszcze-nia, p. 54.

64. Oczkowski M., Dziendzikowska K., Stachoń M., Królikowski T., Gromadzka-Ostrowska J., Wilczak J., Mruk R., Øvrevik J., Myhre O., Magnusson P.A., Kowalska M., Kruszewski M., Lankoff A.The infl uence of diesel exhaust emission on hormonal reproductive parameters in adult male rats – preliminary results. Annual Winter Meeting of the Norwegian Society of Pharmacology and Toxicology (Vintermøtet på Beitostølen 2016), Beitostolen, Norway, 28-30.01.2016, p. 75.

65. Oczkowski M., Gajewska M., Dziendzikowska K., Gromadzka-Ostrowska J., Wilczak J., Królikowski T., Mruk R., Øvrevik J., Kowalska M., Węgierek-Ciuk A., Lisowska H., Kruszewski M., Lankoff A. The changes in hematological profi le of adult male rats after exposure to diesel exhaust emission. Abstracts of the 52nd Congress of the European Societies of Toxicology (EUROTOX). Toxicology Letters, 258S, S182 (2016).

66. Polkowska-Motrenko H., Dybczyński R., Samczyński Z., Chajduk E., Dudek J., Fuks L., Kalbarczyk P. Jądrowe metody analizy – wykorzystanie dla zapewnienia jakości analiz chemicznych (Nuclear analyti-cal methods – application for quality assurance of chemical analysis). Jubileuszowe XXV Poznańskie Konwersatorium Analityczne „Nowoczesne metody przygotowania próbek i oznaczania śladowych ilości pierwiastków”, Poznań, Poland, 7-8.04.2016, p. 91.

67. Pruszyński M., Cędrowska E., Radchenko V., John K.D., Bruchertseifer F., Morgenstern A., D’Huyvetter M.D., Lahoutte T. Anti HER2 nanobody labeled with 225Ac as a potential radiopharmaceutical for TRT. EANN’16. Annual Congress of the European Association of Nuclear Medicine, Barcelona, Spain, 15-19.10.2016. European Journal of Nuclear Medicine and Molecular Imaging, 43, Suppl. 1, S177 (2016).

68. Przybytniak G., Kornacka E., Sadło J., Zimek Z. Radical processes induced in collagen by radiation sterilization. IRaP 2016. 12th International Symposium on Ionizing Radiation & Polymer, Presquîle de Giens, France, 25-30.09.2016, p. 158.


69. Przybytniak G., Walo M. Radiation-induced processes in aliphatic polyesters as seen by EPR spectroscopy and their physico-chemical implications. IRaP 2016. 12th International Symposium on Ionizing Radiation & Polymer, Presquîle de Giens, France, 25-30.09.2016, p. 41.

70. Rode J., Dobrowolski J.Cz., Kaczorek D., Kawęcki R., Zając G., Baranska M. A chiral thiophene derivative – a challenge for VOA calculations. 5th International Conference on Vibrational Optical Activity, Antwerp, Belgium, 11-16.09.2016. Book of abstracts, [1] p.

71. Samczyński Z., Polkowska-Motrenko H., Dybczyński R.S. Techniki analityczne stosowane w procesie certyfi kacji nowych materiałów odniesienia dla nieorga-nicznej analizy śladowej: MODAS 2, MODAS 3, MODAS 4 i MODAS 5 (Analytical techniques ap-plied in the certifcation process of new reference materials for inorganic trace analysis: MODAS 2, MODAS 3, MODAS 4 and MODAS 5). Konwersatorium Spektrometrii Atomowej, Ustroń, Poland, 19-21.09.2016, [1] p.

72. Sartowska B., Barlak M., Starosta W., Waliś L. Surface layers of steel with improved tribological properties formed using high intense pulse plasma beams (HIPPB). PSE 2016. 15th International Conference on Plasma Surface Engineering, Garmisch-Partenkirchen, Germany, 12-16.09.2016, [1] p.

73. Sartowska B., Barlak M., Starosta W., Waliś L., Senatorski J. Re-melting technique with high intense pulsed plasma beams applied for surface modifi cation of steel. Own investigations. THERMEC’2016. International Conference on Processing & Manufacturing of Advanced Materials. Processing, Fabrication, Properties, Applications, Graz, Austria, 29.05.-3.06.2016. Book of abstracts, p. 483.

74. Sartowska B., Orelovitch O., Apel P., Szydłowski A. Particle tracks in polymers. SEM characterization. ION 2016. XI International Conference: Ion implantation and other applications of ions and elec-trons, Kazimierz Dolny, Poland, 13-16.06.2016, [1] p.

75. Skotnicki K., Bobrowski K., De la Fuente J., Cañete A. Generowane radiacyjnie procesy rodnikowe pomiędzy aminokwasami a pochodnymi chinoksalin-2-onu z punktu widzenia ich zastosowań farmakologicznych (Radiation-induced radical processes involving aminoacids and quinoxalin-2-ones derivatives relevant to pharmacological applications). XVII Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Siedlce, Poland, 27-30.09.2016. Materiały konferencyjne, p. 42.

76. Skotnicki K., Bobrowski K., De la Fuente J., Cañete A. Radiation induced radical processes involving new class of cancer chemotherapeutics – quinoxalinones. ICIP 2016. International Conference on Ionizing Processes, Brookhaven, USA, 10-14.10.2016, p. 29.

77. Smoliński T., Pyszynska M., Rogowski M., Chmielewski A.G. Rozwój i optymalizacja metod analitycznych w celu zastosowania ich w procesie hydrometalurgicznym (Development and optimization of radiotracers analytical methods for hydrometallurgical technology). ChemSession’16. XIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 10.06.2016. Streszczenia, p. 173.

78. Smoliński T., Wojtowicz P., Chmielewski A.G. Nano-radioznaczniki o właściwościach magnetycznych i fl uorescencyjnych do znakowania cząsteczek piasku lub gliny (Nano-radiotracers with magnetic and fl uorescence properties for labeling of micro-particles of sand and clay). ChemSession’16. XIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 10.06.2016. Streszczenia, p. 185.

79. Sommer S. Biological dosimetry in Europe is it necessary according emergency responding authorities? RICOMET 2016. International Conference: Risk perception, communication and ethics of exposures to ionizing radiation, Bucharest, Romania, 1-3.06.2016. Book of abstracts, [1] p.

80. Sommer S. Low dose of radiation risk in Polish media space and in Polish Nuclear Energy Program versus up-dated results of INWORKS.


RICOMET 2016. International Conference: Risk perception, communication and ethics of exposures to ionizing radiation, Bucharest, Romania, 1-3.06.2016. Book of abstracts, [1] p.

81. Sommer S., Buraczewska I., Bartłomiejczyk T., Sikorska K. Dozymetria biologiczna w Polsce i w Europie (Situation of biological dosimetry in Poland and Europe). XVII Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Siedlce, Poland, 27-30.09.2016. Materiały konferencyjne, p. 59.

82. Steczek Ł., Narbutt J., Charbonnel M.-C., Moisy P. Solvent extraction investigations on Th and Pu(IV) complexes with hydrophilic SO3-Ph-BTP and SO3-Ph-BTBP ligands. ATALANTE 2016 – Nuclear Chemistry for Sustainable Fuel Cycles, Le Corum, Montpellier, France, 5-10.06.2016, [1] p.

83. Stępkowski T., Kruszewski M. mitoLUHMES – an engineered neuronal cell line for the analysis of mitochondrial motility. Champalimaud Neuroscience Symposium, Lisboa, Portugal, 21-24.09.2016. Abstract book, [1] p.

84. Szreder T., Kocia R., Schmidt H., Modolo G. Selected aspects of the SANEX system radiation chemistry. Proceedings of the 13th DAE-BRNS Biennial Trombay Symposium on Radiation & Photochemistry incorporating 6th Asia Pacifi c Symposium on Radiation Chemistry, (APSRC-2016), Mubai, India, 5-9.01.2016, p. 26.

85. Szreder T., Schmidt H., Modolo G. Early stages of CyMe4BTPhen radiation chemistry in 1-octanol. ATALANTE 2016 – Nuclear Chemistry for Sustainable Fuel Cycles, Le Corum, Montpellier, France, 5-10.06.2016, p. 194.

86. Szreder T., Strzelczak G., Skrzypczak A. Infl uence of the benzyl substituent on radiation chemistry of selected ionic liquids. International Workshop on Radiation and Photochemistry (PUWORP-2016), Pune, India, 10-12.01.2016, p. 7.

87. Terzoudi G.I., Pantelias G., Darroudi F., Barszczewska K., Buraczewska I., Depuydt J., Georgieva D., Hadjidekova V., Hatzi V.I., Karachristou I., Karakosta M., Meschini R., M’Kacher R., Montoro A., Palitti F., Pantelias G., Pepe G., Ricoul M., Sabatier L., Sebastià N., Sommer S., Vral A., Zafi ropou-los D., Wójcik A. Dose assessment inter-comparisons within the RENEB network using G0-lymphocyte prematurely condensed chromosomes. RPW Radiation Protection Week, 2016, Oxford, UK, 19-23.09.2016. Abstracts eBook, p. 132.

88. Walczak R., Bilewicz A. Cyklotronowo otrzymywane radioizotopy 43Sc i 44Sc jako nowe znaczniki dla PET (Cyclotron produced radioisotopes 43Sc and 44Sc as a new markers for PET). ChemSession’16. XIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 10.06.2016. Streszczenia, p. 206.

89. Walczak R., Bilewicz A. Fe3O4-SPION radiolabeled with 177Lu for cancer therapy. 10th International Summer Schools on Nanosciences & Nanotechnologies, Organic Electronics & Nanomedicine, Thessaloniki, Greece, 2-9.07.2016. Book of abstracts, p. 34.

90. Walo M., Przybytniak G., Mirkowski K. Modyfi kacja powierzchni materiałów polimerowych za pomocą radiacyjnie indukowanej polimeryzacji RAFT (Surface modifi cation of polymers materials by RAFT-mediated grafting). XVII Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Siedlce, Poland, 27-30.09.2016. Materiały konferencyjne, p. 87.

91. Węgierek-Ciuk A., Arabski M., Lisowska H., Kowalska M., Lis K., Wolszczak M., Wójcik A., Lankoff A. Infl uence of coralyne on radiation-induced apoptosis and cell cycle progression in A549 cells. ERR 2016. 42nd Conference of the European Radiation Research Society, Amsterdam, Holland, 4-8.09.2016, p. 124.

92. Węgierek-Ciuk A., Arabski M., Lisowska H., Kowalska M., Lis K., Wolszczak M., Wójcik A., Lankoff A. Wpływ koraliny na częstość popromiennych mikrojąder oraz cykl komórkowy w komórkach A549 (Infl uence of coralyne on radiation-induced apoptosis and cell cycle progression in A549 cells). XVII Zjazd Polskiego Towarzystwa Badań Radiacyjnych, Siedlce, Poland, 27-30.09.2016. Materiały konferencyjne, p. 78.


93. Wierzchnicki R. Isotopic composition of CO2 in sparking drinks. Conference – Assuring the integrity of the food chain: Fighting food fraud, Prague, Czech Republic 6-7.04.2016. J. Pulkrabova, M. Tomaniova, J. Hajslova and P. Brereton (Eds.). Book of abstracts, p. 128.

94. Wierzchnicki R. Skład izotopowy CO2 w badaniach autentyczności napojów gazowanych (The isotopic composition of CO2 in the study of the authenticity of carbonated drinks). XXI Konferencja Nowoczesne Metody Instrumentalne w Analizie Śladowej, Warszawa, Poland, 8-9.12.2016. Red. nauk. M.I. Szynkowska, S. Garboś, p. 34.

95. Wierzchnicki R., Samczyński Z., Wasilewska M. Isotopes and trace elements for dairy products origin control. Conference – Assuring the integrity of the food chain: Fighting food fraud, Prague, Czech Republic 6-7.04.2016. J. Pulkrabova, M. Tomaniova, J. Hajslova and P. Brereton (Eds.). Book of abstracts, p. 127.

96. Wilczak J., Dziendzikowska K., Oczkowski M., Królikowski T., Kamola D., Lankoff A., Kruszewski M., Grzelak A., Żuberek M., Gromadzka-Ostrowska J. Wpływ nanocząstek srebra na wybrane parametry stanu zapalnego w jelicie grubym w badaniach modelowych in vivo (Effect of silver nanoparticles on the selected parameters of infl ammation in the colon in model studies in vivo). XXV Ogólnopolskie Sympozjum Bromatologiczne „Jakość zdrowotna żywności i żywienia”, War-szawa-Józefów, Poland, 12-13.09.2016. Streszczenia wykładów, komunikatów i plakatów, p. 83.

97. Zakrzewska-Kołtuniewicz G. Odsalanie metoda destylacji membranowej zasilanej ciepłem z elektrowni jądrowych (Desalination by membranę distillation driven by heat from nuclear power plants). MEMPEP 2016. XI Konferencja Naukowa: Membrany i procesy membranowe w ochronie środowiska, Zakopane, Poland, 15-18.06.2016, p. 38.

98. Zakrzewska-Kołtuniewicz G. The concept of use of membranę processes in nuclear desalination. ACEM16. The 2016 World Congress on Advances in Civil, Environmental, and Materials Research & The 2016 Structures Congress, Jeju, Korea, 28.08-1.09.2016. Book of abstracts, p. 193.

99. Zakrzewska-Kołtuniewicz G., Latek S., Sommer S., Miśkiewicz A. The experience gained within the EAGLE project as a contribution to the implementation of the pro-gramme of Polish nuclear energy. RICOMET 2016. International Conference: Risk perception, communication and ethics of exposures to ionizing radiation, Bucharest, Romania, 1-3.06.2016. Book of abstracts, p. 51.

100. Železnik N., Constantin M., Schneider N., Mays C., Zakrzewska G., Diaconu D. Lays public mental models of ionizing radiation: representations and risk perception in four European countries. Journal of Radiological Protection, 36, S102-S121 (2016).

101. Železnik N., Diaconu D., Constantin M., Zakrzewska-Kołtuniewicz G. Lessons for better education and information material based on implementation of pilot actions. RICOMET 2016. International Conference: Risk perception, communication and ethics of exposures to ionizing radiation, Bucharest, Romania, 1-3.06.2016. Book of abstracts, p. 30.

102. Zwolińska E., Licki J., Bułka S., Chmielewski A.G., Sun Y. Hybrid electron beam technology for high concentrations NOx and SO2 removal from off-gases. 27th Symposium on Plasma Physics and Technology (SPPT 2016), Prague, Czech Republic, 20-23.06.2016. Plasma Physics and Technology, 3, 2, 75 (2016).

103. Zwolińska E., Sun Y.Modelowanie procesu oczyszczania gazów z dwutlenku siarki (SO2) i tlenków azotu (NOx) za pomocą wiązki elektronów w programie „Kinetic” (Modelling of the proces of sulphur dioxide (SO2) and nitro-gen oxides (NOx) removal under electron beam in computer program “Kinetic”). ChemSession’16. XIII Warszawskie Seminarium Doktorantów Chemików, Warszawa, Poland, 10.06.2016. Streszczenia, p. 218.


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7. Sujka M., Cieśla K., Jamroz J. Structure and selected functional properties of gamma-irradiated potato starch. Starch/Stärke, 67, 1002-1010 (2015).

8. Zakrzewska-Kołtuniewicz G. Application of advanced membrane systems in nuclear desalination of water. CEST2015. Proceedings of the 14th International Conference on Environmental Science and Technol-ogy, Rhodos, Greece, 3-5.09.2015. Volume of abstracts, p. 56.

9. Zakrzewska-Kołtuniewicz G. Application of advanced membranę systems in nuclear desalination of water. CEST2015. Proceedings of the 14th International Conference on Environmental Science and Technol-ogy, Rhodos, Greece, 3-5.09.2015. T.D. Lekkas (Ed.). [3] p. (CEST2015_00505).

10. Železnik N., Constantin M., Schneider N., Mays C., Zakrzewska G., Diaconu D. How people perceive ionizing radiation: Comparison in four countries. Proceedings of the International Conference Nuclear Energy for New Europe, Portorož, Slovenia, 14-17.09.2015, pp. 104.1-104.8.

SUPPLEMENT LIST OF THE PUBLICATIONS IN 2015

140 NUKLEONIKA

NUKLEONIKATHE 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), Andrzej Gałkowski (Poland), Evgeni A. Krasavin (Russia), Marek Lankosz (Poland), Stanisław Latek (Poland), Dan Meisel (USA), Jacek Michalik (Poland), Robert H. Schuler (USA), Christian Streffer (Germany), Irena Szumiel (Poland), Alexander Van Hook (USA), Bożena Bursa (secretary)

CONTENTS OF No. 1/2016

Proceedings of the Warsaw Medical Physics Meeting 2014, Warsaw, Poland, 15-17 May 20141. The IOERT IntraLine accelerator – the development, current state, and future plans

P. Adrich, R. Hanke, E. Kulczycka, K. Kosiński, B. Meglicki, A. Misiarz, E. Pławski, M. Staszczak, K. Swat, A. Syntfeld-Każuch, M. Wójtowicz, A. Wysocka-Rabin

2. Accelerator and detector physics at the Bern medical cyclotron and its beam transport lineM. Auger, S. Braccini, A. Ereditato, M. Häberli, E. Kirillova, K.P. Nesteruk, P. Scampoli

3. Prediction of the cumulated dose for external beam irradiation of prostate cancer patients with 3D-CRT techniqueM. Giżyńska, D. Blatkiewicz, B. Czyżew, M. Gałecki, M. Gil-Ulkowska, P. Kukołowicz

4. Application of instruments of nuclear physics to the calculation of theoretical dose distributions in various organs of the human body for beams used in hadrontherapyW. Maliszewska, P. Sękowski, I. Skwira-Chalot

5. Ambient dose equivalent measurements in secondary radiation fi elds at proton therapy facility CCB IFJ PAN in Krakow using recombination chambers E.A. Jakubowska, M.A. Gryziński, N. Golnik, P. Tulik, L. Stolarczyk, T. Horwacik, K. Zbroja, Ł. Góra

6. Synthesis of 11C-methionine through gas phase iodination using Synthra MeIPlus synthesis moduleK. Kilian, A. Pękal, J. Juszczyk

7. Application of the compress sensing theory for improvement of the TOF resolution in a novel J-PET instrumentL. Raczyński, P. Moskal, P. Kowalski, W. Wiślicki, T. Bednarski, P. Białas, E. Czerwiński, A. Gajos, Ł. Kapłon, A. Kochanowski, G. Korcyl, J. Kowal, T. Kozik, W. Krzemień, E. Kubicz, Sz. Niedźwiecki, M. Pałka, Z. Rudy, P. Salabura, N. Gupta-Sharma, M. Silarski, A. Słomski, J. Smyrski, A. Strzelecki, A. Wieczorek, M. Zieliński, N. Zoń

8. Compressed sensing in MRI – mathematical preliminaries and basic examplesŁ. Błaszczyk

9. Numerical model of thyroid counter M. Szuchta, J. Ośko

10. Analysis of dosimetric peaks of MgB4O7:Dy (40% Tefl on) versus LiF:Mg,Ti TL detectors M. Paluch-Ferszt, B. Kozłowska, S. Oliveira de Souza, L. Freire de Souza, D. Nascimento Souza

11. The threshold contrast thickness evaluated with different CDMAM phantoms and software E. Fabiszewska, I. Grabska, K. Pasicz

Regular papers 12. Application of the Böhm chamber for reference beta dose measurements and the calibration of personal

dosimetersK. Skubacz

141NUKLEONIKA

13. New amino bisphosphonate compound for skeletal imaging: Comparison study with methylenediphos-phonic acid (MDP) and (1-hydroxyethane-1,1-diyl) diphosphonic acid (HEDP) T. Assaad

14. Preliminary PM2.5 and PM10 fractions source apportionment complemented by statistical accuracy determination L. Samek, Z. Stegowski, L. Furman


Proceedings of PLASMA-2015 International Conference on Research and Applications of Plasmas, Warsaw, Poland, 7-11 September 20151. Preface

M.J. Sadowski

2. Progress in stellarator research at IPP-Kharkov V.E. Moiseenko, O.V. Lozin, A.M. Shapoval, M.B. Dreval, Yu.S. Kulyk, Yu.K. Mironov, V.S. Romanov, V.K. Pashnev, E.L. Sorokovoy, A.A. Petrushenya, F.I. Ozherel’ev, M.M. Kozulya, V.G. Konovalov, S.M. Maznichenko, I.E. Garkusha

3. Applicability of the dielectric barrier discharge for helium ash measurements in the divertor regionI. Książek, A. Brosławski, H. Janus, E. Pawelec

4. Nanostructured targets for TNSA laser ion accelerationL. Torrisi, L. Calcagno, M. Cutroneo, J. Badziak, M. Rosinski, A. Zaras-Szydlowska, A. Torrisi

5. Multi-energy ion implantation from high-intensity laserM. Cutroneo, L. Torrisi, J. Ullschmied, R. Dudzak

6. Self-similar solution of laser-produced plasma expansion into vacuum with kappa-distributed electronsD. Bennaceur-Doumaz, D. Bara

7. Ambient fi elds generated by a laser sparkK. Rohlena, M. Mašek

8. Thermodynamic and dynamical properties of dense ICF plasmaM.T. Gabdullin, S.K. Kodanova, T.S. Ramazanov, M.K. Issanova, T.N. Ismagambetova

9. Desorption/ablation of lithium fl uoride induced by extreme ultraviolet laser radiationT. Blejchař, V. Nevrlý, M. Vašinek, M. Dostál, M. Kozubková, J. Dlabka, M. Stachoň, L. Juha, P. Bitala, Z. Zelinger, P. Pira, J. Wild

10. Plasma characterization of the gas-puff target source dedicated for soft X-ray microscopy using SiC detectorsA. Torrisi, P. Wachulak, L. Torrisi, A. Bartnik, Ł. Węgrzyński, H. Fiedorowicz

11. Experiments and simulations on the possibility of radiative contraction/collapse in the PF-1000 plasma focusM. Akel, J. Cikhardt, P. Kubes, H.-J. Kunze, S. Lee, M. Paduch, S.H. Saw

12. Studies of plasma interactions with tungsten targets in PF-1000U facilityM.S. Ladygina, E. Skladnik-Sadowska, D.R. Zaloga, M.J. Sadowski, M. Kubkowska, E. Kowalska-Strze-ciwilk, N. Krawczyk, M. Paduch, R. Miklaszewski, I.E. Garkusha

13. Evolution of the small ball-like structures in the plasma focus discharge B. Cikhardtova, P. Kubes, J. Cikhardt, M. Paduch, E. Zielinska, J. Kravarik, K. Rezac, J. Kortanek

14. Measurements of fast electron beams and soft X-ray emission from plasma-focus experiments W. Surała, M.J. Sadowski, R. Kwiatkowski, L. Jakubowski, J. Żebrowski

15. The experimental and theoretical investigations of damage development and distribution in double-forged tungsten under plasma irradiation-initiated extreme heat loadsB. Väli, T. Laas, J. Paju, V. Shirokova, M. Paduch, V.A. Gribkov, E.V. Demina, V.N. Pimenov, V.A. Makhlaj, M. Antonov

16. Research on interactions of plasma streams with CFC targets in the Rod Plasma Injector facilityD.R. Zaloga, R. Kwiatkowski, E. Skladnik-Sadowska, M.J. Sadowski, K. Nowakowska-Langier

17. Microwave plasma for hydrogen production from liquidsD. Czylkowski, B. Hrycak, R. Miotk, M. Jasiński, J. Mizeraczyk, M. Dors

142 NUKLEONIKA

18. The role of magnetic energy on plasma localization during the glow discharge under reduced pressureR. Chodun, K. Nowakowska-Langier, K. Zdunek, S. Okrasa

19. Non-self-sustained discharge with hollow anode for plasma-based surface treatmentI.O. Misiruk, O.I. Timoshenko, V.S. Taran, I.E. Garkusha

20. Investigation of the electron capture process in semiclassical plasma M.M. Seisembayeva, K.N. Dzhumagulova, T.S. Ramazanov

21. Modelling of new generation plasma optical devices I.V. Litovko, A.A. Goncharov, A.N. Dobrovolskiy, L.V. Naiko, I.V. Naiko

22. Advanced laboratory for testing plasma thrusters and Hall thruster measurement campaignA. Szelecka

Regular paper 23. Imaging of hypoxia in small animals with 18F fl uoromisonidasole

K. Kilian, Z. Rogulski, Ł. Cheda, A. Drzał, M. Gerszewska, M. Cudny, M. Elas

24. In memoriam – Professor Gregory R. Choppin (1927-2015)


Proceedings of the 2nd International Conference “Radon in the Environment”, Kraków, Poland, 25-29 May 2015 1. Soil heat fl ux and air temperature as factors of radon (Rn-222) concentration in the near-ground air

layer A. Podstawczyńska, W. Pawlak

2. The infl uence of air conditioning changes on the effective dose due to radon and its short-lived decay products D. Grządziel, K. Kozak, J. Mazur, B. Połednik, M.R. Dudzińska, I. Bilska

3. Radon in the dry carbon dioxide spa of Mátraderecske, Hungary E. Sóki, I. Csige

4. Main results of the international intercomparison of passive radon detectors under fi eld conditions in Marie Curie’s tunnel in Lurisia (Italy) F. Cardellini, E. Chiaberto, L. Garlati, D. Giuffrida, F. Leonardi, M. Magnoni, G. Minchillo, A. Prand-statter, E. Serena, R. Trevisi, R. Tripodi, M. Veschetti

5. Metrological aspects of international intercomparison of passive radon detectors under fi eld conditions in Marie Curie’s tunnel in Lurisia F. Cardellini, E. Chiaberto, L. Garlati, D. Giuffrida, F. Leonardi, M. Magnoni, G. Minchillo, A. Prand-statter, E. Serena, R. Trevisi, R. Tripodi, M. Veschetti

6. Lung cancer mortality and radon exposure in Russia I.V. Yarmoshenko, G.P. Malinovsky

7. Investigation of the infl uence of chamber construction parameters on radon exhalation rate B. Kozłowska, J. Mazur, K. Kozak, A. Walencik-Łata, B. Baic

8. The Laboratory of Natural Radiation (LNR) – a place to test radon instruments under variable condi-tions of radon concentration and climatic variables L. Santiago Quindós Poncela, C. Sainz Fernández, J.-L. Gutiérrez-Villanueva, I. Fuente Merino, S. Celaya González, L. Quindós López, J. Quindós López, E. Fernández Lopez, A. Fernández Villar

9. Outdoor 222Rn behaviour in different areas of SlovakiaK. Holý, M. Műllerová, M. Bulko, O. Holá, T. Melicherová

10. Radon permeability of insulating building materials K. Walczak, J. Olszewski, M. Zmyślony

11. Analysis of simultaneous time series of indoor, outdoor and soil air radon concentrations, meteorologi-cal and seismic data M. Janik, P. Bossew

12. Preliminary results of radon survey in thermal spas in V4 countries M. Műllerová, J. Mazur, P. Blahušiak, D. Grządziel, K. Holý, T. Kovács, K. Kozak, E. Nagy, M. Neznal, M. Neznal, A. Shahrokhi

143NUKLEONIKA

13. Radon problems in mining and post-mining areas in Upper Silesia region, Poland M. Wysocka

14. The characteristics of radon and thoron concentration from soil gas in Shenzhen City of Southern China N.P. Wang, L. Zheng, X.M. Chu, S.J. Li, S.L. Yan

15. Results of the 2015 national indoor radon intercomparison measurements in Serbia S. Forkapić, K. Bikit, V. Arsić, J. Ilić, G. Pantelić, M. Živanović

16. Factors underlying persistently high radon levels in a house located in a karst limestone region of Ire-land – lessons learned about remediation S.C. Long, D. Fenton, C. Scivyer, E. Monahan

17. Distribution of indoor radon concentrations between selected Hungarian thermal baths A. Shahrokhi, E. Nagy, A. Csordás, J. Somlai, T. Kovács

18. Radon emission rate and analysis of its infl uencing parameters T. Neugebauer, H. Hingmann, J. Buermeyer, V. Grimm, J. Breckow

19. Construction of new houses on a uranium vein outcrop: a case study from the Czech Republic V. Goliáš, G. Tumurkhuu, P. Kohn, O. Šálek, J. Plášil, R. Škoda, J. Soumar

20. The natural radioactivity of the Carpathian national parks and radon evaluation V.T. Maslyuk, O.I. Symkanich, N.I. Svatyuk, O.O. Parlag, S.M. Sukharev

21. The use of multivariate analysis of the radon variability in the underground laboratory and indoor en-vironment J. Filipović, D. Maletić, V. Udovičić, R. Banjanac, D. Joković, M. Savić, N. Veselinović

22. First steps towards national radon action plan in Serbia V. Udovičić, D. Maletić, M. Eremić Savković, G. Pantelić, P. Ujić, I. Čeliković, S. Forkapić, D. Nikezić, V. M. Marković, V. Arsić, J. Ilić

23. Preliminary results of spatial distribution of uranium and thorium in soil profi les near a uranium indus-trial site, Guangdong province, China J. Wang, J. Liu, Y.H. Chen, G. Song, D.Y. Chen, T.F. Xiao, H.S. Li, C.L. Wang, F. Jiang

24. Outdoor radon concentration in China Q.F. Wu, Z.Q. Pan, S.L. Liu, C.H. Wang

25. Thoron emanation and exhalation of Slovenian soils determined by a PIC detector-equipped radon monitor J. Jónás, Z. Sas, J. Vaupotic, E. Kocsis, J. Somlai, T. Kovács

26. Results of radon CR-39 detectors exposed in schools due two different long-term periods Z. Stojanovska, B. Boev, Z.S. Zunic, P. Bossew, S. Jovevska


Proceedings of the Summer School of Plasma Diagnostics PhDiaFusion 2015: Soft X-ray Diagnos-tics for Fusion Plasma, Bezmiechowa, Poland, 16-20 June 20151. Diagnostics of laser-produced plasmas

D. Batani, A. Morace, Y. Maheut, K. Jakubowska, L. Volpe

2. Optimization of soft X-ray tomography on the COMPASS tokamak M. Imríšek, J. Mlynář, V. Löffelmann, V. Weinzettl, T. Odstrčil, M. Odstrčil, M. Tomeš

3. Comparison of silicon drift detectors made by Amptek and PNDetectors in application to the PHA system for W7-X N. Krawczyk, J. Kaczmarczyk, M. Kubkowska, L. Ryć

4. Diagnostic systems for the nuclear fusion and plasma research in the PF-24 plasma focus laboratory at the IFJ PANŁ. Marciniak, A. Wójcik-Gargula, A. Kulińska, J. Bielecki, U. Wiącek

5. Energy composition of high-energy neutral beams on the COMPASS tokamak K. Mitosinkova, J. Stöckel, J. Varju, V. Weinzettl

6. Nuclear fusion and its large potential for the future world energy supply J. Ongena

144 NUKLEONIKA

7. Modelling of the soft X-ray tungsten spectra expected to be registered by GEM detection system for WEST Ł. Syrocki, E. Szymańska, K. Słabkowska, M. Polasik, G. Pestka

8. Diagnostics of the plasma parameters based on the K X-ray line positions for various 4d and 4f metals E. Szymańska, Ł. Syrocki, K. Słabkowska, M. Polasik

9. Calculation of edge ion temperature and poloidal rotation velocity from carbon III triplet measure-ments on the COMPASS tokamak M. Tomeš, V. Weinzettl, T. Pereira, M. Imríšek, J. Seidl

Regular papers 10. Modelling of thermal hydraulics in a KAROLINA calorimeter for its calibration methodology valida-

tionA. Luks, K. Pytel, M. Tarchalski, N. Uzunow, T. Krok

11. Study on radiation-induced radicals giving rise to stable EPR signal suitable for the detection of irradia-tion in L-sorbose-containing fruits G.P. Guzik, W. Stachowicz

12. Infl uence of natural radium contamination of barium chloride on the determination of radium isotopes in the water samples using / liquid scintillation spectrometry C.N. Dinh, M. Czechowska, J. Nowak, P. Jodłowski

13. Radiocatalytic degradation of dissolved organic compounds in wastewaterJ. Jiménez-Becerril, A. Moreno-López, M. Jiménez-Reyes

InformationINSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY

NUKLEONIKADorodna 16, 03-195 Warszawa, Poland

phone: +48 22 504 11 32, fax: +48 22 811 15 32, e-mail: [email protected] texts are available on-line at http://www.nukleonika.pl

145POSTĘPY TECHNIKI JĄDROWEJ

POSTĘPY TECHNIKI JĄDROWEJ

EDITORIAL BOARD

Stanisław Latek (Editor-in-Chief), Wojciech Głuszewski, Maria Kowalska, Łukasz Sawicki, Andrzej Mikulski, Marek Rabiński, Edward Rurarz, Elżbieta Zalewska

CONTENTS OF No. 1/20161. Wywiad z prof. Krzysztofem Kurkiem Dyrektorem Narodowego Centrum Badań Jądrowych (Interview

with Prof. Krzysztof Kurek Director of the National Centre for Nuclear Research)S. Latek, A. Mikulski, E. Zalewska

2. Wywiad z prof. Jerzym Niewodniczańskim – aktywne życie: Akademia Górniczo-Hutnicza, Państwowa Agencja Atomistyki i energetyka jądrowa (Interview with Prof. Jerzy Niewodniczański – active life: AGH University of Science and Technology, National Atomic Energy Agency and nuclear energy)M. Nowina-Konopka

3. 60 lat Instytutu Fizyki Jądrowej im. Henryka Niewodniczańskiego Polskiej Akademii Nauk (60 years of the Henryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences)M. Nowina-Konopka

4. Atom to najlepszy wybór dla Polski – potwierdzają to analiza i praktyka (Both analysis and practice confi rm: Atom is the best choice for Poland)A. Strupczewski

5. Praca reaktora badawczego MARIA w 2015 roku (Research reactor MARIA operation in 2015)A. Gołąb, M. Tarchalski

6. Energetyka jądrowa Japonii po katastrofi e w elektrowni Fukushima Daiichi (Nuclear energy in Japan after the Fukushima Daiichi accident)K. Rzymkowski

CONTENTS OF No. 2/2016 1. 60 lat Zjednoczonego Instytutu Badań Jądrowych w Dubnej i udziału polskich uczonych w jego pracach

(The 60th anniversary of the Joint Institute for Nuclear Research in Dubna and participation of Polish scientists in its activities)M. Waligórski, W. Chmielowski, M. Budzyński, W. Nawrocik

2. Wywiad z prof. Jurijem Cołakowiczem Oganesjanem, kierownikiem naukowym Laboratorium Reakcji Ją-drowych Zjednoczonego Instytutu Badań Jądrowych (Interview with Prof. Yuri Tsolakovich Oganessian, scientifi c director of the Flerov Laboratory of Nuclear Reactions)S. Latek, W. Chmielowski

3. Spektroskopia anihilacji pozytonów w Zjednoczonym Instytucie Badań Jądrowych w Dubnej (Positron annihilation spectroscopy at the Joint Institute for Nuclear Research in Dubna)P. Horodek

4. Działalność sektora projektów naukowych i kriogenicznych – Sektor nr 1 NIKO LFWE JINR oraz perspek-tywy wykorzystania technologii nadprzewodnikowych w nauce i gospodarce krajowej (Activity of section of scientifi c and cryogenic projects – Section No. 1 NIKO of Department LFWE JINR and perspectives of use superconducting technologies in science and national industry)H. Malinowski

5. Laboratorium Fizyki Neutronowej im. Franka ZIBJ w Dubnej i „Polska Grupa Neutronowa” (Frank Laboratory of Neutron Physics of JINR in Dubna and “Polish Neutron Group”)D. Chudoba

6. Rozmowa z mgr. inż. Andrzejem Szozdą, byłym ministrem energetyki i energii atomowej (Interview with Andrzej Szozda, former Minister of Power Industry and Nuclear Energy)A. Mikulski, S. Latek

146 POSTĘPY TECHNIKI JĄDROWEJ

CONTENTS OF No. 3/2016 1. Instytut Fizyki Plazmy i Laserowej Mikrosyntezy – 40 lat badań naukowych dla zrównoważonego rozwoju

(The Institute of Plasma Physics and Laser Microfusion – 40 years of research for sustainable development)M. Bielski

2. Energetyka jądrowa w projekcie „Strategia na rzecz odpowiedzialnego rozwoju” (Nuclear energy in “Strategy for Responsible Development Plan”)A. Mikulski

3. Kontrakty różnicowe w energetyce jądrowej (The contract for difference (CfD) in the nuclear energy sector)M.M. Szołucha

4. Ochrona ludności w pomieszczeniach, przed narażeniem od radonu i innych naturalnych źródeł promie-niowania (Protection of the public against exposure indoors due to radon and other natural sources of radiation)T. Musiałowicz

5. Obliczenia neutronowe z użyciem kodów SCALE i PARCS (Neutronic calculations using SCALE and PARCS codes)E. Staroń, S. Suchcicki

6. Pywające elektrownie jądrowe (Floating nuclear power plants)K. Rzymkowski

7. Opakowania stosowane w sterylizacji radiacyjnej (Packaging used in radiation sterilization)E.M. Kornacka

8. Społeczno-techniczne zarządzanie dużymi wypadkami jądrowymi (Socio-technical management of big nuclear accidents)S. Latek

CONTENTS OF No. 4/2016 1. Jubileusz sześćdziesięciolecia Międzynarodowej Agencji Energii Atomowej (Sixtieth anniversary of the

International Atomic Energy Agency)S. Latek, E. Zalewska

2. Energetyka jądrowa po Umowie Paryskiej i wyborach w USA i nie tylko... (Nuclear power after Paris Agreement and American elections and more...)D.W. Kulczynski

3. Koncepcja organizacyjna Organizacji Wsparcia Technicznego w Polsce (Organizational concept of Tech-nical Support Organization in Poland)P. Krajewski, S. Sommer

4. Instytut Fizyki Plazmy i Laserowej Mikrosyntezy – 40 lat badań dla energetyki przyszłości (Institute of Plasma Physics and Laser Microfusion – 40 years of research for secure energy in the future)J. Wołowski et al.

5. Spektrometria aktywacyjna dla potrzeb Drugiej Kampanii Deuterowo-Trytowej na Tokamaku JET (The activation spectrometry for the purpose of the Second Deuterium-Tritium Experimental Campaign on JET tokamak)E. Łaszyńska, S. Jednoróg

6. Badania historycznych szkieł przy użyciu metod jądrowych (Studies of historical glass with the use of nuclear methods)J.J. Kunicki-Goldfi nger, E. Pańczyk

InformationINSTITUTE OF NUCLEAR CHEMISTRY AND TECHNOLOGY

POSTĘPY TECHNIKI JĄDROWEJDorodna 16, 03-195 Warszawa, Poland

phone: +48 22 504 12 48, fax: +48 22 811 15 32, e-mail: [email protected]

147INTERVIEWS IN 2016

INTERVIEWS IN 2016

1. Chmielewski A.G.http://pavlodarnews.kz, 02.11.2016.

2. Chmielewski A.G.Polish scientist presents “green” technologies of XXI in Pavlodar. KAZINFORM International News Agency, http://www.inform.kz, 03.11.2016.

3. Kruszewski M.Miłosz M.: Terapia celowana to przyszłość walki z nowotworami (Targeted therapy – the future of the fi ght against cancer). Dziennik Gazeta Prawna, 14, 22 stycznia (2016).

4. Latek S.Wiścicki T.: Masa krytyczna (Critical mass). Newsweek Historia, 5, 32-37 (2016).

5. Łada W.Krakowiak K., Nowak N.: Dzień dobry Warszawo. TVP3 Warszawa, 25.03.2016.

6. Rogowski M.Kapiszewski J.: Atomowy recykling z witaminą C (Nuclear recycling with vitamin C). Dziennik Gazeta Prawna, 24 (4171), A25, 5-7 lutego (2016).

7. Zakrzewska-Kołtuniewicz G.Zyśk J.: Nauka dla energii jądrowej (Science for nuclear energy). Środowisko, 1 (517), (2016).

148 THE INCT PATENTS AND PATENT APPLICATIONS IN 2016

THE INCT PATENTS AND PATENT APPLICATIONS IN 2016

PATENTS

1. Sposób pozyskiwania i separacji cennych pierwiastków metali, zwłaszcza z ubogich rud uranowych oraz ścieków radioaktywnych (Method for separation and obtaining of valuable metals particularly from low-grade uranium ores and radioactive effl uents)G. Zakrzewska-Trznadel, W. Łada, A. Jaworska-Sobczak, A. Miśkiewicz, E. Dłuska, S. WrońskiPolish Patent

2. Klej termotopliwy do klejenia polietylenu i innych poli(alfa-olefi n), zwłaszcza do izolacji złączy preizo-lowanych rur ciepłowniczych, oraz sposób jego wytwarzania (Hot-melt adhesive for gluing polyethylene and other polyolefi ns, used for the insulation of joints in pre-insulation of hot water pipes, and method for its production)G. Przybytniak, A. Nowicki, I. Legocka, K. MirkowskiPolish Patent

3. Sposób unieszkodliwiania odpadów radioaktywnych w „syntetycznej skale” (A method of the disposal of radioactive waste in the “synthetic rock”)T. Smoliński, A.G. Chmielewski, A. Deptuła, W. Łada, T. OlczakPolish Patent

4. Sposób wytwarzania stabilizowanego ditlenku cyrkonu w postaci matrycy inertnej do transmutacji ak-tynowców mniejszościowych (Method for producing of stabilized zirconium dioxide in the form of inert matrix for the transmutation of minor actinides)M. Brykała, R. Walczak, M. Rogowski, W. Łada, D. WawszczakPolish Patent

5. Sposób otrzymywania diagnostycznych ilości radionuklidu 99mTc (Method for the obtaining of diagnostic amounts of the 99mTc radionuclide)A. Bilewicz, M. GumielaPolish Patent

6. Sposób unieruchamiania radionuklidów metali z odpadowych roztworów wodnych z zastosowaniem biosorbenta pochodzenia roślinnego (Immobilization of the metallic radionuclides present in aqueous radioactive wastes using natural sorbent of the plant origin)L. Fuks, A. Oszczak, W. Dalecka, W. ŁadaPolish Patent

7. A method of the disposal of radioactive waste in the “synthetic rock” T. Smoliński, A. Chmielewski, A. Deptuła, W. Łada, T. OlczakEP2693443 (A2)

PATENT APPLICATIONS

1. Kompozyt poliuretanowy, zwłaszcza w postaci kształtek do zastosowań w hydrobudownictwie do bu-dowy wałów przeciwpowodziowych i/lub umocnień nabrzeży oraz sposób jego wytwarzania (Polyure-thane composite, in particular in the form of moldings for application in the construction of levees and/or marine application and its manufacturing)P. Kalbarczyk, M. Motrenko, H. Polkowska-MotrenkoPolish Patent Application P-416897

2. Kompozyt cementowy, zwłaszcza w postaci kształtek do zastosowań w hydrobudownictwie do budowy wałów przeciwpowodziowych i/lub umocnień nabrzeży oraz sposób jego wytwarzania (Cement com-posite, in particular in the form of moldings for application in the construction of levees and/or marine application and its manufacturing)P. Kalbarczyk, M. Motrenko, H. Polkowska-MotrenkoPolish Patent Application P-416898

149THE INCT PATENTS AND PATENT APPLICATIONS IN 2016

3. Sposób otrzymywania diagnostycznej ilości radionuklidu 43Sc (Method for the obtaining of diagnostic amounts of the 43Sc radionuclide)A. Bilewicz, R. Walczak, A. Majkowska-PilipPolish Patent Application P-415874

4. Radiofarmaceutyk diagnostyczny do obrazowania poziomu cholinoesteraz, sposób jego wytwarzania oraz jego zastosowanie (The diagnostic radiopharmaceutical for imaging of cholinesterases level, its synthesis and application)E. Gniazdowska, P. KoźmińskiPolish Patent Application P-415771

5. Biokompatybilny nośnik żelaza, sposób jego syntezy i zastosowanie medyczne (The biocompatible carrier of iron, the process of its synthesis and medical use)H. Lewandowska-Siwkiewicz, G. Wójciuk, M. KruszewskiPolish Patent Application P-418581

6. Sposób witryfi kacji zużytych sorbentów z wbudowanymi w ich strukturę wysokoaktywnymi pierwiast-kami metodą zol-żel (Method for the vitrifi cation with sol-gel process of sorbents with high-level radio-active elements embbeded in their stucture)M. Siwek, D. Chmielewska-Śmietanko, P. Wojtowicz, W. ŁadaPolish Patent Application P-417953

7. Sposób wytwarzania radioizotopowego znacznika i znacznik radioizotopowy (Method for preparation of radiotracer and a radiotracer)T. Smoliński, P. Wojtowicz, A.G. ChmielewskiPolish Patent Application P-420055

8. Sposób higienizacji odpadów ściekowych (Method of wastewater hygienization)A.G. Chmielewski, J. Palige, O. Roubinek, Z. Zimek, U. Gryczka, J. Usidus, K. Pietrzak, R. EdgecockPolish Patent Application P-419131

150 CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2016

CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2016

1. SPOTKANIE „MODELE MENTALNE PROMIENIOWANIA JONIZUJĄCEGO JAKO NARZĘ-DZIE BUDOWANIA KOMUNIKACJI ZE SPOŁECZEŃSTWEM – OCENA BADAŃ PRZE-PROWADZONYCH W RAMACH PROJEKTU EAGLE” (MEETING “MENTAL MODELS OF IONIZING RADIATION AS A TOOL TO BUILD COMMUNICATION WITH THE PUBLIC – EVALUATION OF RESEARCH CARRIED OUT WITHIN THE EAGLE PROJECT”), 27 JANUARY 2016, WARSZAWA, POLAND

Organized by the Institute of Nuclear Chemistry and Technology

Organizing Committee: Prof. Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc., Agnieszka Miśkiewicz, Ph.D., Katarzyna Kiegiel, Ph.D., Dorota Gajda, M.Sc., Anna Abramowska, M.Sc.

2. VII KRAJOWA KONFERENCJA RADIOCHEMII I CHEMII JĄDROWEJ (VII NATIONAL CONFERENCE ON RADIOCHEMISTRY AND NUCLEAR CHEMISTRY), 17-20 APRIL 2016, LUBLIN, POLAND

Organized by the Maria Curie-Skłodowska University (UMCS), AGH University of Science and Technol-ogy, Institute of Nuclear Chemistry and Technology, Polish Chemical Society – Lublin Division

Organizing Committee: Małgorzata Wiśniewska, Ph.D., D.Sc., UMCS professor, Elżbieta Grządka, Ph.D., Jacek Patkowski, Ph.D., Ewa Skwarek, Ph.D., Barbara Kubica, Ph.D., D.Sc., AGH professor, Leon Fuks, Ph.D., Jolanta Narkiewicz-Michałek, Ph.D., D.Sc., UMCS professor

3. SEMINAR ERASMUS+ KA1, 9-13 MAY 2016, WARSZAWA, POLANDOrganized by the Institute of Nuclear Chemistry and Technology

Organizer: Yongxia Sun, Ph.D., D.Sc., professor in INCT

4. SYMPOZJUM „ZASTOSOWANIE PROMIENIOWANIA JONIZUJĄCEGO W PRZETWÓR-STWIE MATERIAŁÓW” W RAMACH PROJEKTU “JOINT INNOVATIVE TRAINING AND TEACHING/LEARNING PROGRAM IN ENHANCING DEVELOPMENT AND TRANSFER KNOWLEDGE OF APPLICATION OF IONIZING RADIATION IN MATERIALS PROCESS-ING” PROGRAMU ERASMUS+/SYMPOSIUM “APPLICATIONS OF IONIZING RADIATION IN MATERIALS PROCESSING” IN THE FRAME OF THE PROJECT ENTITLED “JOINT INNOVATIVE TRAINING AND TEACHING/LEARNING PROGRAM IN ENHANCING DE-VELOPMENT AND TRANSFER KNOWLEDGE OF APPLICATION OF IONIZING RADIA-TION IN MATERIALS PROCESSING” OF ERASMUS+ PROGRAMME, 12 MAY 2016, WAR-SZAWA, POLAND

Organized by the Institute of Nuclear Chemistry and Technology; Centre for Innovation and Technology Transfer Management, Warsaw University of Technology

Organizing Committee: Yongxia Sun, Ph.D., D.Sc., professor in INCT, Grażyna Przybytniak, Ph.D., D.Sc., professor in INCT

5. MEETING CONCERNING ENHANCING SAFETY AND CONTROL FEATURES OF EXIST-ING RADIATION PROCESSING FACILITIES, 29 MAY-4 JUNE 2016, WARSZAWA, POLAND

Organized by the Institute of Nuclear Chemistry and Technology, International Atomic Energy Agency

Organizer: Zbigniew Zimek, Ph.D.

6. SEMINARIUM „ANALIZA SPOŁECZNO-EKONOMICZNYCH EFEKTÓW WDRAŻANIA POL-SKIEGO PROGRAMU ENERGETYKI JĄDROWEJ” W RAMACH PROJEKTU “STUDYING

151CONFERENCES ORGANIZED AND CO-ORGANIZED BY THE INCT IN 2016

THE SOCIAL AND SOCIO-ECONOMIC EFFECTS OF THE IMPLEMENTATION OF THE POLISH NUCLEAR POWER PROGRAMME USING NEW METHODOLOGY” IAEA CRP 18541/R1 (SEMINAR “ANALYSIS OF SOCIO-ECONOMIC EFFECTS OF THE IMPLEMEN-TATION OF THE POLISH NUCLEAR POWER PROGRAMME” IN THE FRAME OF THE PROJECT “STUDYING THE SOCIAL AND SOCIO-ECONOMIC EFFECTS OF THE IMPLE-MENTATION OF THE POLISH NUCLEAR POWER PROGRAMME USING NEW METHOD-OLOGY” IAEA CRP 18541/R1), 21 JULY 2016, WARSZAWA, POLAND

Organized by the Institute of Nuclear Chemistry and Technology, International Atomic Energy Agency

Organizing Committee: Agnieszka Miśkiewicz, Ph.D., Dorota Gajda, M.Sc.

7. CORE COMMITTEE MEETING #3 (CCM#3) YOUNG GENERATION EUROPEAN NUCLEAR SOCIETY, 7-9 OCTOBER 2016, WARSZAWA, POLAND

Organized by the European Nuclear Society, Institute of Nuclear Chemistry and Technology

Organizing Committee: Dorota Gajda, M.Sc., Barbara Filipowicz, M.Sc., Magdalena Rejnis-Strzelak, M.Sc., Eileen Langeggner, Ph.D.

8. SZKOLENIE DLA PRACOWNIKÓW PAŃSTWOWEJ INSPEKCJI SANITARNEJ „NAPRO-MIENIOWANIE ŻYWNOŚCI – KONTROLA, WYKRYWANIE, METODYKA BADAŃ” (TRAIN-ING FOR EMPLOYEES OF THE STATE SANITARY INSPECTION “FOOD IRRADIATION – CONTROL, DETECTION, RESEARCH METHODOLOGY”), 29-30 NOVEMBER 2016, WAR-SZAWA, POLAND

Organized by the Institute of Nuclear Chemistry and Technology

Organizing Committee: Grażyna Liśkiewicz, Magdalena Sadowska, M.Sc., Grzegorz Guzik, M.Sc., Wacław Stachowicz, Ph.D. (consultant)

9. EuCARD-2 WORKSHOP WITH INDUSTRY “LOW ENERGY ELECTRON BEAMS FOR IN-DUSTRIAL AND ENVIRONMENTAL APPLICATIONS”, 8-9 DECEMBER 2016, WARSZAWA, POLAND

Organized by the Science and Technology Facilities Council, UK; CERN – The European Organization for Nuclear Research; Institute of Nuclear Chemistry and Technology; Fraunhofer Institute for Organic Electronics, Electron Beam and Plasma Technology FEP; Centre for Innovation and Technology Transfer Management, Warsaw University of Technology

Organizing Committee: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc., Sunil Sabharwal, Ph.D., Bumsoo Han, Ph.D., Frank-Holm Roegner, Ph.D., Rob Edgecock, Ph.D., Henrik Bjerke, Ph.D., Vlad Skarda, Ph.D., Prof. Ryszard Romaniuk, Ph.D., D.Sc.

10. 12th LOWRAD INTERNATIONAL CONFERENCE “THE EFFECTS OF LOW DOSES AND VERY LOW DOSES OF IONIZING RADIATION ON HUMAN HEALTH AND BIOTOPES”, 12-13 DECEMBER 2016, WARSZAWA, POLAND

Organized by the World Council of Nuclear Workers, Low Radiation International Network, Polish Radia-tion Research Society, Institute of Nuclear Chemistry and Technology

Organizing Committee: Nicolas Foray, Ph.D., Sylwester Sommer, Ph.D., Ewa M. Nowosielska, Ph.D., Aneta Cheda, Ph.D.

11. SEMINAR “LOW DOSE OF RADIATION – POTENTIAL RISK AND BENEFITS”, 13 DECEM-BER 2016, WARSZAWA, POLAND

Organized by the Polish Radiation Research Society, Institute of Nuclear Chemistry and Technology

Organizing Committee: Nicolas Foray, Ph.D., Sylwester Sommer, Ph.D., Ewa M. Nowosielska, Ph.D., Aneta Cheda, Ph.D.

152 Ph.D. THESES IN 2016

Ph.D. THESES IN 2016

1. Paweł Karol Biełuszka, M.Sc. (INCT Ph.D. student)Ekstrakcja uranu w układach z kontaktorami membranowymi (Extraction of uranium in systems with membrane contactors)supervisor: Prof. Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology, 08.04.2016

2. Patryk Wojtowicz, M.Sc. (INCT Ph.D. student)Synteza szkieł krzemionkowych metodą zol-żel i ocena możliwości ich zastosowania w procesie zestala-nia odpadów promieniotwórczych (Synthesis of silica glass using sol-gel method and evaluation of the possibilities of their use in the process of radioactive waste solidifi cation)supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology, 08.04.2016

3. Piotr Jakub Lipiński, M.Sc. (Mossakowski Medical Research Centre, Polish Academy of Sciences, War-szawa, Poland)Novel aspects of chiral QSPR analysissupervisor: Prof. Jan Czesław Dobrowolski, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology, 01.07.2016

4. Małgorzata Nyga, M.Sc. (INCT Ph.D. student)Generowanie rodników utleniających i ich reaktywność w wytypowanej grupie cieczy jonowych (Gen-eration of oxidizing radicals and their reactivity in a selected group of ionic liquids)supervisor: Prof. Krzysztof Bobrowski, Ph.D., D.Sc.Institute of Nuclear Chemistry and Technology, 02.12.2016

5. Łukasz Steczek, M.Sc. (Co-tutelle, INCT Ph.D. student)Complexation of actinides Am(III), Th(IV), Pu(IV) and U(VI) with poly-N-dentate ligands SO3-Ph-BTP and SO3-Ph-BTBPsupervisors: Philippe Moisy, Ph.D., Prof. Jerzy Ostyk-Narbutt, Ph.D., D.Sc.University of Montpellier 2, France, 12.12.2016

153EDUCATION

EDUCATION

Ph.D. PROGRAMME IN CHEMISTRY

The Institute of Nuclear Chemistry and Technology holds a four-year Ph.D. degree programme for graduates of chemical, physical and biological departments of universities, for graduates of medical universities and to engineers in chemical technology and material science.

The main areas of the studies are: • chemical aspects of nuclear energy,• radiation chemistry and biochemistry, • chemistry of radioelements, • isotopic effects, • radiopharmaceutical chemistry, • analytical methods, • chemistry of radicals, • application of nuclear methods in chemical and environmental research, material science and 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 fi nal 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;• fi nal examination and public defence of the dissertation thesis.

In 2016, the following lecture series and lectures were organized:• Nuclear chemistry – Prof. Aleksander Bilewicz (Institute of Nuclear Chemistry and Technology,

Warszawa, Poland);• Chemical studies of environmental samples – selected aspects – Prof. Jerzy Golimowski (Faculty of

Chemistry, University of Warsaw).The qualifi cation interview for the Ph.D. programme takes place in the mid of September. Detailed

information can be obtained from: • head: Prof. Aleksander Bilewicz, Ph.D., D.Sc.

(phone: +48 22 504 13 57, e-mail: [email protected]); • secretary: Ewa Gniazdowska, Ph.D., D.Sc., professor in INCT

(phone: +48 22 504 11 78, e-mail: [email protected]).

TRAINING OF STUDENTS

Institution Country Number of participants Period

Aleksander Fredro High School No. 81 (Warszawa) Poland 30 one-day course

Cardinal Stefan Wyszyński University in Warsaw, Faculty of Mathematics and Natural Sciences Poland 1 1 month

The Jan Paweł II Secondary School No. 123 with bilingual and integration classes (Warszawa) Poland 22 one-day course

University of Warsaw, Faculty of Chemistry Poland

3 2.5 weeks

2 3 weeks

2 3.5 weeks

154 EDUCATION

MASTER’S AND BACHELOR’S DISSERTATIONS

1. Marcelina BednarczykMaster’s dissertation: Radiotoksyczność biokoniugatu znakowanego radionuklidem 223Ra względem gle-jakowych komórek nowotworowych oraz macierzystych komórek glejakowych (Radiotoxicity of NaA-si-lane-PEG-SP(5-11) bioconjugate labelled with -emitter 223Ra towards glioblastoma cancer cells and glio-blastoma stem cells)supervisors: Agnieszka Majkowska-Pilip, Ph.D., Izabela Skwira-Chalot, Ph.D.University of Warsaw, Faculty of Physics

2. Justyna Małgorzata KiecMaster’s dissertation: Badanie powinowactwa receptorowego radiobiokoniugatu Trastuzumabu na komór-kach z nadekspresją receptora HER2 (Receptor binding affi nity studies of trastuzumab radiobioconju-gate on cells with HER2-overexpression)supervisors: Maciej Jan Kamiński, Ph.D., D.Sc., Marek Pruszyński, Ph.D.University of Warsaw, Faculty of Physics

3. Weronika MaliszewskaMaster’s dissertation: Synteza i badanie pochodnych antybiotyków do obrazowania infekcji bakteryjnych dla diagnostyki PET (Synthesis and study of antibiotics derivatives for PET-imaging of bacterial infections)supervisors: Izabela Skwira-Chalot, Ph.D., Przemysław Koźmiński, Ph.D.University of Warsaw, Faculty of Physics

4. Agata PiądłowskaMaster’s dissertation: Znakowanie cząstek biologicznie aktywnych dla diagnostyki SPECT (Labelling of biologically active molecules for SPECT diagnostics)supervisors: Prof. Piotr Durka, Ph.D., D.Sc., Przemysław Koźmiński, Ph.D.University of Warsaw, Faculty of Physics

5. Małgorzata SiwekBachelor’s dissertation: Witryfi kacja krzemionkowego sorbentu cezu metodą zol-żel (Vitrifi cation of cesium silica sorbent by sol-gel method)supervisors: Prof. Eugeniusz Molga, Ph.D., D.Sc., Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.supervisor in INCT: Dagmara Chmielewska-Śmietanko, M.Sc.Warsaw University of Technology, Faculty of Chemical and Process Engineering

6. Paulina SkrobańskaBachelor’s dissertation: Bioługowanie uranu w bioreaktorze z mieszadłem (Bioleaching of uranium in stirred bioreactor)

Institution Country Number of participants Period

University of Warsaw, Faculty of Physics Poland

2 2 weeks

2 3 weeks

1 9 months

Warsaw University of Life Sciences – SGGW, Faculty of Food Sciences Poland

52 one-day course

2 3.5 weeks

Warsaw University of Technology, Faculty of Chemical and Process Engineering Poland 3 1 month

Warsaw University of Technology, Faculty of Chemistry Poland

2 3.5 weeks

1 1 month

2 3 months

Warsaw University of Technology, Faculty of Physics Poland

1 2 weeks

1 3.5 weeks

1 1 month

155EDUCATION

supervisor: Prof. Eugeniusz Molga, Ph.D., D.Sc.supervisor in INCT: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.Warsaw University of Technology, Faculty of Chemical and Process Engineering

7. Lena StachurskaBachelor’s dissertation: Badanie kinetyki sorpcji kobaltu na sorbencie krzemionkowym (Sorption ki-netics study of Co-60 onto silica material)supervisors: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc., Prof. Eugeniusz Molga, Ph.D., D.Sc. supervisor in INCT: Dagmara Chmielewska-Śmietanko, M.Sc.Warsaw University of Technology, Faculty of Chemical and Process Engineering

8. Anna WawrzynowskaMaster’s dissertation: Synteza oraz badania in vitro biokoniugatów Substancji P znakowanych radio-nuklidem 177Lu (Synthesis and in vitro studies of Substance P bioconjugates labeled with 177Lu radionu-clide)supervisor: Agnieszka Majkowska-Pilip, Ph.D.Warsaw University of Life Sciences – SGGW, Faculty of Agriculture and Biology

9. Maciej WójcikMaster’s dissertation: Znakowanie biokoniugatu Sc-DOTA-oktreotyd radionuklidem 18-F poprzez mostek metaliczny (Labelling Sc-DOTA bioconjugate with 18-F by a metallic bridge)supervisors: Piotr Suffczyński, Ph.D., D.Sc., Przemysław Koźmiński, Ph.D.University of Warsaw, Faculty of Physics

156 RESEARCH PROJECTS AND CONTRACTS

RESEARCH PROJECTS AND CONTRACTS

RESEARCH PROJECTS GRANTED BY THE NATIONAL SCIENCE CENTRE

IN 2016

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 modifi ed 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 fi ltration of aqueous solutions and suspensions proceeding in membrane apparatuses with different confi gurations.supervisor: Agnieszka Miśkiewicz, Ph.D.

6. The infl uence 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 perfl uorinated 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.

11. Bioconjugates of multimodal nanoparticles for targeted alpha and hyperthermia therapy. Synthesis, retention studies of recoiling daughter radionuclides and preliminary cell.supervisor: Edyta Cędrowska, M.Sc.

12. In vitro and in vivo preclinical studies of NaA nanozeolite funcionalized with antibodies anti-PSMA and labeled with radium radioisotope for targeted prostate cancer therapy.supervisor: Prof. Anna Lankoff, Ph.D., D.Sc.

PROJECTS GRANTED BY THE NATIONAL CENTRE FOR RESEARCH AND DEVELOPMENT

IN 2016

1. Conspan BlueGas – technology for treatment of fl owback fl uids from gas-bearing shales hydraulic frac-turing with water recycling and reclamation of valuable metals (programme BlueGas).

157RESEARCH PROJECTS AND CONTRACTS

IAEA RESEARCH CONTRACTS IN 2016

1. Based on starch-PVA system and cellulose reinforced active packaging materials for food prepared using of radiation modifi cation (PackRad).No. 17493supervisor: Krystyna Cieśla, Ph.D., D.Sc., professor in INCT.

2. The study of the infl uence of the environmental factors on the isotopic compositions of dairy products.No. 18056supervisor: Ryszard Wierzchnicki, Ph.D.

3. Application of advanced membrane systems in nuclear desalination.No. 18539/ROsupervisor: Prof. Grażyna Zakrzewska-Kołtuniewicz, Ph.D., D.Sc.

4. Studying the social and socio-economic effects of the implementation of the Polish nuclear programme using new methodology.No. 18541/ROsupervisor: Agnieszka Miśkiewicz, Ph.D.

5. Application of low energy electron beam for microbiological control of food and agricultural products.No. RC-19000supervisor: Urszula Gryczka, M.Sc.

6. Radiometric methods applied in hydrometallurgical processes development and optimization.No. 18945supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

7. Silicide/silicate coatings on zirconium alloys for improving the high temperature corrosion resistance.No. 19026supervisor: Bożena Sartowska, Ph.D.

8. Recovery of uranium and accompanying metals from various types of industrial wastes.No. 18542supervisor: Katarzyna Kiegiel, Ph.D.

9. Electron beam for preservation of biodeteriorated cultural heritage paper-based objects.No. 18493supervisor: Dagmara Chmielewska-Śmietanko, M.Sc.

10. Synthesis of 50 g synthesized nanotracer material by sol-gel process including a detailed report with the methodology and characterization of the material.No. 201506067-VGsupervisor: Tomasz Smoliński, M.Sc.

11. New cyclotron method for 47Sc production and conjugation of 47Sc to monoclonal antibodies.No. 20488supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc.

Konsorcjum naukowe: Pyrocat Catalyse World (leader), Institute of Nuclear Chemistry and Technology, Polish Geological Institute – National Research Institute

2. The integrated system of sewage treatment, biogas production and its enrichment in the methane.supervisor: Jacek Palige, Ph.D.

3. Syntheses of radiopharmaceuticals based on scandium radionuclides for positron emission tomography (Petscand).supervisor: Prof. Aleksander Bilewicz, Ph.D., D.Sc.

IAEA TECHNICAL AND REGIONAL CONTRACTS IN 2016

1. Introducing and harmonizing standardized quality control procedures for radiation technologies.RER 1014

2. Regional Training Course on Dosimetry and Electron Beam Facilities.RER 1014

158 RESEARCH PROJECTS AND CONTRACTS

PROJECTS WITHIN THE FRAME OF EUROPEAN UNION FRAME PROGRAMMES

IN 2016

1. FP7 – EURATOM, Fission: Advanced fuels for generation IV reactors: reprocessing and dissolution (ASGARD).principal investigator: Danuta Wawszczak, Ph.D.

2. FP7 – Safety of actinide separation processes (SACSESS).principal investigator: Prof. Jerzy Narbutt, Ph.D., D.Sc.

3. 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.

4. 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.

5. 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.

OTHER INTERNATIONAL RESEARCH PROGRAMMES IN 2016

1. New nanostructured porous materials with advanced/tailored properties (with Joint Institute for Nu-clear Research, Dubna, Russia).supervisor: Bożena Sartowska, Ph.D.

2. Studies on high temperature and radiation resistant coatings on zirconium alloys for application in nuclear technologies.No. 04-5-1076-2009/2016supervisor: 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.

4. Measurement of the depth profi ling of the cesium atom on the surface of the adsorbent for its recovery from the spent nuclear waste by time-of-fl ight elastic recoil detection analysis (ToF-ERDA).No. 20152054 (Central European Research Infrastructure Consortium project)supervisor: Danuta Wawszczak, Ph.D.

5. Fostering of scientifi c and R&D collaboration in the fi eld of radiation technologies.No. 2015/A/1 (International Irradiation Association programme)supervisor: Prof. Andrzej G. Chmielewski, Ph.D., D.Sc.

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

159LIST OF VISITORS TO THE INCT IN 2016

LIST OF VISITORS TO THE INCT IN 2016

1. Adliene Diana, Kaunas University of Technology, Lithuania, 12.05.2016

2. Calinescu Ioan, University Politehnica of Bucharest, Romania, 09-13.05.2016

3. D’angelantonio Mila, Institute of Polymers, Composites and Biomaterials (IPCB), National Research Council (CNR), Italy, 25.01-03.02.2016

4. De Capua Francesco, National Institute for Nuclear Physics (INFN), Rome, Italy, 14-15.01.2016

5. Etoom Mohammad Amer, International Atomic Energy Agency (IAEA), Austria, 18-22.07.2016

6. Foray Nicolas, Cancer Research Centre of Lyon, France, 13.12.2016

7. Fuente Julio de la, University of Chile, Santiago de Chile, Chile, 01-30.09.2016

8. Gębicki Janusz M., Macquarie University, Sydney, Australia, 20.09.2016

9. Gu Zhaolin, Xi’an Jiaotong University, China, 09-13.05.2016

10. Kieran Murray, CelgenTek Ltd, Ireland, 05-06.05.2016

11. Krasavin Eugene, Joint Institute for Nuclear Research (JINR), Dubna, Russia, 25.04.2016

12. Lavric Vasile, University Politehnica of Bucharest, Romania, 09-13.05.2016

13. Malavasi Aldo, International Atomic Energy Agency (IAEA), Austria, 29-31.08.2016

14. Marchini Marianne, University of Bologna, Italy, 25.01-03.02.2016

15. Motawee Hamza, Atomic Energy Commission of Syria, Damascus, Syria, 01-28.11.2016

16. Nichipor Henrietta, Joint Institute for Power and Nuclear Research “Sosny”, National Academy of Sciences of Belarus, Minsk, Belarus , 08-21.05.2016

17. Orelovitch Oleg L., Joint Institute for Nuclear Research (JINR), Dubna, Russia, 10-20.05.2016, 05-15.12.2016

18. Poorbaygi Hosein, Nuclear Science and Technology Research Institute, Teheran, Iran, 15-20.02.2016

160 THE INCT SEMINARS IN 2016

THE INCT SEMINARS IN 2016

1. Prof. Janusz M. Gębicki (Macquarie University, Sydney, Australia)Pulse radiolysis studies of protein oxidation

2. Prof. Janusz Gołaszewski, Ph.D., D.Sc. (University of Warmia and Mazury, Olsztyn, Poland)Chemurgy – alians strategiczny chemii i rolnictwa w tworzeniu wartości dodanej biogospodarki (Chemurgy – strategic alliance of chemistry and agriculture in creation additive value of bioeconomy)

3. Urszula Gryczka, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)Wpływ promieniowania jonizującego na właściwości wybranych polisacharydów (Effects of ionizing radiation on the properties of selected polysaccharides)

4. Magdalena Gumiela, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)Wydzielanie technetu-99m z naświetlonej protonami tarczy molibdenowej (Separation of technet-ium-99m from proton irradiated molybdenum target)

5 Jadwiga Hatrwich, Ph.D., D.Sc. (Jagiellonian University, Medical College, Faculty of Pharmacy, Kraków, Poland)Dobrostan lipoprotein, nowe metody badania (Welfare of lipoproteins, new testing methods)

6. Barbara Janota, M.Sc. (National Centre for Nuclear Research, POLATOM Radioisotope Centre, Otwock-Świerk, Poland)Badania przedkliniczne oraz opracowanie i przygotowanie formy farmaceutycznej HYNIC-Eksen-dyny-4 agonisty receptora GLP-1 (Preclinical studies, the development and preparation of the pharma-ceutical form HYNIC-Exendin-4, the receptor agonist of GLP-1)

7. Prof. Eugene Krasavin (Joint Institute for Nuclear Research, Laboratory of Radiation Biology, Dubna, Russia)55 years of radiobiological research at JINR’s accelerators

8. Prof. Marcin Kruszewski, Ph.D., D.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)Naprawa uszkodzeń DNA – już chemia czy jeszcze biologia? Nagroda Nobla 2015 (DNA damage repair – chemistry already or still biology? Nobel Prize 2015)

9. Prof. Małgorzata Lewandowska-Szumieł, Ph.D., D.Sc. (Medical University of Warsaw, Warszawa, Poland)Komórki w hodowli jako producenci wyrobów medycznych (Cells in culture as manufacturers of medi-cal devices)

10. Prof. Aldo Malavasi (Deputy Director General of the International Atomic Energy Agency, Vienna, Austria)IAEA Program on Nuclear Science and Applications

11. Justyna Pijarowska-Kruszyna, M.Sc. (National Centre for Nuclear Research, POLATOM Radioiso-tope Centre, Otwock-Świerk, Poland)Innowacyjna metoda syntezy znacznika do obrazowania transportera dopaminy (DAT) przy użyciu tech-niki pozytonowej tomografi i emisyjnej (PET) (The innovative synthesis method of [18F]FECNT ligand for imaging of dopamine transporter (DAT) using positron emission tomography (PET) technique)

12. Jurij Reichman, Ph.D. (Radioactive Waste Management Enterprise in the Chernobyl Exclusion Zone)Postępowanie z odpadami promieniotwórczymi w Czarnobylskiej Strefi e Wykluczenia (Radioactive waste management in the Chernobyl Exclusion Zone)

13. Magdalena Rejnis-Strzelak, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)Nowe aspekty chemiczne procesów oddzielania ameryku(III) od produktów rozszczepienia uranu ekstrahentami diglikoloamidowymi (New chemical aspects of the processes of the separation of americium(III) from fi ssion products by diglycolamide extractants)

14. Prof. Janusz Rosiak, Ph.D., D.Sc. (Łódź University of Technology, Faculty of Chemistry, Institute of Applied Radiation Chemistry, Łódź, Poland)Radiacyjne tworzenie biomateriałów polimerowych (Formation of biopolymers by radiation)

161THE INCT SEMINARS IN 2016

15. Łukasz Steczek, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)Chemia koordynacyjna aktynowców z ligandami poli-N-dentnymi (Coordination chemistry of actinides with poly-N-dentate ligands)

16. Liang Zhao, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)Magnetyczne sorbenty do usuwania cezu z roztworów wodnych (Magnetic sorbent for the removal of caesium in aqueous solutions)

17. Ewa Zwolińska, M.Sc. (Institute of Nuclear Chemistry and Technology, Warszawa, Poland)Usuwanie NOx i SO2 występujących w wysokich stężeniach w gazach odlotowych powstałych po spalaniu olejów diesla za pomocą technologii hybrydowej wykorzystującej wiązkę elektronów. Studium teore-tyczne oraz praktyczne (The removal of high concentration of NOx and SO2 in diesel oils exhaust gases with the use of the hybrid electron beam technology. A theoretical and experimental study)

162 LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2016

LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2016

LECTURES

1. Bartoś B., Majkowska-Pilip A., Walczak R., Pruszyński M., Bilewicz A. New separation method of separation no-carrier-added 47Sc from titanium targets.IAEA Coordination Meeting “Therapeutic radiopharmaceuticals labelled with new emerging radionu-clides (67Cu, 186Re, 47Sc)”, Vienna, Austria, 05-09.09.2016.

2. Chmielewski A.G. Building nuclear competences in Poland.Seminar of the project “Baltic region initiative for long lasting innovative nuclear technologies” (BRIL-LIANT), Warszawa, Poland, 29.02.-01.03.2016.

3. Chmielewski A.G. Radiacyjne przetwórstwo materiałów – nanotechnologie (Radiation processing of materials – nanotech-nology).Sympozjum „Zastosowanie promieniowania jonizującego w przetwórstwie materiałów” w ramach pro-jektu “Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing” programu Erasmus+/Sym-posium “Applications of ionizing radiation in materials processing” in the frame of the project entitled “Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing” of Erasmus+ programme, War-szawa, Poland, 12.05.2016.

4. Chmielewski A.G., Palige J., Usidus J., Krylowicz A.Polska myśl techniczna w wytwarzaniu i użytkowaniu biometanu w energetyce, przemyśle i transporcie (Polish engineering in the manufacture and use of biomethane in the energy, industry and transport).Konferencja Naukowo-Techniczna SEP Oddział Zamojski, Parczew, Poland, 02.06.2016.

5. Chmielewski A.G. Nuclear energy to protect environment and climate.French-Polish Forum of Research and Innovation, 2nd edition, Kraków, Poland, 08.06.2016.

6. Chmielewski A.G. Role of radiation and radio-chemistry in modern nuclear power development.3rd International Workshop on Radiation Effects in Nuclear Technology, Hefei, China, 19-21.06.2016.

7. Chmielewski A.G. RER2016035 – Radiotracer techniques and nuclear control systems for protecting and sustainably managing of natural resources and ecosystems.TCEU Workshop to Review and Design Regional TC Project Proposals for 2018-2019 in the Field of Isotope and Radiation Technology Applications, 27.06.-01.07.2016.

8. Chmielewski A.G. Additives infl uencing the radiation crosslinking of industrial polymers.The second cycle of the intensive learning programme in URCA in the frame of the project entitled “Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing” of Erasmus+ programme, Reims, France, 05-15.09.2016.

9. Chmielewski A.G. Future development of radiation processing. State of the art of radiation processing. Emerging tech-nologies. Commercialization.The second cycle of the intensive learning programme in URCA in the frame of the project entitled “Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing” of Erasmus+ programme, Reims, France, 05-15.09.2016.

163LECTURES AND SEMINARS DELIVERED OUT OF THE INCT IN 2016

10. Chmielewski A.G. Gamma irradiation and industrial facilities.The second cycle of the intensive learning programme in URCA in the frame of the project entitled “Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing” of Erasmus+ programme, Reims, France, 05-15.09.2016.

11. Chmielewski A.G. Radiation crosslinking for the cable industry, rubber materials and for medical devices.The second cycle of the intensive learning programme in URCA in the frame of the project entitled “Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing” of Erasmus+ programme, Reims, France, 05-15.09.2016.

12. Chmielewski A.G. Presentation of Polish capabilities of nuclear R&D.Polish-Spanish Nuclear Business Day, Warszawa, Poland, 13.10.2016.

13. Chmielewski A.G., Gryczka U., Zimek Z.EB wastewater/sludge treatment.Workshop in the frame of the project EuCARD-2: Enhanced European Coordination for Accelerator Research and Development, Huddersfi eld, UK, 17-18.10.2016.

14. Chmielewski A.G. Electron beam fl ue gas treatment.International Investment Forum ERTYS INVEST 2016, Pavlodar, Kazakhstan, 02.11.2016.

15. Chmielewski A.G. Waste management.18th International Meeting on Radiation Processing IMRP 2016, Vancouver, Canada, 07-11.11.2016.

16. Chmielewski A.G. Operation experiences on industrial and pilot scale fl ue gas e-beam treatment plants.EuCARD-2 Workshop with Industry “Low energy electron beams for industrial and environmental ap-plications”, Warszawa, Poland, 08-09.12.2016.

17. Chmielewski A.G.Recent developments of EB/X systems and applications based on IMRP 2016 reports.EuCARD-2 Workshop with Industry “Low energy electron beams for industrial and environmental ap-plications”, Warszawa, Poland, 08-09.12.2016,

18. Chmielewski A.G. Europe, Europe... Where we are and where we go? TC RER and EU programmes. The examples – EuCARD 2, ARIES and Erasmus+ 2.IAEA TC Project RER 1017 Expert Meeting to Discuss the Safe and Reliable Operation of Irradiation Facilities, Vienna, Austria, 12-15.12.2016.

19. Chmielewski A.G. Recent developments of EB/X systems and applications based on IMRP 2016 reports.IAEA TC Project RER 1017 Expert Meeting to Discuss the Safe and Reliable Operation of Irradiation Facilities, Vienna, Austria, 12-15.12.2016.

20. Dybczyński R.S., Pyszynska M., Kulisa K., Bojanowska-Czajka A. The new temperature-assisted method for the selective determination of yttrium in the mixed rare earths by RP-HPLC.XI International Conference “Ion chromatography and related techniques 2016”, Zabrze, Poland, 20-21.04.2016.

21. Dziawer Ł., Koźmiński P., Pruszyński M., Wąs B., Bilewicz A. Gold nanoparticle-substance P(5-11) conjugate as a carrier for 211At in alpha particle therapy.12th Cycleur Workshop, Bern, Switzerland, 23-24.06.2016.

22. Fuks L., Cholerzyński A. Odpady radioaktywne w Polsce, stan obecny i krajowe prace badawcze (Radioactive waste in Poland, current state and the national research projects).Seminarium „Elektrownia jądrowa – jej znaczenie dla Polski i dla Pomorza”, Warszawa, Poland, 23.02.2016.


23. Gajda D.Uran w Polsce? – prawda i mity (Uranium in Poland? – truth and myths).Akademickie Forum Energii Jądrowej, Kraków, Poland, 19-20.05.2016.

24. Gajda D. Uran – sąsiad którego nie znam (Uranium – my unknown neighbour).IX Festiwal Filozofi i „Filozofi a i technika”, Olsztyn, Poland, 07-09.09.2016.

25. Głuszewski W. Use of radiation crosslinking in the production of polyethylene foam.EuCARD-2 Workshop with Industry “Low energy electron beams for industrial and environmental ap-plications”, Warszawa, Poland, 08-09.12.2016.

26. Grosbois J. de, Chmielewski A.G.Non-power NTM programmes development.Meeting of the International Nuclear Management Academy (INMA) Steering Committee and Advi-sory Board Groups, Manchester, UK, 03-06.05.2016.

27. Gryczka U., Chmielewski A.G., Edgecock R., Zimek Z., Palige J.Hybrid biogas-EB system for electricity.and biofertilizer production.EuCARD-2 Workshop with Industry “Low energy electron beams for industrial and environmental ap-plications”, Warszawa, Poland, 08-09.12.2016,

28. Han B., Chmielewski A.G. Radiation technologies for environment protection.18th International Meeting on Radiation Processing IMRP 2016, Vancouver, Canada, 07-11.11.2016.

29. Palige J. Małe biogazownie rolnicze – kierunki rozwoju, możliwości i ograniczenia (Small agricultural biogas plants – development, capabilities and limitations).Konferencja Naukowo-Techniczna SEP Oddział Zamojski, Poland, 02.06.2016.

30. Pruszyński M. Promieniowanie – wróg czy sojusznik? (Radiation – enemy or ally?).IX Festiwal Filozofi i „Filozofi a i technika”, Olsztyn, Poland, 07-09.09.2016.

31. Przybytniak G. Od nauki do technologii – sieciowanie radiacyjne polimerów (From science to technology – radiation crosslinking of polymers).Sympozjum „Zastosowanie promieniowania jonizującego w przetwórstwie materiałów” w ramach pro-jektu “Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing” programu Erasmus+/Sym-posium “Applications of ionizing radiation in materials processing” in the frame of the project entitled “Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing” of Erasmus+ programme, War-szawa, Poland, 12.05.2016.

32. Przybytniak G. Application of electron beam of the modifi cation of medical devices.EuCARD-2 Workshop with Industry “Low energy electron beams for industrial and environmental ap-plications”, Warszawa, Poland, 08-09.12.2016.

33. Rogowski M., Brykała M., Deptuła A. Synthesis of uranium carbides by complex sol-gel process (CSGP).ASGARD 8th Project Meeting, Cologne, Germany, 26-27.01.2016.

34. Rogowski M., Brykała M., Deptuła A. Synthesis of uranium dioxide doped with MA surrogates by complex sol-gel process (CSGP).ASGARD 8th Project Meeting, Cologne, Germany, 26-27.01.2016.

35. Rogowski M., Brykała M., Deptuła A. Synthesis of uranium carbides by complex sol-gel process (CSGP).ASGARD 9th Project Meeting, Gotland, Sweden, 20-22.06.2016.

36. Rogowski M., Brykała M., Deptuła A. Synthesis of uranium dioxide doped with MA surrogates by complex sol-gel process (CSGP).ASGARD 9th Project Meeting, Gotland, Sweden, 20-22.06.2016.


37. Roubinek O., Chmielewski A., Palige J., Dobrowolski A., Usidus J., Kryłowicz A., Chrzanowski K. Biogaz z odpadów rolno-spożywczych i osadów miejskich biologicznych oczyszczalni ścieków do zasi-lania pojazdów mechanicznych (Biogas from agriculture and municipal waste treatment stations sedi-ment as a fuel for municipal transport).II Międzynarodowa Konferencja “Nowoczesne technologie, konstrukcje, materiały dla sektora chemii i energetyki”/2nd International Conference “Modern technologies, constructions, materials for chemical and power engineering”, Kędzierzyn-Koźle/Opole, Poland, 27-28.10.2016.

38. Sartowska B., Starosta W., Waliś L., Barlak M.Modyfi kacja warstwy wierzchniej stopów cyrkonu intensywnymi impulsami plazmowymi (Modifi cation of the surface layer of zirconium alloys with intense pulse plasma beams).Nowoczesne Technologie w Inżynierii Powierzchni, Łódź-Spała, Poland, 25-28.09.2016.

39. Sartowska B., Starosta W., Waliś L., Barlak M. Experiments with zirconium alloy coatings using Si based compounds.22 International Quench Workshop, Karlsruhe, Germany, 18-20.10.2016.

40. Smoliński T., Chmielewski A.G., Roubinek O., Rogowski M., Pyszynska M. Górnictwo rud i “górnictwo miejskie” – możliwości odzysku metali z odpadów kopalnianych i odpadów komunalnych (Ore mining and “urban mining” – possiblity of recovery of metals from mining waste and urban waste).II Międzynarodowa Konferencja “Nowoczesne technologie, konstrukcje, materiały dla sektora chemii i energetyki”/2nd International Conference “Modern technologies, constructions, materials for chemical and power engineering”, Kędzierzyn-Koźle/Opole, Poland, 27-28.10.2016.

41. Sommer S., Buraczewska I., Kowalska M. Dose effect curve for dicentric and micronucleus assays for proton beam of the Bronowice Cyclotron Centre for the biological dosimetry purpose.RadioWARSAW Meeting, Warszawa, Poland, 19.05.2016.

42. Sun Y. TL-IRMP Project introduction.Sympozjum „Zastosowanie promieniowania jonizującego w przetwórstwie materiałów” w ramach pro-jektu “Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing” programu Erasmus+/Sym-posium “Applications of ionizing radiation in materials processing” in the frame of the project entitled “Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing” of Erasmus+ programme, War-szawa, Poland, 12.05.2016.

43. Trojanowicz M. Application of electron beam irradiation in remediation of wastewaters.EuCARD-2 Workshop with Industry “Low energy electron beams for industrial and environmental ap-plications”, Warszawa, Poland, 08-09.12.2016.

44. Walczak R. Cyclotron production of theranostic pair 43Sc-47Sc on calcium targets.12th Cycleur Workshop, Bern, Switzerland, 23-24.06.2016.

45. Zakrzewska-Kołtuniewicz G. The possibility of nuclear cogeneration for desalination in the future NPP in Poland.Technical Meeting on Operating Experience with, and Project Feasibility of, Process Heat Applications, Budapest, Hungary, 23-25.05.2016.

46. Zakrzewska-Kołtuniewicz G., Wołkowicz S. Zasoby uranu w Polsce (Uranium resources in Poland).Seminarium „Elektrownia jądrowa – jej znaczenie dla Polski i dla Pomorza”, Warszawa, Poland, 23.02.2016.

47. Zimek Z. Zastosowanie akceleratorów elektronów w przetwórstwie materiałów (Application of electron accel-erators in material processing).Sympozjum „Zastosowanie promieniowania jonizującego w przetwórstwie materiałów” w ramach pro-jektu “Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing” programu Erasmus+/Sym-posium “Applications of ionizing radiation in materials processing” in the frame of the project entitled “Joint innovative training and teaching/learning program in enhancing development and transfer


knowledge of application of ionizing radiation in materials processing” of Erasmus+ programme, War-szawa, Poland, 12.05.2016.

48. Zimek Z. Basics of radiation physics.The second cycle of the intensive learning programme in URCA in the frame of the project entitled “Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing” of Erasmus+ programme, Reims, France, 05-15.09.2016.

49. Zimek Z. Comparison between e-, gamma and X-ray facilities: advantages and limitations.The second cycle of the intensive learning programme in URCA in the frame of the project entitled “Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing” of Erasmus+ programme, Reims, France, 05-15.09.2016.

50. Zimek Z. Criterions for accelerator selection on the basis of technical performance and cost of operation.The second cycle of the intensive learning programme in URCA in the frame of the project entitled “Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing” of Erasmus+ programme, Reims, France, 05-15.09.2016.

51. Zimek Z. Electrical measurements and computed prediction of dose distribution, computer modeling for the control of radiation dose.The second cycle of the intensive learning programme in URCA in the frame of the project entitled “Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing” of Erasmus+ programme, Reims, France, 05-15.09.2016.

52. Zimek Z. General aspects of particle accelerators technology (electrons, protons, helions, swift heavy irons) X-ray sources.The second cycle of the intensive learning programme in URCA in the frame of the project entitled “Joint innovative training and teaching/learning program in enhancing development and transfer knowledge of application of ionizing radiation in materials processing” of Erasmus+ programme, Reims, France, 05-15.09.2016.

53. Zimek Z. Electron acceleratora for radiation processing – industrial application, reliability and economical aspects.EuCARD-2 Workshop with Industry “Low energy electron beams for industrial and environmental ap-plications”, Warszawa, Poland, 08-09.12.2016,

SEMINARS

1. Chajduk EwelinaNowe materiały odniesienia na potrzeby analizy specjacyjnej (New certifi ed reference materials for speciation analysis). POLLAB – the Club of Polish Testing Laboratories, Warszawa, Poland, 06.12.2016.

2. Chajduk EwelinaSprawozdanie z badań Rośliny 15 “Oznaczanie zawartości pierwiastków śladowych w przyprawach i zio-łach przyprawowych” organizowanych przez IChTJ w 2016 r. (Report on Profi ciency Testing Plants 15 “Determination of trace elements in spices and herb-spices” organized by the INCT in 2016). POLLAB – the Club of Polish Testing Laboratories, Warszawa, Poland, 06.12.2016.

3. Chmielewski Andrzej G. Chemia jądrowa – obawy i nadzieje (Nuclear chemistry – fear and hope). University of Warsaw, Biological and Chemical Research Centre, Warszawa, Poland, 14.01.2016.

4. Chmielewski Andrzej G. Radiochemia i chemia jądrowa – kierunki rozwoju (Radiochemistry and nuclear chemistry – main di-rections of development).


Warsaw University of Technology, Chemiczne Koło Naukowe “FLOGISTON”, Warszawa, Poland, 22.03.2016.

5. Chmielewski Andrzej G. Electron beam sludge hygienization and hybrid biogas production. University of Huddersfi eld, Huddersfi eld, United Kingdom, 17.10.2016.

6. Chmielewski Andrzej G. Nuclear energy and environmental protection. S. Toraighyrov Pavlodar State University, Pavlodar, Kazakhstan, 01.11.2016.

7. Kołacińska Kamila Bieżący stan programu budowy pierwszej elektrowni jądrowej (Polish Nuclear Power Programme – update). Warsaw School of Economics, Collegium of Business Administration, Warszawa, Poland, 18.03.2016.

8. Pruszyński MarekPromieniowanie wokół nas (Radiation around us). Aleksander Fredro High School No. 81, Warszawa, Poland, 31.03.2016.

9. Pruszyński MarekMedycyna nuclearna – zastosowanie znakowanych biomolekuł jako radiofarmaceutyków diagnostycznych i terapeutycznych (Nuclear medicine – application of labelled biomolecules as diagnostic and therapeutic radiopharmaceuticals). University of Warsaw, Faculty of Chemistry, Warszawa, Poland, 24.05.2016.

10. Pruszyński MarekNanobodies labelled with -emitting 225Ac as potential new therapeutic radiopharmaceutical. Vrije Universiteit Brussel, Brussels, Belgium, 07.10.2016.

11. Pruszyński MarekNanobodies – new probe for cancer diagnosis and theraphy. The Institute of Cancer Research, London, United Kingdom, 28.11.2016.

12. Szreder TomaszWybrane zagadnienia chemii radiacyjnej w przemyśle jądrowym (Selected aspects of radiation chemistry in nuclear industry). Polish Radiation Research Society, Łódź Branch, Poland, 31.05.2016.

13. Trojanowicz Marek Miniaturyzacja analizy przepływowej. Początki i aktualne tendencje rozwojowe (Miniaturization of fl ow analysis. The origins and current trends). Jagiellonian University, Faculty of Chemistry, Kraków, Poland, 11.05.2016.

14. Trojanowicz Marek Sprzęganie przepływowych układów przetwarzania próbek z wysokosprawnymi metodami rozdzielania (Coupling of the fl ow systems of processing samples with high effi ciency separation methods). Jagiellonian University, Faculty of Chemistry, Department of Analytical Chemistry, Kraków, Poland, 12.05.2016.

15. Trojanowicz Marek Application of ionizing radiation as effi cient AOP method for remediation of waters and wastewaters. University of Pavia, Department of Civil Engineering and Architecture, Pavia, Italy, 26.10.2016.

16. Trojanowicz Marek Perfl uorinated surfactants as new class of persistent organic pollutants (POP) – occurence, analysis and removal from environmental samples. University of Pavia, Department of Civil Engineering and Architecture, Pavia, Italy, 26.10.2016.

17. Trojanowicz Marek Pharmaceutical residues in environment – importance, analysis, and removal. University of Pavia, Department of Civil Engineering and Architecture, Pavia, Italy, 27.10.2016.

18. Trojanowicz Marek Nanotechnology in modern separation methods of chemical analysis. University of Pavia, Department of Civil Engineering and Architecture, Pavia, Italy, 28.10.2016.

168 AWARDS IN 2016

AWARDS IN 2016

1. Institute of Nuclear Chemistry and Technology has obtained the status of the IAEA Collaborating Centre for Radiation Processing and Industrial Dosimetry for another 5 years (2016-2020)

2. The therapeutic radiopharmaceutical based on astatine-211-labelled gold nanoparticles and method of preparationPlatinum Medal at the International Warsaw Invention Show IWIS 2016, Warszawa, Poland, 10-12.10.2016 Łucja Janiszewska, Marek Pruszyński, Przemysław Koźmiński, Agnieszka Majkowska, Aleksander Bilewicz

3. The biocompatibile carrier of iron, the process of its synthesis and medical useGold Medal at the International Warsaw Invention Show IWIS 2016, Warszawa, Poland, 10-12.10.2016 Anna Lewandowska, Marcin Kruszewski, Grzegorz Wójciuk

4. A method of synthesis mixed oxide fuels precursors MOX-type in the form of spherical particles powdersSilver Medal at the International Warsaw Invention Show IWIS 2016, Warszawa, Poland, 10-12.10.2016 Marcin Brykała, Marcin Rogowski, Wiesława Łada, Andrzej Deptuła

5. Method for producing stabilized of zirconium dioxide in the form of inert matrix for actinide transmu-tation minorityBronze Medal at the International Warsaw Invention Show IWIS 2016, Warszawa, Poland, 10-12.10.2016 Marcin Brykała, Rafał Walczak, Marcin Rogowski, Wiesława Łada, Danuta Wawszczak

6. The therapeutic radiopharmaceutical based on astatine-211-labelled gold nanoparticles and method of preparationDiploma and special award of the Romanian Inventors Forum at the International Warsaw Invention Show IWIS 2016, Warszawa, Poland, 10-12.10.2016 Łucja Janiszewska, Marek Pruszyński, Przemysław Koźmiński, Agnieszka Majkowska, Aleksander Bilewicz

7. Medal for recognition of scientifi c achievements due to the application of radiation techniques to study the photochemical reactions in cooperation research projects with the Adam Mickiewicz University in Poznań Krzysztof Bobrowski

8. Commander Order of Academic Palms granted by the Prime Minister of France at the request of the Ministry of National Education, Higher Education and Research for outstanding professional achieve-ments and support for the French strategies in the fi eld of nuclear energy) Andrzej G. Chmielewski

9. Sposób otrzymywania sferycznych ziaren trójtlenku itru (Preparation of ytrrium trioxide in form of spherical grains; authors: A. Deptuła, W. Łada, D. Wawszczak, E. Iller, L. Królicki, J. Ostyk-Narbutt)Diploma of the Ministry of Science and Higher EducationInstitute of Nuclear Chemistry and Technology

10. Nowa technologia otrzymywania mikrosfer trójtlenku itru do zastosowania w terapii raka wątroby (Production of yttrium trioxide microspheres for reduce tumour by new technology)Award in the category “Innovative researcher” at the I National Conference Innovative Researchers Wrocław, Poland, 30.05.2016Wiesława Łada, Danuta Wawszczak

11. Statuette “AMBASADOR INNOWACYJNOŚCI 2015” granted by the Association of Polish Inventors and Rationalizers, and Foundation Haller Pro Inventio for invention “Preparation of ytrrium trioxide in form of spherical grains” (authors: A. Deptuła, W. Łada, D. Wawszczak, E. Iller, L. Królicki, J. Os-tyk-Narbutt)Institute of Nuclear Chemistry and Technology

12. Optymalizacja zautomatyzowanych oznaczeń 90Sr i 99Tc metodami analizy przepływowej z detekcją ICP-MS (Optimization of fully automated fl ow injection systems dedicated for determination of 90Sr and 99Tc with ICP-MS detection)

169AWARDS IN 2016

Diploma for the best oral presentation at the VII National Conference on Radiochemistry and Nuclear Chemistry, Lublin, Poland, 17-20.04.2016Kamila Kołacińska

13. Mineralogy and uranium leaching of ores from Triassic Peribaltic sandstones (authors: D. Gajda, K. Kie-giel, G. Zakrzewska-Kołtuniewicz, E. Chajduk, I. Bartosiewicz, S. Wołkowicz)First degree award in the category of fundamental and technical sciences for graduate students and scientifi c staff for the best publications on nuclear energy granted by PGE EJ 1Dorota Gajda

14. Carbonization of solid uranyl-ascorbate gel as an indirect step of uranium carbide synthesis (authors: M. Brykała, M. Rogowski, T. Olczak)Distinction in the category of fundamental and technical sciences for graduate students and scientifi c staff for the best publications on nuclear energy granted by PGE EJ 1Marcin Rogowski

15. Unikatowe cechy radiacyjnej konserwacji dużych zbiorów obiektów o znaczeniu historycznym (Unique features of radiation conservation of high collections of objects of historical interest; author: W. Głu-szewski)First degree award in the category of popular science for graduate students and scientifi c staff for the best publications on nuclear energy granted by PGE EJ 1Wojciech Głuszewski

16. The title of honorary professor of S. Toraighyrov Pavlodar State UniversityAndrzej G. Chmielewski

17. Honory award “For health protection” granted by the Minister of HealthMarcin Kruszewski

18. Sfunkcjonalizowane nanozeolity, jako nośniki radioizotopów 223Ra, 224Ra i 225Ra w celowanej terapii radionuklidowej (Functionalized nanozeolites as a carrier for 223Ra, 224Ra and 225Ra for targeted radio-nuclide therapy)First degree award of the Polish Nculear Society for the best doctoral thesis in 2015-2016 concerning nuclear sciencesAgata Piotrowska

19. Dobór kryteriów oceny degradacji radiacyjnej i termicznej kabli (Criteria for the evaluation of radiation and thermal degradation of cables)Second degree award of the Polish Nculear Society for the best doctoral thesis in 2015-2016 in the fi eld of nuclear sciencesJacek Boguski

20. First degree team award of Director of the Institute of Nuclear Chemistry and Technology in 2016 for a series of twenty original publications on the application of quantum chemistry methods and graph theory for interpretation and prediction of the results of X-ray and vibrational spectroscopy structural studiesMichał H. Jamróz, Katarzyna Łuczyńska, Krzysztof Łyczko, Monika Łyczko, Sławomir Ostrowski, Joanna E. Rode, Wojciech Starosta, Jan Cz. Dobrowolski

21. Second degree team award of Director of the Institute of Nuclear Chemistry and Technology in 2016 for a series of fi ve publications on the study of nanoparticles effect on human and animal cellsAnna Lankoff, Kamil Brzóska, Sylwia Męczyńska-Wielgosz, Katarzyna Sikorska, Tomasz M. Stępkowski, Maria Wojewódzka, Marcin Kruszewski

22. Third degree team award of Director of the Institute of Nuclear Chemistry and Technology in 2016 for a series of four publications dedicated to the radiation- and photochemically-induced radical processes in amino acids and sulphur-containing peptidesKrzysztof Bobrowski, Dariusz Pogocki, Gabriel Kciuk

23. Third degree team award of Director of the Institute of Nuclear Chemistry and Technology in 2016 for a series of four publications on effective separation of minority actinides from fi ssion products of uran-ium in spent nuclear fuelJerzy Ostyk-Narbutt, Łukasz Steczek, Magdalena Rejnis-Strzelak

24. Second degree team award of Director of the Institute of Nuclear Chemistry and Technology in 2016 for the application achievements in 2014-2015 – the technology for radiation modifi cation of semicon-ductor devices used in photovoltaic sources using the low energy electronZbigniew Zimek, Andrzej Rafalski, Sylwester Bułka, Stanisław Celiński-Mysław, Izabela Fąfrowicz-Ja-nowska

170 AWARDS IN 2016

25. Second degree team award of Director of the Institute of Nuclear Chemistry and Technology in 2016 for the application achievements in 2014-2015 – the process for removing sulphur dioxide and nitrogen oxides from exhaust gases with high content of carbon dioxide using high-energy electron beamsYongxia Sun, Ewa Zwolińska

26. Distinction of the fi rst degree of Director of the Institute of Nuclear Chemistry and Technology in 2016 for the achieved progress in the preparation of Ph.D. thesis and professional activity, including pub-lished articles, and participation in the preparation and realization of research projectsŁucja Dziawer

27. Distinction of the second degree of Director of the Institute of Nuclear Chemistry and Technology in 2016 for the achieved progress in the preparation of Ph.D. thesis and professional activity, including published articles, and participation in the preparation and realization of research projectsMagdalena Gumiela

28. Distinction of the second degree of Director of the Institute of Nuclear Chemistry and Technology in 2016 for the achieved progress in the preparation of Ph.D. thesis and professional activity, including published articles, and participation in the preparation and realization of research projectsRafał Walczak

29. Distinction of the third degree of Director of the Institute of Nuclear Chemistry and Technology in 2016 for the achieved progress in the preparation of Ph.D. thesis and professional activity, including pub-lished articles, and participation in the preparation and realization of research projectsEwa Zwolińska

30. Award of Director of the Institute of Nuclear Chemistry and Technology in 2016 for management of Erasmus 2 programmeYongxia Sun

31. Award of Director of the Institute of Nuclear Chemistry and Technology in 2016 for the cooperation with industrial partners in the fi eld of radiation technologiesZbigniew Zimek

32. Award of Director of the Institute of Nuclear Chemistry and Technology in 2016 for coordination of activities of the Mazovian Valley of Green ChemistryMarta Walo

33. Award of Director of the Institute of Nuclear Chemistry and Technology in 2016 for coordination of activities of the Mazovian Valley of Green ChemistryUrszula Gryczka

34. Award of Director of the Institute of Nuclear Chemistry and Technology in 2016 for the achievements of the Laboratory for Detection of Irradiated Food as a reference laboratory of the Minister of HealthGrażyna Liśkiewicz

35. Award of Director of the Institute of Nuclear Chemistry and Technology in 2016 for the development of research topics and obtaining grants in the fi eld of radiopharmaceuticalsAleksander Bilewicz

36. Award of Director of the Institute of Nuclear Chemistry and Technology in 2016 for activity concerning implementation of the EC Directive on the control of radionuclides concentrations in waterEwa Gniazdowska

37. Award of Director of the Institute of Nuclear Chemistry and Technology in 2016 for participation in the preparation of basic concept of Technical Support Organization for nuclear energy and activity in or-ganization of research support for radiation protection in PolandSylwester Sommer

171INDEX OF THE AUTHORS

INDEX OF THE AUTHORS

A

Abramowska Anna 60Adamska Renata 106

B

Barlak Marek 81Bartłomiejczyk Teresa 64 Bobrowski Krzysztof 19Bojanowska-Czajka Anna 70Brykała Marcin 53Brzóska Kamil 65Budlewski Tadeusz 35Bułka Sylwester 31Buraczewska Iwona 64

C

Chajduk Ewelina 70, 75Chmielewski Andrzej G. 97

D

Dobrowolski Andrzej 120 Dobrowolski Jan Cz. 42Dudek Jakub 67, 70

F

Fuks Leon 48

G

Gajda Dorota K. 60Głuszewski Wojciech 25Gniazdowska Ewa 35, 39Grądzka Iwona 65Gumiela Magdalena 39Guzik Grzegorz 117

H

Herdzik-Koniecko Irena 48

J

Jamróz Michał H. 42

K

Kaczor Daniel 25 Kalbarczyk Paweł 75Karlińska Magdalena 110 Kiegiel Katarzyna 60Kierzek Joachim 87Kołacińska Kamila 70Kołodziejczak Paweł 81Kołodziejczyk Małgorzata 23

Koob Stephen P. 93Kornacka Ewa Maria 20Korzeniowska-Sobczuk Anna 110Kostkiewicz Bogusław 35Kowalska Maria 64Koźmiński Przemysław 35, 39, 70Kruszewski Marcin 67 Kunicki-Goldfi nger Jerzy J. 93

L

Leontieva Tatjana 48Lewandowska Hanna 67 Lewandowska-Szumieł Małgorzata 23 Liśkiewicz Grażyna 115

M

Majkowsla-Pilip Agnieszka 35 Maskalchuk Leanid 48Męczyńska-Wielgosz Sylwia 67Miłkowska Magdalena 84Miśkiewicz Agnieszka 57, 60Miśta Ewelina 75

N

Nichipor Henrietta 97, 100

O

Olczak Tadeusz 53Ostrowski Sławomir 42

P

Palige Jacek 120Pańczyk Ewa 87Pasieczna-Patkowska Sylwia 57Piądłowska Agata 39Polkowska-Motrenko Halina 75Prohazkova Simona 70Pruszyński Marek 39Przybytniak Grażyna 20Pyszynska Marta 70

R

Raszkowska-Kaczor Aneta 25Rode Joanna E. 42Rogowski Marcin 53 Roubinek Otton 120

S

Sadło Jarosław 23, 67Sadowska Magdalena W. 115 Sartowska Bożena 57, 84

172 INDEX OF THE AUTHORS

Sikorska Katarzyna 64, 65, 67Skotnicki Konrad 19Smoliński Tomasz 53Sołtyk Wojciech 120Sommer Sylwester 64Starosta Wojciech 81, 84Stasiek Andrzej 25Stępkowski Tomasz 65Stobiński Leszek 75Sudlitz Marcin 27 Sun Yongxia 97, 100

T

Taras-Goślińska Katarzyna 19Trojanowicz Marek 70

W

Waliś Lech 87Wawrzynowska Anna 35Wawszczak Danuta 53Weker Władysław 87 Widawski Maciej 87 Wierzchnicki Ryszard 106Wójciuk Grzegorz 67

Z

Zakrzewska-Kołtuniewicz Grażyna 57, 60Zawadzki Michał 87 Zimek Zbigniew 20, 27, 31 Zwolińska Ewa 100

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