Book of Abstracts

2021

Băile Govora, Romania

October 26-29, 2021
Senior Editor: Roxana IONETE - National Research and Development Institute for
Cryogenics and Isotopic Technologies – ICSI Rm. Valcea, Romania
Technical box:
Layout: Camelia ASPRITA
Cover: Camelia ASPRITA
ISSN: 2810-3203
ISSN-L: 2810-3203
 XXIIIrd International Conference
New Cryogenic and Isotope Technologies for Energy and Environment
26–29 October 2021, Băile Govora, Romania

CONTENTS

HYDROGEN ENERGY TECHNOLOGIES

HET 1-LP Julia Amici, Cecilia Andrea Calderón, Daniele Versaci, Simone
Siccardi, Guillermina Luque, Daniel Barraco, Ezequiel Leiva, Carlotta
Francia, Silvia Bodoardo
Enabling Safer Lithium-Metal Cells Through Composite Solid
Electrolytes Toward 19
HET 2-LP M. Pourkashanian
Research Challenges for Zero Carbon and Sustainable Fuels:
Prospects and the Pathway Forward for the Clean Energy of the
Future 21
HET 3-LP Tayfur Ozturk
Development of Amorphous/Nanocrystalline LSC Based Cathodes
for IT-SOFC 22
HET 4-O Mihai Bălan
Green Hydrogen in Romania: Elements of a Strategy 24
HET 5-O Marius Enache, Tudor Prisecaru, Răzvan Cârlănescu
Combustion of Hydrogen-Methane Mixtures in Gas Turbines 25
HET 6-O Viorel Chihaia, Valentin Alexiev, Dana A. Neacşu, Daniel G. Angelescu
The Electronic Structure of the α-MgH2 Grain Boundaries 31
HET 7-O Andrei Vlad Cojocea, Mihnea Gall, Tudor Cuciuc, Ionuț Porumbel,
Gabriel Dediu
Schlieren Visualization of Hydrogen Fuelled Detonation Flow 32
HET 8-O Alina Constantin
Nuclear Hydrogen Projects to Support Clean Energy Transition 38
HET 9-O Marius Adrian Husanu, Adrian Iulian Borhan, Daniel Ghercă,
Camelia Borca, Ioana Radu, Georgiana Bulai, Aurel Pui
Electronic and Structural States of Al:SrTiO3 Photocatalyst for
Water-Splitting 39
HET 10-O Iulian Iancu
Hydrogen, the Key to the Green Transition "Common Responsibility,
Differentiated Application" 41

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 XXIIIrd International Conference
New Cryogenic and Isotope Technologies for Energy and Environment
26–29 October 2021, Băile Govora, Romania

HET 11-O Ioan Iordache, Virgil Dumbravă

TEACHY - Road to Smart Specialization 42
HET 12-O Andreea D. Neacşu, Viorel Chihaia, Valentin Alexiev, Daniel G.
Angelescu
Prediction of the Equilibrium Shape of the Mg-based Nanoparticles
by Wulff Construction 43
HET 13-O Marian Nițulescu, Valentin Silivestru, Niculae Toma, Cristian
Slujitoru, Valentin Petrescu, Alexandru Șerban
Screw Compressor Used to Compress a Mixture of H2 and Natural Gas 45
HET 14-O Sorin Popescu, Stela Dinescu, Iulian Vlăduca, Mihai Joavina,
Ramona Manuela Stanciuc, Ana Maria Obreja
Feasibility of H2 Production by CH4 Formation, Corroborated with CO2
Storage in Salt Mines Formed by Dilution 50
HET 15-O Tudor Prisecaru
Reserved title 51
HET 16-O Vladimir Tanasiev, Maria Paraschiv, Tudor Prisecaru
Control of a Bioregenerative Raw Material Hydrogen Production
Process Through Artificial Intelligence 52
HET 17-O Mircea Eremia, Nicolae Napoleon Antonescu, Mihai Minescu,
Florinel Dinu, Mihai Varlam, Ioan Iordache, Lucian Toma, Mihai
Sanduleac, Iulian Iancu, Călin Vilt
Energy Storage and Hydrogen Technologies 54
HET 18-P Daniel G. Angelescu, Viorel Chihaia, Dana A. Neacsu
Molecular Dynamic Study on the Stability of MgH2 Surfaces 56
HET 19-P Adrian Armeanu, Elena David , Dan Mocanu, Gabriel Rasoi
Development of Hydrogen-Enriched Gas Production Systems from
Renewable Sources with Applications in Clean Energy Generation 57
HET 20-P George Călianu, Mihail Eugen Resteanu, Ionel Calcan, Maria Simona
Răboacă
Blockchain Real Time Data Acquisition from RES 58
HET 21-P Elena David, Adrian Armeanu
Thermochemical Conversion of Organics Derived from Biomass Over
Fe/Al2O3 Catalyst for Hydrogen Rich Gas Production 62
HET 22-P Gheorghe Badea, Maria Simona Răboacă, Ioan Așchilean,
Raluca A. Felseghi
Standalone Green Hybrid Energy System for a Small Community.
Case Study 64

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 XXIIIrd International Conference
New Cryogenic and Isotope Technologies for Energy and Environment
26–29 October 2021, Băile Govora, Romania

HET 23-P Mihaela Iordache, Mircea Răceanu, Adriana Marinoiu

Innovative Concept of Electrochemical Conversion of CO2 With
Generation of H2 67
HET 24-P Ana-Maria Nasture, Laurenţiu Pătularu, Florin Lungu, Stefan-Ionuţ
Spiridon, Eusebiu Ionete
Efficiency and Safety Aspects for a High Pressure PEM Electrolyser
at ICSI Rm. Valcea 71
HET 25-P Anişoara Oubraham, Ioan-Sorin Sorlei, Elena Marin, Simona Borta,
Adriana Marinoiu
Development of Cu/ZnO/Al2O3 Catalysts for the Synthesis of Green
Methanol by CO2 Hydrogenation 76
HET 26-P Gabriel Răsoi, Ioan Iordache, Maria Simona Răboacă, Adrian
Armeanu
Design and Concept of an Experimental Hydrogen Storage System
Based on Metal Hydride Materials for Energy Applications
Research: A Case Study 79
HET 27-P Ioan-Sorin Sorlei, Adriana Marinoiu
A Brief Review of Fuel Cell Electric Vehicles' Energy Management
Strategies and Their Topologies 81
HET 28-P Maria Simona Răboacă, Ionel Calcan, Mihail Eugen Resteanu, Alin
Nicolae Corbu, George Călianu
Opal RT Platform for Blockchain Real Time Data Acquisition 84
HET 29-P Maria Simona Răboacă, Alexandru Creangă, Adrian Onu, Cătălin
Turfin, Daniel Furtună, Selian Senocico, Andrei Traciu
Enabling Peer-to-Peer Electric Vehicles Charging 88
HET 30-P Maria Simona Răboacă, Nicu Bizon, Oana Vasilica Grosu
Opal RT Techonology an Real-Time Testing Techniques 92
HET 31-P Maria Simona Răboacă, Andrei Robu, Andrei Viziteu, Daniel
Furtună, Stelian Senocico, Andrei Traciu
Dynamic Dataset Generation of Ev Charging Networks for
Reinforcement Learning Algorithms 96

LITHIUM BATTERY TECHNOLOGIES

LBT 1-O Raul-Augustin Mitran
Thermal Energy Storage Nanomaterials Based on Mesoporous
Silica Matrices 101
LBT 2-O Aishui Yu
Study on the Water-Soluble Binder for Silicon-Based Anode in
Lithium-Ion Batteries 104

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 XXIIIrd International Conference
New Cryogenic and Isotope Technologies for Energy and Environment
26–29 October 2021, Băile Govora, Romania

LBT 3-O Răzvan Mahu

Li-Ion Battery Simulation Solution – with ANSYS Software 107
LBT 4-O Teddy Tite, H. Ghannam, M. Buga, C. Ungureanu, A. A. Zăuleţ, I.
Stavarache, G.E. Stan, E. Matei, C. C. Negrilă, A.C. Galcă,
M-C. Bartha, M. Baibarac
Doped Vanadium Oxide Films by Physical Vapour Deposition
Method for Energy Storage Application 109
LBT 5-O Danuţ-Ionel Văireanu, Florin-Mihai Benga, Ioana-Alina Ciobotaru,
Adnana Alina Spînu-Zăuleţ
Myths and Reality in Using and Misusing Lithium Based
Rechargeable Batteries 113
LBT 6-P Mihaela Buga, Adnana Spînu-Zăuleţ, Cosmin Ungureanu, Radu
Andrei, Alin Chiţu, Mihai Varlam, Simon Clark
Hybrid Power-Energy Electrodes for Next Generation Lithium-Ion
Batteries – HYDRA 114
LBT 7-P Andreea Culcea, Cristina Obreja, Mihai Iordoc
Battery-Type Positive Electrode for Li-Ion Supercapatteries 116
LBT 8-P Claudiu Fleacă, F. Dumitrache, M. Buga, A. Spînu-Zăuleţ, C.
Ungureanu, S. Enache, A.-M. Banici, E. Duţu, M. Dumitru
Laser Pyrolysis SnOx Nanoparticles - Characterization And
Testing For Li-Ion Battery Anodes 120
LBT 9- P Adnana Spînu-Zăuleţ, Mihaela Buga, Cosmin Ungureanu,
Danuţ Ionel Văireanu
Tris(Trimethylsilyl) Borate as an Efficient Electrolyte Additive for
Nickel-Rick NMC811 Cathode in Lithium-Ion Battery 121
LBT 10- P Cosmin Ungureanu, Adnana Spînu-Zăuleţ, Radu Andrei, Alin Chiţu,
Alecsandra Sobolu, Raul-Augustin Mitran, Eugeniu Vasile, Mihaela
Buga
Silica-Based Materials as High-Performance Lithium-Ion Battery
Anodes 123

MATERIAL SCIENCE FOR ENERGY AND ENVIRONMENT (MEE)

MEE 1-O Ashok Vaseashta, Roxana Elena Ionete
Technology Accelerator Network Modality to Promote Innovation
Ecosystem in Materials Science for Energy and Environment 127
MEE 2-O Andreea Dogaru, Adriana Marinoiu, Mihaela Florea, Mihai
Varlam, Simona Nica
Preparation and Electrochemical Evaluation of Covalently
Functionalized Reduced Graphene Oxide Materials 129

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 XXIIIrd International Conference
New Cryogenic and Isotope Technologies for Energy and Environment
26–29 October 2021, Băile Govora, Romania

MEE 3-O Ada Saccà, A. Carbone, I. Gatto, R. Pedicini, S. Maisano,

A. Stassi, Enza Passalacqua
Composite Nafion® Membranes with Differently Doped Nano-
crystalline Yttria-Stabilised-Zirconia (YSZ) for Proton Exchange
Membranes Fuel Cells (PEMFCs) Applications in Drastic
Conditions 133
MEE 4-O Valeria Harabagiu
Polysaccharide-based polyelectrolyte membranes for fuel cells 138
MEE 5-O Norbert Wagner, Maryam Nojabaee, Martina Gerle, Alexander
Kube, Fabian Bienen, Kaspar Andreas Friedrich
Electrochemical Impedance Spectroscopic Investigations of
Porous and Gas Diffusion Electrodes for Various Applications 139
MEE 6-O Ashok Vaseashta
Nanofibers of Electret Polymers for Tactile Sensing and Wearable
Electronics 144
MEE 7-O Adrian Iulian Borhan, Daniel Ghercă, Alin Constantin Dîrțu,
Mircea Nicolae Palamaru, Alexandra Raluca Iordan
3D self-Assembled SrTi1-xAlxO3/FeOOH Heterostructures Into
Complex Architectures with Effective Photocatalytic Applications 145
MEE 8-O Gabriela Buema, Daniel Gherca, Adrian Iulian Borhan, Nicoleta
Lupu, Horia Chiriac
Hierarchical MgO Prepared Through One-Pot Slow Pyrolysis
Process of MgAl-LDH and ITS Superb Cadmium Adsorption
Properties 147
MEE 9-O Oana-Georgiana Dragos-Pînzaru, George Stoian, Firuţa Borza,
Nicoleta Lupu
Effect of the Preparation Conditions on the Catalytic Efficiency of
CoPt Catalyst for MOR 152
MEE 10-O Dan Enache, Ion Dobrin, George Dumitru, Radu Pintea, Stefania
Zamfir
Superconducting Quadrupole Lens. Design and Numerical
Modelling 157
MEE 11-O Marius Enachescu
Reserved Title 160
MEE 12-O Daniel Gherca, Adrian Iulian Borhan, Mircea Nicolae Palamaru,
Alexandra Raluca Iordan
Self-Assembled SrTiO3/NiFe2O4 /Carbon Nanotubes as Sponge-Like
Nanoheterostructure for Environmental Applications 161

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 XXIIIrd International Conference
New Cryogenic and Isotope Technologies for Energy and Environment
26–29 October 2021, Băile Govora, Romania

MEE 13-O Ciprian Iacob, Radu Andrei, Silviu Badea, Irina Petreanu,
Adnana Zăuleţ, Violeta Niculescu
Solid polymer Electrolytes for Solid-state Batteries 163
MEE 14-O Daniela Ion-Ebraşu, Radu Dorin Andrei, Stanică Enache, Simona
Căprărescu, Constantin Cătălin Negrilă, Cătălin Jianu, Adrian
Enache, Iulian Boerașu, Elena Carcadea, Mihai Varlam, Bogdan
Ștefan Vasile
Hydrothermal Functionalization of the CVD Grown 3D-Graphene
Foam for Hydrogen Evolution Reaction in Alkaline Environment 165
MEE 15-O Mihaela Diana Lazăr, Monica Dan, Maria Miheţ
Combined CO2 and Steam Reforming of Methane – Viable Way for
Syngas Production 167
MEE 16-O Adriana Marinoiu, Elena Carcadea
Single-stage Synthesis of Nitrogen-doped Graphene Oxide 170
MEE 17-O Nicolae Aldea, Florica Matei, Vasile Rednic
Working Gas Influence on Stirling Engine Efficiency. A Theoretical
Approach for Ideal Gases 172
MEE 18-O Violeta-Carolina Niculescu, Silviu-Laurenţiu Badea, Amalia Soare,
Stănică Enache, Marius Constantinescu, Felicia Bucura, Claudia
Sandru
Fe-BTC Metal-Organic Framework for Efficient Photocatalytic
Oxidation of Neutral Red from Water 173
MEE 19-O Cristina Niţă, Biao Zhang, Joseph Dentzer, Camélia Matei
Ghimbeu
Hard Carbon Derived from Waste Biomass for Na-ion Batteries 176
MEE 20-O Dumitru Sacerdoțianu, Ancuța-Mihaela Aciu, Cristina Maria Nițu
Increasing the Accuracy in Diagnosing the Condition of Cellulose
Insulation in Transformer Units Through Analysis and
Implementation of a New Marker 178
MEE 21-O Amalia Soare, Ioana Csaki, Cristina Oprea, Ioan Costina
High Temperature Oxidation Of Alternative Bond Coat Materials as
Part of Thermal Barrier Coating 184
MEE 22-O Athanasios Tiliakos, Mihaela Iordache, Adriana Marinoiu
Ionic Conductivity and Dielectric Relaxation of NASICON
Superionic Conductors at the Near-Cryogenic Regime 185
MEE 23-P Sanda Voinea, Cornelia Nichita, Iulia Armeanu, Bianca
Şolomonea, Cornelia Diac, Paul Dogaru
Capacity absorbance of biodegradable material used to remove
hydrocarbons 186

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 XXIIIrd International Conference
New Cryogenic and Isotope Technologies for Energy and Environment
26–29 October 2021, Băile Govora, Romania

MEE 24-P Monica Dan, Oana Grad, Maria Miheţ, Gabriela Blăniţă,
Diana Lazăr
Metallic-Nanoparticles on Mesoporous Silica Structures 187
MEE 25-P Simona Borta, Mihaela Iordache, Dorin Schitea, Ioan-Sorin Sorlei,
Cătălin Capriş, Adriana Marinoiu
Development of Novel NASICON Ceramic Electrolyte Membrane
for Seawater Batteries with High Rate of Conductivity 188
MEE 26-P Marian Curuia, Cătălin Brill
Design and Applications of Rotating Feedthrough Based on
Magnetic Fluids 192
MEE 27-P Monica Dan, Oana Grad, Maria Miheţ, Angela Kasza, Diana Lazăr
Sustainable Laboratory Method for PGM Recovery from Spent
Automotive Catalytic Convertors 193
MEE 28-P Hajar Ghannam, M. Buga, C. Ungureanu, A. A. Zăuleţ, A. C. Galca,
M. Y. Zaki, E. Matei, I. Stavarache, C. C. Negrilă, G.E. Stan, M-C.
Bartha, M. Baibarac, T. Tite, A. Chahboun
Advanced Electrode Based on Zinc Oxide and Vanadium Oxide-
Graphene for Sodium-Ion Battery: Influence of Morphology and Doping 195
MEE 29-P Mihaela Iordache, Simona Borta, Claudia Sişu, Thanos Tiliakos,
Adriana Marinoiu
Solid State Electrolyte (Na3Zr2Si2PO12) with Improved Ionic
Conductivity 198
MEE 30-P Anca Mihaela Istrate, Valeriu Drăgan, Raluca Maier, Romică
Stoica, Andrei Mandoc, Alexandra Despa
Step-by-Step Design Process of a Liquid Hydrogen Tank 201
MEE 31-P Iulia Ioana Lungu, Simona Nistorescu, Mihaela Balas, Ecaterina
Andronescu, Florian Dumitrache, Athanasios Tiliakos
Iron Oxide Nanoparticles Synthesized by Laser Pyrolysis for
Oncological Applications 203
MEE 32-P Elena Marin, Anişoara Oubraham, Simona Borta, Violeta
Niculescu, Adriana Marinoiu
Synthesis and Characterization of Brominated Poly(2,6-dimethyl
phenylene oxide) Polymer 205
MEE 33-P Adriana Marinoiu, Amalia Soare
Single-stage Synthesis of Graphene Oxide Functionalized with
Platinum-Cobalt-Ceria 207
MEE 34-P Adriana Marinoiu, Elena Marin, Amalia Soare, Violeta Niculescu,
Felicia Bucura, Anca Zaharioiu, Marius Constantinescu
Single-stage Synthesis of Graphene Oxide Doped with Iodine 209

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 XXIIIrd International Conference
New Cryogenic and Isotope Technologies for Energy and Environment
26–29 October 2021, Băile Govora, Romania

MEE 35-P Adriana Marinoiu, Anişoara Oubraham, Mihaela Iordache,

Simona Borta, Athanasios Tiliakos
Membrane Electrode Assemblies for PEMFCs Including Fully
Integrated Graphene-based Electrodes Prepared by Laser and
Microwave Methods 211
MEE 36-P Adriana Marinoiu, Irina Petreanu, Mihaela Iordache, Simona
Nica, Claudia Sişu, Sorin Sorlei, Cătălin Capriş, Elena Carcadea
Synthesis of Graphene-based Materials Functionalized with Azulene
and PEMFC Functionality Testing with Innovative Electrodes 213
MEE 37-P Robert Ducu, Cristina Obreja, Andreea Culcea, Mihai Iordoc
Bio-Supercapattery’s Modified Electrodes Based on High Content
Bacteria-Secreted Electron Shuttles Biofilms 217
MEE 38-P Anişoara Oubraham, Elena Marin, Simona Borta, Violeta
Niculescu, Amalia Soare, Adriana Marinoiu
Functionalization of the Poly(2,6-dimethyl phenylene oxide)
Polymer with Bromine 219
MEE 39-P Irina Petreanu, Amalia Soare, Stănică Enache, Ciprian Iacob
Amino-Functionalised Silica Nanoparticles – Synthesis and
Characterization 221
MEE 40-P Claudia-Valentina Popa, Sorin Avrămescu, Eliza Oprea, Mihai
Coman, Maria Marinescu, Irina Mirela Pietreanu, Ciprian Iacob
Antioxidant and UV Protection Effect of Selected Types of Berries 223
MEE 41-P Simona Rada, M. Unguresan, M. Zagrai, S. Macavei
Advanced Electrode Materials: Electrochemical and Mechanical
Performances 225
MEE 42-P Irina-Maria Sturzeanu
Influence of the Thermal Stress Regime on the Properties of
C25/30 Concrete Used for Nuclear Buildings 229
MEE 43-P Felicia Vasuţ, Anişoara Oubraham, Amalia Maria Soare, Adriana
Marinoiu, Daniela Ion-Ebraşu, Mirela Drăgan, Stănică Enache,
Ramona Ionela Zgavarogea
Comparison of Producing Platinum on Reduced Graphene Oxide
Nanosheets Obtained Under Microwave Irradiation, Using
Reducing Agents 231
MEE 44-P Adriana Vulcu, Camelia-Berghian Grosan, Monica Dan, Alin
Sebastian Porav
Nitrogen-Doped Graphene Catalysts Efficient in Oxygen
Reduction Reaction in Alkaline Media 233

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 XXIIIrd International Conference
New Cryogenic and Isotope Technologies for Energy and Environment
26–29 October 2021, Băile Govora, Romania

ISOTOPES IN ENVIRONMENTAL STUDIES AND LIFE QUALITY

APPLICATIONS (IEL)
IEL 1- O Constantin Apetrei
Multisensory Systems Based on Electrochemical Sensors and
Biosensors Used in the Analysis and Monitoring of Natural
Waters Quality 237
IEL 2-O Carmen Lidia Chiţescu, Antoaneta Ene, Irina Elisabeta Geană,
Aida Mihaela Vasile, Corina Teodora Ciucure
Pollutants in the Aquatic Ecosystems of the Lower Danube and
North Western Black Sea Basins 239
IEL 3-O Karel Lemr, Lucie Borovcová, Marianna Nytka
Ion Mobility-Mass Spectrometry: Principles and Applications 243
IEL 4-O Matteo Perini
Application of Stable Isotope Ratio Analysis for the
Characterization of Pharmaceuticals, Cosmetics and Supplements 246
IEL 5-O Aurel Perșoiu
Large-Scale Atmospheric Circulation Patterns Embeded in the Stable
Isotope Composition of Precipitation 248
IEL 6-O Silviu Badea, Elisabeta-Irina Geană, Corina Ciucure, Violeta-
Carolina Niculescu, Radu Tamaian, Roxana-Elena-Ionete
Biodegradation of Pentachlorophenol by Sphingobium
Chlorophenolicum DSM 7098 and Detection of ITS Metabolites by
UHPLC-Q-Orbitrap HRMS 251
IEL 7-O Oana Botoran, Diana Costinel, Roxana Elena Ionete
Isotopic Models for Detecting Food and Beverage Authenticity 254
IEL 8-O Ionuţ Făurescu, Octavian Duliu, Carmen Varlam, Denisa Făurescu,
Diana Bogdan, Diana Costinel
Environmental Radiocarbon and CO2 Level in the Atmosphere of
Ramnicu Valcea, Romania 259
IEL 9-O Adina Frum, Cecilia Georgescu, Felicia Gligor, Carmen Dobrea,
Maria Muresan, Diana Stegaruş, Ovidiu Tiţa
The Development of a Food Supplement with Antioxidant
Properties 263
IEL 10-O Elisabeta-Irina Geană, Corina Teodora Ciucure, Constantin
Nechita
The Distribution of Persistent Organic Pollutants (Pops) in the
Environment-Plant Chain ‒ Baia Sprie and Copșa Mica Case Study 265
IEL 11-O George Cristian Curcă, Güner Gemai, Mariana Roșu
Application of Stable Isotope Analysis in Forensic Anthropology 270

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 XXIIIrd International Conference
New Cryogenic and Isotope Technologies for Energy and Environment
26–29 October 2021, Băile Govora, Romania

IEL 12-O Andreea Maria Iordache, Cezara Voica, Constantin Nechita

Climate Change Shifts the Trend of Metalloid Content in the Last
Two Decades 271
IEL 13-O Ira-Adeline Simionov, Ștefan-Mihai Petrea, Alina Mogodan,
Aurelia Nica, Victor Cristea
The use of Freshwater Bryozoans as Emerging Bioindicators for
Water Pollution in Danube Delta 276
IEL 14-O Anca Maria Zaharioiu, Roxana Elena Ionete, Claudia Sandru,
Silviu Laurenţiu Badea, Marius Gheorghe Miricioiu, Oana Romina
Botoran
The Influence of an Altitudinal Gradient on the Conifer-Soil
Relationship in a Temperate Forest of Romania 277
IEL 15-P Asimopolos Laurenţiu, Natalia-Silvia Asimopolos, Violeta Carolina
Niculescu
Geological and Geophysical Considerations Regarding the
Mineral and Geothermal Waters from the Ramnicu Valcea -
Govora Area 281
IEL 16-P Asimopolos Natalia, Violeta Carolina Niculescu, Laurenţiu
Asimopolos, Delia Cristina Papp
Geological study about the hydromineral and geothermal deposit
Călimănești – Căciulata 286
IEL 17-P Oana Romina Botoran, Marius Gheorghe Miricioiu, Diana Costinel,
Roxana Elena Ionete
Carbon isotopes in evergreen plants as climatic markers 291
IEL 18-P Gheorghe Bulubaşa, Alina Niculescu, George Ana, Ciprian Bucur,
Iulia Stefan
A New Method for Helium Isotopes Separation by Gas
Chromatography 295
IEL 19-P Corina Teodora Ciucure, Carmen Lidia Chiţescu, Elisabeta-Irina
Geană
Multiclass Organic Contaminants Residues in Fish Muscle Tissue
of Different Species Collected from Middle and Lower Course of
the Olt River, Romania 296
IEL 20-P Diana Costinel, Roxana Ionete, Oana Botoran
Aspects regarding the transport of water with different H-O
concentrations from soil to plants 301
IEL 21-P Elisabeta-Irina Geană, Corina Teodora Ciucure, Amalia Soare,
Stanica Enache, Livia Alexandra Dinu
Electrochemical Detection of Glyphosate Based on Molecularly
Imprinted Polypyrrole-Modified Gold Electrode and Dispersed
Gold Nanoparticles on Reduced Graphene Oxide 306

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 XXIIIrd International Conference
New Cryogenic and Isotope Technologies for Energy and Environment
26–29 October 2021, Băile Govora, Romania

IEL 22-P Nicoleta Cobîrzan, Maria Simona Răboacă, Raluca A. Felseghi,

Simona Stanca
Overview of IoT Paradigm for the Sustainable Construction Sector 311
IEL 23-P Crina Vicol, Elena Gorincioi, Gheorghe Duca
13
C NMR Investigations of Radical Scavenging Activities of
Ascorbic Acid and Resveratrol Using 1,1-Diphenyl-2-picrylhydrazyl 312
IEL 24-P Roxana Elena Ionete, Diana Costinel, Oana Romina Botoran,
Claudia Şandru, Mihaela Iordache, Andreea Maria Rădulescu
Water Chemistry and O-H-N Stable Isotopes Pattern as Tools for
Tracing Sources of Contamination 317
IEL 25-P Roxana Elena Ionete, Oana Romina Botoran, Diana Costinel
Using Isotopic Profile of Fruits to Differentiate Botanical Origin –
Preliminary Data 322
IEL 26-P Adriana Marinoiu, Simona Nica, Marian Curuia, Mihai Varlam
Bringing Together Quantum Sieving Process and Metal-organic
Frameworks to Develop a New Hydrogen 325
IEL 27-P Adriana Marinoiu, Simona Nica, Gheorghe Ioniţă
Chemical Affinity Separation (CAQS) for the MOF Study in
Isotopic Exchange Separation – Triazolate-Based Ligand Synthesis
for the Production of the MFU-4L MOF 327
IEL 28-P Papp Delia Cristina, Laurentiu Asimopolos, Violeta Carolina
Niculescu, Natalia-Silvia Asimopolos
Interpretation of Isotopic Data for Groundwaters in the Olănești
Area Comparisons with Other Carpathian Zones 332
IEL 29-P Diana Popescu (Stegaruş), Corina Ciucure, Cristea (Iancu) Ramona,
Ecaterina Lengyel, Violeta Niculescu
Determination of Pesticide Residues in Honey: a Preliminary
Study from Various Romanian Honey Producers 337
IEL 30-P Violeta Popescu
Chemical Profile, Antimicrobial Activity of Essential Oil and
Elemental Composition of Dill (Anethum graveolens L.) Plants
Growing in Moldova 339
IEL 31-P Claudia Sandru, Mihaela Iordache, Andreea Iordache, Ramona
Zgavarogea, Roxana Ionete
Bioaccumulation of Heavy Metals in Different Fish Species from
Olt River, Romania 341
IEL 32-P Radu Tamaian, Violeta-Carolina Niculescu
Red & Blue – Computational Insights on Ecotoxicology and
Potential Treats Against Aquatic Ecosystems 342

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 XXIIIrd International Conference
New Cryogenic and Isotope Technologies for Energy and Environment
26–29 October 2021, Băile Govora, Romania

IEL 33-P Irina Vagner, Carmen Varlam, Denisa Faurescu, Diana Bogdan,
Ionut Faurescu
Adapting Direct CO2 Absorption Method for Radiocarbon
Measurement of the Environmental Samples 347

TRITIUM R&D AND TECHNOLOGICAL TRANSFER FOR FUSION AND

FISSION
TFF 1-O Andrew Roberts, Nicolae Trantea, Laura Moscu Thijov,
Adrian Cojanu
Cernavoda Tritium Removal Facility Project Status and Objectives 353
TFF 2-O Bidica Nicolae, Narcisa Ghimis
A New Method to Generate Very Low Gas Flows for Calibration of
Hydrogen Permeation Measurement. Part 1: Concept and Feasibility
Testing 355
TFF 3-O Huang Hongtao
Study on Hydrogen Isotope Permeation Behavior and Surface
Modification Technology of FeCrAl 358
TFF 4-O Dmitry Kuzmin
Experimental Setup for the Study of a Hydrophobic Platinum Catalyst
in a Direct-flow Reactor 359
TFF 5-O Jiang Ma
Effects of Fe/Cr/Ni/Mn on hydrogen adsorption, dissociation and
diffusion in hydrogen permeation barrier of alfa-Al2O3 360
TFF 6-O Ni Muy
Tritium Transport Behavior in Fusion Reactor and the Environmental
Effect 360
TFF 7-O Alina Elena Niculescu, George Ana, George Bulubaşa, Iulia Stefan,
Ciprian Bucur, Anisia Bornea
Micro-Channel Reactor for Low Level H2 Oxidation Within an O2
Stream: Preliminary Tests in View of Integration in a H2 Generator
Within CECE Process 361
TFF 8-O Iulian Pavel Niţă, A. R. Olteanu, Camelia Coman, Hortensia Beznila
Advantages and constraints of specific Autocad Plant 3D functions
for dynamic management - Case study for the Cernavoda N.P.P.
plant - detritiation installation 362
TFF 9- O Iulian Pavel Niţă, Raluca Fako, Sorin Meglea, Cristian Postolache
Involvement of Magurele Professional Comunity in Transat Project
Activities and Future R&D Developments 363

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26–29 October 2021, Băile Govora, Romania

TFF 10- O Cristian Postolache, Irene Popovici, George Bubueanu, Viorel

Fugaru, Catalin Stelian Tuta
Tritium Effects in Polymers 364
TFF 11- O Guang Ran
In-situ TEM Investigation on the Evolution and Mechanism of
Dislocation loops in BCC Metal Materials During Ion Irradiation 366
TFF 12- O Liviu Stefan
Extension of Tritium Removal Facility PESTD with R&D Capabilities –
TRI-VALCEA 367
TFF 13- P Diana Chiper
Obtaining of Tritiated Polystyrene Thin Layers Through Radio-
Induced Grafting Onto Polyethylene Terephthalate Foils 368
TFF 14- P Diana Chiper
Radiological Characterization of Metal Samples 369
TFF 15- P Cristina Elena Diaconescu, Liliana Bujoreanu, Ionut Florea, Ilie
Prisecaru
Assessment of the Tritium and Gamma Ray Emitters Activities in
Liquid Radioactive Waste Generated by TRIGA Reactor 370
TFF 16- P Valentina Neculae, Cristian Dulama, Relu Dobrin
Experimental Tests for the Implementation of a Method for
Measuring Tritium on Metal Surfaces 371
TFF 17- P C. Cimpeanu, C. M. Barna, Cristian Postolache, A. Luca, M.-R. Ioan
Radiological Characterisation and Decontamination of Various
Surfaces from Former Radiochemistry Laboratories 374
TFF 18- P Cristian Postolache, George Bubueanu, Catalin Stelian Tuta,
Andi Sebastian Cucoanes
Synthesis of Tritium Labelled Thymidine and Uridine 377
TFF 19- P Anisia Mihaela Bornea, Marius Valentin Zamfirache
Calculation Program for the Processing of Low-Concentrated Tritium
and Deuterium Waste Through the CECE Isotopic Separation Process 379
TFF 20-P Badea Gheorghe, Mateescu Ovidiu, Mateescu Monica,
Pavel Dragos-Iulian, Mateescu Ioan
Optimal Solution for Cutting Down CO2 Emissions in Floor Heating
Appliances (summary) 381

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“New Cryogenic and Isotope Technologies for Energy and Environment” – EnergEn 2021
26–29 October 2021, Băile Govora, Romania

HYDROGEN ENERGY TECHNOLOGIES

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“New Cryogenic and Isotope Technologies for Energy and Environment” – EnergEn 2021
26–29 October 2021, Băile Govora, Romania

ENABLING SAFER LITHIUM-METAL CELLS THROUGH COMPOSITE SOLID

ELECTROLYTES TOWARD

Julia Amici1, Cecilia Andrea Calderón2, Daniele Versaci1, Simone Siccardi1,

Guillermina Luque3, Daniel Barraco2, Ezequiel Leiva3, Carlotta Francia1,
Silvia Bodoardo1
1
Electrochemistry Group, Department of Applied Science and Technology (DISAT), Politecnico di
Torino, Corso Duca degli Abruzzi, 24, 10129 Torino, Italia;
2
Instituto de Física Enrique Gaviola, Facultad de Matemática, Astronomía, Física y Computación,
Universidad Nacional de Córdoba, Av. Medina Allende s/n, ciudad universitaria, Córdoba, Argentina;
3
Instituto de Investigaciones en Fisicoquímica de Córdoba, Facultad de Ciencias Químicas,
Universidad Nacional de Córdoba, Haya de la Torre esq. Medina Allende, ciudad universitaria,
Córdoba, Argentina.
Corresponding author: [email protected]

Nowadays, electrical energy storage is one of the most critical issue to answer
global warming by effectively replacing fossil energies by renewable ones. The Li-
ion technology, widely studied and available on the market for multiple application
is now reaching its limits and does not represent alone a viable option toward
energetic transition. Therefore, one option currently under study is the use of
metallic lithium as anode both in Li-ion cells and in the so-called “post Li-ion
technologies”. In this perspective, lithium metal anode represents the “holy grail”
of battery research for its extremely high theoretical specific capacity (3860 mA h g-
1
), the lowest redox potential (-3.040 V vs the standard hydrogen electrode) and a
low gravimetric density (0.534 g cm-3).
However, metallic Li also presents many challenges derived primarily from
dendrite formation upon cycling causing both safety issues and poor cycling
performance. In addition, liquid electrolytes contain combustible organic solvents
that can cause leakage and fire risks during overcharge or abused operations,
especially in large-scale operation. Therefore, replacement of liquid electrolytes
with a solid electrolyte has been recognized as a fundamental approach to
effectively address the above problems. Generally, all solid-state electrolytes can be
classified into 3 categories: solid polymer electrolytes (SPE), inorganic ceramic
electrolytes (ICE) and solid composite electrolytes (SCE). While SPEs suffer from
poor ionic conductivity at room temperature and low thermal and electrochemical
stability, and ICEs from poor interfacial contact with electrodes, SCEs solve these
issues and benefit from both their advantages such as good ionic conductivity, good
flexibility and intimate contact with the electrodes. For example, the preparation of

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26–29 October 2021, Băile Govora, Romania

methacrylate-based polymer matrix, in a one pot, solvent free, thermally induced

radical polymerization, allows the addition of a wide range of organic and inorganic
additives up to really high ratio. Meanwhile, eventual activation with small amount
of liquid electrolyte allowed to obtain SCEs with outstanding room-temperature
conductivities for metallic lithium batteries. The simplicity of the formulation and
the preparation method open the road to highly versatile electrolytes, adaptable in
function of the final application. In particular, the use of inorganic additive
permitted to enhance mechanical properties thus avoiding lithium dendrites
nucleation and stabilizing Li stripping/platting in Li metal cells, while addition of
dextrin based nanosponges limiting oxygen cross-over phenomenon in Li-O2 cells
allowed to stabilize SEI layer, hence greatly improving cells safety in both cases.

Acknowledgments: Authors kindly acknowledge Polar project (progetto per

l’internazionalizzazione della ricerca tra Politecnico di Torino e Argentina, prof Silvia
Bodoardo) and ENEA: Piano Triennale Di Realizzazione 2019-2021 Della Ricerca Di
Sistema Elettrico Nazionale [Accordo di programma ministero dello sviluppo
economico- ENEA] (Prof. Silvia Bodoardo), for the research funding.

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26–29 October 2021, Băile Govora, Romania

RESEARCH CHALLENGES FOR ZERO CARBON AND SUSTAINABLE FUELS: PROSPECTS

AND THE PATHWAY FORWARD FOR THE CLEAN ENERGY OF THE FUTURE

M. Pourkashanian

Energy Institute at the University of Sheffield, UK

Corresponding author: [email protected]

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26–29 October 2021, Băile Govora, Romania

DEVELOPMENT OF AMORPHOUS/NANOCRYSTALLINE LSC BASED

CATHODES FOR IT-SOFC

Tayfur Ozturk

ENDAM, Center for Energy Materials and Storage Devices Middle East Technical University, Ankara Turkey
Innova-scope Materials Technologies,ODTU Teknokent, Ankara, Turkey
Corresponding author: [email protected]

There is a considerable interest in the reduction of operating temperature of

solid oxide fuels cell (SOFC). Thus, numerous studies have been conducted to
develop the so-called intermediate temperature SOFCs. The bottle neck in IT-SOFCs
is the cathode material as there are suitable alternatives for anode and electrolyte
that could operate with acceptable kinetics at temperatures as low as 600°C. In the
case of cathode materials, the main problem is oxygen reduction reaction (ORR)
which becomes unacceptably slow at reduced temperatures.
In this study, a combinatorial approach was used to develop cathode materials
with improved performance at temperatures in the range 500-700°C. A thin film
composite cathode library was obtained by co-sputtering of LSC-113 and LSC-214
onto suitably positioned substrates each with controlled compositions. The cathode
library was screened with an electrochemical impedance spectroscopy using
symmetric cells. The study showed that the compositions with volume fractions in
the range 0.40 < LSC-214 < 0.60 is particularly significant in yielding cathodes of
improved performance. Refocusing the combinatorial screening to this range
yielded LSC-113:LSC-214=0.45:0.55 as the most favorable compositions. Taking
ASR=0.15 Ω·cm2 as a useful benchmark, the study showed that cathodes in this
range may be used at temperatures as low as 575°C. It was further shown that
composite cathodes have amorphous structures in co-sputtered conditions, and
could remain so when used at reduced temperatures. At temperatures close to
700°C the amorphous cathode turns into nanocrystalline two phase structure with
grains not more than 10 nm in size.
Although LSC based composite cathodes in amorphous/ nanocrystalline form display
quite attractive properties, they are known to suffer from Sr-segregation, thus their
performance deteriorates in extended use. In the current study, this segregation is
verified by a specially designed experiment where a (La0.8Sr0.2)CoO3 - (La0.5Sr0.5)2CoO4
bilayer is deposited and annealed for an extended period of time. Then the stability of
the composite cathode in amorphous form was investigated over an extensive range of
compositions (La0.8Sr0.2)CoO3:(La0.5Sr0.5)2CoO4 = 0.10:0.90 - 0.90:0.10. Prolonged
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annealing of the cathodes at temperature of the same initial area specific resistance
shows an exceptionally stable cathode performance as measured by electrochemical
impedance spectroscopy responses. It is therefore concluded that co-sputtered
(La0.8Sr0.2)CoO3 - (La0.5Sr0.5)2CoO4 dual phase cathodes with their amorphous/
nanocrystalline structures, especially at mid-compositions, provide an extremely stable
microstructure with a strong resistance to Sr segregation.
The current work implies a new class of composite cathodes that are amorphous
with enhanced ORR kinetics. They may be employed at the temperatures which are
sufficiently low e.g. 575°C so that, aided by their inherent resistance to crystallization,
they remain amorphous.

Key words: IT-SOFCs, Material Library, Screening, Symmetric Cells, (La0.8Sr0.2)CoO3,

(La0.5Sr0.5)2CoO4, Sr Segregation.

Acknowledgments: The work reported in this paper was carried out within EU
FP7 ERAfrica program with the project title HENERGY. The support was provided by
the Scientific and Technological Research Council of Turkey (TUBITAK) with a project
number 114M128, which the authors gratefully acknowledge.

References
Sari D., Piskin F., Torunoglu Z. C., Yasar B., Kalay Y. E., and Ozturk T., Combinatorial development of
nanocrystalline/amorphous (La,Sr)CoO3-(La,Sr)2CoO4 composite cathodes for IT-SOFCs, Solid
State Ionics., 326, 124 (2018).
Sari, D Yasar, B Piskin, F Kalay, YE Ozturk, T Segregation Resistant Nanocrystalline/Amorphous (La,
Sr) CoO3-(La,Sr)(2)CoO4 Composite Cathodes for IT-SOFCs, Journal of the Electrochemical
Society, 166, 2019, F1157-F1163, DOI10.1149/2.0201915jes
Torunoglu Z.C., Sari D., Demircan O., Kalay Y.E., Ozturk T. Kuru Y. One pot synthesis of
(La,Sr)CoO3/(La,Sr)2CoO4 for IT-SOFCs cathodes, Int. J. Hydrogen. Energy 43 (2018) 18642–
18649.

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26–29 October 2021, Băile Govora, Romania

GREEN HYDROGEN IN ROMANIA: ELEMENTS OF A STRATEGY

Mihai Bălan

Energy Policy Group (EPG)

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26–29 October 2021, Băile Govora, Romania

COMBUSTION OF HYDROGEN-METHANE MIXTURES IN GAS TURBINES

Marius Enache1, Tudor Prisecaru2, Razvan Carlanescu1

1
INCD Turbootoare COMOTI, 220D, Iuliu Maniu Blvd, setor 6, București, Romania
2
University Politehnica of Bucharest, Splaiul Independenţei nr. 313, sector 6, Bucureşti,, Romania
Corresponding author: [email protected]

In the field of combustion, a special attention was given lately especially to the
search for new, greener and more efficient fuels. Among them, hydrogen is
intensely studied worldwide as a possible alternative fuel since new ways for
producing and transporting it developed lately. Different studies are trying to
confirm the possibility of the hydrogen transport using the existing natural gas
distribution network, by mixing the two gases. Because the properties of the new
mixture have a strong influence on the combustion parameters, using the existing
equipment would face new problems, like the risk of flashback, the effects of higher
temperatures, and the modification of the flame front.
In this context, this work presents a new innovative type of injector, designated
for the combustion of a premixed hydrogen–methane fuel in various proportions.
Based on the characteristics and dimensions of an existing combustion chamber of
a micro gas turbine (Garret GTP30-67), different regimes for different types of
injectors were CFD numerically simulated and compared.

Numerical simulation of methane and methane-hydrogen blending in various

concentrations ranging from 0% to 100% hydrogen was pursued, addressing three
different methods of varying the percentage of hydrogen in the fuel mixture.
The conclusions were similar to those previously found in the literature. With
increasing of the percentage of hydrogen in the composition of the mixture, there is
a clear rise of the temperatures the flame front is approaching the injector and the
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26–29 October 2021, Băile Govora, Romania

frontal walls of the combustor, phenomena that can damage the injector, the walls,
or the other elements of the engine. Therefore, the need to find new constructive
solutions arises.
As an innovative solution, a new type of injector was developed, the
dimensions and optimization being chosen following the CFD calculations and
simulations, for several injector types and different regimens.

The numerical simulations also showed the operation of the injector in a combustion
chamber dimensional with similar dimensions to the initially studied Garrett combustion
chamber, operating with a mixture of hydrogen-methane in varying proportions.

Also, this new type of injector has been integrated at the conceptual level in a
new combustion chamber, which has a special swirling system and partial
premixing combustion, a concept that has been transformed into a patent, which
has participated in international fairs, obtaining a very good appreciation.
Finally, based on the design resulting from the numerical calculations and
numerical simulations performed previously, the first prototype of the swirler
injector was executed from titanium powder, using a metal 3D printer.
For experimentation phase, a new testing installation was built, specially
designed to integrate the new combustion chamber and the new injector, starting
from the existing equipment and adapting the combustion chamber testing
facilities of INCD Turbomotoare COMOTI.
The operation of the injector was studied in a combustion chamber that respects
the dimensional proportions of the initially studied combustion chamber, at
atmospheric pressure and with the parameters calculated in similitude conditions.

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Mixtures of CH4 and H2 were used in the proportions of 0%, 10%, 20%, 40% and
60% of hydrogen. The outer wall was made of a quartz tube, to help viewing the
flame and to estimate its stability. Measurements have been made at various points
for pressures, temperatures, pollutant emissions.

Also, CFD numerical simulations were performed for comparison. Good

performance in regards of the flame stability has been observed, with reduced lean
blowout limits and the values are getting better as the percentage of hydrogen increases.
Comparing with similar experiments in the literature, it has been shown that the new
swirler has higher stability characteristics compared to a similar classical injector, with a
total premix and higher swirl number, with favorable results to the injector in this work.
For the 60% H2 regime and above this value, there were strong vibrations and an
increase in the acoustic pressure, potentially destructive, which is why experiments did
not exceed this percentage of hydrogen, the conclusion being that over these
proportions, for this case, the solution should be improved by classical methods (water,
nitrogen, steam, etc.). The main pollutant emissions (CO and NOx) were measured,
following the optimal operating values from this point of view, with satisfactory results at
this stage.
The mixture of fuel was premixed prior
to introduction into the experimental rig,
using specially prepared gas cylinders, ready
premixed to the desired volume ratio. An
improvement in combustion parameters
could be noticed, from the point of view of
flame stability, with lower lean blowout
limits for this variant (dilution air) compared
to the variant in the previous step (no
dilution air). The level of CO emissions is
lower. There is a significant decrease in the
maximum CO and NOx content with addition of dilution air.
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The study of the blowout limits for this case compared with the operation without
dilution air, is heading to a very significant decrease of these limits for the case of
dilution. It is also noted that in the case of the 60% H2 concentration, the operation
becomes unstable and noisy starting with the 0.04kg/s air regime, at 0.05 Kg/s cannot
work, while with dilution it is stable over the entire flow rate.
The pollutant emissions measured for this variant fall within the normal range.
These experiments being performed on similitude calculated parameters and for
nominal operating regimes with increased pressures, temperatures and airflows, it can
be concluded that the flame stability and the CO emission values will improve. Also,
possible future constructive iterations on the geometric forms of the injector may lead
to an improvement in mixing in the combustion chamber, which will lead to a decrease
in the percentage of CO. With respect to NOx emissions, for these tests they have
slightly higher values as the proportion of hydrogen in the mixture increases, due to the
increase in temperature, which leads to thermal dissociation and the formation of
thermal NOx, by Zeldovich mechanism. Increasing pressure on real mode nominal
operation regime is expected to have a positive influence on this aspect.

Variation of CO and NOx pollutant emissions for 0%H2 and 40%H2. (air mass flow rate at 0.04 kg/s)

For this variant with addition of dilution air, an improvement in the 60% hydrogen
burning compared to the non-dilution variant can also be observed, reducing the
acoustic vibrations, so the dilution air variant would lead to the extension of the
operating range to a the broader range of proposed blends, to higher proportions of
hydrogen in the mixture.

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Also thermo-acoustic measurements were conducted, to evaluate closer the flash-

back phenomenon happening above 60% H2. New ideas are being developed to avoid
this unwanted consequences and to improve the flame stability, in order to reach higher
volumes of H2, up to 100%. The research regarding this matter is under development.
As a general conclusion, it can be said that the premises and the results obtained
are generally positive, with good combustion characteristics and stability, opening the
possibility of realization of a partially premixed combustion chamber meeting the usual
requirements in the field, at low values
for pollutant emissions. The data
obtained confirms the possibility of
future development and improvement
of the new type of injector and
combustion chamber for optimization
and use in other potential industrial
applications.
Thus, the initial assumptions and
the concept of injector in an innovative
combustion chamber are true, the
main objectives being reached and the
proposed aim is achieved by
demonstrating the possibility of
successfully using the hydrogen-methane mixture in industrial turbomachines field.

Key words: hydrogen combustion, turbine, methane-hydrogen mixture, combustion

chamber, swirler, pollutant emissions

References
M. Aigner, EU-Turbines & GERG Workshop, Brussels, Burning Natural Gas / Hydrogen Mixtures in DLN Gas
Turbines October 2011
R. Carlanescu, T. Prisecaru, M. Prisecaru, I. Soriga, Swirl Injector for Premixed Combustion of Hydrogen–
Methane Mixtures, Journal of Energy Resources Technology, 140(7), 2018. Paper No: JERT-16-1506;
doi: 10.1115/1.4039267
C. Carlanescu, I. Manea, C. Ion, S. Sterie, Turbomotoare - Fenomenologia Producerii Si Controlul Noxelor,
Editura Academiei Tehnice Militare, 1998
R. Carlanescu, T. Prisecaru, R. Kuncser, E. Pop, The optimization of a swirl injector for combustion of
hydrogen fuel mixtures flame temperature of hydrogen in combination with gaseous fuels, U.P.B. Sci.
Bull., Series D, 81 (1), ISSN 1454-2358, 2019
M. Fossum, R.V. Beyer, Co-combustion: Biomass Fuel Gas and Natural Gas, SINTEF Energy Research,
Technical Report TRA 473, ISBN 82-594-1296-94, 1998
E.-I. Koytsoumpa, C. Bergins, B. Buddenberg, S. Wu, O. Sigurbjornsson, K.C. Tran, E. Kakaras, The Challenge
of Energy Storage in Europe: Focus on Power to Fuel, ASME J. Energy Resour. Technol., 138(4), p.
042002, 2016

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26–29 October 2021, Băile Govora, Romania

S. McAllister, J-Y. Chen, A. C. Fernandez-Pello, Fundamentals of Combustion Processes, Chapter 2 -

Thermodynamics of Combustion, Springer, ISBN 978-1-4419-7943-8, 2011
V. Pimsner, C.A. Vasilescu, G.A. Radulescu, Energetica turbomotoarelor cu ardere interna, Ed. Academiei
Republicii Populare Romania, 1964
T. Prisecaru, Simularea Numerica a Proceselor de Arder a Combustibililor Gazosi si Solizi Pulverizati, Editura
Bren, Bucuresti, ISBN 973-8143-76-4, 2001

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26–29 October 2021, Băile Govora, Romania

THE ELECTRONIC STRUCTURE OF THE α-MgH2 GRAIN BOUNDARIES

Viorel Chihaia1, Valentin Alexiev2, Dana A. Neacsu1, Daniel G. Angelescu1

1
Romanian Academy, “Ilie Murgulescu” Institute of Physical Chemistry, Splaiul Independentei 202,
060021 Bucharest, Romania
2
Institute of Catalysis, Bulgarian Academy of Sciences, Acad G Bonchev St, Bldg. 11, 1113 Sofia,
Bulgaria
Corresponding author: [email protected]

The polycrystalline materials and the ball milled powder

contain a large number of extended defects like dislocations,
stacking faults and grain boundaries. Some experimental
data suggest that the hydrogen diffusion rate through the
area with such defects is much higher than in the case of the
crystalline materials. Thus, the interface diffusion could play
a fundamental role in the decomposition and formation of
the magnesium-based hydrides. Despite the importance of
this topic in the identification of the efficient procedures for
the hydrogen storage and decomposition, there is no
systematic atomistic description of the hydrogen migration
through the grain boundaries and the interfaces of the
magnesium-based hydride materials.
The electronic density
In the present contribution we report the results of the of 5(001)[-130] tilt
DFT electronic structure calculations performed by code grain boundary for
CASTEP, [Clark et al., 2005] in order to elucidate the the -MgH2
structure of the grain boundaries and interfaces between
the magnesium-based materials (especially, considering the polymorph α-MgH2),
and the hydrogen diffusion through these interfaces.

Key words: DFT calculations, Grain Boundary, Magnesium Hydride

Acknowledgments: The work was supported by a grant of the Romanian

Ministry of Education and Research, CCCDI - UEFISCDI, project number PN-III-P2-2.1-
PED-2019-4816, within PNCDI III.

References
S. J. Clark, M. D. Segall, C. J. Pickard, P. J. Hasnip, M. J. Probert, K. Refson and M. C. Payne, First
principles methods using CASTEP, Zeitschrift fuer Kristallographie, 220(5-6) pp. 567-570 (2005).
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26–29 October 2021, Băile Govora, Romania

SCHLIEREN VISUALIZATION OF HYDROGEN FUELLED DETONATION FLOW

Andrei Vlad Cojocea, Mihnea Gall, Tudor Cuciuc, Ionuț Porumbel, Gabriel Dediu

INCD Turbomotoare COMOTI, 220D, Iuliu Maniu Blvd, sector 6, București, Romania
Corresponding author: [email protected]

The paper presents the undergoing experimental work carried out at COMOTI
in recent years, which aims at exploring and expanding the scientific foundations of
an early stage combustion technology based on detonation. This new and radical
approach of creating mechanical energy, addresses to the Europe effort of
decarbonizing both the transportation and the industrial power sectors, as it makes
use of a highly efficient Hydrogen combustion, coping with its otherwise hazardous
propensity to explosion. The presented experimental work focuses on a Hydrogen
fuelled Pulsed Detonation Combustor (PDC) that converts the chemical energy
stored in the fuel, into kinetic energy of the jet and heat, further converted into
thrust, employing properly designed nozzles. The solution presents significant
advantages in terms of efficiency. A PDC is a constant volume combustor, because
the high-speed explosive combustion process is able to burn the combustible
mixture fed inside before any volume changes may occur. The thermodynamic cycle
is based on the so-called Humphrey cycle [Hrițcu, 2004], which is significantly more
efficient than the constant pressure combustion, Brayton cycle, typical used for the
modern gas turbine engines [Kailasanath, 2000]. If a detonation wave is used
instead of a regular flame to burn the combustible mixture, as in a PDC, the speed
of the burning process increases by several orders of magnitude, together with a
further increase in thermal efficiency. [Hrițcu, 2004; Wintenberger and Shepherd
2006]. A theoretical comparative study [Kailasanath, 2000] of the efficiencies of the
three cycles (constant pressure, constant volume, and detonation), indicates a
thermodynamic efficiency of 27% for the Brayton cycle, 47% for the Humphrey
cycle, and 49% for the detonation cycle. A more recent, semi-empirical comparative
study of the detonation vs. Brayton cycle efficiency was carried out by our research
team [Cuciumita et al., 2016]. The study relied on detonation experimental data,
which showed a 16% increase in theoretical cycle efficiency over the Brayton cycle,
while more than doubling the cycle averaged power for the same amount of fuel.
Furthermore, NOx production may be expected to be lower in a PDC, due to
the significantly lower residence time [Plavnik, 2006]. However, this aspect is
arguable, since the overall combustion temperatures and pressures are higher for
detonation and NOx production rates are known to increase under these conditions

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[Göke1 et al., 2014]. The overall NOx production levels of the proposed new
propulsion technology will remain to be determined within the project.
A clear benefit from the standpoint of reducing the environmental impact will be,
nevertheless, resulting from the lack of Carbon-based reaction products (such as CO, CO2,
or Unburned Hydrocarbons - UHC), since Hydrogen is a very well-suited detonation fuel.
The experimental work was carried out on COMOTI`s detonation test rig located in
Măgurele. Ilfov. The test rig has supplying capabilities of up to 1 kg/s air at a pressure of
11 bar, and a temperature of 550 K, while the Hydrogen and Oxygen lines, can deliver
pressures up to 20 bar.
The PDC is valveless, suited for high operation frequency, and controlled by a system
of shock waves generated by two supersonic jets impinging on a Hartmann type
resonator [Hartmann,1919; Hartmann, 1939]. The Hartmann resonator is an acoustic
wave generator driven by shock wave oscillations in an over-expanded air jet [Morch,
1964]. The Mach disk occurring in the supersonic jet downstream of the nozzle is forced
to oscillate in the jet axial direction in the presence of a cavity aligned with the jet flow
direction and placed in a bluff body. Usually, the bluff body is placed near the end of the
first cell of the supersonic jet pattern. The interaction between the supersonic jets and
the Hartmann oscillators creates an aerodynamic system capable of functioning as an
aerodynamic valve for the PDC, allowing a significantly higher operating frequency when
compared to early types of PDCs controlled by mechanical valves. An exhaust pipe of 500
mm length is attached to the PDC, to direct the exhaust gas to the atmosphere. Specific
details on the PDC design are provided by Cuciuc et al., 2017.
In the following, a set of Schlieren images of the flow at the end of the exhaust pipe
are presented and discussed. The images were captured from an 8”, Iris Broadcast
Services Schlieren system using a Phantom V2512 high speed camera with 25,600 fps @
1280 x 800 resolution and 1,000,000 fps @ 128 x 32 resolution. The inlet air pressure of
the PDC was set to 8 bar, at atmospheric temperature (27°C). The inlet Hydrogen
pressure was set to 11 bar (absolute pressure). At ignition (triggered by a spark plug), a
detonation wave is created by the coupling of a leading shock wave and a combustion
wave [Weiss et al., 2019]. Figure 1 presents the exit of this leading shock wave from the
exhaust pipe.

Time = 0.00 µs Time = 13.88 µs Time = 27.76 µs

Figure 1. The leading shock wave exits the exhaust pipe.
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“New Cryogenic and Isotope Technologies for Energy and Environment” – EnergEn 2021
26–29 October 2021, Băile Govora, Romania

Based on the Schlieren data, the velocity of the shock wave (V) was estimated at
1206.77 m/s. As the leading shock wave propagates through the atmosphere, a Mach
disk system, characteristic to underexpanded supersonic jets (Rezay Haghdoost et al.,
2019). This system is presented in Figure 2, as the Mach number of the supersonic flow
increases (left of Figure 2), reaches a maximum (center), and decreases (right hand side
of Figure 2).

Time = 97.16 µs Time = 277.60 µs Time = 360.88 µs

Figure 2. A Mach disk system is formed.

The supersonic flow Mach number and the angle of the oblique shock wave are
related by the following equation:

(1)

where M is the flow Mach number and θ is the first quadrant angle made by the
oblique shock wave with the horizontal.
Since the minimum oblique shock wave angle can be measured to be 43.83°,
the maximum Mach number of the flow can be estimated at 1.44.
As shown in Figure 3, high temperature burned gases start exiting the pipe. The
high temperature of these gases, together with the inertial effects, decrease the
flow velocity, as the momentum of the initial explosion triggered by the spark plug
in the combustible mixture is exhausted, causing a decrease in the Mach number
observed in Figure 2.
The estimated delay between the combustion products front and the leading
shock wave (Δt) is of 555.2 µs. Assuming that the shock and combustion waves
were coupled into a detonation wave at ignition (at the location of the spark plug),
and knowing the length of the exhaust pipe (l) of 500 mm, the average flow velocity
(v) the flow and the shock wave propagation can be estimated as:

(2)

where Δτ is the time it takes the leading shock wave to travel the exhaust pipe,
which can be determined from the estimated leading shock wave velocity (V):
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26–29 October 2021, Băile Govora, Romania

(3)
Thus, v = 537.61 m/s.

Time = 596.84 µs Time = 638.48 µs Time = 2220.80 µs

Figure 3. Combustion products start exiting the exhaust pipe.

Even if it is impossible to witness in a static picture, the Schlieren video shows a

reversal of the flow at 2.221 ms, from the moment the leading shock wave exits the
exhaust pipe. The rapidly moving flow creates a sub-atmospheric static pressure in the
exhaust pipe, and, once the momentum of the flowing gas exiting the pipe is exhausted,
the surrounding air is entrained into the exhaust pipe, as seen in Figure 4.

Time = 2234.68 µs Time = 2540.04 µs Time = 4108.48 µs

Figure 4. Reversed flow in the exhaust pipe.

The occurrence of the reversed flow causes part of the burned gas to remain
trapped inside the detonation chamber and the upstream part of the exhaust pipe, if
the inertial force driving the entrained fresh air exceeds the pressure force pushing the
trapped combustion products downstream. Once the pressure in the downstream of
the exhaust pipe raises towards atmospheric, the momentum of the entrained air
decreases, and the remaining higher pressure of the trapped burned gases pushes the
outwards, resuming normal flow in the exhaust pipe This process is shown in Figure 5.

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“New Cryogenic and Isotope Technologies for Energy and Environment” – EnergEn 2021
26–29 October 2021, Băile Govora, Romania

Time = 4122.36 µs Time = 6148.84 µs Time = 9674.36 µs

Figure 5. Combustion products are eliminated from the system.

By 9.67 ms from the moment the leading shock wave leaves the exhaust pipe,
it appears that all the combustion products have left the PDC system. However, a
precise evaluation is not possible on Schlieren data alone, as the pipe is already hot
from the previous detonation and even fresh air is heated up in the exhaust pipe,
making it a difficult decision on whether the Schlieren images show burned gases or
heated air.
In any case, the time length between the fresh air that flows through the PDC
and exhaust pipe at a pressure high enough to prevent the opening of the
aerodynamic valves, and a new admission of fuel into the PDC is down time in the
PDC operation and decreases the efficiency of the system (Cuciumita et al. 2016).
For the PDC studied here, a new leading shock wave appears at 9.94 ms from the
previous one, leaving a “dead” time of only 263.72 µs. The estimated frequency is
100.559 Hz, matching closely the spark plug frequency of 100 Hz.
In conclusion, the Schlieren visualizations presented here allows the
identification of the processes that occur during the PDC operation: a leading shock
wave followed immediately by a supersonic underexpanded jet, that creates a
Mach disk structure. The shock wave velocity was estimated at about 1200 m/s,
and the flow Mach number at about 1.4. After a time of about 500 µs, the burned
gas front appears at the end of the exhaust pipe. The average flow during this
phase is about 500 m/s. Next, after about 2 ms from the leading shock wave, the
flow reverses and surrounding air is entrained into the exhaust pipe for about 2 ms.
Then the flow returns to the normal direction and the combustion products are
exhausted. The cycle repeats at a frequency of about 100 Hz.

Key words: Hydrogen combustion, detonation, flow visualization, shock waves

Acknowledgments: The research presented here was funded under the ESA project
no. 1000027451-8000015065-3, Pulsed Detonation Thruster (PDT) and national research
Programe 2, Subprograme 2.1., Experimental and demonstration project no. 454PED ⁄
2020PED Pulsed Detonation Engine (PDE).

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26–29 October 2021, Băile Govora, Romania

References
T.Cuciuc, C.E. Hritcu, G.G. Ursescu, I. Porumbel, C.F. Cuciumita, Valveless Pulsed Detonation
Chamber Controlled by Hartmann Oscillators, Paper 219, Proceedings of the 6th CEAS Air and
Space Conference "Aerospace Europe", Ed. B.G. Gherman, I. Porumbel, October 16 - 20,
Bucharest, Romania
C.F. Cuciumita, T. Cuciuc, I. Porumbel, Evaluation of the Cycle Avg. Perf. of PDE Based on Thermodyn.
Cycle Comp., GT2016 - 57310, Proc. ASME Turbo Expo 2016, Seoul, South Korea, 13 – 17 June
S. Göke1, S. Schimek, S. Terhaar, T. Reichel, K. Göckeler, O. Krüger, J. Fleck, P. Griebel, C.O.
Paschereit, Influence of Pressure and Steam Dilution on NOx and CO Emissions in a Premixed
Natural Gas Flame, Journal of Engineering, Gas Turbines and Power, 136 (9), 2014
J. Hartmann, 1919, About a New Method for Generating Sound Vibrations, Letters of the Royal
Danish Academy of Mathematics and Physical Sciences, 1 (13)
J. Hartmann, 1939, Construction, Performance, and Design of Acoustic Air - Jet Generator, Journal of
Scientific Instrumentation, 16, pp. 140 - 149
C.E. Hriţcu, Research on Pulsed Operation Combustion Chambers, Ph.D. Thesis, "Gh. Asachi" Tecnical
Uniersity Iaşi, 2004
K. Kailasanath, Review of Propulsion Applications of Detonation Waves, AIAA J., 38(9), 2000
K.A. Morch, 1964, A Theory for the Mode of Operation of the Hartmann Air Jet Generator, Journal of
Fluid Mechanics, 20 (1), pp. 141 - 159
th
G. Plavnik, Pulse Combustion Technology, 14 North American Waste to Energy Conference,
NAWTEC14-3195, Tampa, Florida, USA, 2006.
M. Rezay Haghdoost, D.M. Edgington-Mitchell, C.O. Paschereit, K. Oberleithner, Investigation of the
Exhaust Flow of a PDC at different Operating Conditions based on High-Speed Schlieren and PIV,
AIAA-2019-1512, AIAA Scitech 2019 Forum, January 7-11, 2019, San Diego, CA, USA
S. Weiss, M. D. Bohon, C. O. Paschereit, E. J. Gutmark, Computational Study of Reactants Mixing in a
Rotating Detonation Combustor Using Compressible RANS, Flow, Turbulence and Combustion,
pp. 1- 29, 2019
E. Wintenberger, J.E. Shepherd, Thermodynamic Cycle Analysis for Propagating Detonations, Journal
of Propulsion and Power, 22 (3), pp. 694 - 697, 2006

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 XXIIIrd International Conference
“New Cryogenic and Isotope Technologies for Energy and Environment” – EnergEn 2021
26–29 October 2021, Băile Govora, Romania

NUCLEAR HYDROGEN PROJECTS TO SUPPORT CLEAN ENERGY TRANSITION

Alina Constantin

International Atomic Energy Agency, Wagramer Str. 5, 1220 Wien, Austria

Corresponding author: [email protected]

Hydrogen is expected to be a game changer in the fight against climate change,

being able to play multiple roles in clean energy transition, such as decarbonizing
heavy industry, energy storage, used directly or in the form of derived fuels such as
ammonia and synthetic fuels and helping to balance supply and demand in energy
systems based on variable renewable sources. As a consequence, significant
increases in the hydrogen production are foreseen by 2050, with all the generation
coming from zero-carbon processes (electrolysis/ thermochemical cycles using
zero-carbon electricity and heat) or from a low carbon process using steam
methane reforming with carbon capture and storage. Nuclear energy can be
capitalized on both electricity and heat to provide a clean and reliable source of
hydrogen through various processes. There are currently various demonstration
projects undergoing in several countries to showcase using nuclear energy from the
current rector fleet or advanced reactors in the production of clean hydrogen. This
paper offers an insight on these projects and also highlights the activities of the
United Nations’ International Atomic Energy Agency in assessing technical and
economic aspects of hydrogen production using nuclear energy for near term
deployment.

Key words: energy transition, hydrogen economy, nuclear hydrogen.

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“New Cryogenic and Isotope Technologies for Energy and Environment” – EnergEn 2021
26–29 October 2021, Băile Govora, Romania

ELECTRONIC AND STRUCTURAL STATES OF Al:SrTiO3 PHOTOCATALYST FOR

WATER-SPLITTING

Marius Adrian Husanu1,2, Adrian Iulian Borhan2,3,*, Daniel Ghercă2,3, Camelia Borca4,
Ioana Radu2, Georgiana Bulai2, Aurel Pui2
1 2
National Institute of Materials Physics, Atomistilor 405A, 077125 Magurele, Romania; “Alexandru Ioan
3
Cuza” University of Iasi, Romania; National Institute of Research and Development for Technical Physics, 47
4
Mangeron Bv, Iasi 700050, Romania; Paul Scherrer Institut – Swiss Light Source, Villigen 5232, Switzerland
*
Corresponding authors: Tel: +40754205093/fax: +40232201313
E-mail address: [email protected]; [email protected]

The development of photocatalytic systems with convenient electronic properties

suitable for absorbing the visible component of sunlight while delivering optimal
potentials remains challenging [Martindale, et al., 2015; Osterloh, 2013; Ahsan et al.,
2018]. Al-doped SrTiO3 is considered the reference material in the photocatalytic water
splitting (POWS), however, little is really known about Al's influence on the electronic
structure of SrTiO3. As the defects such as vacancies and dislocations are considered as
recombination sites, higher crystallinity of the photocatalyst obtained by using Al3+ as
additive is often aimed to decrease the recombination rates. Moreover, Ti3+ states
associated with the oxygen vacancies may provide an additional route to quench the
electron-hole recombination.
In this context, recent results obtained in combined first-principles DFT calculations
and X-ray absorption synchrotron experiments - EXAFS will be presented, aiming to
disentengle the site of Al dopant within the STO matrix: interstitial, substitutional or as
Al2O3 at the interface and discuss possible implications resulting from their particular
electronic structure. Our results aim to define suitable strategies to control charge
trapping sites in metal oxides and to improve their photocatalytic properties through
facilitation of the electron and hole transfer towards the co-catalysts.

Figure 1. Illustration of a substitutional doping of Al into the STO bulk (left). X-ray absorption spectra
recorded at the K-edge of Al for Al-doped STO samples prepared by two different methods and
different Al concentrations (right).

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26–29 October 2021, Băile Govora, Romania

Key words: Al:SrTiO3, X-ray absorption synchrotron experiments – EXAFS, first-

principles DFT calculations, charge trapping sites, POWS.

Acknowledgments: This work was supported by a grant of the Romanian Ministry

of Education and Research, CNCS - UEFISCDI, project number PN-III-P1-1.1-TE-2019-2037
within PNCDI III and by a grant of the Romanian Ministry of Education and Research,
CNCS - UEFISCDI, project number PN-III-P4-ID-PCE-2020-1385. M.A.H. aknowledges the
support of the Romanian Ministry of Education and Research through CNCS - UEFISCDI,
project number PN-III-P4-ID-PCE-2020-2540.

References
R. Ahsan et al., RSC Advances, 2018, 8, 14258–14267
F. E. Osterloh, Chem. Soc. Rev., 2013, 42, 2294–2320
B.C.M. Martindale, et al., J. Am. Chem. Soc., 2015, 137, 6018−6025

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“New Cryogenic and Isotope Technologies for Energy and Environment” – EnergEn 2021
26–29 October 2021, Băile Govora, Romania

HYDROGEN, THE KEY TO THE GREEN TRANSITION "COMMON RESPONSIBILITY,

DIFFERENTIATED APPLICATION"

Iulian Iancu

Institutul Naţional de Cercetări Economice al Academiei Române „Costin C. Kiriţescu”

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26–29 October 2021, Băile Govora, Romania

TEACHY - ROAD TO SMART SPECIALIZATION

Ioan Iordache1,2*, Virgil Dumbrava2

1
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
2
University Politehnica of Bucharest, Bucharest, Romania
Coresponding author: [email protected]

TeacHy2020 represents a project that is funded by the Horizon 2020 program, through
FCH JU. The 12 partners from 11 European countries have contributed to the setting up of
20 didactical modules
TeacHy2020 project, the acronym for Teaching Fuel Cell and Hydrogen Science and
Engineering across Europe within Horizon 2020, is designed to be useful for universities
master programs’ addressing hydrogen and fuel cell technology and economy, points out
the benefits obtained by its implementation. The project aims to increase the number of
students, PhD students and specialists whose focus is the implementation of hydrogen and
fuel cell in the renewable energy and alternative fuels, by offering essential tools for
teachers in European universities.
The need for qualified personnel is growing as the hydrogen industry is developing,
gradually creating a specific market. TeacHy2020 particularly addresses university and
postgraduate education in hydrogen technologies throughout Europe. The objective of the
consortium members is to guide students into a scientific field of great interest and current
importance, in order to clarify aspects that will contribute to the development of a
hydrogen economy.
Training of industrial staff activating in the hydrogen and fuel cell technology area will
turn into a critical component of securing the competitiveness in the coming decades.
Qualified education is still a problem faced by all European hydrogen industries, but it is
also relatable to academia and research. Even though important steps in integrating
hydrogen into university curricula have been made, expertise has rarely reached a level
sufficient for immediate entry into industrial and research positions, and this is also
applicable in other R&D areas. Insufficient specialized information during academic or
vocational training will adversely affect a potential hydrogen technology career and will
require employers to undertake a large amount of "on the job" training. At the same time,
employers face the risk of a lack of general basic knowledge of personnel, which is key in
leveraging innovation in technology and product developments, an important shortcoming
and potential threat for the development of the European supply chain in hydrogen
business. The attempt of research institutions to recruit suitable research personnel or PhD
students is not easier, because there are still very few candidates with sufficient
background.

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26–29 October 2021, Băile Govora, Romania

PREDICTION OF THE EQUILIBRIUM SHAPE OF THE Mg-BASED

NANOPARTICLES BY WULFF CONSTRUCTION

Andreea D. Neacsu1, Viorel Chihaia1, Valentin Alexiev2, Daniel G. Angelescu1

1
Romanian Academy, “Ilie Murgulescu” Institute of Physical Chemistry, Splaiul Independentei 202,
2
060021 Bucharest, Romania; Institute of Catalysis, Bulgarian Academy of Sciences, Acad G Bonchev
St, Bldg. 11, 1113 Sofia, Bulgaria
Coresponding author: [email protected]

The poor kinetic and thermodynamic properties of magnesium require high ab- and
de-sorption temperatures. By reducing the size of the magnesium grains to the
nanoscale, by confining, alloying and mixing them with additives and catalysts, practical
solutions for the improvement of the reaction speed at lower temperatures are
provided.

The predicted shapes for the magnesium and -MgH2 magnesium hydride nanoparticles by DFT
calculations and Wulff construction algorithm.

In the present contribution we report the results of the DFT electronic

structure calculations performed by code CASTEP,[1] for the accurate evaluation of
the surface energies of the most stable faces of the hcp-magnesium and α-MgH2 of

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26–29 October 2021, Băile Govora, Romania

the magnesium hydride. The Wulff construction algorithm is used for building of the
magnesium and magnesium hydride nanoparticles.
Key words: Magnesium, Magnesium Hydride, Nanoparticles, DFT calculations,
Wulff Construction Algorithm

Acknowledgments: The work was supported by a grant of the Romanian

Ministry of Education and Research, CCCDI - UEFISCDI, project number PN-III-P2-2.1-
PED-2019-4816, within PNCDI III.

References
S. J. Clark, M. D. Segall, C. J. Pickard, P. J. Hasnip, M. J. Probert, K. Refson and M. C. Payne, "First
principles methods using CASTEP", Zeitschrift fuer Kristallographie 220(5-6) pp. 567-570 (2005).

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26–29 October 2021, Băile Govora, Romania

SCREW COMPRESSOR USED TO COMPRESS A MIXTURE OF H2 AND NATURAL GAS

Marian Nițulescu, Valentin Silivestru, Niculae Toma, Cristian Slujitoru, Valentin

Petrescu, Alexandru Șerban

COMOTI, 220 D Iuliu Maniu Bd., sector 6, cod 061126, OP 76, CP174 Bucharest, Romania,
Coresponding author: [email protected]

Abstract: Screw compressors are part of the group of volumetric compressors -

positive displacement compressors. Due to its advantages, we believe that this type
of compressor can find a wide use in the gas industry.
In this article we will present the achievements of NRDI for Gas Turbines
COMOTI related to the development of a new range of screw compressors, with
operating parameters adapted to the new requirements. We would also like to
mention that, in Romania, COMOTI is the only company that designs, manufactures,
experiments, delivers, provides technical assistance and spare parts for two types of
compressors: centrifugal compressors and oil injection screw compressors.
The long-term strategy of COMOTI is to high capitalize, in conditions of high
efficiency and profitability, genuine, technological and constructive solutions, by
developing and manufacturing new and performant products and technologies,
with a wide field of applicability in the horizontal industry. Continuous research and
development have allowed this type of screw compressor to find a position on the
market, the range of sizes diversifying in a much more explosive way than any other
type of compressor in the last decade.
Due to the technologies that have developed recently – laboratory research,
scientific studies, pilot projects – the European Union imposes restrictions on other
technologies, in order to boost the emergence and development of the hydrogen
industry. The goal is to decarbonize companies, the hydrogen industry being able to
solve two essential needs: to replace fossil fuels, without harmful emissions at the
combustion into atmosphere (in industry and transport); to produce hydrogen and
deliver it on a large scale, without significant impact on the environment, using
existing assets, in comparable efficiency and safety conditions.
Starting from these aspects, COMOTI approached the possibility of
manufacturing, and achieved manufacturing – in the first phase – of a screw
compressor which had to compress a mixture of H2 and natural gas, then
developing a new version of screw compressor used only for H2 compression. The
paper presents the changes made on the design of typical screw compressor in
order to adapt to new compressed gas mixture.

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26–29 October 2021, Băile Govora, Romania

Key words: screw compressor, efficiency, test configurations, H2 and natural gas
mixture.

OVERVIEW
COMOTI provides a wide range of compression equipment, in which the
compression units are oil injection screw compressors. If, at the beginning, the
compression units were purchased entirely from the company GHH-Rand Germany, in
time, the reliance gained from the German partner, meant that in a relatively short
period of time the manufacturing license of CU screw compressors was assimilated by
COMOTI. Thus, in April 2010 COMOTI was certified as a manufacturer – under license –
of CU type screw compressors.
The compression equipment made under the license of Ingerssol Rand (owner
of GHH-Rand) have as maximum parameters: 31 bar abs. for pressure discharge,
and 3000 Nm3/hour of gas flow delivered. The requests/signals received from the
potential beneficiaries, imposed the necessary approach of designing a new family
of screw compressors, capable of developing discharge pressures at 45 bar abs.,
respectively flow rates of approx. 5000 Nm3/hour in a first phase, following that in
the next phase to achieve discharge pressures at 75 bar.
The development of the new family of compressors also took into account the
requests from buyers to COMOTI to analyze the possibility that these compressors
can safely compress a mixture of H2 - about 50% - with natural gas, gas mixture to
be used either as gas fuel for piston engines or as fuel for gas turbines. The
induction of H2 into the mixture brings the above-mentioned advantages
(replacement, even partial, of fossil fuels/use of existing assets with minimal
modifications).

OIL INJECTED SCREW COMPRESSOR TYPE CHP90 G

The experience gained by COMOTI in the design and manufacture of
compression equipment created the premises for a challenge – achievement of a
screw compressor with oil injection, derived from the CU 90G compressor, capable
of providing following parameters:
- discharge pressure max. 45 bar abs.;
- nominal suction pressure 5 bar abs.;
- flow rate approx. 1000 Nm3/hour.
Basically, the option of making only some imperatively necessary changes was
chosen (the pair of rotors, bearings and other internal parts as labyrinths, balancing
piston, aso were preserved), imposed by the operating conditions (parameters,
respectively gas composition):
- the housings have been resized in order to withstand the test pressure of 76
bar abs., performing strength calculations to optimize the housing shape;

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26–29 October 2021, Băile Govora, Romania

- the WCC grade A216 casting steel material (according to API 619,
respectively ISO 10440) replaced cast iron EN-GJS 250 material;
- the suction/discharge flanges have been adapted to the types of flanges
recommended by the norms (not square flanges).
The change of material was imposed by the possibility of using screw compressor to
compress a mixture of H2 with natural gas (were also taken into account the maximum
operating parameters – pressure, temperature –, according to Nelson diagram). Due to
its structure, H2 generates the phenomenon of material cracking (H2 has a very low
density of 0.09 kg/Nm3 compared to natural gas which is 0.773 kg/Nm3). The resizing of
the housing was done by iterations, using the ANSYS calculation program – see Figure 1 –
taking into account the test pressure of 76 bar abs.

a) left side view b) right side view c) axial section d) radial section
Figure 1

To increase the safety in operation, the former seal of compressor was redesigned,
and was mounted a double mechanical seal (manufactured by SC ROSEAL SA from
Odorheiul Secuiesc), see Figure 2. The assembled compressor is shown in Figure 3.

Figure 2 Figure 3

The testing of the compressor on our stand was done with air as working fluid,
the test being performed on the closed circuit stand in order to achieve suction
pressures higher than atmospheric pressure. This was a mechanical test, made for
the systems and equipment of the stand checking – see Figure 4.

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26–29 October 2021, Băile Govora, Romania

Figure 4

The data acquisition of the measured parameters is done continuously in Xcel

files, the parameters being able to be used for the elaboration of specific operation
diagrams (speed/flow, respectively power/speed) for different speeds of the driving
rotor. On the screen of the monitor, in the synoptic diagram, the parameters can be
viewed (also continuously). Upon operator’s command the data can be stored, in a
separate file (in the stabilization phases), the data can be then processed for
determination of volumetric and adiabatic efficiencies) – see Figure 5.

Figure 5. Temperature and vibration monitoring was done with a Fluke equipment –see Figure 6 –
respectively with a vibration tester (VIBER –X5 MKIII) – see Figure 7.

Figure 6 Figure 7
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26–29 October 2021, Băile Govora, Romania

The development of the test showed that the mechanical operation of the
compressor meets the required conditions. COMOTI manufactured a screw compressor,
with the parameters of the one mentioned and delivered it to a foreign company, which
requests the operation of the compressor with a mixture of H2 (56%) and natural gas. The
company performed the reception tests, and switched to running the compressor in
load, the parameters being in accordance with required conditions.

CONCLUSIONS

The tests in our stand and at the beneficiary showed that the modifications
made ensure the safe operation of the screw compressor compression used for
compressing a mixture of H2 and natural gas.

References
Nikola Stosic, Ian K. Smith, Ahmed Kovacevic: Improving screw compressor performance
https://www.researchgate.net/publication/289206577_Improving_screw_compressor_performance
ISO10440 Rotary-type Positive Displacement Compressors for Petroleum, Petrochemical and Natural Gas
Industries (API 619)
ISO 1217 – Displacement compressors – Acceptance tests (PTC 9)
ISO 5167-2 – Measurement of fluid flow by means of pressure differential devices in circular cross-
section conduits running full – Part 2 Orifice plates

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26–29 October 2021, Băile Govora, Romania

FEASIBILITY OF H2 PRODUCTION BY CH4 FORMATION, CORROBORATED WITH CO2

STORAGE IN SALT MINES FORMED BY DILUTION

Sorin Popescu1, Stela Dinescu1, Iulian Vlăduca2, Mihai Joavina2, Ramona Manuela
Stanciuc2, Ana Maria Obreja3
1
University of Petrosani, Department of Mechanical, Industrial and Transport Engineering, University
2
Street 20, Petrosani, România; National Research and Development Institute for Gas Turbines
3
COMOTI Bucuresti, Iuliu Maniu Bd. nr. 220D, 061126, sect.6, România; University of Bucharest,
Faculty of Geology and Geophysics, Strada Traian Vuia nr. 6, 020956, România
Corresponding author: [email protected]

Abstract: H2 production by metane reforming, is a mature production process, most

used in the world and it contributes about 50% of the world's hydrogen production.
Therefore, because of this increasing importance of H2, various studies have investigated
H2 production by reforming, and over storage of the CO2 secundary gas produced. Steam
reforming of methane in natural gas (“gray hydrogen”), takes place with high carbon
dioxide emissions. From 1000 Nm3 CH4 in combination with water and termal energy
results about 2 tones CO2 and 0.35 tones H2. The hydrogen demand is directed to many
different process industries like fats and oil processing, chemicals, pharmaceutical,
metallurgy, semiconductor production and aerospace industries. The investments of the
capital, the operating costs and primary energy requirements should be evaluated by
decision makers [1]. The hydrogen production will be linked to the storage of CO2 for
periods of at least 20 years, in order to make production profitable in conjunction with
the declaration of the technology as passing from the gray area to the blue area, as clean
technology. The CO2 storage facilities can be conducted with private or with European or
other type of funds, and can be done in the conserved and unused wells resulted from
salt exploitation like existing ones in Targu Ocna county, Romania.

Reference
R. E. Stoll, F. von Linde, Hydrogen - what are the costs?, Caloric Anlagenbau GmbH, Graefelfing, Germany.
available on https://www.caloric.com/wp-content/uploads/2018/11/Hydrogen-What-are-the-costs.pdf

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26–29 October 2021, Băile Govora, Romania

RESERVED TITLE

Tudor Prisecaru

University Politehnica of Bucharest, Department of Thermodynamics, Engines,

Thermal and Cooling Equipment, Romania
Coresponding authors: [email protected]

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“New Cryogenic and Isotope Technologies for Energy and Environment” – EnergEn 2021
26–29 October 2021, Băile Govora, Romania

CONTROL OF A BIOREGENERATIVE RAW MATERIAL HYDROGEN PRODUCTION

PROCESS THROUGH ARTIFICIAL INTELLIGENCE

Vladimir Tanasiev1, Maria Paraschiv2, Tudor Prisecaru3

1
University Politehnica of Bucharest, Energy Production and User, Romania
2
University Politehnica of Bucharest, Department Name, Romania
3
University Politehnica of Bucharest, Department of Thermodynamics, Engines,
Thermal and Cooling Equipment, Romania
Coresponding authors: [email protected];
[email protected]; [email protected]

INTRODUCTION AND PURPOSE

The EU ETS (Emissions Trading System) is considered to be the main pillar in

EU’s strategy to reduce the CO2 emissions and combat major climate changes. It is
the first CO2 market and the biggest one reaching a market value of 229 billion
euros in 2020. In 2021, the EC has promoted a legislative package setting the paths
for 2030 goals, namely 55% net reduction in greenhouse gas emissions. The ETS
tool has been proven to be highly effective, reducing the emissions by roughly 35%
between 2015 and 2019 [https://www.reuters.com/article/us-europe-carbon-
idUSKBN29W1HR; https://ec.europa.eu/clima/policies/ets_en].
By consequence, it is clear that EU is moving toward green ways of energy
production through the restrictive policies in the last two decades. Hydrogen is
getting an increased attention from Europe because of its advantages to be used in
industry, transport, power and building sector. Due to its properties, it can be used
as a feedstock, fuel, energy carrier or storage. However, being at its early stage in
terms of production, usage and applications, hydrogen represents a small fraction
in EU energy mix. Moreover, hydrogen is largely produced from fossil fuels and coal
which releases an important quantity of CO2 in atmosphere [https://ec.europa.eu/
energy/sites/ener/files/hydrogen_strategy.pdf].
Nevertheless, hydrogen is a strong candidate in achieving 2030 goals and is
expected to decarbonize an important part of the EU energy consumption by 2050.
In this regard, we propose a concept for producing hydrogen using bioregenerative
raw materials. We particularly focus to collect the vegetal mass on the lake surfaces.
According to the Danube Delta Biosphere Reserve (DDBR) Administration, 70% of the
Delta vegetation is dominated by reeds [http://romaniaeden.travel/wp-content/
uploads/2020/01/Brosura-prezentare-RBDD-lb-romana.pdf].

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The proposed concept is focused on two key aspects, producing the hydrogen using
bioregenerative raw materials and returning to the natural circuit the lacustrine
surfaces for wild habitat.
The structure of this paper is organized as follows: In the first section, a short
introduction and main objectives are presented. In the second section, the
methodology for producing hydrogen out of bioregenerative raw materials is
emphasized. In the third section an overview of monitoring data processing using
artificial intelligence algorithms, and storage solutions are presented. In the last
section main findings, conclusions and research directions are presented.

Key words: AI, Blue Hydrogen.

References
https://www.reuters.com/article/us-europe-carbon-idUSKBN29W1HR
https://ec.europa.eu/clima/policies/ets_en
https://ec.europa.eu/energy/sites/ener/files/hydrogen_strategy.pdf
http://romaniaeden.travel/wp-content/uploads/2020/01/Brosura-prezentare-RBDD-lb-romana.pdf

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“New Cryogenic and Isotope Technologies for Energy and Environment” – EnergEn 2021
26–29 October 2021, Băile Govora, Romania

ENERGY STORAGE AND HYDROGEN TECHNOLOGIES

Mircea Eremia1, Nicolae Napoleon Antonescu1, Mihai Minescu1, Florinel Dinu1,

Mihai Varlam2, Ioan Iordache2, Lucian Toma1, Mihai Sanduleac1, Iulian Iancu1,
Calin Vilt3
1
Politechnica Univesity of Bucharest, Romania; Petroleum and Gas Univesity from Ploiesti, Romania
2
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
3
Romanian National Committee of World Energy Council, Romania
Coresponding author: [email protected]

Energy is a commodity that, in principle, cannot be stored, as it is produced in

close correlation with the consumption.
The boom development of energy generation from renewable energy sources
(particularly wind and photovoltaic sources), together with the objectives of the Paris
Agreement on Climate Change COP 21-concluded in December 2015-, required
intensified research efforts to identify new storage technological solutions meant to take
over the very high generation volatility from renewable energy sources, because they
brought about several management changes for worldwide Power Systems safe
operation.
Besides the conventional pump storage technologies, promoted for over 50 years,
the Hydrogen technology has become particularly attractive. The R 4.0 Digital
Revolution led to an important global technological emulation, which highly impacted
the strongly development of the energy sector.
To solve up these comprehensive issues facing global energy, about 8 storage
technologies have been researched and analysed so far, according to international
studies.
At the G20 meeting of the most developed countries (Osaka, June 2019), the
International Energy Agency-IEA in Paris presented a Report, according to which the G20
decided that Hydrogen technology would have to be developed and replace fossil fuel
heavy transport by 2050, by allocating significant funds to improve efficiencies and
significantly reduce the costs related to hydrogen fuel cells production. With a view to
supporting these ambitious goals, funds and subsidies will be used to develop new
industrial capacities which will radically change the world economy, the whole heavy
road, trucks and buses, rail and naval transport and to further on pass to these new
hydrogen propulsion technologies.
Hydrogen production is achieved through several technologies, the electrolysis
being preferred as it results in the production of green ecological hydrogen, whose use
in fuel cells produces energy and water. Thus, some circular economy goals imposed by
international agreements were met, mainly the decarbonisation targets envisaged by
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26–29 October 2021, Băile Govora, Romania

the Paris COP 21 Agreement to limit climate change. Energy produced from volatile
wind and photovoltaic sources for small to medium quantities and also nuclear
generation capacities for large quantities are considered.
The impact of these decisions is very high in the field of transport, car building and,
especially, in energy.
Decision makers agreed that energy transition to zero emissions by 2050 would be
fast and the hydrogen needed in transports would be produced in energy systems. Thus,
huge generation needs will result, which have not yet been scientifically and accurately
estimated because they must be correlated with the industrial capacity possibilities of
the machine building industry which will manufacture the new generations of trucks,
buses and ships powered by hydrogen fuel cells and with the storage and distribution
infrastructure of this new energy carrier.
The European Commission Communication of 8 July 2020, on the action plan for the
development of hydrogen based technologies, is a tremendous step forward that opens
a new technological era on R4.0 Digital Revolution. In June 2020, Germany and France
announced their strategies for the development of this new hydrogen technological
concept.
In order to decrease emissions and increase the heating value, hydrogen is
being already used in natural gas highways injection, at higher concentrations
combustion temperatures up to 200 degrees, which caused problems in adapting
materials. There are applications for heating systems that run on hydrogen. In the
first stage, these new installations were developed in isolated areas, where other
fuels are more difficult to reach. Hydrogen technology comes with a spectacular
and highly flexible solution between energy and gases for storage and flattening the
production/consumption curves, both for electricity and also for gases, where
storage and pressurization in national gas transmission systems have a very high
flexibility over a cycle of over 24 hours.
Romania has a very good research experience on hydrogen technologies conducted
within the National Institute for Scientific Research (ICSI) in Govora, where a dedicated
laboratory was built about 8 years ago, and where two models of hybrid vehicles
equipped with fuel cells were built. They have been operating, with excellent results,
for over 5-6 years. ICSI, together with the Hydrogen Association, Politehnica and Oil and
Gas Universities and the Romanian National Committee of the World Energy Council,
supported by Government's Sustainable Development Department, have laid the
foundation of the Romanian Hydrogen Hub which aims at interdisciplinary correlating
the development of these industries, as an intersectoral concept and industrial-scale
pilot projects to validate research and technology in practice as shown in schedules 1
and 2, herewith attached.

Acknowledgments: In order to implement this concept, there are to be used

both own funds and European Union funds, as about 40 billion euros were
budgeted to all EU member countries for 2021-2027

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“New Cryogenic and Isotope Technologies for Energy and Environment” – EnergEn 2021
26–29 October 2021, Băile Govora, Romania

MOLECULAR DYNAMIC STUDY ON THE STABILITY OF MgH2 SURFACES

Daniel G. Angelescu, Viorel Chihaia, Dana A. Neacsu

Romanian Academy, “Ilie Murgulescu” Institute of Physical Chemistry, Splaiul Independentei 202,
060021 Bucharest, Romania
Coresponding author: [email protected]

The metal hydrides have attracted considerable attention over the last decade
because of their safety and high gravimetric and volumetric storage capacities, and
among them, MgH2 have been extensively investigated with efforts being made to
improve its adsorption/desorption characteristics. The theoretical studies of the
adsorption and desorption processes impacted generally first-principle (DFT)
calculations whereas computational calculations of large number (hundreds or
thousands) atom systems have been less frequently reported. Among many
interatomic potentials developed for the Mg-H system, two well-parametrized AD-
(angular dependent) [Smirnova et al., 2018] and BO(bond-order)-formalism [Zhou
et al. 2019] interatomic potentials have been recently developed to capture the
(de)hydrogenation chemical processes within molecular dynamics simulations. Here
we present predicted surface energy calculations for stoichiometric and non-
stoichometric/symmetric slabs of various orientations employing molecular
dynamics simulations. The computational outcomes provided quantitative insights
into surfaces that were more stable and allowed a robust theoretical method for
selecting surfaces prone to hydrogen release.

Key words: Mg-H structure, interatomic potentials, molecular dynamics simulations.

Acknowledgments: The computational calculations were supported by a grant from

the Romanian Ministry of Education and Research, PN-III-P2-2.1-PED-2019-4816, CCCDI -
UEFISCDI.

References
D. E. Smirnova, S. V. Starikov, and A. M. Vlasova, Comput. Mater. Sci., 154, 295, (2018).
X. W. Zhou, S. Kang, T. W. Heo, B. C. Wood, V. Stavila, and M. D. Allendorf, ChemPhysChem 20, 1404,
(2019).

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26–29 October 2021, Băile Govora, Romania

DEVELOPMENT OF HYDROGEN-ENRICHED GAS PRODUCTION SYSTEMS FROM

RENEWABLE SOURCES WITH APPLICATIONS IN CLEAN ENERGY GENERATION

Adrian Armeanu, Elena David , Dan Mocanu, Gabriel Rasoi

National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Coresponding author: [email protected]@icsi.ro

This paper presents an experimental study for obtaining hydrogen-enriched gas

from the conversion of biomass, which is an important source of energy, especially
in rural areas. As the sustainable use of biomass does not lead to a net increase in
CO2 emissions, there would be global climate benefits resulting from the
widespread use of biomass. The article also describes some advanced biomass
conversion systems that could play a role in the long-term energy system. The
gasification of biomass is almost as old as burning, but it is less developed because
it has not been found in a commercial interest as strong as burning. There is
currently a major interest in the conversion of biomass into gaseous or combustible
liquids due to three motivating factors: benefits of renewable energy,
environmental benefits, socio-political benefits. The main objective will be to
develop a thermo-chemical conversion process of biomass to produce hydrogen-
rich gas, in order to obtain electric energy in combustion cells or in low-power
systems. The activities will involve studies on the coupling of a cell biomass
gasification process (BG) and laboratory investigations to determine the key
parameters of the gasification process in a fixed bed or fluidized bed (catalytic
conversion of tar and methane, degree of solids mixing, process temperature, etc.).

Key words: Biomass, Hydrogen rich gas production, Renewable energy technologies,
Clean energy, Storage system.

Acknowledgments: This paper was realized through the Core Program, carried
out with the support of MCI, project no. PN 19 11 03 01/2019-2022.

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26–29 October 2021, Băile Govora, Romania

BLOCKCHAIN REAL TIME DATA ACQUISITION FROM

RENEWABLE ENERGY SOURCES

George Călianu, Mihail Eugen Resteanu, Ionel Calcan, Maria Simona Răboacă

National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Coresponding authors: [email protected]; [email protected];
[email protected]; [email protected]

1. Introduction
Blockchain Technologies have attached a lot of attention in the past years in
Romania. In this content, in ICSI Energy Department was developed an experimental
stand (photovoltaic panel, wind turbine, battery, electrolyzer, hydrogen tank and fuel
cell), that use IoT and Blockchain with the goal to real time data acquisition from
renewable energy sources (RES) [Kang E.S. et al., 2018; Khatoon A. et al., 2019].
The novelty of this paper consists in synergy between real time data acquisition
from photovoltaic panels (PV) and Blockchain technology [Pervez H. and Hang I. U.,
2019; Pieroni A. et al., 2018]. The major advantage is collecting data from energy
source into the blockchain without other parties which ensure a high trust level of data.
Another advantage consists in estimation of energy future production from
photovoltaic panels based on the data collected in the blockchain by using Artificial
Intelligence (AI) algorithms on that collection [van Leeuwen, G. et al., 2020; Zheng, W.
et al., 2019].

2. The concept of the blockchain real time data acquisition from RES
In this paper we present an Blockchain real time data acquisition from PV,
presented in figure 1.

Figure 1. The concept of the blockchain real time data acquisition from RES
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26–29 October 2021, Băile Govora, Romania

3. Results

Figure 2. Monitoring current in real time of the photovoltaic panel

Figure 3. Monitoring tension in real time of the photovoltaic panel

Figure 4. Monitoring temperature in real time of the photovoltaic panel

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Figure 5. Monitoring (current, tension, temperature) in real time of the photovoltaic panel

During experimental data validation of blockchain real time data acquisition

from photovoltaic panel, figures 2,3,4,5 present the results of PV monitoring for
current, tension and panel temperature.

4. Conclusions: A platform (hardware and software) was developed for real

time data acquisition from renewable energy sources.

Future research direction will be developed during this innovative concept

“Blockchain Real Time Data Acquisition from RES” as:
 Monitoring Green Hydrogen from renewable energy sources;
 Monitoring Green Hydrogen for Hydrogen Charging Stations;
 Estimation of Green Hydrogen production using AI that learn from data
stored in Blockchain;

Key words: Blockchain, Real Time Data Acquisition, Renewable Energy Sources,
Photovoltaic panels, Hydrogen Fuel Cell Technology, Artificial Intelligence.

References:
Kang E.S., Pee S.J., Song J.G., Jang J.W., A blockchain-based energy trading platform for smart homes in a
microgrid. Proceedings of the 3rd International Conference on Computer and Communication
Systems (ICCCS), Nagoya, Japan, 27–30 April 2018; IEEE: Piscataway, NJ, USA, 2018; pp. 472-476.
Khatoon A., Verma P., Southernwood J., Massey B., Corcoran P., Blockchain in energy efficiency: Potential
applications and benefits. Energies, 2019, 12, 3317.
Pervez H., Haq I.U., Blockchain and IoT based disruption in logistics. In Proceedings of the 2019 2nd
International Conference on Communication, Computing and Digital systems (C-CODE), Islamabad,
Pakistan, 6–7 March 2019; pp. 276-281.
Pieroni A., Scarpato N., Di Nunzio L., Fallucchi F., Raso M., Smarter city: Smart energy grid based on
blockchain technology. Int. J. Adv. Sci. Eng. Inf. Technol. 2018, 8, 298-306.
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26–29 October 2021, Băile Govora, Romania

Van Leeuwen G., AlSkaif T., Gibescu M., van Sark W., An integrated blockchain-based energy
management platform with bilateral trading for microgrid communities. Appl. Energy, 2020, 263,
114613.
Zheng W., Zheng Z., Chen X., Dai K., Li P., Chen R., NutBaaS: A blockchain-as-a-service platform. IEEE
Access, 2019, 7, 134422-134433.

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26–29 October 2021, Băile Govora, Romania

THERMOCHEMICAL CONVERSION OF ORGANICS DERIVED FROM BIOMASS OVER

Fe/Al2O3 CATALYST FOR HYDROGEN RICH GAS PRODUCTION

Elena David, Adrian Armeanu

National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Coresponding author: [email protected]

Hydrogen attracted much attention for its high conversion efficiency and as
clean energy source. In the usual methods, hydrogen is mainly produced from fossil
fuels, such as coal gasification and natural gas reforming, etc [Holladay et al., 2009;
Navarro et al., 2007]. In order to improve the economy of hydrogen production,
the biomass and its organic derivatives are widely used to produce hydrogen by the
catalytic conversion process, among which bio-ethanol and bio-tar being two of
most promising renewable resources [Ni et al. 2007, Furusawa et al., 2013]. The
annual yield of ethanol in the world reaches 20-25 billions of gallons [Xiu et
Shahbazi, 2012]. Bio-ethanol reforming is an important method for hydrogen
production from renewable resources. Bio-tar, as a by-production or an
unavoidable waste during thermal conversion of biomass depending on different
processes (up to 70 wt% for pyrolysis and up to 20 wt% for gasification [Xiu et
Shahbazi, 2012; Li et Suzuki, 2010]), is a complicated mixture of hundreds of organic
compounds, mainly composing of alcohols, phenols, aromatic hydrocarbons (such
as benzene, toluene , naphthalene and 1-methylnaphthalene, etc.).
Starting from these considerations, in this paper, four types of organics derived
from biomass (ethanol/toluene/phenol/1-methylnaphthalene) were supposed to
catalytically decomposition and steam reforming over Fe/Al2O3 for production of
hydrogen rich gas and carbon materials. In the reaction of decomposition, the
oxygen functional group presents in phenol and ethanol structure has promoted
the production of hydrogen and carbon structures, while a small quantity of
toluene and 1-methylnaphthalene was cracked to hydrogen and amorphous
carbon. On the other hand ,in the reaction of reforming, the yields of hydrogen rich
gas and carbon structures have sharply increased. More than 2 mol/(g-cata∗h) of
H2 and 0.02mol/(g-cata∗h) of carbon structures formed were obtaining after the
reaction of toluene and ethanol reforming. Of the four organic compounds, 1-
methylnaphthalene was difficult to be reformed and as a consequence, a small
amount of carbon structures were obtained. As a conclusion, the organic

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compounds with low molecular weight and low degree of unsaturation have
conduced to the formation of hydrogen rich gas.

Key words: biomass; organic compounds; decomposition; steam reforming;

catalyst; hydrogen.

Acknowledgments: This paper was realized through the Core Program, carried
out with the support of MCI, project no. PN 19 11 03 01/2019-2022.

References
Furusawa T., Saito K., Kori Y., Miura Y., Sato M., Suzuki N., Steam reforming of naphthalene/benzene with
various types of Pt- and Ni-based catalysts for hydrogen production. Fuel, 2013; 103:111-21.
Li C., Suzuki K., Resources, properties and utilization of tar. Resour Conserv Recycl, 2010; 54:905-15.
Holladay J.D., Hu J., King D.L., Wang Y., An overview of hydrogen production technologies. Catal Today,
2009; 139:244-60.
Navarro R.M., Peña M.A., Fierro J.L.G., Hydrogen production reactions from carbon feedstocks: fossil fuels
and biomass. Chem Rev., 2007; 107:3952-91.
Ni M., Leung D.Y.C., Leung M.K.H., A review on reforming bio-ethanol for hydrogen production. Int J
Hydrogen Energy, 2007; 32:3238-47.
Xiu S., Shahbazi A., Bio-oil production and upgrading research: a review. Renew Sustain Energy Rev., 2012;
16:4406–14.

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26–29 October 2021, Băile Govora, Romania

STANDALONE GREEN HYBRID ENERGY SYSTEM FOR A SMALL COMMUNITY.

CASE STUDY

Gheorghe Badea1, Maria Simona Răboacă1,2,*, Ioan Așchilean3,

Raluca A. Felseghi3,4
1
Faculty of Building Services Engineering, Technical University of Cluj-Napoca, Bd. 21 Decembrie
1989, no.128-130, 400604 Cluj-Napoca, Romania
2
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
3
Faculty of Civil Engineering, Civil Engineering and Management Department, Technical University of
Cluj-Napoca, Constantin Daicoviciu street, No.15, 400020 Cluj-Napoca, Romania
4
Faculty of Electrical Engineering and Computer Science, Ștefan cel Mare University of Suceava,
Universităţii Street, No.13, 720229 Suceava, Romania
Coresponding author: [email protected]

Globally, increasing energy consumption - regardless of its type, makes it

increasingly difficult to provide the primary energy resources needed to meet the
demand of the energy sector in conditions of environmental protection [Ozturk & Dincer,
2020]. The energy efficiency of consumption in all activity sectors and decarbonization of
the energy system through the extensive use of clean alternative energy resources
available on-site are the solutions used as sustainable [Filote et al., 2020].
This research work proposes the power supply based on solar resources of a
small community and presents the case study results based on the simulation of a
power supply system [iHOGA PRO+ Software Version 2.5, 2020] designed with
photovoltaic panels as solar energy conversion equipment, for which two energy
storage solutions are considered: batteries bank and hydrogen energy technology
[Aşchilean et al., 2021].
The small community's main energy demands of 70% are due to residential
consumers and 30% to public consumers [Răboaca & Felseghi, 2019]. The energy
system proposed for sizing must supply power generated from clean resources with
an average daily load of 38.46 kWh/day.

Average Hourly Load (W)

4000 max min
load (W)

2000

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 hour

Figure 1. Average Hourly Load

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26–29 October 2021, Băile Govora, Romania

The graph in the 60 minutes step of the average daily load is drawn in Figure 1
having the main values: AC maxim hourly active power load in the year of 4250 W;
average hourly AC power: aparent of 1602 W.
The energy system based on the solar resource from the hypothesis configured
and subjected to the analysis is presented schematically in Figure 2, and the operating
principle can be described as follows: the energy system uses solar energy as a primary
renewable source and photovoltaic panels as conversion technology, and to cover the
peak load and intermittency due to weather conditions, it uses the energy stored in the
battery bank together with the fuel cell, which consumes hydrogen (secondary energy
source), hydrogen that is obtained electrolytically locally on-site by harnessing the
resulting solar energy sources in excess.

Figure 2. Power System Scheme

The optimal energy system configured to satisfy 100% the energy small
community demands has the following main components: photovoltaic panels with
a total rated power of 32.5 kWp; batteries bank E total = 30.24 kWh; fuel cell –
rated power = 10 kW; electrolyser =10 kW; H2 tank of 30 kg; inverter = 5200 W; PV
battery charge controller of 608 A.
The energy balance during one year of operation of this system is illustrated in
Figure 3a, and the carbon dioxide emissions embodied in the studied clean energy
system are 62.82% lower than if the electricity supply of the small community
would be made from the grid.

Energy (kWh/year) 4500 CO2 Emissions (kgCO2/year)

25000
4000
20000 3500
25420 3000
15000
2500
10000 8717 2000 4142
14040 6037
5000 1500
9163
894 2345 1679 1000
0 1540
500
0
grid case study
CO2 4142 1540

Figure 3.a. Energy Balance Figure 3.b. CO2 Emissions

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The system initial investment cost is 221110 €; with a 25 years lifespan, the
Total System Costs is 381932 €, and the energy Levelized Cost is 1,09 €/kWh.

Key words: clean energy; hybrid energy system; standalone energy system;
green hydrogen.

References
Așchilean, I., Cobîrzan, N., Bolboaca, A., Boieru, R., & Felseghi, R. A. (2021). Pairing solar power to
sustainable energy storage solutions within a residential building: A case study. International
Journal of Energy Research, 45(10), 15495-15511.
iHOGA PRO+ Software Version 2.5, Electrical Engineering Department, University of Zaragoza, Spain,
2020.
Filote, C., Felseghi, R. A., Raboaca, M. S., & Aşchilean, I. (2020). Environmental impact assessment of
green energy systems for power supply of electric vehicle charging station. International
Journal of Energy Research, 44(13), 10471-10494.
Ozturk, M., & Dincer, I. (2020). Life cycle assessment of hydrogen-based electricity generation in
place of conventional fuels for residential buildings. International Journal of Hydrogen
Energy, 45(50), 26536-26544.
Răboaca, M. S., & Felseghi, R. A. (2019, October). Energy Efficient Stationary Application Supplied
with Solar-Wind Hybrid Energy. In 2019 International Conference on Energy and Environment
(CIEM) (pp. 495-499). IEEE.

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INNOVATIVE CONCEPT OF ELECTROCHEMICAL CONVERSION OF CO2 WITH

GENERATION OF H2

Mihaela Iordache, Mircea Răceanu, Adriana Marinoiu

National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Coresponding author: [email protected]

Excessive emissions of CO2 from the combustion of fossil fuels are the main
causes of climate change and environmental pollution, which are the global issues
to be solved for a sustainable society. These issues require the development of new
types of systems and technologies for energy conversion and storage based on
renewable energy [Jinhyup Han, 2018]. Carbon capture, use and storage
technologies have been extensively studied to use carbon dioxide (CO2), a
greenhouse gas, as a resource. However, no efficient technologies have been
proposed so far due to the low conversion rate of efficiency and high energy
requirements. Studies show that global warming and climate change are the result
of carbon dioxide (CO2) generated by human activities over the centuries [Kaldellis
J.K., 2007; Marinoiu A., 2014; Marinoiu A., 2015]. Thus, many countries and
organizations have made great efforts to reduce their carbon footprint and,
recently, carbon capture, use and storage/sequestration (CCUS) technology has
been studied to recycle CO2 as a resource. In this regard, considerable research has
focused on the chemical conversion of CO2 into high value-added carbon
compounds such as methanol, organic materials and plastics. However, due to the
low conversion efficiency, it has been pointed out that it cannot be an effective
technology to reduce greenhouse gases. Limiting carbon emissions in the
atmosphere requires the efficient use of carbon dioxide and its capture through the
well-designed platform. Metal-CO2 batteries are currently proving to be a way to
use CO2 and produce energy simultaneously. In particular, Na-CO2 batteries are
considered an alternative to Li batteries due to the abundance and low cost of
sodium ions. The Na-CO2 cell can continuously produce electricity and hydrogen by
efficiently converting to CO2 from the spontaneous dissolution of CO2 into an
aqueous solution. In addition, this system has the advantage that no CO 2 is
regenerated during the charging process, unlike aprotic metal-CO2 cells. The scope
of this work is the development of an innovative technology for chemical
conversion of CO2 with H2 generation, using an electrochemical cell containing a
conducting membrane of Na ions (Na3Zr2Si2PO12) [Guin, M., 2016; Narayanan, S.,

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2019]. Recently, aprotic (non-aqueous) metal-CO2 batteries have also been studied
for the production of electrical energy using CO2. However, during the generation of
electric energy, solid carbonate products accumulate on the surface of the
electrode, which deteriorates the performance and discharge capacity. In addition,
because CO2 is regenerated in the charging process, aprotic metal-CO2 batteries are
not an efficient CCUS technology for utilizing and reducing CO2. Thus, a hybrid Na-
CO2 battery has been designed that produces continuously electricity and hydrogen
simultaneously through efficient CO2 conversion with very stable operation more
than 1,000 hours of spontaneous dissolution of CO2 in an aqueous solution
[Changmin Kim, 2018]. Unlike existing aprotic CO2 metal batteries, the proposed
system does not regenerate CO2 during the charging process. Therefore, this Na-
CO2 hybrid cell, which adopts efficient CCUS technologies, uses not only CO2 as a
resource for generating electricity, but also produces a source of clean energy,
hydrogen. The cell contains a Na-ion conducting membrane (herein, Na3Zr2Si2PO12)
with its surface exposed to seawater, so that the anode compartment and the
seawater catholyte are separated and only Na-ion transport between the
electrodes is allowed. The anode compartment is composed of an anode (Na metal)
attached to a current collector immersed in a non-aqueous electrolyte, which is
used as a buffer layer between the anode and the membrane for facile Na-ion
transfer. The cell consists of two compartments, an anode and a cathode, which are
separated by a NASICON ceramic electrolyte (Na3Zr2Si2PO12). The anode
compartment is composed of a sodium metal anode attached to a current collector
and a non-aqueous liquid electrolyte. The cathode part consists of a cathode
current collector and seawater catholyte (Fig. 1).

Figure 1. (a) Schematic diagram of the seawater battery (top) and disintegrated cell components of
the coin-type cell (bottom) and (b) assembled coin-type cell and flow-cell tester
(4TOONE Energy Co.,Ltd)

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This system could work continuously with Na metal and CO2 as fuel at the
anode and feedstock gas at the cathode, respectively. Na is regarded as a promising
candidate as a substitute for Li in terms of its electrochemically similar behavior
along with low cost (30 times cheaper than Li) from natural abundance and
environmental friendliness. The Na metal anode is kept in an organic electrolyte to
prevent a direct corrosion from an aqueous electrolyte separating by Na super ionic
conductor (NASICON) membrane. The overall reaction mechanisms are composed
of a chemical reaction and an electrochemical reaction (Fig. 2).

Figure 2. Schematic Illustration of Hybrid Na-CO2 System and its Reaction Mechanism

The Na-CO2 cell has a system three distinctive advantages. First, it uses a fast
kinetic hidrogen evolution reaction (HER) as a discharge reaction thanks to a
spontaneous one dissolution of CO2, allowing the supply of a high current
compared to the current aprotic system. Second, unlike conventional aprotic CO2
batteries, in which solid products are clogged with electrodes, this system can
continuously produce hydrogen in the gas phase during discharge without
damaging the electrode. Third, the proposed system has the great unprecedented
advantage of not regenerating CO2 while recycling Na metal loading process.
Therefore, this Na-CO2 hybrid cell really fulfills the purpose of a real CCUS
technology, because it consumes CO2 efficiently throughout the process. This new
system could serve as a a new technology for the use of CO2 and a cornerstone for
the future use of renewable energy technologies.

Key words: chemical conversion CO2, electrochemical cell, hydrogen production,

electrical energy.

Acknowledgments: This work is supported by Ministry of Research, Innovation,

Digitization from Romania by the National Plan of R & D, Project No. PN 19 11 02 01
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and by UEFISCDI, Project PN-III-P2-2.1-PED-2019-1894 (Contract No. 460PED/2020)

and PN-III-P2-2.1-PED-2019-2079 (Contract No. 469PED/2020).

References
Changmin Kim, Jeongwon Kim, Sangwook Joo, Yunfei Bu, Meilin Liu Jaephil Cho, and Guntae Kim, Efficient
CO2 Utilization via a Hybrid Na-CO2 System Based on CO2 Dissolution, iScience 9, 278–285 November
30, 2018, https://doi.org/10.1016/j.isci.2018.10.027
Guin, M., Tietz, F., Guillon, O., 2016. New promising NASICON material as solid electrolyte for sodium-ion
batteries: Correlation between composition, crystal structure and ionic conductivity of Na3+xSc2SixP3-
xO12. Solid State Ionics 293, 18–26.
Jalalian-Khakshour, A., Phillips, C.O., Jackson, L., Dunlop, T.O., Margadonna, S., Deganello, D., 2020. Solid-
state synthesis of NASICON (Na3Zr2Si2PO12) using nanoparticle precursors for optimisation of ionic
conductivity. J. Mater. Sci. 55, 2291–2302. https://doi.org/10.1007/s10853-019-04162-8.
Jinhyup Han, Soo Min Hwang, Wooseok Go, S.T. Senthilkumar, Donghoon Jeon, Youngsik Kim,
Development of coin-type cell and engineering of its compartments for rechargeable seawater
batteries, Journal of Power Sources, Volume 374, 15 January 2018, Pages 24-30,
https://doi.org/10.1016/j.jpowsour.2017.11.022.
J.K. Kaldellis, D. Zafirakis, Optimum energy storage techniques for the improvement of renewable energy
sources-based Electricity generation economic efficiency, Energy 32, 2295 - 2305 (2007).
Marinoiu A, Carcadea E, Ionete R, Raceanu M, Cobzaru C, Iordache I, et al., 2014, Carbon dioxide reusing
for methane fuel obtaining over heterogeneous catalysts as a possible source of energy. Prog Cryog
Isot, 17: 23-30.
Marinoiu A, Cobzaru C, Raceanu M, Varlam M, Carcadea E, Cernatescu C, et al., 2015, Carbon dioxide
conversion to methane over supported nickel base catalysts. Rev Roum Chim, 60:249–56.
Narayanan, S., Reid, S., Butler, S., Thangadurai, V., 2019. Sintering temperature, excess sodium, and
phosphorous dependencies on morphology and ionic conductivity of NASICON Na3Zr2Si2PO12. Solid
State Ionics, 331, 22–29. https://doi.org/10.1016/j.ssi.2018.12.003.

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EFFICIENCY AND SAFETY ASPECTS FOR A HIGH PRESSURE PEM

ELECTROLYSER AT ICSI RM. VALCEA

Ana-Maria Nasture1,2 , Laurenţiu Pătularu1, Florin Lungu1,3,

Stefan-Ionuţ Spiridon1, Eusebiu Ionete1

1
National R&D Institute for Cryogenics and Isotopic Technologies – ICSI Rm. Valcea, Romania,
2
Computers and Automation Department, Politehnica University of Bucharest, Romania
3
Faculty of Power Engineering, Politehnica University of Bucharest, Romania
Corresponding author: [email protected]

Abstract: With the increased availability of electrolysers and its ability to

produce green hydrogen from renewables in order to both replace the currently
used grey hydrogen from steam methane reforming as well as facilitate the
evolution of hydrogen-based energy system technologies such as fuel cells or
energy storage technologies, Proton Exchange Membrane (PEM) Electrolysers are
becoming an excellent candidate in balancing renewable power and the most
promising device for high purity and efficiency hydrogen production.

Key words: PEM-Electrolyser, High-Pressure, High-Purity, BOP, PEM, PEM-

Electrolyser efficiency

1. Introduction

Nowadays, there are different types of water electrolysers available on the

market, ranging from solid oxide electrolysers [Phillips R., Dunnill C.W. 2016] to
alkaline electrolysers [Phillips R., Dunnill C.W. 2016] and Proton Exchange
Membrane (PEM) electrolysers [Carmo M. et al., 2013]. But the PEM electrolysers,
in comparison with the alkaline ones, present multiple advantages, such as: higher
hydrogen production with a smaller footprint and the ability to work under more
flexible conditions as well as high-cost reduction potential through mass
production. PEM electrolysis is capable of producing high purity hydrogen while
being free of any carbon emissions, having oxygen as the only by-product.
Conventional production installations based on PEM Electrolysers have been
designed to deliver hydrogen at low pressure in the range of 10 to 30 bar [Ayers K.
E. et al. 2010; Marangio F. et al., 2009], with a normal purity of 99.995%. Additional
dryers and De-Oxo units can be added to increase the level of H2 purity up to
99.999%. Even if these additional options (increased capital costs, complexity of the

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installation, and decreased overall energy efficiency) satisfy most end-users

(excluding analytical testing, semiconductor industry), problems still exist with low
output pressures. In order to eliminate these drawbacks, the use of a high-pressure
PEM Electrolyser for low-capacity installations is considered to be the best choice,
as it provides the ability to obtain ultraclean hydrogen (99.9999%) while being at a
sufficiently high-pressure value to avoid additional mechanical compression
requirements (i.e., additional energy consumption that can be translated in
lowering the overall resulting H2 production efficiency) for final storage.
There are two ways to improve the efficiency of a PEM Electrolyser: first is to
improve the elements of electrolyser assembly (construction, composition,
materials, geometry): membrane electrode assemblies (MEAs) [Ouimet R.J. et al.,
2021], current collectors (gas diffusion layers), and separator plates; and second is
to improve the efficiency of BoP (Balance of Plant) [Mancera J.J.C. et al., 2020],
using different approaches for process architecture, sensors and transmitters for
controlling & monitoring the whole H2 production plant (i.e., water management,
thermal management, power management, pressure and purifying management),
optimisation control algorithms.
In order to integrate an electrolyser stack into a functional architecture (Fig. 1),
it is mandatory to follow some highly important steps that will guarantee the safety
and long-time operation resumed in the following system description.

Figure 1. Functional architecture for a PEM-El stack

2. BoP for a PEM Electrolyser

Having the two methods to improve the efficiency of a PEM Electrolyser, we

choose the second method in order to improve the overall system efficiency.
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System description:
1. The anode circuit of the electrolysis unit, where electrochemical water
separation occurs, is needed to be supplied with deionized water. The Thermal
Management and Water Loop block will be in charge (control and monitor) of all
the critical parameters of the anode circuit:
 The flow of deionized water, controlled through a recirculation pump
between certain thresholds, for adjusting the operating temperature of the
electrolyser;
 Deionized water conductivity;
 The level of deionized water in the reservoir, maintained between safety
limits through an external water supply;
 The temperature and pressure of the deionized water at the inlet and outlet
of the EL;
 The safe evacuation of the generated oxygen.
2. The electrolyser is energized from the DC power source to a fixed voltage
value within the working range of the electrolyser, the current being electronically
limited from the power supply to follow a pre-set activating curve ramp type which
represents the Power Management Loop.
3. In the cathode side of the electrolyser where the water saturated molecular
hydrogen is generated, the Pre-purifying loop will monitor and assure the safety of
operational parameters with a key focus on water demisting from gas flow, at
minimum level, while also recovering the DI water from the gravimetrical and
coalescence separation process.
4. Low water content (<4000ppmv) hydrogen flow will be directed to the
regenerative PSA (Pressure Swing Adsorption) Dryer unit that will ultra-purify the
gas flow up to 99.9999%. The entire hydrogen pressure line (from the EL output to
the input of the storage media) is maintained at 100barg through the integration of
a back pressure type regulator.

3. Efficiency of a water electrolysis system

From a mathematical modelling point of view, the overall reaction for a PEM
electrolyser is the following:

(1)

The most common electrolyser model was used, which is:

(2)

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where Vel_o is the open circuit voltage, Vel_act is the activation overpotential, Vel_ohmic
is the ohmic overpotential, and Vel_conc is the concentration overpotential.
The stack voltage efficiency can be calculated using:

(3)
∗ ∗ ∗ ∗

Vrever_cell is the reversible voltage which is equal to the ratio between free
enthalpy during the course of the formation of a mole of water at standard
pressure and the negated value of the product between the number of cells in the
stack, cell voltage, and twice the Faraday constant [Dopp R., 2012], [Medina P. and
Santarelli M., 2010], [Zhang H. et al., 2012]; ncell is the PEM Electrolyser stack’s
number of cells; Vcell is the operating cell voltage.
The efficiency of the overall system (PEM Electrolyser voltage efficiency and
power consumption of auxiliars components – i.e., water circulation pump, valves,
sensors, controller electronics, power electronics and thermal management) is
given by the ratio between the lowering heating value (LHV) of the hydrogen
produced over the electricity used, written as:

( )
(4)
( )

In this particular case – i.e., 9.3 kW/h Electrolyser with an active electrode area:
184 cm² (ø 153 mm), and number of cells: 20 pcs., the resulting system efficiency is
showed in Fig. 2.

Figure 2. Run-time efficiency from power on to steady-state of the Electrolyser system

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4. Conclusions

The new Hydrogen-based Economy will determine a higher demand of

hydrogen gas. The R&D is focused on: integration of green energy and hydrogen
production (hydrogen as an energy storage from renewable sources); improving
technology and materials for PEM Electrolysers; optimizing the balance of plant;
increasing the life time and reliability while reducing costs. Our team's efforts have
so far been translated into an architecture successfully implemented around 9.3kW
PEM Electrolyser conduct us to an overall efficiency of around 73.78%. There are
still ongoing development phases regarding the control algorithms, the drying and
purifying method, the reduction of the overall power consumption in order to
obtain an even better efficiency and safety.

References
Ayers, K. E. et al.; “Research Advances towards Low Cost, High Efficiency PEM Electrolysis”; ECS
Transactions, 2010, vol. 33, no. 1, pp. 3–15
Carmo, M.; Fritz, D.L.; Mergel, J.; Stolten, D.; “A comprehensive review on PEM water electrolysis”;
Int. J. Hydrogen Energy, 2013, 38, 4901–4934
Dopp R.; “High rate and high efficiency hydrogen generation via water electrolysis catalysed by nano
powder”; https://web.archive.org/web/20120322204531/http://www.grid‐shift.com/white_
papers/docs/3D_Water_Electrolysis_Abstract%202.htm;
Mancera J.J.C., Manzano F.S., Andujar J.M., Viva F.J., Calderon A.J.; “Optimized Balance of Plant for a
medium-size PEM electrolyzer. Design, Modelling and Control”, Electronics, 2020, Volume 9,
Issue 5, Article Number 871, DOI10.3390/electronics9050871
Marangio, F., Santarelli, M., and Calì, M.; “Theoretical model and experimental analysis of a high
pressure PEM water electrolyser for hydrogen production”; International Journal of Hydrogen
Energy, 34: 1143–1158, 2009
Medina P. ; Santarelli M.; “Analysis of water transport in a high pressure PEM electrolyzer”; Int. J.
Hydrogen Energy, vol. 35, no. 11, pp. 5173–5186, Jun. 2010.
Ouimet R.J., Ebaugh, T. A., Mirshekari G., Bliznakov S., Bonville L. J., Maric R., “Current Status on the
Manufacturing of Nanomaterials for Proton Exchange Membrane Energy Systems by Vapor-
Based Processes”, Energy Fuels, 2021, 35, 3, 1933–1956, Publication Date:January 20, 2021
https://doi.org/10.1021/acs.energyfuels.0c03670
Phillips, R.; Dunnill, C.W.; “Zero gap alkaline electrolysis cell design for renewable energy storage as
hydrogen gas”; RSC Adv. 2016, 6, 100643–100651.
Zheng, Y.; Wang, J.; Yu, B.; Zhang, W.; Chen, J.; Qiao, J.; Zhang, J.; “A review of high temperature
coelectrolysis of H2O and CO2 to produce sustainable fuels using solid oxide electrolysis cells
(SOECs)”; Advanced materials and technology. Chem. Soc. Rev. 2017, 46, 1427–1463.
Zhang H., Su S., Lin G., Chen J.; “Efficiency Calculation and Configuration Design of a PEM Electrolyzer
System for Hydrogen Production”; International Journal of Electrochemical Science, vol. 7, pp.
4143-4157, May 1, 2012 2012.

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DEVELOPMENT OF Cu/ZnO/Al2O3 CATALYSTS FOR THE SYNTHESIS OF GREEN

METHANOL BY CO2 HYDROGENATION

Anişoara Oubraham, Ioan-Sorin Sorlei, Elena Marin, Simona Borta,

Adriana Marinoiu

National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Coresponding author: [email protected]

In 2021 the European Commission adopted a series of legislative proposals

setting out how it intends to achieve climate neutrality in the EU by 2050, including
the intermediate target of an at least 55% net reduction in greenhouse gas
emissions by 2030 [Climate Action - European Commission. 2021].
Carbon dioxide (CO2) is one of greenhouse gases, which can cause global
warming. Most of energy in the world is currently from combustion of
carbonaceous fuels, which are coal, oil, and natural gas [P. Borisut, 2019]. The
primary energy sources that have the most negligible CO2 emissions are solar
energy, nuclear energy, wind energy, hydro and biomass.[L.C. Grabow, 2011].
Methanol (CH3OH) is a chemical compound that can be used both as a fuel in
the aerospace and automotive industries, and in the production of chemicals and
fuels as a basic raw material. Thermo-catalytic hydrogenation of CO2 to CH3OH by
heterogeneous catalysis is one of the promising approaches that has attracted
much attention in recent researches. Major advances processes have been made in
the development of various catalysts, including metals, metal oxides and
intermetallic compounds [D. Belotti, 2017; X. Jiang, 2020].
Methanol synthesis starting from pure sources and controlled concentrations
of CO2 and H2, greatly simplifies the chemistry and reaction products. In essence,
the chemistry reaction reported below:

CO2 +3H2 ⇋ CH3OH +H2O + heat

This process represents an eco-friendly solution for the methanol production

by allowing reducing the intensity of fossil fuel consumption and mitigating the CO 2
emission as well.
The catalyst of choice for methanol synthesis are Cu, ZnO, Al2O3 materials.

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The conventional catalysts for synthesis of methanol have proven to be

structure sensitive, because its activity can vary by orders of magnitude, depending
on how it is prepared. [D.S. Marlin, 2018].
The conventional preparation methodology for the Cu/ZnO/Al2O3 catalyst is co-
precipitation which includes three stages:
- the precipitation of the precursors in the form of hydroxycarbonates,[ J.
Schumann, 2016]
- the controlled calcination of these hydroxycarbonate precursors to produce
highly dispersed CuO–ZnO species with some residual carbonates which are
responsible for maintaining high porosity and surface area,
- the reduction of these oxidized phases to obtain the active catalyst as Cu0 or
+
Cu nanoparticles decorating the phases of ZnO or partially reduced ZnOx. [A.
Marinoiu, 2016].
Reactor design in methanol synthesis and in any chemical process is important
for preserving catalyst life, for achieving acceptable production rate and quality,
and for controlling process conditions.
Experimental reactor for the conversion of CO2 to methanol by reduction with
hydrogen at high
temperature and pressure up to 1 atm. The peripheral panels show:
- i) the mass spectroscopy system for analysis,
- ii) the gas supply system,
- iii) the internal compartment which includes the main reactor and the flow
control system.

Key words: innovative catalysts, green methanol, CO2 hydrogenation, CO2

conversion.
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Acknowledgments: This work is supported by Ministry of Research, Innovation,

Digitization from Romania by the National Plan of R & D, Project No. PN 19 11 02 01
and by UEFISCDI, PN-III-P2-2.1-PED-2019-2079 (Contract No. 469PED/2020).
References
A. Marinoiu, C. Cobzaru, M. Raceanu, M. Varlam, E. Carcadea, C. Cernatescu, I. Stefanescu, Revue
Roumaine de Chimie, 2015, 60(2-3), 249-256;
Climate Action - European Commission. 2021. Delivering the European Green Deal - Climate Action -
European Commission. [online] Available at: <https://ec.europa.eu/clima/policies/eu-climate-
action/delivering_en> [Accessed 6 September 2021].
D. Belotti, M. Rivarolo, L. Magistri, A.F. Massardo, Journal of CO2 utilization, 2017, 21, 132.
D.S. Marlin, E. Sarron, O. Sigurbjornsson, Frontiers in Chemistry, 2018, 6, 446
https://ec.europa.eu/clima/policies/eu-climate-action/delivering_en
J. Schumann, A. Tarasov, N. Thomas, R. Schlögl, M. Behrens, Applied Catalysis A: General Journal,
2016, 516, 123
L.C. Grabow, M. Mavrikakis, ACS Catalysis, 2011, 1, 365.
P. Borisut, A. Nuchitprasittichai, Frontiers in Energy Research, 2019, 7, 1.
X. Jiang, X. Nie, X. Guo, C. Song, J. Chen, Chem. Rev., 2020, 120, 7984.

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DESIGN AND CONCEPT OF AN EXPERIMENTAL HYDROGEN STORAGE SYSTEM

BASED ON METAL HYDRIDE MATERIALS FOR ENERGY APPLICATIONS RESEARCH:
A CASE STUDY

Gabriel Răsoi, Ioan Iordache, Maria Simona Răboacă, Adrian Armeanu

National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Coresponding author: [email protected]

This paper presents technical concepts and design regarding of an experimental

hydrogen storage system based on metal hydride materials, who was developed and
implemented in a research project and which will be used for energy applications in
various fields.
At the same time, in this paper are shown the general requirements for establishing
the design data, equipment sizing and establishing the main elements of the
experimental storage model.
Hydrogen is an energy vector and a candidate for an efficient energy carrier,
efficient and cost-effective for future energy and global economic security. The
persistent problem of prompt integration of hydrogen into the world economy remains
its storage.
Hydrogen storage is a key issue of a viable economy of hydrogen and its
production. One of the needs lies in ensuring that hydrogen is stored in light and
compact tanks for later use in hydrogen propelled vehicles.
Recently, technical engineering solutions have been developed for the
implementation of new hydrogen storage systems based on hydride nanomaterials,
especially for commercial vehicles equipped with fuel cells, which combine
compactness, high adjustable weight and good dynamics. of hydrogen loading/
unloading.
The hydrogen storage system has been successfully integrated in a prototype fuel
cell power module for electric forklift.
Hydride materials have the advantage of having the lowest primary energy
consumption, can be connected to simple and cheap supply systems and have a high
degree of passive security.
Nanostructured materials and metal hydrides can be stored in containers of
different shapes and sizes that have to meet some minimum requirements: have
sufficient mechanical strength to withstand pressure variations due to hydrogen
sorption and desorption and allow good flow of hydrogen flow to loading/unloading.

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Constructively, the first such equipment was a cylindrical vessel made of metals
or composite materials. Sorption and desorption of hydrogen are achieved by
means of temperature variations. In principle, hydrogen adsorption takes place at
normal or lower temperatures, while desorption is achieved by heating the mass of
hydrides either through an outer shell or through a heating system disposed within
the container.
The different storage methods are chosen depending on the field of use of
hydrogen as an alternative solution to current fuels: petroleum products, methane
gas or electricity. For large quantities, liquefied hydrogen tanks are used. For small
quantities, especially metal hydrides and nanostructured materials are used.

Key words: experimental storage hydrogen, hydride materials, energy applications,

nanostructured materials, fuel cell.

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A BRIEF REVIEW OF FUEL CELL ELECTRIC VEHICLES' ENERGY MANAGEMENT

STRATEGIES AND THEIR TOPOLOGIES

Ioan-Sorin Sorlei, Adriana Marinoiu

National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Coresponding author: [email protected]

In order to continue using fossil fuels, which means 80% of the world’s energy de-
mand, there are two main problems [Nunez, 2019]. The first problem is the limited
amount of fossil fuel, and sooner or later these sources will be consumed. Estimates of
petroleum companies show that by 2023 there will be a peak in the exploitation of fossil
fuels, petrol and natural gas, and then they will start to decline [Adomaitis, N., 2019].
The second and most important problem is that fossil fuels cause serious environ-
mental problems such as: global warming, acid rain, climate change, pollution, ozone
depletion, etc. Estimates show that the worldwide destruction of the environment costs
about $5 trillion annually [Worland, 2016]. The solution proposed for the two global
problems first appeared in 1970 as the “Hydrogen energy system” [Fuel Cell History—
Fuel Cell Today, 2020]. In the last decade through research and development work in
universities and laboratories of research institutes around the world shows that hydro-
gen is an excellent source of energy with many unique properties. It is the cleanest and
most efficient fuel [Korn, 2019].
The unique property of hydrogen in electrochemical processes is that it can be con-
verted into electricity in the fuel cell system which makes it much more efficient than
the conversion of conventional fuels into mechanical energy [Arshad A., 2019]. This
unique property of hydrogen has led to the manufacture of hydrogen fuel cells and
makes them a very good choice for automotive companies.
The alternative to fossil fuels found by car manufacturers for fuelling vehicles is rep-
resented by other energy sources, such as: battery systems, ultracapacitors or fuel cells.
Electric Vehicles (EVs) and Fuel Cell Electric Vehicles (FCEVs) are the most viable
solutions for reducing Greenhouse Gases (GHG) and other harmful gases for the
environment. Although EVs and FCEVs can reduce emissions to a certain value, they do
not reduce them to absolute zero [Xun, 2018].
Thus, the renewable energy transport infrastructure allows FCEVs to become a
preferable choice, because they attract great attention in the road and rail transport
sector (and not only), without using fossil fuels [Liu et al., 2018]. FCEVs and FCHEVs use a
combination of Fuel Cells (FC), and batteries (B) or/and Ultracapacitors (UC) (Fig. 1) [Das,
2017].
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Figure 1. Configuration of a fuel cell hybrid electric vehicle

The research stages for FCHEVs include the development of vehicles and the
improvement of their efficiency. Be-side the fuel cell system, they use the battery
and/or ultracapacitor pack as a complementary power source to provide the
required power on the DC bus. The topologies of FCEVs are described in detail of
[Liu et al., 2018]. To increase the power density and to meet the demand for load
power, it is necessary to integrate an energy management system. The energy
management strategies: rule-based strategies, optimization-based strategies and
learning-based strategies (Fig. 2) of FCEVs is based on many important control
techniques [Yue, 2019] such as finite state machine management strategies, grey
wolf optimizer, model predictive control, fuzzy logic control, genetic algorithms,
hierarchical prediction as well as other control techniques developed so far for the
energy management system.

Figure 2. The benefits of driving information prediction for energy

management systems optimization
This paper aims to update and introduce the new technologies regarding the
FCEVs topology and Energy Management Strategies (EMS). In this regard, the paper
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will analyse recent research in the field, helping potential researchers and
developers to get a more detailed picture of FCEV technologies.

Key words: fuel cell electric vehicle; DC/DC converter topologies; energy management
strategy; rule-based; global optimization; real-time optimization.

Acknowledgments: This work is supported by Ministry of Research, Innovation,

Digitization from Romania by the National Plan of R & D, Project No. PN 19 11 02 01
and by UEFISCDI, Project PN-III-P2-2.1-PED-2019-2079 (Contract No. 469PED/2020).

References
Adomaitis N., Oil Demand To Peak In Three Years, Says Energy Adviser DNV GL. 2019. Available online:
https://www.reuters.com/article/us-oil-demand-dnv-gl/oil-demand-to-peak-in-three-years-says-
energy-adviser-dnv-gl-idUSKCN1VV2UQ (accessed on 9 January 2020).
Arshad A. et al., Energy and exergy analysis of fuel cells: A review. Thermal Sci. Eng. Progress, 2019, 9, 308–
321.
Das H.S. et al., Fuel cell hybrid electric vehicles: A review on power conditioning units and topologies.
Renew. Sustain. Energy Rev. 2017, 76, 268–291.
Fuel Cell History—Fuel Cell Today. Available online: http://www.fuelcelltoday.com/history#Contents
(accessed on 9 January 2020).
Korn T., Volpert G., The hybrid model of the new hydrogen combustion engine as the most efficient
powertrain of tomorrow. In Der Antrieb von Morgen 2019; Proceedings; Liebl, J., Ed.; Springer
Vieweg: Wiesbaden, Germany, 2019.
Liu S. et al., Hierarchical MPC control scheme for fuel cell hybrid electric vehicles. IFAC-PapersOnLine, 2018,
51.31, 646–652.
Nunez C., Fossil Fuels, Explained. 2019. Available online: https://www.nationalgeographic.com/
environment/energy/reference/fossil-fuels/ (accessed on 9 January 2020).
Worland J., Air Pollution Costs Global Economy Trillions Annually, World Bank Says. 2016. Available online:
https://time.com/4484027/air-pollution-economic-toll-world-bank/ (accessed on 9 January 2020).
Xun Q., Liu Y., Holmberg E., In A Comparative Study of Fuel Cell Electric Vehicles Hybridization with Battery
or Supercapacitor, Proceedings of the 2018 International Symposium on Power Electronics, Electrical
Drives, Automation and Motion (SPEEDAM), Amalfi, Italy, 20–22 June 2018; IEEE: Piscataway, NJ, USA,
2018. p. 389–394.
Yue M. et al., Review on health-conscious energy management strategies for fuel cell hybrid electric
vehicles: Degradation models and strategies. Int. J. Hydrog. Energy, 2019, 44, 6844–6861.

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OPAL RT PLATFORM FOR BLOCKCHAIN REAL TIME DATA ACQUISITION

Maria Simona Raboaca, Ionel Calcan, Mihail Eugen Resteanu,

Alin Nicolae Corbu, George Calianu

National Research and Development Institute for Cryogenic and Isotopic Technologies—ICSI Rm.
Valcea, Uzinei Street, No. 4, P.O. Box 7 Raureni, 240050 Valcea, Romania
Corresponding authors: [email protected]; [email protected];
[email protected]; [email protected]

1. INTRODUCTION

Opal RT Technology [Abu-Rub H. et al., 2014; Cao C. et al., 2017; Edrington C.S.
et al., 2015; Huerta F. et al., 2016] is generally used for the simulation of electrical
networks using the RT Lab Application [Benigni A. et al., 2020; Montoya J. et al.,
2020; Pouria S., Samereh Y., 2014], which proposes unique methods and specific
solutions for real time simulation of the system [Bhandakkar A.A., Mathew L., 2017;
Bian D. et al., 2015; Dinkhah S., 2019], at the level of microseconds (µs). With RT
Lab each period of a voltage (current) can be simulated and analysed in real time
[Gómez-Luna E. et al., 2019]. In this study was acquired real-time data (voltage,
current) in order to save in the blockchain. For this, a series of scripts in Python (the
standard language for scripting in the RT Lab platform) are used, which take the
information in real time or after the completion of the acquisition and place it in
the blockchain to ensure a high level of data trust. The novelty of the paper consists
in the acquisition of real-time data using the combination of Opal RT and Blockchain
technologies.

2. DESCRIPTION OF THE CONCEPT

Figure 1. The concept of Blockchain Real Time Data Acquisition using Opal RT
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3. Results
In figures 2, 3, 4, 5 are presented the results of data acquisition using Opal RT.

Figure 2. Diagram for SM_Master and SC_Console

Figure 3. OP5142 Analog In/Out – Automatically generated by RT-Lab during compilation

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Figure 4. Real time results during acquisition

Figure 5. Graphical representation of real time acquisition

4. Conclusions: The Blockchain technology is suitable as high level trust

database for real time data acquisition and simulations results from Opal RT.
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Future research directions:

 Development of an emulator for different equipments (fuel cell,
electrolyzer);
 Comparativ study for data acquisition between OpalRT and IoT.

References:
Abu-Rub H, Malinowski M, Al-Haddad K. Hardware‐in‐the‐Loop Systems with Power Electronics: A
Powerful Simulation Tool. Power Electronics for Renewable Energy Systems, Transportation
and Industrial Applications, IEEE. 2014; 573-590. 10.1002/9781118755525.ch18a.
Benigni A, Strasser T, De Carne G, Liserre M, Cupelli M, Monti A. Real-Time Simulation-Based Testing
of Modern Energy Systems: A Review and Discussion. IEEE Industrial Electronics Magazine.
2020; 14(2): 28-39, 10.1109/MIE.2019.2957996
Bhandakkar AA, Mathew L. Real-Time-Simulation of IEEE-5-Bus Network on OPAL-RT-OP4510
Simulator. IOP Publishing Ltd, IOP Conference Series: Materials Science and Engineering. 3rd
International Conference on Communication Systems (ICCS-2017). 2017; 331:012028-012040.
10.1088/1757-899X/331/1/012028
Bian D, Kuzlu M, Pipattanasomporn M, Rahman S, Wu Y. Real-time co-simulation platform using
OPAL-RT and OPNET for analyzing smart grid performance. IEEE Power & Energy Society
General Meeting. 2015; 1-5, 10.1109/PESGM.2015.7286238.
Cao C, Wang, L Chen B, Harper J, Bohn T, Dobrzynski D, Hardy K. Real-Time Modeling to Enable
Hardware-in-the-Loop Simulation of Plug-In Electric Vehicle-Grid Interaction. Proceedings of
the ASME 2017 International Design Engineering Technical Conferences and Computers and
Information in Engineering Conference. 13th ASME/IEEE International Conference on
Mechatronic and Embedded Systems and Applications. 2017. 9: V009T07A034.
10.1115/DETC2017-67390.
Dinkhah S. Vehicle to rid (V2G) for reliable Microgrid Operation: Voltage/ Frequency Regulation and
Real Time OPAL – RT Digital Simulation. Texas Tech University, Saleh Dinkhah. 2019; 1-73.
Edrington CS, Steurer M, Langston J, El-Mezyani T, Schoder K. Role of Power Hardware in the Loop in
Modeling and Simulation for Experimentation in Power and Energy Systems. Proceedings of the
IEEE. 2015; 103(12): 2401-2409, 10.1109/JPROC.2015.2460676
Gómez-Luna E, Palacios-Bocanegra L, Candelo-Becerra JE. Real-time Simulation with OPAL-RT
Technologies and Applications for Control and Protection Schemes in Electrical Networks.
Journal of Engineering Science and Technology Review. 2019; 12(3): 136 – 144.
Huerta F, Gruber JK, Prodanovic M, Matatagui P. Power-hardware-in-the-loop test beds: evaluation
tools for grid integration of distributed energy resources. IEEE Industry Applications Magazine.
2016; 22(2): 18-26, 10.1109/MIAS.2015.2459091.
Montoya J, Brandl R, Vishwanath K et. al. Advanced Laboratory Testing Methods Using Real-Time
Simulation and Hardware-in-the-Loop Techniques: A Survey of Smart Grid International
Research Facility Network Activities. Energies. 2020; 13: 3267- 3304, 10.3390/en13123267.
Pouria S, Samereh Y. State of the art: hardware in the loop modeling and simulation with its
applications in design, development and implementation of system and control software.
International Journal of Dynamics and Control. 2014; 3: 470-479. 10.1007/s40435-014-0108-3.

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ENABLING PEER-TO-PEER ELECTRIC VEHICLES CHARGING

Maria Simona Raboaca1,2, Alexandru Creanga3, Adrian Onu3, Catalin Turfin3,

Daniel Furtuna3 , Selian Senocico3 , Andrei Traciu3
1
National Research and Development Institute for Cryogenic and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street, No. 4, P.O. Box 7 Raureni, 240050 Valcea, Romania
2
Faculty of Electrical Engineering and Computer Science, Stefan cel Mare University of Suceava,
Universitătii Street, No.13, 720229 Suceava, Romania
3
Research and Development Department, ASSIST Software, Romania, 720043 Suceava, Romania
Corresponding authors: [email protected]; [email protected],
[email protected], [email protected], [email protected], [email protected]

1. INTRODUCTION

Blockchain has provided the world a new way to decentralise the execution of
code and assuring a new trusted way of making secure and transparent transactions. It
also provides a unique way to develop internal economies without a central authority
[Godwin C. et al., 2020]. The novelty of this paper consists in elaborating a software
architecture [Meheden M. et al., 2021] which enables charging station owners
(organisations and individuals) to be participate in charging stations networks and earn
tokens. The concept of the “ENABLING P2P EV CHARGING” which is currently being
implemented in the Smart EVC project is presented in figure 1.

2. THE CONCEPT OF THE P2P EV CHARGING

Figure 1. Enabling P2P EV Charging

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3. RESULTS

The following flow was followed to test the performance from the Smart EVC
Backend APIs (.NET Core) to the Blockchain module APIs (Ruby) to the Kovan
Network where our ERC20 test token was deployed.

Figure 2. SmartEVC REST API for ERC20 token deposits

Figure 3. Duration of a request from the web interface (Swagger) to query the Ruby APIs and the
Kovan Network (Smart EVC ERC20 token)

Figure 4. Web3 Kovan Network transaction result

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Figure 5. Sample screen of Smart EVC mobile application which aims to

interact with the Blockchain ERC20 token

4. CONCLUSIONS

The current Smart EVC flow – sending a transaction using Swagger from the
Smart EVC Backend service to the Smart EVC Blockchain service (which interacts
with Kovan Network (Ethereum)) is validated from functional perspective and from
architectural perspective. Performance optimisations need to be made on the cloud
side (Azure) in order to optimise the TTFB (Time to first byte).
Future research directions will be developed during this innovative concept
“ENABLING P2P EV CHARGING” as:
 Performance and load testing on the live Ethereum network
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 Market mechanisms and evolution in EV charging stations networks based

on Blockchain.
 Agent based modelling simulations to study the potential of extending P2P
EV charging stations networks.

Key words: Blockchain, ERC20, P2P, EV charging stations

Acknolegement: This research was funded by a grant of the Romanian Ministry

of Education and Research, CCCDI—UEFISCDI, project number 40PTE of 01.06.2020,
within PNCDI III

References:
Godwin C. Okwuibe, Zeguang Li, Thomas Brenner, Ole Langniss, A Blockchain Based Electric Vehicle
Smart Charging System with Flexibility ⁎⁎ This project is sponsored by Oli Systems GmbH,
Stuttgart., IFAC-PapersOnLine, Volume 53, Issue 2, 2020, Pages 13557-13561, ISSN: 2405-8963,
https://doi.org/10.1016/j.ifacol.2020.12.800.
Meheden M., Musat A., Traciu A., Viziteu A., Onu A., Filote C., Răboacă M.S., Design Patterns and Electric
Vehicle Charging Software. Appl. Sci., 2021, 11, 140. https://doi.org/10.3390/app11010140

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OPAL RT TECHNOLOGY AN REAL-TIME TESTING TECHNIQUES

Maria Simona Raboaca1,2, Nicu Bizon1,3,4, Oana Vasilica Grosu2

1
National Research and Development Institute for Cryogenic and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street, No. 4, P.O. Box 7 Raureni, 240050 Valcea, Romania;
2
Ștefan cel Mare University of Suceava, Romania
3
University of Pitesti, Faculty of Electronics, Communications and Computers, 110040
Pitesti, Romania
4
University Politehnica of Bucharest, 313 Splaiul Independentei, 060042, Bucharest, Romania;
Corresponding authors: [email protected]; [email protected]; [email protected]

1. INTRODUCTION

Due to its fast reliability and performance, OPAL RT simulators are viable and
technically available. The OPAL RT simulator accommodates the programs: eFPGAsim,
ePHASORsim, eMEGAsim, HYPERSIM. EMEGAsim is a more scalable and flexible real-
time digital simulation program that includes RTE Event software, ARTEMIS and RT-
LAB. This paper uses the OP5600 to acquire real-time data using RT-Lab.
The execution process (Fig. 1) in RT-Lab and OPAL-RT is presented in Figure 1.
As RT-lab, it works simultaneously with OPAL-RT interfaces, the communications in
both systems are bidirectional.

Figure 1. The complete execution process RT-Lab

The data is processed by OP5660 and sent to MATLAB/Simulink for controller

design. Conversely, the real-time generated controller requires pulses and sends
the signal to the physical inverters and converters via the OPAL-RT interfaces.
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2. HIL (Hardware-in-the-Loop)

Hardware-in-the-loop (HIL) testing leverages real-time simulation to connect

real equipment and systems, through sensors and actuators, and "tricks" them into
believing they are connected to real equipment.

Figure 2. Devices that can be tested using HIL

3. POWER HARDWARE-IN-THE-LOOP (PHIL)

Hardware-in-the-Loop (HIL) extension, Power Hardware-in-the-Loop (PHIL)

involves creating a virtual power interface between the digital simulation and the
devices being tested. Usually, the power interface involves power amplifiers
(voltage and/or current), which must be carefully selected depending on the
application. Figure 3 presents the devices that can be tested using PHIL.

Figure 3. Devices that can be tested using PHIL

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4. CONCLUSIONS

In the initial MIL stage, the model is run in the native development
environment, such as Simulink in this process. The connection between the
components of the subsystem takes the form of a signal bus, regardless of how the
signals can be physically implemented and the model runs during the processor,
often much faster than in real time and not necessarily at a fixed time for each
stage. In the SIL stage, the nature of the connections between the components of
the subsystem remains the same as in MIL, but the model is now compiled in C
code and run at a fixed time step. In the HIL stage, the model is separated into two
distinct subsections; a plant model and control. The installation model is compiled
and run on a real-time simulation platform, while the controller is compiled and
programmed for the target hardware to be used in the implementation.
By defining the breakdown of the model in terms of functional and interface
layers, ensuring a standard of communication between the two layers, the layers
can be successfully decoupled, while maintaining a high level of cohesion. In this
way, a model can go through the different stages of development of MIL, SIL and
HIL without having to maintain several variants of the complete model.

References:
Bermudez M., Gomozov O., Kestelyn X., Barrero F., Nguyen N.K., Semail E., Model predictive optimal
control considering current and voltage limitations: Real-time validation using OPAL-RT
technologies and five-phase permanent magnet synchronous machines. Mathematics and
Computers in Simulation. 2019; 158: 148-161, 10.1016/j.matcom.2018.07.005.
Bian D., Kuzlu M., Pipattanasomporn M., Rahman S., Wu Y., Real-time co-simulation platform using
OPAL-RT and OPNET for analyzing smart grid performance. IEEE Power & Energy Society
General Meeting. 2015; 1-5, 10.1109/PESGM.2015.7286238.
Bizon N., Nonlinear control of fuel cell hybrid power sources: Part II—Current control. Appl. Energy.
2011; 88(7): 2574–2591. 10.1016/j.apenergy.2011.01.044.
Delavari A., Brunelle P., Kamwa I., Real-time Closed-loop PQ Control of NPC Multi-level Converter
Using OPAL-RT and Speedgoat Simulators. IEEE Electrical Power and Energy Conference (EPEC).
2018; 1-5, 10.1109/EPEC.2018.8598323.
Felseghi R.A., Carcadea E., Raboaca M.S., Trufin C.N., Filote C., Hydrogen Fuel Cell Technology for the
Sustainable Future of Stationary Applications. Energies. 2019; 12: 4593-4620.
10.3390/en12234593.
Montoya J., Brandl R., Vishwanath K. et al., Advanced Laboratory Testing Methods Using Real-Time
Simulation and Hardware-in-the-Loop Techniques: A Survey of Smart Grid International
Research Facility Network Activities. Energies. 2020; 13: 3267- 3304, 10.3390/en13123267.
Noureen S.S., Roy V., Bayne S.B., An overall study of a real-time simulator and application of RT-LAB
using MATLAB simpowersystems. IEEE Green Energy and Smart Systems Conference (IGESSC).
2017; 1-5, 10.1109/IGESC.2017.8283453.
Song J., Hur K., Lee J., Lee H., Lee J., Jung S., Shin J., Kim H., Hardware-in-the-Loop Simulation Using
Real-Time Hybrid-Simulator for Dynamic Performance Test of Power Electronics Equipment in
Large Power System. Energies. 2020; 13: 3955. 10.3390/en13153955.
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Song J., Oh S., Lee J., Shin J., Jang G., Application of the First Replica Controller in Korean Power
Systems. Energies. 2020; 13: 3343. 10.3390/en13133343.
Summers A., Johnson J., Darbali-Zamora R., Hansen C., Anandan J., Showalter C.A., Comparison of
DER Voltage Regulation Technologies Using Real-Time Simulations. Energies. 2020; 13: 3562.
10.3390/en13143562.
Syed M.H., Guillo-Sansano E., Mehrizi-Sani A., Burt G.M., Facilitating the Transition to an Inverter
Dominated Power System: Experimental Evaluation of a Non-Intrusive Add-On Predictive
Controller. Energies. 2020; 13: 4237. 10.3390/en13164237.
Vogel S., Nguyen H.T., Stevic M., Jensen T.V., Heussen K., Rajkumar V.S., Monti A., Distributed Power
Hardware-in-the-Loop Testing Using a Grid-Forming Converter as Power Interface. Energies.
2020; 13: 3770. 10.3390/en13153770.

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DYNAMIC DATASET GENERATION OF EV CHARGING NETWORKS FOR

REINFORCEMENT LEARNING ALGORITHMS

Maria Simona Raboaca1,2, Andrei Robu3, Andrei Viziteu3, Daniel Furtuna3 , Stelian
Senocico 3 Andrei Traciu3
1
National Research and Development Institute for Cryogenic and Isotopic Technologies - ICSI Rm.
Valcea,Uzinei Street, No. 4, P.O. Box 7 Raureni, 240050 Valcea, Romania
2
Ștefan cel Mare University of Suceava, Romania
3
ASSIST Software, Tipografiei, 1 Suceva, Romania
Corresponding author: [email protected], [email protected], [email protected],
[email protected], [email protected], [email protected]

1. INTRODUCTION

Reinforcement learning (RL) is the method of machine learning training

based on rewarding desired or undesired behaviours [Wang, et al., 2018]. In Smart
EVC project we are elaborating a RL algoritm to optimise and help EV drivers to take
charging decisions based on path costs when traveling using a long route and an EV
[Meheden et al., 2021].

2. The novelty of this paper consists in addressing one big challenge, the lack
of real-world data, which is needed for RL algorithms and hence our plan to build a
dataset generator, or a long route simulator, which simulates decisions, EV drivers,
EVs, charging station networks and long routes behaviour.

3. The concept of the “RL” which is currently being implemented in the Smart
EVC project is presented in figure 1.

Figure 1. RL(DQN) model and high-level architecture in Smart EVC

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4. RESULTS

Running the simulator will provide accurate datasets to be used in training the
DQN model.

Figure 2. Setup and input data for the simulator

Figure 3. Sample simulation with 10+ cars and path cost

Figure 4. Sample Smart EVC mobile application which will make use of the RL implementation
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5. CONCLUSIONS

The generated datasets from the simulator provide a good way to start training
the RL algorithms using raw and labelled data. Future research directions will be
developed during this innovative concept “Dynamic datasets generation for RL
models” as:
 Adding more cities
 Comparing generated datasets with real-world datasets
 Testing the RL model in the laboratory (TRL5)

Key words: Reinforcement learning, DQN, EV charging stations, EV long trip

planning, ML

Funding: This research was funded by a grant of the Romanian Ministry of

Education and Research, CCCDI—UEFISCDI, project number 40PTE of 01.06.2020,
within PNCDI III.

References:
Meheden M., Musat A., Traciu A., Viziteu A., Onu A., Filote C., Răboacă M.S., Design Patterns and Electric
Vehicle Charging Software. Appl. Sci. 2021, 11, 140. https://doi.org/10.3390/app11010140
S. Wang, S. Bi and Y. A. Zhang, A Reinforcement Learning Approach for EV Charging Station Dynamic
Pricing and Scheduling Control, 2018 IEEE Power & Energy Society General Meeting (PESGM),
2018, pp. 1-5, doi: 10.1109/PESGM.2018.8586075.

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LITHIUM BATTERY TECHNOLOGIES

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THERMAL ENERGY STORAGE NANOMATERIALS BASED ON

MESOPOROUS SILICA MATRICES

Raul-Augustin Mitran

“Ilie Murgulescu” Institute of Physical Chemistry, Romanian Academy, 202 Splaiul Indepedentei,
Bucharest, 060021, Romania
Coresponding author: [email protected], [email protected]

The efficient storage and utilization of heat is a key process for a number of
different technologies and applications. Some examples include food preservation,
zero-energy buildings, thermal protection of batteries, electronics and personnel, solar
and waste heat storage and utilization etc. Heat storage can be achieved through three
main strategies: sensible, latent and chemical and their combinations. Of these, latent
heat storage brings several advantages, such as reversibility, relatively constant
operating temperature, high energy density (100-400 J/g), low cost and good lifetimes.
Most often, the liquid-solid phase transition is used for storage, while materials with
high heat of fusion are denoted “phase change materials” (PCMs). Nonetheless, pure
PCMs have some drawbacks arising from the change in molar volume upon phase
transition, which can lead to leakage, decreased thermal conductivity and loss of heat
storage over time. These drawbacks can be alleviated by creating shape-stabilized or
form-stable PCMs, composite materials which retain their macroscopic shape even
when the heat storage component is in liquid state. Shape-stabilized PCMs can be
obtained by either encapsulation with an inert shell [Zhang et al,. 2014] or by
impregnation into a high porosity matrix [Mitran et al., 2018].
Mesoporous silica nanomaterials (MSN) are a type of high-porosity matrices,
possessing large pore volumes (~1 cm3/g), high surface area (~1000 m2/g), easily
obtained and monodisperse pores between 2-50 nm [Kresge et al., 1992]. MSN also
exhibit high chemical and thermal stability to temperatures of at least 600°C, as
well a non-toxic nature and an easily adjustable chemical synthesis leading to large
variety of textural properties. Typically, the pore size, arrangement and total volume
can be directly controlled by the synthesis conditions. The surface properties of the
silica pore walls can also be modified by grafting different organic groups or through
the addition of ad-atoms into the silica framework, leading to a large variety of
mesoporous silica matrices.
The recent advancements made in using mesoporous silica for obtaining shape-
stabilized phase change materials are presented herein. Depending on the temperature
range, two types of nanocomposites were investigated. First, materials containing

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organic PCMs were obtained for applications at or above room temperature (30-70°C).
Fatty acids were investigated as the thermal storage phase. Mesoporous silica materials
with pore diameters ranging from 2 to 30 nm were used. It was found that the organic
molecules can be distributed into two crystalline phases, corresponding to the
interparticle space and silica mesopores (Fig. 1). The interparticle phase has similar
properties to bulk, while the phase nanoconfined into the mesopores has reduced
melting points and melting-freezing temperature hysteresis (Fig. 1). A non-melting fatty
acid layer also exists at the interface between the silica pore walls and melting phase.
This layer leads to a significant reduction of heat storage in the case of mesoporous silica
with smaller pore diameters (2-8 nm). Reducing the volume fraction occupied by the
non-melting layer is an important goal in order to increase the heat storage capacity of
these materials. Based on the experimental results, a theoretical model of the non-
melting layer volume was constructed [Mitran et al., 2015]. It was found that MSN with
large pore diameters are the best matrices. Next, different nanocomposite synthesis
methods were investigated in terms of their influence on the resulting thermal storage
properties and PCM phase distribution. Furthermore, organic group functionalization
was shown to significantly affect the non-melting layer distribution through
supermolecular bonding between the grafted groups and nanoconfined PCM molecules
[Matei et al., 2019].

Figure 1. Schematic representation of MSN-based PCMs and nanoconfinement

temperature depression

The second area of mesoporous silica based thermal storage is at high

temperatures, above 200°C. The high temperature nanocomposites can be used in
solar thermal energy storage and industrial waste heat reutilization applications.
However, little research has been performed in this area so far. Our research has
focused on checking the feasibility of obtaining high temperature MSN-based
materials. Various molten salts were employed as the heat storage phase, having

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diverse operating temperatures, in the 220-530°C range. The specific chemical

composition necessary for obtaining shape-stabilized thermal storage materials was
studied, while the influence of MSN porosity on the composites thermal properties
was investigated [Mitran et al., 2019].
Significant progress has been made towards understanding the aspects
affecting the total storage capacity and the factors which govern the synthesis of
mesoporous silica containing phase change materials. Nonetheless, this is a
relatively new field of research. The composite materials exhibit great versatility in
terms of both matrix and storage phase, and only a fraction of this chemical space
has been explored so far.

Key words: thermal energy storage, mesoporous silica, phase change

materials, nanoconfinement.

Acknowledgments: This research was funded by Romanian Executive Agency

for Higher Education Research Development and Innovation Funding, grant number
PN-III-P1-1.1-TE-2019-1456, no. 166/2020.

References
Kresge C.T., Leonowicz M.E., Roth W.J., Vartuli J.C., Beck J.S. Ordered mesoporous molecular sieves
synthesized by a liquid-crystal template mechanism. Nature. 1992;359(6397):710-2.
Matei C., Buhǎlţeanu L., Berger D., Mitran R.A. Functionalized mesoporous silica as matrix for shape-
stabilized phase change materials. International Journal of Heat and Mass Transfer.
2019;144:118699.
Mitran R.A, Berger D., Matei C.. Phase Change Materials Based on Mesoporous Silica. Current
Organic Chemistry. 2018;22(27):2644-63.
Mitran R.A., Berger D., Munteanu C., Matei C. Evaluation of Different Mesoporous Silica Supports for
Energy Storage in Shape-Stabilized Phase Change Materials with Dual Thermal Responses. The
Journal of Physical Chemistry C. 2015;119(27):15177-84.
Mitran R.A., Petrescu S., Şomǎcescu S., Mocioiu O.C., Buhǎlţeanu L., Berger D. Matei C.
Nanocomposite phase change materials based on NaCl–CaCl2 and mesoporous silica. J Therm
Anal Calorim. 2019;138(4):2555-63.
Zhang G., Li J., Chen Y., Xiang H., Ma B., Xu Z., Ma X. Encapsulation of copper-based phase change
materials for high temperature thermal energy storage. Solar Energy Materials and Solar Cells.
2014;128:131-7.

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STUDY ON THE WATER-SOLUBLE BINDER FOR SILICON-BASED ANODE IN

LITHIUM-ION BATTERIES

Aishui Yu

Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials,
Institute of New Energy, Collaborative Innovation Center of Chemistry for Energy Materials, Fudan
University, Shanghai, 200438, China
Corresponding author: [email protected]

Compared with the traditional graphite anode (372 mAh g-1), silicon possesses
a higher theoretical specific capacity (4200mAh g-1), which is highlighted as one of
the most promising next-generation anode materials. However, the significant
volume change (~400%) of silicon during alloying and dealloying process leads to
severe particle pulverization, unstable solid-electrolyte interphase (SEI) formation,
electrode delamination and loss of electrical contact in the electrode level,
rendering rapid capacity fading and limited cycle life, which greatly hinder its
application in lithium-ion batteries. Binders have been proven to be one of the
effective ways to solve the intractable problems of silicon-based materials. Binder is
a key material to bind the active material and the conductive additive together, and
glue them to the current collector. Herein, we have developed several novel water-
soluble binders to alleviate the dramatic volume expansion, reduce the severe
capacity loss, and effectively improve the electrochemical performance of silicon-
based materials.
Two kinds of neutral natural polysaccharides (gellan gum and guar gum) are
modified through carboxymethylation to improve its water solubility, dispersibility
as well as electronegativity. The carboxylate (-COO-) in the modified polysaccharide
structure can promote well dispersion of silicon particles and conductive agent
through space charge repulsion effect, and can form strong hydrogen bonds with
silicon particles, greatly reducing side reactions caused by the direct contact
between silicon particles and electrolyte. Furthermore, both modified natural
polysaccharides possess rigid skeleton composed of six-membered pyran-rings,
which can effectively inhibit the volume expansion of Si materials and improve the
cycle stability of silicon electrodes.

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Figure 1. Carboxymethyl guar gum for Si-based anode.

We also use four-arm polyethylene glycol (4 arm-PEG) to chemically crosslink

natural corn cellulose gum (CFG), and prepare a high-performance three-dimensional
polysaccharide gel binder for silicon anode. The multi-branched structure of natural
corn cellulose gum and abundant polar functional groups such as carboxyl and hydroxyl
can yield robust chemical bonds with Si particles, exhibiting high mechanical properties
and strong bonding strength, which can effectively restrict the volume expansion of Si
particles during charge and discharge cycles.

Figure 2. CFG hydrogel binder for Si materials

In addition, we design a new type of conductive self-healing hydrogel (ESVCA)

binder with three-dimensional conductive network, good tensile properties and fast
self-healing ability, which can form compact coating layer on the surface of silicon
particles through in-situ polymerization. The three-dimensional self-healing
network structure can effectively suppress the volume change of silicon particles
during the alloying and dealloying process, and maintain the mechanical integrity of
Si-based electrode. The continuous 3D electron transport path ensures high
conductivity and good electrical contact between the active silicon particles,
thereby realizing appealing electrochemical performance for Si-based anodes in
long-term cycles.

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Figure 3. Conductive self-healing hydrogel (ESVCA) binder.

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Li-ION BATTERY SIMULATION SOLUTION – WITH ANSYS SOFTWARE

Răzvan Mahu

TENSOR SRL
Coresponding author: [email protected]

Battery simulation involves multi-physics, multi-scale, and the couple of them.

This makes battery one of the most interesting and challenging simulations.
Concerning physics, electrochemistry is the most fundamental in battery.
Simulation models based on electrochemistry are also called physics-based models.
The length scale for 3d electrochemistry in a battery application is approximate
10e-4 m, which is extremely small compared with the size of just a battery cell. For
Li-on batteries, Newman P2D model could be used to model the electrochemistry
between electrodes, which is still short of even a battery cell. Due to the intensive
computational resources required for electrochemistry calculation, various reduced
order model (ROM) approaches are available. With the help of model reduction, we
could study the impact of different particle shapes on the battery electrochemical
performance.
Let’s move onto electrical. Battery is primarily an electrical device. The most
commonly used model for predicting battery electrical performance is the battery
equivalent circuit model, aka, ECM. ECM models are behavior models, requiring the
so-called HPPC data for model parameter identification. For higher frequency
applications, ECM parameters are determined from electrochemical impedance
spectroscopy (EIS) data. Due to its fast performance, ECM is often used to simulate
a battery module or even a pack with as many as 500 cells. The capability to be able
to couple ECMs with 3rd part tools is often viewed as a welcome feature. Such
becomes quite possible through FMI and FMU.
Last but not least is the thermal performance of a battery. Even though Li-on
batteries have relatively high thermal efficiency (>85%), its sensitivity to temperature
makes it critical to manage temperature correctly. For Li-on batteries, it is often
required to have in-cell temperature variation of less than 4 degrees, and cell to cell
variation less than 6 to 8 degrees. Battery thermal management simulation using CFD is
a mature application of CHT. But system integration of battery simulation demands
faster and compact models. Thermal network models and reduced order models
(ROMs) play a key role here.
While simulating battery single physics is already challenging, we have to
consider the coupling of different physics. Electrochemistry is the fundamental
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physics behind batteries. If electrochemistry works as we desired, there is no need

to couple different physics since electrochemistry itself includes all physics. But as
mentioned, due to small length scale associated with electrochemistry, it is a
practical simulation tool only up to electrode level at most. Therefore, coupling of
different physics becomes necessary for any application that is beyond just a pair of
electrodes. Electrochemistry models could be used to create the performance data,
for example the HPPC data, for battery ECM model. This is very valuable when the
battery prototype is not available and therefore HPPC test is not possible.
Electrochemistry could also be used as a sub-model for heat generation for a
thermal model, which in turn could provide the electrochemistry model the
required temperature to update the material and transport properties. The huge
discrepancy in the length scale for these two models demands a very ingenious way
of coupling. When battery ECM is available, one could also couple the ECM with a
thermal model. Two-way coupling is typically required. For the electric/thermal
coupling, an electric engineering typically is more interested in the electrical
aspects and a thermal engineer, on the other hand, is more interested in the
thermal aspects. Such requests demand the simulation tools to be flexible enough
to focus on either electric or thermal even though the coupling is the same in both.
As if this is not enough, there are important niche applications that do not fit
into any of the schemes. Battery aging is one of such. One could either model aging
under electrochemistry as additional physics or sub-model. Another approach is to
model aging based on test data. They are both useful with different focus in mind.
Battery thermal abuse or run-away is another example. Thermal abuse could also
be modeled under electrochemistry. But due to its complexity, a more practical
approach is to derive global reaction mechanisms for the battery material.

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DOPED VANADIUM OXIDE FILMS BY PHYSICAL VAPOUR DEPOSITION METHOD

FOR ENERGY STORAGE APPLICATION

T. Tite1, H. Ghannam1,2, M. Buga3, C. Ungureanu3, A. A. Zaulet3, I. Stavarache1, G.E.

Stan1, E. Matei1, C. C. Negrila1, A.C. Galca1, M-C. Bartha1, M. Baibarac1
1
National Institute of Materials Physics, RO-077125 Magurele, Romania
²Abdelmalek Essaadi University, FSTT , Thin Films and Nanomaterials Lab., 90000 Tangier, Morocco
3
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Coresponding authors: [email protected]; [email protected]

Advanced electrochemical energy storage is internationally considered as one of

the disruptive technologies of the future [S. Lobe et al., 2021]. On the main trends that
drive energy storage development in our daily life is the rise of electrical devices,
Internet of Things and battery-powered medical devices and implants. Lithium-ion
batteries have revolutionized our society, since its first commercialization in 1991 by
Sony. Lithium-ion battery (LIBs) possess higher energy density compared to other
rechargeable battery systems which made them key technology in advancing portable
electronic devices and, more recently, electric vehicles and renewable energy storage
[Grey C. P. and Hall D. S., 2020; Slattery M. et al.2021]. Their impact on our society is so
notable that its ground-breaking development, in particular by John B. Goodenough,
Stanley Whittingham, and Akira Yoshino have been acknowledged by the Nobel Prize in
Chemistry in 2019.
Despite its great success and mature custom manufacturing market, in regards
to our greed towards energy consumption, LIBs still need improvements in energy
power density, speed charge capabilities, cost, and cyclic durability. In this context,
in recent years, extensive efforts have been devoted to either improve LIBs by
replacing commercial anodes or cathodes (e.g. LiCoO2, LiNiO2, LiMn2O4), improve
electrolyte properties or designing new batteries without Lithium (Li) responding to
the concern raised by the limited Li and Cobalt resources [A. El Kharbachi et al.
2020; Z. Qi and H. Wang, 2020]. Among new materials investigated in the literature,
carbonaceous materials (e.g. graphene) and layered metal oxides (LMO) are
outstanding materials due to their unique physico-chemistry properties and their
promises in both fundamental research and industrial field [Xu X. et al., 2020; Wang
Q. et al., 2018; Olabi A. G. et al., 2021].
Recently Vanadium-based nanomaterials LMO, such as vanadium oxides have
attracted considerable attention as promising family for new advanced energy
storage devices owing to their high specific capacities, wide availability, and low
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cost [Xu X. et al., 2020]. Vanadium oxides (VOx) exist in various compositions (e.g.
V2O5, VO2, V2O3 and VO) with respectively different oxidation states (+5, +4, +3 and
+2) [Li Z. et al., 2016]. V2O5 is in particular the most stable phase of the series. VO2 exist
as different polymorphs [e.g. VO2(M) and VO2(B)]. It is believed that V2O5 and VO2(B) are
the best candidates for future batteries. To be convincible, V2O5 and VO2(B) can attain a
theoretical capacity of 294 mAhg-1 [Li Z. et al., 2016] and 324 mAhg-1[10] which is higher
than known cathode materials such as LiCoO2 (140 mAhg-1), LiFePO4 (170 mAhg-1), and
LiMn2O4 (148 mAhg-1) [9]. However, the low diffusion coefficient of Li+ ions (10-14–10-12
cm2s-1) and the low electrical conductivity (10-7–10-6 S cm-1) of VOx hinder its rate
capability for viable applications [Li Z. et al., 2016]. Extensive strategies have been
developed to improve their electrochemical performances through various structural,
compositional and surface engineering, as well as cation doping [Li Z. et al., 2016] and
composites (e.g. with graphene) [Nandi D. et al., 2020; Liu Q. et al., 2015]. Among these
methods, cation doping has been an effective approach to improve lithium ion
intercalation, mainly because the introduction of exogenous ions into VOx lattice may
tune the ion occupation and the electronic structure of the host material.
On the other hands, vanadium oxides electrodes have been prepared by
various approaches, including sol-gel, hydrothermal synthesis [Xu X. et al., 2020; Li Z.
et al., 2016]. Aside those techniques, although not systematically applied, the
development of thin films VOx electrodes by physical vapour deposition (PVD) could
be attractive techniques for future advanced ESDs. Indeed, PVD instrumentations
such as thermal evaporation, magnetron sputtering (MS), pulsed laser deposition
(PLD) are among the most promising techniques for the efficient co-integration of
micro smart electronics devices (e.g. medical implants, labs-on-chip, credit cards)
and micro energy sources [Uzakbaiuly B. et al., 2021]. Others advantages include
high adherence of films (which could guarantee long-term durability of
electrochemical electrode); purity; easy engineering of the film properties by tuning
the deposition parameters; control to atomic level the film thickness in contrast to
spin-coating or dip-coating; good reproducibility of source material stoichiometry.
Furthermore, thin film cathode or anode materials can provide satisfying
electrochemical performance without binder and conductive additives through either
nanostructure or nanocomposite modification techniques [Z. Qi and H. Wang, 2020].
The use of thin-film technology may offer others various advantages such as the
reduction of the charge-transfer resistance of the electrolyte–electrode interface [C.M.
Julien and A. Mauger, 2019]. In addition, generally, electrochemical electrodes are
prepared by a conventional coating method following by a drying process for several
hours. By introducing PVD coating of the conductive current collector, we shall be
suppressing this time-consuming step. However, the fabrication of VOx cathodes by
PVD for energy storage application is still scarcely reported.
In this work, we report the synthesis of undoped and doped vanadium oxide
polymorphs by PVD (e.g. PLD and MS) on graphene and aluminium foils. The
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physico-chemical properties of the thin films were multi-parametrically surveyed by

SEM, EDXS, Raman, GIXRD and spectroscopic ellipsometry. The characterization
indicates we have obtained after rapid thermal annealing in oxygen or in neutral
atmosphere, V2O5 or VO2(B) respectively, with good crystallinity (Fig. 1) and
different morphology (Fig. 2). The electrochemical properties have been evaluated
by cyclic voltammetry, and impedance spectroscopy and galvanostatic discharge-
charge cycling in various electrolytes. Compared with the bare electrode, VO x
electrodes on graphene exhibited enhanced electrochemical properties (Figure3).
We show the tailoring of the electrodes properties by doping or its synergetic
integration with other additives could represent an excellent strategy to boost
further their performances. This work provides alternative approach to prepare thin
films based on vanadium oxides directly on the metallic current collector for
application in electrochemical energy storage.

Figure 1. Raman spectra of vanadium oxides thin films obtained after thermal annealing

Figure 2. SEM images obtained on undoped and doped vanadium oxides thin films.

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30
Graphene/Al foil
5% wt SnO2-VOx
20 5% wt SnO2-VOx/Graphene/Al foil

Current (mA) per area

10

-10

-20 Electrolyte : PBS - PH 7

0.0 0.2 0.4 0.6 0.8

E V(Ag/AgCl)

Figure 3. CV curves of electrodes obtained in PBS.

Key words: Physical vapour deposition, vanadium oxide, Carbon, Battery, Doping.

Acknowledgments: The authors thank CNCS-UEFISCDI for the financial support

in the framework of grants PN-III-P2-2.1-PED-2019-4519.

References
A. El Kharbachi, O. Zavorotynska, M. Latroche, F. Cuevas, V. Yartys, and M. Fichtner, J. Alloys Compd.
817, 153261 (2020).
C.P. Grey and D.S. Hall, Nat. Commun. 2020 111 11, 1 (2020).
C.M. Julien and A. Mauger, Coatings 9, 386 (2019).
Z. Li, C. Zhang, C. Liu, H. Fu, X. Nan, K. Wang, X. Li, W. Ma, X. Lu, and G. Cao, Electrochim. Acta
(2016).
Q. Liu, Z.-F. Li, Y. Liu, H. Zhang, Y. Ren, C.-J. Sun, W. Lu, Y. Zhou, L. Stanciu, E.A. Stach, and J. Xie, Nat.
Commun. 2015 61 6, 1 (2015).
S. Lobe, A. Bauer, S. Uhlenbruck, and D. Fattakhova-Rohlfing, Adv. Sci. 8, 2002044 (2021).
D. Nandi, V.B. Mohan, A.K. Bhowmick, and D. Bhattacharyya, J. Mater. Sci. 2020 5515 55, 6375
(2020).
A.G. Olabi, M.A. Abdelkareem, T. Wilberforce, and E.T. Sayed, Renew. Sustain. Energy Rev. 135,
110026 (2021).
Z. Qi and H. Wang, Research 2020, 1 (2020).
M. Slattery, J. Dunn, and A. Kendall, Resour. Conserv. Recycl. 174, 105755 (2021).
B. Uzakbaiuly, A. Mukanova, Y. Zhang, and Z. Bakenov, Front. Energy Res. 0, 213 (2021).
Q. Wang, J. Xu, W. Zhang, M. Mao, Z. Wei, L. Wang, C. Cui, Y. Zhu, and J. Ma, J. Mater. Chem. A 6,
8815 (2018).
X. Xu, F. Xiong, J. Meng, X. Wang, C. Niu, Q. An, and L. Mai, Adv. Funct. Mater. 30, 1904398 (2020).
Q. Yang, Z. Zou, X. Wu, S. Li, and Y. Zhang, Batter. 2019, Vol. 5, Page 46 5, 46 (2019).

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MYTHS AND REALITY IN USING AND MISUSING LITHIUM

BASED RECHARGEABLE BATTERIES

Dănuţ-Ionel Văireanu1, Florin-Mihai Benga1, Ioana-Alina Ciobotaru1,

Adnana Alina Spînu-Zăuleţ2
1
University POLITEHNICA of Bucharest, Faculty of Applied Chemistry and Materials Science, 1-7 Polizu
Street, 011061, Bucharest, Romania
2
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania

With the current increased demand for lithium rechargeable batteries,

although the process of manufacturing them became somehow well established,
the huge variety of applications fields led inevitably to very different operation
circumstances, especially in the discharge stage. This determined, besides the
sound scientifically manufacturers recommendations, the appearance of empirical
so called "useful practical advices", more or less true, have direct positive or
negative consequences on batteries performances and lifespan. This presentation
attempts to present some of these myths appeared in conjunction with the normal
use or misuse of these rechargeable batteries.

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HYBRID POWER-ENERGY ELECTRODES FOR NEXT GENERATION LITHIUM-ION

BATTERIES – HYDRA

Mihaela Buga1, Adnana Spînu-Zăuleţ1, Cosmin Ungureanu1, Radu Andrei1,

Alin Chiţu1, Mihai Varlam1, Simon Clark2
1
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
2
SINTEF Industry, Sustainable Energy Technology, Strindvegen 4, 7034 Trondheim, Norway
Corresponding author: [email protected]

Batteries are considered by the European Green Deal a key enabling technology
for the competitiveness of many sectors, as reported in all seminal documents and
roadmaps of the European Battery Alliance EBA250, the Batteries Europe Partnership
Association BEPA, Batteries2030+, and the Batteries Europe ETIP. The main goal is to
make the upcoming EU battery industry competitive, to boost a sustainable and circular
EU battery value chain. Over the past years the battery industry has been building
partnerships along the value chain to exchange ideas on how create sustainable, durable
and recyclable batteries to respond to a growing demand in EVs, electronics and energy
storage.
Thus, Li-ion battery technology is at the core of the imminent massive vehicle
electrification. The forecasted growth rate of electrified vehicles (xEV) will be the main
driver for the rapid increase in the Li-ion battery market. Sustainable battery cell
production, including reduction of critical raw materials content, use of green chemistries
and environmentally friendly manufacturing
processes are of key importance in building a
competitive Li-ion battery industry which results in
a minimum of carbon emissions both in production
and use. For Europe, being far behind the
technological battery developments of Asia, these
points which require significant changes to state-of-
the-art cell production, offer a golden opportunity
of introducing new competitive approaches to get a
more significant share of the Li-ion battery market
cells. Today, a state-of-the-art Li-ion battery cell can
provide 640 Wh/L, not yet close to its fundamental
limits illustrated by its volumetric and gravimetric
energy density. An increasing gap exists between
the energy demands and what current rechargeable battery technology can supply, and
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EU already targets improving cell-level energy densities to at least 750 Wh/L 4. In order
to bridge this gap a change in the overall battery chemistry is required, including the
electrodes (anode and cathode) and the electrolyte (Steen et al., 2017).
The core technological approach of the HYDRA project consists of using hybrid
electrode technology to overcome the fundamental limits of current Li-ion battery
technology in terms of energy, power, safety and cost to enter the age of
generation 3b of Li ion batteries.
HYDRA, taking its name from the mythological beast, will use a multi-headed
integrative approach: In addition to novel material development and scale-up of
components and battery cells manufacturing, assisted by modelling, HYDRA will
build a synergy with strong investments by the project’s industrial partners and
foster reaching and keeping a significant market share for Europe.
The necessary competitiveness will be obtained by hybridizing high energy with high
power materials. These materials will be implemented at the cell/electrode level, via
sustainable, eco-designed scaled-up manufacture and safe electrolyte systems,
demonstrated in pilot scale to TRL6, and will be ready for commercialization 3 years after
the project end.
To reach this target, HYDRA mobilizes a strong industry commitment: the
partnership includes a strong value-chain of suppliers with global competitiveness for xEV
batteries and a direct liaison to the market in sectors such as automotive and maritime
transport, ensuring a fast-uptake of results. Ecological and economical sustainability also
keep a strong importance, as HYDRA will be performing life cycle assessments and value-
chain analyses on local and global scales. All aspects from raw materials via battery cell
production and end-use/market to recycling and 2nd life usage will be evaluated.
The HYDRA concept uses abundant electrode materials like iron, manganese and
silicon, and eliminates the use of the CRMs cobalt and natural graphite, with a net CRM
reduction of >85%. The new materials will be produced in an environmentally friendly,
energy-efficient manner, using water in place of organic solvents
(https://h2020hydra.eu/)

Key words: Batteries; electrochemistry, hybrid electrodes, high energy, automotive

Acknowledgments: The Hydra project has received funding from the

European Union’s Horizon 2020 research and innovation programme
under GA No. 875527.

References
Steen M., Lebedeva N., Di Persio F., and Boon-Brett L., EU Competitiveness in Advanced Li-ion
Batteries for E-Mobility and Stationary Storage Applications – Opportunities and Actions, EUR
28837 EN, Publications Office of the European Union, Luxembourg, (2017), ISBN 978-92-79-
74292-7, doi:10.2760/75757, JRC108043.
https://h2020hydra.eu/

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BATTERY-TYPE POSITIVE ELECTRODE FOR LI-ION SUPERCAPATTERIES

Andreea Culcea, Cristina Obreja, Mihai Iordoc

National Institute for Research and Development in Electrical Engineering ICPE-CA, 313 Splaiul Unirii,
030138, District 3, Bucharest, Romania, EU
Coresponding author: [email protected]

The hybridization of energy storage devices can be of a different types based on the
different types of electrode assembly. The combination could be the assembly of one
type of capacitive electrode (electrical double layer) with other kinds of capacitive
electrode (pseudocapacitive), and this
device can be named as a hybrid supercapacitor. In the second case, one battery
electrode with another capacitive electrode can be combined to form a two-terminal
device which should be called a hybrid energy storage device. However, in the
literature, this device is also called a hybrid supercapacitor, which is misleading.
Recently, a new name was proposed for the battery and capacitive-based electrode
device as “Supercapattery” (Chen, 2017).
With regard to the battery-type positive electrode materials, various materials such
as transition metal oxides like MnO2, RuO2 and electronically conducting polymers (CP)
like Polyaniline (PANI) and polypyrrole (PPy) have been investigated extensively for
possible applications in hybrid supercapacitors. The conducting polymers (CP) offer the
advantages of lower cost in comparison with metal oxides and high charge density in
contrast to carbon materials. CP is one of the most promising materials which is
frequently used as electrode material for hybrid supercapacitor due to its properties
such as easy synthesis, controllable electric conductivity, chemical stability and couple
oxidation states which contribute to its high specific capacitance. The oxidation and
reduction processes are accompanied by doping (intercalation) and dedoping
(deintercalation) of counter-anions respectively. Since these processes are reversible,
charge storage in CP is facilitated to yield a pseudocapacitance behavior. Additionally,
separation of charges takes place at the CP electrolyte interface and this gives rise to the
existence of double layer capacitance. Thus, the total capacitance, is the sum of both
pseudocapacitance and double layer capacitance. The main drawback of using CP as
supercapacitor electrode is mainly concerned with their low cycle life because during
the doping/dedoping process (insertion/deinsertion of counter ions) they undergo
swelling and shrinkage leading to mechanical degradation of the electrodes. To
overcome this problem, research has focused on synthesizing CP/carbon based
materials (such as graphene) / metal oxides (MO) / metal nanoparticles (MNp)

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composite electrodes. One of the challenging issues in the development of high

performance supercapacitor is to improve its electronic conductivity of the CP electrode
which is reversibly controlled both by the charge transfer doping and by protonation.
Extensive research work has been focused on enhancing electronic conduction of the
electrodes by using metal doping.
The growing interest in application of polypyrrole (PPy) for electrodes of hybrid
supercapacitors is attributed to high specific capacitance, relatively large voltage
window, high electrical conductivity, low cost, and advanced chemical and mechanical
properties of this material. The high specific capacitance of PPy results from redox
reactions, which allow charge storage in the bulk of the electrode material. Many
fundamental investigations have been conducted with the objective to investigate the
charging mechanism of PPy in different electrolytes and to utilize high theoretical
specific capacitance of PPy (620 Fg-1) in electrodes of supercaps. The electrosynthesis of
PPy can be favoured by adjusting electrolyte ionic strength and pH; in this case, a high
electrolyte concentration and a neutral or slightly acid pH value increase the quality of
the polypyrrole film. Also, the electrochemical method employed in the
electropolymerization process strongly affects the properties of the obtained film
(Iordoc, 2015).
In this paper, cyclic voltammetry was chosen as the electrochemical synthesis
method for PPy-Gr-MO-MNp composite films instead of galvanostatic or potentiostatic
methods. There are two reasons: cyclic voltammetry allows to yield smoother coatings
and it is possible to monitor the redox properties of the deposits during the experiment,
while galvanostatic and potentiostatic polymerizations allow the evaluation of the
electrochemical properties only in the end of the experiment. PPy coatings show weak
mechanical properties that can be improved by the addition of graphemes (Gr), as has
been observed previously for several polymeric matrices, thus obtaining a more
resistant and durable support. Graphenes also improve the electrical conductivity of
polymer films, lowering the impedance modulus of these materials. The electrochemical
stability of polypyrrole is also increased by the addition of Gr, MO and MNp. On the
other hand, the electrochemical activity of PPy in dedoped state (which is the discharge
state in supercapacitor) could be a serious problem because of the typical volumetric
shrinkage during ejection of counterions (doped ions). Furthermore, the conductance of
PPy is very low at dedoped state, which would result in high ohmic polarization of
supercapacitor and low reversibility and stability of supercapacitor, as well. The problem
has to be solved before the application. It has been already confirmed that composite
materials based on PPy-Gr-MO-MNp coatings are very interesting electrode materials
for supercapacitor application.
The aim of this study is to investigate electrochemical behaviour as supercapacitor
electrodes of PPy-Gr-MO-MNp composite layers in Li-ion electrolyte. We expect that the
large surface area and high conductivity of the Gr enhance the energy storage capacity.
PPy provides not only additional capacitance as an active material, but also improves
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the adhesion between the Gr and substrate. Furthermore, PPy acts as a conducting
binder for connecting every individual Gr leading to an increase of the electrochemical
capacitance.
Conductive polymeric coatings were achieved by using cyclic voltammetry in 0.2M
H2SO4 acid aqueous solutions. Pyrrol electropolymerization was carried out by potential
cycling (50 succesive cycles) between 0.2- 0.85V/SCE, at a constant scan rate of 20 mVs-
1
. Chemical reagents of analytical grade used for electrochemical polymerization of
pyrrole were pyrrol, 99% purity and sulfuric acid (98%). The solutions containing
dissolved pyrrole were prepared using bidistilled water; to encourage pyrrol dissolution,
3-5 mL of ethanol were added. Before the beginning of each electrochemical
polymerization the solutions were kept in darkness to avoid air oxidation and pre-
polymerization. Li-ion electrolyte (LIIE) (LiPF6 1M in Ethylene Carbonate : Dimethyl
Carbonate 50:50 + 1% Vynilene Carbonate + 1% Antraqinone + 3%LiI + 0,3% Biphenyl)
was the media for investigation of electrochemical behaviour of PPy-Gr-MO-MNp
composite films.

Electropolimerization of pyrolle

A VoltaLab 40 potentiostat/galvanostat with dynamic EIS (Electrochemical

Impedance Spectroscopy) connected to a computer through VoltaMaster 4 Software
interface was used for the electrochemical measurements. The electrochemical
behaviour of the samples were studied in a 2016 type coin cell closed system. The
working electrode is a plate with surface area of 1 cm2 consisting in aluminium support
that will be covered with PPy-Gr-MO-MNp composite coating. The cell contains, apart
from the working electrode, a copper counterelectrode. The experiments were carried
out in stationary conditions at room temperature in a glovebox with 5N argon
controlled atmosphere having maximum 13ppm O2 and 3ppm H2O. Impedance
measurements were performed on the frequency range between 100kHz and 1mHz

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with an AC wave of 10 mV (peak-to-peak); the impedance data were obtained at a rate

of 10 points per decade change in frequency. Charge-discharge cycles were running on a
Neware multichannel battery tester

Key words: supercapattery, polypyrolle, Li-ion electrolyte, graphene, metal

oxide, metal nanoparticle

References
Chen, G.Z., Int. Mater. Rev. 62 (4), (2017), 173-202.
Iordoc, M., REV. CHIM., 66, (2), (2015), 196-200.

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LASER PYROLYSIS SnOx NANOPARTICLES - CHARACTERIZATION AND TESTING

FOR Li-ION BATTERY ANODES

C. Fleacă1, F. Dumitrache1, M. Buga2, A. Spînu-Zăuleţ2, C. Ungureanu2, S. Enache2,

A.-M. Banici1, E. Duţu1, M. Dumitru1
1
National Institute for Laser, Plasma and Radiation Physics - INFLPR, Atomistilor no.409, Magurele,
Bucharest, Romania
2
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Coresponding author: [email protected]

We report the laser pyrolysis synthesis of nanoparticles (NPs) composed from tin
monoxide as majority phase (and small amounts of SnO2 and β-Sn phases) starting
from Sn(CH3)4 volatile precursor vapors by using C2H4 sensitizer accompanied by low
amount of O2. The presence of SnO was confirmed by X-ray diffraction and also by
Raman analyses. SEM images reveals the presence of agglomerated spherical
nanoparticles with size around 30-80 nm. The NPs were mixed with cabon black and
CMC binder, deposed by spraying from aqueos media and dried, followed or not by
calendring in order to obtain anodes tested for Li-ion batteries in CR2032 half cells
using LiPF6 salt in organic carbonates mixture (EC:EMC:DEC (3:5:2 vol.%) + 3 wt.% FEC)
electrolyte. Calendred and uncalendred anodes were analysed by CV (Cyclic
voltammetry) where the peaks corresponding to the SnOx reduction to Sn, their
subsequent alloying reaction with Li to form LixSn and SEI surface-electrolyte layer
formation -during reduction and the alloy delithiation -during oxidation can be seen
and Electrochemical Impedance spectroscopy before and after long cycling which
reveals differences between the two electrodes, the uncalendred one exhibiting a
slightly lower value of charge transfer resistance after cycling. Charge-discharge
measurements at different rates (C/10;C/5;C/3.3/;C/2.5, 1C and again C/10) in a
voltage range from 0.01V to 2V were also performed, resulting for calendred anode a
discharge capacity of 876,2 mAh/g (after 5cycles) at C/10 and of 642.3 mAh/g (after
5cycles) at 1C, showing also best rate performance, whereas for uncalendred electrode
the performances were slightly inferior, yet both electrodes presenting a 100%
couloumbic efficiency. However, after 200 charge-discharge cycles at 1C, the
uncalendred electrode keeps a higher discharge capacity of 169.56 mAh/h than those
of calenderd one (125.59 mAh/g). The long cycling performance of these SnOx-based
anodes can be improved by adding flexible conductive additives such as RGO (reduced
graphene oxide), a direction which is under our investigation.

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TRIS(TRIMETHYLSILYL) BORATE AS AN EFFICIENT ELECTROLYTE ADDITIVE FOR

NICKEL-RICK NMC811 CATHODE IN LITHIUM-ION BATTERY

Adnana Spînu-Zăuleţ1, Mihaela Buga1, Cosmin Ungureanu1,2,

Danuţ Ionel Văireanu1,2
1
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
2
Faculty of Applied Chemistry and Materials Science, Politehnica University of Bucharest, 060042
Bucharest, Romania
Coresponding author: [email protected]

Lithium-ion batteries with high energy density cathodes, have attracted great
interest due to the urgent demand of energy storage technologies for electric
vehicles, hybrid electric vehicles and smart grids.
In particular, nickel-rich layered oxide LiNi0.8Mn0.1Co0.1O2 (NMC811) material is one
of the most promising cathode candidates for the next generation lithium-ion batteries
(generation 3a) due to the high gravimetric capacity (~ 200 mAh/g), high voltage and
low cost given by the small content of cobalt. Despite all this advantages, there are also
some issues to be overcome for NMC811, as poor cycling stability that is caused by the
instability of electrode/electrolyte interfaces at high voltage. In order to improve the
interfacial stability of high voltage NMC811, different film forming electrolyte additives
have been studied such as triphenylphosphine oxide [Beltrop, 2018], S-containing
(1,3,2-dioxathiolane 2,2-dioxide (DTD), DTD + prop-1-ene-1,3-sultone (PES), methylene
methanedisulfonate (MMDS) and Si-containing tris(trimethylsilyl) phosphate (TTSP)
[An, 2019] and tris(trimethylsilyl) phosphite [Liu, 2020; Laveda, 2019]. According to
Fuqiang An et al., the Si-containing additives showed better long-term durability
performance and storage performance than S-containing additives. As example,
tris(trimethylsilyl) borate (TMSB) has the ability to inhibit the surface of the positive
electrode and stabilise the cathode electrolyte interface (CEI), reducing the active
lithium loss during cycling [Liao, 2016; Wang, 2017].
In this study, the boron compound - tris(trimethylsilyl) borate is used as additive
into the standard electrolyte EC/DMC with 1M LiPF6 for NMC811/graphite full cells
system. Electrochemical characterization, morphological and surface analysis have
been conducted in order to reveal the improvements beyond state of art via safe
electrolyte systems.

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Figure 1. NMC811 electrode manufacturing Figure 2. TMSB additive

Key words: LiNi0.8Mn0.1Co0.1O2, tris(trimethylsilyl) borate, electrolyte additive,

lithium-ion batteries, cycling performance.

Acknowledgments: This research was financially supported by the Romanian

National Research Programs PN-III-P1-1.1-PD-2019-0555, PD26/2020, project title
“Borate based electrolyte additives to improve performances of Li-ion cells”.

References
F. An, H. Zhao, W. Zhou, Y. Ma, P. Li, S-containing and Si-containing compounds as highly effective
electrolyte additives for SiOx-based anodes/NMC811 cathodes in lithium-ion cells, Sci. Rep. 9
(2019) 14108.
K. Beltrop, S. Klein, R. N lle, A. Wilken, J. J. Lee, T. K.-J. K ster, J. Reiter, L. Tao, C. Liang, M. Winter, X.
Qi, T. Placke, Triphenylphosphine Oxide as Highly effective Electrolyte Additive for
Graphite/NMC811 Lithium-Ion Cells, Chem. Mater. 30 (2018), 2726–2741.
J. V. Laveda, J. E. Low, F. Pagani, E. Stilp, S. Dilger, V. Baran, M. Heere, C. Battaglia; Stabilizing
Capacity Retention in NMC811/Graphite Full Cells via TMSPi Electrolyte Additives, ACS Appl.
Energy Mater. 2 (2019) 10 7036–7044.
X. Liao, P. Sun, M. Xu, L. Xing, Y. Liao, L. Zhang, L. Yu, Weizhen Fan, Weishan Li, Application of
tris(trimethylsilyl)borate to suppress self-discharge of layered nickel cobalt manganese oxide
for high energy battery, Appl. Energy 175 (2016) 505-511.
H. Liu, A. J. Naylor, A. S. Menon, W. R. Brant, K. Edstrom, R. Younesi, Understanding the Role of
Tris(trimethylsilyl) Phosphite (TMSPi) in LiNi0.8Mn0.1Co0.1O2 (NMC811)/Silicon-Graphite (Si-Gr)
Lithium-Ion Batteries, Adv. Mater. Interfaces 7 (2020) 2000277.
Y. Wang, H. Ming, J. Qiu, Z. Yu, M. Li, S. Zhang, Y. Yang, Improving cycling performance of LiCoPO 4
cathode material by adding tris(trimethylsilyl) borate as electrolyte additive, J. Electroanal.
Chem. 802 (2017) 8–14.

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SILICA-BASED MATERIALS AS HIGH-PERFORMANCE LITHIUM-ION

BATTERY ANODES

Cosmin Ungureanu1,2, Adnana Spînu-Zăuleţ1, Radu Andrei1, Alin Chiţu1,

Alecsandra Sobolu1, Raul-Augustin Mitran3, Eugeniu Vasile4, Mihaela Buga1
1
National Research and Development Institute for Cryogenic and Isotopic Technologies—ICSI Rm.
Valcea, Uzinei Street, No. 4, P.O. Box 7 Raureni, 240050 Valcea, Romania
2
Faculty of Power Engineering, Politehnica University of Bucharest, 060042 Bucharest, Romania
3
“Ilie Murgulescu” Institute of Physical Chemistry, Romanian Academy, 202 Splaiul Indepedentei,
060021 Bucharest, Romania
4
Faculty of Applied Chemistry and Materials Science, Politehnica University of Bucharest, 060042
Bucharest, Romania
Corresponding author [email protected]; [email protected]

Lithium-ion batteries (LIBs) have attracted great attention as power source for
portable consumer electronics and electric vehicles due to their high energy density and
long-life cycle. Although organic electrode materials have been investigated as early as
inorganic electrode materials, the leading technology of LIBs mainly adopts inorganic
compounds as electrode materials because of their good electrochemical performance
[Breeze, 2014]. The development of it promotes the research of LIBs with higher capacity
and higher energy. For cathode materials, it is difficult to give obvious capacity
improvement in recent research. While for anode materials, a large space to enhance still
exist.
Graphite, widely used in the commercial LIBs now, possesses the relatively low
specific capacity of around 375 mAh/g, but Si possesses the highest theoretical specific
capacity (4200 mAh/g) among all kinds of anode materials and appropriate potentials for
Li insertion and extraction (<0.5V vs Li+/Li), which makes the Si-based materials become
the ideal anode materials in the next generation LIBs [Zhao, Lehto , 2021]. However,
several drastic challenges prevent the practical application of Si anodes. The primary one
is its huge volume change (~300%) upon full lithiation and the resultant
expansion/shrinkage stress during lithiation/delithiation, which causes the cracking of Si,
the formation of an unstable solid electrolyte interface (SEI) layer on the Si surface, and Li
trapping in active Si material, consequently leading to fast reversible capacity loss and low
initial coulombic efficiency (ICE). Also, binders have become a non-ignorable part although
merely occupy a small mass content. Binders are used to link active materials and
conducting agent together to ensure active materials bonded onto the current collector
during subsequent cycling. Furthermore, the usage of proper binders could provide a
business-like way to improve cycling stability and maintain volume change upon
lithiation/delithiation processes of Si based electrodes to some content. Porous silica-
based materials are a promising alternative to graphite anodes for Li-ion batteries due to
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their high theoretical capacity, low discharge potential similar to pure silicon, superior
cycling stability compared to silicon, abundance, and environmental friendliness.
However, several challenges prevent the practical application of silica anodes, such as low
coulombic efficiency and irreversible capacity losses during cycling. To achieve the goal of
fabricating the anode materials with good performance, several steps would be carried
out. The primary one is to design and modify suitable structures. Recent studies involved
the use of SiO2 based systems to bring more stability and higher conductivity to LIBs in
which several porous Si-SiO2, SiO2/carbon (SiO2-C) or carbon/SiO2/carbon (C-SiO2-C)
structures were used [Gu et al., 2018; Su et al., 2017; Ali et al., 2020]. It was demonstrated
that different SiOx-C composite structures had much better performance in terms of
electronic conductivity and cycling stability compared with Si (Ali et al., 2020). One of the
main strategies to tackle the challenges of silica as an anode material has been developed
to prepare carbon-coated SiO2 composites by carbonization in argon atmosphere.
Herein, we propose a simply preparation route of SiO2 – carbon composites as
anode materials for lithium-ion batteries. The resulted carbon-coated SiO2 composites
were characterized using X-ray diffraction, X-ray photoelectron spectroscopy,
thermogravimetry, transmission and scanning electron microscopy coupled with energy-
dispersive X-ray spectroscopy, cyclic voltammetry, and charge–discharge cycling.
The SiO2-carbon composites with different sucrose concentration exhibits
improved electrochemical performance electron conductivity, coulombic efficiency and
cycling stability after 200 cycles, without electrode degradation.

Key words: Lithium-ion batteries, anode, silica, cycling stability.

Acknowledgments: The work has been funded by the Romanian Ministry of

Research Innovation and Digitalization, NUCLEU Program-Financing Contract no.
9N/2019, under Project PN 19 11 03 01.

References
Ali S., et al., Photo cured 3D porous silica-carbon (SiO2–C) membrane as anode material for high
performance rechargeable Li-ion batteries, Journal of Alloys and Compounds, 812, (2020),
152127.
Breeze P., Power System Energy Storage Technologies in Power Generation Technologies (Second
Edition), ed. P. Breeze, Newnes, Boston, https://doi.org/10.1016/B978-0-08-098330-1.00010-7,
(2014), 195-221.
Gu Z, et al., Yolk structure of porous C/SiO2/C composites as anode for lithium-ion batteries with
quickly activated SiO2, Journal of Alloys and Compounds, 757, (2018), 265-272.
Su J., Zhao J., Li L, Zhang C., Chen C., Huang T. and Yu A., Three-Dimensional Porous Si and SiO2 with
in Situ Decorated Carbon Nanotubes As Anode Materials for Li-ion Batteries, ACS Applied
Materials & Interfaces, 9, (2017), 17807-17813.
Zhao X. and Lehto V.-P., Challenges and prospects of nanosized silicon anodes in lithium-ion
batteries, Nanotechnology, 32, (2021), 042002 (22pp).

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MATERIAL SCIENCE FOR ENERGY AND ENVIRONMENT

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TECHNOLOGY ACCELERATOR NETWORK MODALITY TO PROMOTE INNOVATION

ECOSYSTEM IN MATERIALS SCIENCE FOR ENERGY AND ENVIRONMENT

Ashok Vaseashta1, Roxana Elena Ionete2

1
International Clean Water Institute, Manassas, VA, USA;
Ghitu Institute of Electronic Engineering and Nanotechnology, Chisinau, Moldova
2
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Corresponding author: [email protected]

The global demand for innovative, efficient, and agile designs continues to grow
exponentially due to interdependence of energy, environment and overall quality of life.
The overall landscape is complex as the energy sector faces two significant yet
conflicting imperatives: rapidly rising global demand, as billions of people in emerging
economies strive to achieve the quality of life; and the environmental challenge, which
needs a low-carbon footprint.
One of the possible ways to meet these challenges is through significant and rapidly
adopted technological breakthroughs. Therefore, in the near future joint research
efforts need to focus more directly on producing knowledge database required to
understand and diagnose the challenges that confront both societies and economies, as
a result of global change (Mauser et al., 2013) and to find practical solutions for a more
sustainable world. To meet this need, we present Technology Accelerator Network
(TechXNET) modality using convergence of technologies and global interconnectivity to
create an ecosystem of innovations. Figure 1a shows the interconnections between
main contributors for innovation outcome and technology convergence for innovation
acceleration.

Figure 1 (a: Schematic draw of the interconnections between main contributors for innovation
outcome, and (b): Technology convergence for innovation acceleration
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The roots of convergence is in the late 20th – early 21st century when a meta-
area of knowledge has foreseen with the aim to improve human performance by
collaborative work between nano-science and nanotechnology, bio-technology and
biomedicine, information technology and cognitive science (Roco and Bainbridge,
2002; Bainbridge and Roco, 2016). Convergent-like approaches (Vaseashta, 2014) to
problem solving go beyond interdisciplinary research since a partnership between
scientists (from engineering, physical sciences, computation, and life science),
industry partners, public officials and policymakers has to be accomplished. This
tendency is reinforced by the dominance of globalization, which has led to a hyper-
competitive environment at regional/global level, towards a faster use of basic
scientific and technological advances for economic and/or strategic advantage.
The concept of Technology Accelerator Network is an extension of an earlier
project (Moschner et al., 2019), modified to develop a new capability to accelerate
novel, visionary, disruptive and primarily user-inspired research in areas of regional
(horizontal) priorities that support overall (vertical) priorities by way of convergence of
science and technologies, international network-to-network partnerships from
industries, government and non-government organizations, think-tank groups,
foundations willing to promote the novel cause to solve grand challenges of the 21st
century. The goal is to bring multidisciplinary systems thinking and analysis to apply
innovative solutions to major challenges like climate changes or energetic
independence, in creative new ways. The presentation outlines advanced science and
technology convergence methodologies, databases to for network-to-network
international collaborative activities, key characteristics of such collaborative
accelerators, and benefit to such collaborate accelerator in all fields of science,
engineering and STEM education.

Key words: Accelerator programs, Convergence, Innovations, Interconnectivity

References
Bainbridge, W. S., & Roco, M. C. (Eds.). (2016). Handbook of science and technology convergence.
Switzerland: Springer International Publishing.
Mauser, W., Klepper, G., Rice, M., Schmalzbauer, B. S., Hackmann, H., Leemans, R., & Moore, H.
(2013). Transdisciplinary global change research: the co-creation of knowledge for
sustainability. Current Opinion in Environmental Sustainability, 5(3-4), 420-431.
Moschner, S. L., Fink, A. A., Kurpjuweit, S., Wagner, S. M., & Herstatt, C. (2019). Toward a better
understanding of corporate accelerator models. Business Horizons, 62(5), 637-647.
Roco, M.C., & Bainbridge, W.S. (2002). Converging Technologies for Improving.
Vaseashta, A., Foresight, (2014) 16(1). Advanced Sciences Convergence based methods for
surveillance of emerging trends in science, technology, and intelligence.

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PREPARATION AND ELECTROCHEMICAL EVALUATION OF COVALENTLY

FUNCTIONALIZED REDUCED GRAPHENE OXIDE MATERIALS

Andreea Dogaru1, Adriana Marinoiu2, Mihaela Florea3, Mihai Varlam2,

Simona Nica1
1
Romanian Academy, "C D. Nenitzescu" Institute of Organic Chemistry,
Splaiul Independentei 202 B, Bucharest, Romania
2
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
3
National Institute of Materials Physics, 405A Atomistilor, Magurele, Romania
Corresponding author: [email protected]

The ongoing energy crisis and environmental pollution has shifted research
attention toward the development of new energy conversion technologies and storage
systems. In this regard, proton exchange membrane fuel cells are promising clean energy
sources and offer advantages for both portable and stationary applications. These
devices can generate electrical energy through catalyzed chemical reactions at anode
and cathode, namely hydrogen oxidation and oxygen reduction. A key challenge in their
development is finding of an electrocatalyst with superior performance of the otherwise
slow oxygen reduction reaction (ORR) occurring at fuel cell cathode [M. Lefèvre, 2008].
So far, high cost, poisoning Pt-based systems have been the most efficient cathode
catalysts [C. Cui, 2013]. Currently, graphene is a promising candidate as catalyst support
material for PEMFCs due to its outstanding mechanical, structural, and electronic
properties [H. Su, 2021]. Combining the synergic properties of graphene and structural
properties of conducting organic moieties might allow the production of an advanced
type of diffusion layer with low-cost fabrication technique. It is worth mentioning that
among these systems, there are only few examples of reduced graphene oxide
functionalized with organic molecules [S. Joshi, 2020; A. Wang, 2016].
Owing to its fascinating photophysical and redox properties, azulene has attracted
an increasing interest toward designing a large variety of materials ranging from
electrochromic materials, organic/polymeric conductors or conductive charge-transfer
complexes [H. Xin, 2017; X. Fu, 2020]. Due to its dipolar structure (Scheme 1), with the
five-membered ring carrying the negative charge (cyclopentadienyl anion) and the seven-
membered ring the positive charge (tropylium cation), azulene possesses an electron
distribution that provides intrinsic redox activity. Thus, azulene undergo anode as well as
cathode reactions, providing materials with high electrical conductivity [K.-P. Zeller,
1985]. Cation and bipolaron radical of 1,3-polyazulene exhibits high electrical

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conductivity: 1.22 S/cm following oxidation reaction and maintain this conductivity
through protonation with trifluoracetic acid [F. Wang, 2003].

Scheme 1

We have recently produced azulene-functionalized reduced graphene oxide

through 1,3-dipolar cycloaddition [A. Marinoiu, 2021; A. Marinoiu, 2020]. Following
straightforward Prato reaction [M. Maggini, 1998] with sarcosine and formyl-azulene,
the azomethine ylide reacts to a double bond of reduced graphene oxide (rGO) to
yield pyrrolidinoazulenyl-rGO (Scheme 2). When performed following traditional
reaction set-up, the reaction takes place in DMF with heating for five days [A. Marinoiu,
2020]. Improvement of the reaction conditions, especially reduced reaction time, was
achieved by microwave-assisted reaction, as we have recently reported in a patent
application [A. Marinoiu, 2021].

Scheme 2

The graphene-azulene hybrid materials (rGO-Az) was purified by multiple filtration/

redispersion cycles. The structure of the isolated azulene functionalized graphene
materials was established using IR and XPS spectroscopies. The presence of azulene
within the graphene-hybrid material was confirmed by spectroscopic techniques. A
comparison of the IR spectrum of the reduced graphene oxide with the one
corresponding to the hybrid rGO-Az materials reveals new stretching vibration at 747 and
772 cm-1, assigned to the N-C bond resulted from the 1,3- dipolar cycloaddition. In
addition, absence of the carbonyl stretch at about 1700 cm-1 for the rGO-Az in relation to
the spectra of free Az-CHO indicates reaction of the aldehyde moieties. Investigations of
the specific surface area shows Type IV isotherm with an abrupt increase at high relative
pressure, typical for mesoporous structure with uniform pore size distribution. The pore
diameters implied a hierarchical porous structure in rGO-Az structure: (i) micropores
work as reaction volume; (ii) mesopores work on the kinetic diffusion process; (iii) open
channels of macropores act as gas channels. Thermogravimetric investigations revealed

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increased stability of the resulting materials, in agreement with our supposition that,
upon functionalization, the structural characteristics of graphenes are at least preserved.
The covalently functionalized graphene materials are designed to function as
innovative proton-to-cell membrane fuel cell (PEMFC), thus electrochemical
investigations were performed. Preliminary results indicate that the signal associated
with electro-catalytical activity has a linear dependency on the scaling speed, and reveal
a limited diffusion reaction within composite material. Figure 1 illustrates the behavior of
azulene-functionalized graphenic materials in a potential range of 0.0-0.8 V. When
applying low scaling speeds (≤50 mV s− 1), shape of cyclic voltammetry (CV) plot is
pseudo-rectangular; when increasing the scaling speed the shape of the CV plot deviates
from the ideal behavior, probably due to the different structure of graphenic materials,
especially the nitrogen concentration introduced through pyrollidinic moiety.

Figure 1. Experimental results: cyclic voltammetry for prepared azulene-functionalized graphenes in

KOH electrolyte 0.1 M, potential range - 0.8 + 0.8 V, scan rate 25 mV/s, 100 cycles

All graphenic materials functionalized with azulene possess a good electrochemical

stability to over 100 cycles, also keeping over 95 % of their electrochemical activity. Based
on these results it is worth emphasizing the increased stability of the cycle corresponding
to these composite materials while the differences between them are limited.

Acknowledgments: The financial support from UEFISCDI, PN-III-P2-2.1-PED-

2019-2079 (469PED/2020) project is gratefully acknowledged.

References
C. Cui, L. Gan, M. Heggen, S. Rudi, P. Strasser, Nat. Mater., 2013, 12, 765.
X. Fu, H. Han, D. Zhang, H. Yu, Q. He, D. Zhao, Chem. Sci., 2020, 11, 5565.
S. Joshi, R, Siddiqui, P. Sharma, R. Kumar, G. Verma, A. Saini, Sci. Rep., 2020, 10, 9441.
M. Lefèvre, E. Proietti, F. Jaouen, J.-P. Dodelet, Science, 2009, 324, 71.
M. Maggini, G. Scorrano, M. Prato, J. Am. Chem. Soc., 1993, 115, 9798.
A. Marinoiu, S. Nica, E. Carcadea, M. Varlam ˮGraphene materials functionalized with azulene
obtained in the microwave fieldˮ - A 00508/26.08.2021, 2021.

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A. Marinoiu, S. Nica, E. Carcadea, C. Capris, M. Varlam, ˮCovalent graphene functionalized with

azulene and process for obtainingˮ - A 00804/03.12.2020, 2020 .
H. Su, Y. H. Hu, Energy Sci Eng., 2021, 9, 958.
A. Wang, W. Yu, Z. Huang, F. Zhou, J. Song, L. Long, M. P. Cifuentes, M. G Humphrey, L. Zhang, J.
Shao, C. Zhang, Sci. Rep., 2016, 6, 23325.
F. Wang, Y. H. Lai, N. M. Kocherginsky, Y. Y. Kosteski, Org. Lett., 2003, 5, 995
H. Xin, X. Ga, ChemPlusChem, 2017, 82, 945 and references cited threin.
K.-P. Zeller, Azulene. In Houben-Weyl; Methoden der Organischen Chemie, 4th ed.; Georg Thieme:
Stuttgart, 1985; Vol. V, Part 2C, 127.

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COMPOSITE NAFION® MEMBRANES WITH DIFFERENTLY DOPED NANO-

CRYSTALLINE YTTRIA-STABILISED-ZIRCONIA (YSZ) FOR PROTON EXCHANGE
MEMBRANES FUEL CELLS (PEMFCs) APPLICATIONS IN DRASTIC CONDITIONS

A. Saccà, A. Carbone, I. Gatto1, R. Pedicini, S. Maisano, A. Stassi,

Enza Passalacqua
National Research Council of Italy, Institute for Advanced Energy Technologies “Nicola Giordano”,
via S. Lucia sopra Contesse, 5 - 98126 Messina (Italy)
Coresponding author: [email protected]

The European Strategy plan for the Energy Technologies foresees that at least
65% of the electric energy should derive from renewable energy sources and CO2
emissions reduced by 50% within 2050. In this context, Polymer Electrolyte Fuel
Cells (PEFCs) play an important role, above-all in terms of clean, safe and efficient
electric power generation with low environment impact and, hence, independence
from fossil fuels [https://www.governo.it/sites/governo.it/files/PNRR.pdf].
As known, Direct H2-PEFCs (DH-PEFCs) convert the chemical energy of the
reaction between H2 and air, respectively fed at anode and cathode sides, in
electrical energy, generating water and heat. This occurs thanks to electrochemical
reactions at the electrodes and the protons transportation from anode to cathode
through the polymeric membrane, considered the core of the PEFC. In order to
expand the application field, the research interest has been addressed towards
development of High-Temperature PEFCs (HT-PEFCs). The increase of working
temperature [R. Zeis, 2015] produces several important benefits, such as the
improvement of the catalyst activity, the impurities tolerance and the simplification
of the thermal and water management of the system [S.N. Lvov, 2004].
In drastic conditions, the most commonly used perfluoro-sulphonic membranes
(in particular, Nafion®) are subjected to swelling and de-swelling processes that
lower its particularly high proton conductivity and mechanical strength with a
consequent performance failure.
Different solutions have been considered to overcome these obstacles [A.
Chandan, 2013], such as the development of membranes based on: i) short-side
chain perfluorinated sulphonic acid (SSCA-PFSA) [J. Li, 2014] or ii) thermo-stable
polyaromatic polymers [A. Carbone, 2008]; iii) reinforced membranes [A. Saccà,
2014; N.S. Khattra, 2013]; iv) organic/inorganic polymer matrices containing
hygroscopic and/or proton conductor fillers to develop composite membranes [G.G.
Kumar, 2009]. The aim consists in the enhancing of the water retention and the
mechanical properties of the membranes when hydrophilic inorganic oxides, such
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as SiO2, TiO2, ZrO2 are added [G. Alberti, 2003] and in the improvement of the
proton conductivity when proton conductors, such as heteropolyacids (PWA,
PMoA, SiWA, etc.) are used to modify the polymer matrix [A. Saccà, 2008].
In particular, inorganic sulphated or phosphated zirconia nanoparticles fillers
with acidic functionalities can contribute to the proton conductivity of the
membranes [J. Chabé, 2012], while nano-sized Yttria-Stabilized-Zirconia (YSZ) fillers
seem to provide hybrid membranes stable at high temperature with a reduced
methanol crossover [I. Stamatin, 2006].
It was demonstrated that nano-YSZ becomes a proton conductor below 120°C
in water-saturated air [S. Kim, 2009] and this low-temperature proton conductivity
is greatly dependent on the grain size of nanostructured YSZ [H.J. Avila-Paredes, E.
Barrera-Calva, 2010; H.J. Avila-Paredes, J. Zhao, 2010]. YSZ has been investigated as
a possible additive to mitigate the degradation by free radicals of the membranes
[T. Weissbach, 2016] and the interest in such YSZ based-materials as filler for
Proton Exchange Membranes (PEMs) has been increased to work at intermediate
temperatures <150°C [T. Wilberforce, 2016].
Hence, composite Nafion® membranes represent a possible solution to operate
at temperatures higher than 100°C and low RH in DH-PEFCs and YSZ based-
materials have got important properties to be investigated for the aim.
For these reasons, in our previous works, [A. Saccà, 2006; G. Giacoppo, 2012; G.
Giacoppo, 2013], a commercial Zirconia stabilised with an 8 mol.% of Yttria, usually
used as conductor for Solide Oxide Fuel Cells (SOFCs) at extremely high cell
temperature [R. Xu 2017; S-J Hao, 2017], was used as a filler for Nafion® composite
membranes in a single HT-PEFC and also in self-made stack configuration. A 10 wt.% of
this commercial filler was found to be the optimal content in terms of performance at
high temperature. Starting from evidence that a protonic conduction at low-
temperature in nano-YSZ was hypothesized [H. J. Avila-Paredes, E. Barrera-Calva,
2010], in the actual work [A. Saccà, 2018; A. Saccà, 2019], a YSZ filler containing an 8
mol. % of yttrium oxide was synthesised and its ideal content was investigated. This
filler was synthesised by basic hydrolysis and successive doping of zirconia with a
suitable amount of a c-Y2O3, used as a phase inductor. Highly homogeneous and wide
size composite Nafion® membranes with a variable content of this filler (3, 5, 10 wt.%)
were cast by a widely standardised procedure [A. Saccà, 2005], verifying the
electrochemical behaviour under drastic conditions of T and RH.

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Figure 1. I-V curves at 120 °C, 75%RH as a function of YSZ total content.

Successively, once individuated the total optimal YSZ content (5wt%.), with the aim
of evaluating the influence of Y2O3 doping level in ZrO2 lattice, differently doped fillers
using four Y2O3 loadings (from 4.8 up to 15 mol.%) were synthesised and the
corresponding membranes have been cast and characterized.
A deep chemical-physical characterisation in terms of XRD, Ion Exchange Capacity
(IEC), water uptake and swelling at different temperatures (room T, 80 and 95°C), ex-situ
oxidative stability tests (Fenton’s tests) to evaluate the degradation, N2 adsorption-
desorption tests (BET), Scanning-Electron-Microscopy (SEM), Dynamo-Mechanical
Analysis (DMA) on fillers and membranes was carried out, together to an electrochemical
characterisation based on proton conductivity measurements, polarisation curves,
Accelerated Degradation Tests (ADTs) and H2-crossover tests in a single cell, at high T and
reduced RH.
On the basis of obtained overall results, it was possible to establish that a fraction of
Y3+ cations in syn-YSZ is able to replace the protons of Nafion® sulphonic groups,
maintaining unaltered water retention and swelling of the membrane. In fully humidified
conditions and 80 < T < 120°C, proton conductivity (PC) of the composite membranes is
higher than pristine Nafion, meaning that the filler has intrinsic proton conduction
properties, due to the presence of proton charge carriers in this temperature range.
When higher T and reduced RH (120°C, 75%RH) are used, PC of membranes increases as
a function of YSZ content with respect to pristine Nafion membrane, probably due to an
enhancement of the path continuity within the polymer matrix when the filler loading is
increased. In these drastic conditions, the electrochemical characterisation individuated
in the composite membrane containing a 5 wt. % of syn-YSZ (NsynYSZ5) the highest
electrochemical performance with a cell potential of 0.617 V (@ 0.5 A cm-2) against a
value of 0.534 V for pristine Nafion and highest stability and degradation resistance in
ADTs, exceeding 0.55 V (@0.4 A cm-2) and supplying 48 cycles against to the 28 cycles of
the reference membrane, cast through the same standardised casting method.
Regarding the different ZrO2 doping level, XRD analysis demonstrated the presence
of a mixed t-, m-, c-crystalline structure in which the tetragonal and monoclinic phases
decrease increasing the Yttria loading. An average crystalline size of about 29-37 nm and

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nanometric agglomerates with size decreasing as a function of increasing Y2O3 amount

were found. From BET measurements, the formation of a c-ZrO2 mesoporous structure
was demonstrated, while SEM revealed a size reduction of the agglomerates increasing
the doping level.
From mechanical and chemical-physical characterisation, it was evidenced that the
composite membranes have a similar Glass Transition Temperature (Tg) and a higher
mechanical resistance for higher doping levels up to 90°C if compared to reference
membrane. After this T, the membranes are equally mechanically stable. Moreover, the
supposed ability of the YSZ fillers to retain water in the interfacial layers between the
grains seems to constrain the swelling and enhances the acidic properties of the
composite membranes. Due to this aspect, the membranes with higher doping levels of
Y2O3 in the ZrO2 structure showed an increased IEC, probably attributable to a partial
proton conduction. In addition, the filler provides a positive influence on PC, especially at
higher T (95°C) and lower humidification (75%RH). From the measurements of chemical
oxidative stability, the developed fillers with a higher yttria loadings (12 and 15 mol.%)
showed to have an antioxidant effect. This is confirmed from ADT results, carried out in
drastic conditions for a PEFC (95°C and 50% RH).

Figure 2. I-V curves after ADT @ 95°C, 50%RH

The composite membranes containing the highly yttria-doped fillers seem to be

promising samples for the selected application, since they were able to work more
than 110 cycles maintaining an optimal performance with very low H2-crossover
values within the targets supplied by DoE as references.

Key words: Yttria-Stabilised-Zirconia (YSZ), Y2O3 doping level, Nafion-YSZ Composite

Membranes, HT-PEFC, Accelerated Degradation tests (ADT).

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References
G. Alberti, M. Casciola, Annu. Rev. Mater Res., 33, (2003) 129
H.J. Avila-Paredes, E. Barrera-Calva, H.U. Anderson, R.A. De Souza, M. Martin, Z.A. Munira, S. Kim, J
Mat Chem, 20, (2010) 6235
H.J. Avila-Paredes, J. Zhao, S. Wang, M. Pietrowski, R.A. De Souza, A. Reinholdt, Z.A. Munir, M.
Martin, S. Kim, J Mat Chem, 20, (2010) 990
A. Carbone, R. Pedicini, A. Saccà, I. Gatto, E. Passalacqua, J. Power Sources, 178, (2008) 661
J. Chabé, M. Bardet, G. Gébel, Solid State Ionics, 229, (2012) 20
A. Chandan, M. Hattenberger, A. El-kharouf, S. Du, A. Dhir, V. Self, B.G. Pollet, A. Ingrama, W.
Bujalski, J Power Sources, 231, (2013) 264
G. Giacoppo, O. Barbera, A. Carbone, I. Gatto, A. Saccà, R. Pedicini, E. Passalacqua, Int J Hydrogen
Energy, 38, (2013) 11619
G. Giacoppo, A. Carbone, I. Gatto, A. Saccà, R. Pedicini, O. Barbera, E. Passalacqua, J Fuel Cell Sci
Technol, 9, (2012)
S.-J. Hao, C. Wang, T.-L. Liu, Z.-M. Mao, Z.-Q. Mao, J.-L. Wang, Int J Hydrogen Energy, 42, (2017)
29949
https://www.governo.it/sites/governo.it/files/PNRR.pdf
S. Kim, H.J. Avila-Paredes, S. Wang, C.T. Chen, R.A. De Souza, M. Martin, Z.A. Munir, Phys Chem
Chem Phys, 11, (2009) 3035
N.S. Khattra, Z. Lu, A.M. Karlsson, M.H. Santare, F.C. Busby, T. Schmiedel, J Power Sources, 228,
(2013) 256
G.G. Kumar, A.R. Kim, K.S. Nahma, R. Elizabeth, Int J Hydrogen Energy, 34, (2009) 9788
J. Li, M. Pana, H. Tang, RSC Adv, 4, (2014) 3944
S.N. Lvov, M.V. Fedkin, E. Chalkova, M.B. Pague, Prepr Pap-Am Chem Soc, Div Fuel Chem, 49, (2004)
606
A. Saccà, A. Carbone, I. Gatto, R. Pedicini, E. Passalacqua, Polymer Testing, 65, (2018) 322
A. Saccà, A. Carbone, E. Passalacqua, A. D’Epifanio, S. Licoccia, E. Traversa, J Power Sources, 152,
(2005) 16
A. Saccà, A. Carbone, R. Pedicini, M. Marrony, R. Barrera, M. Elomaa, E. Passalacqua, Fuel Cells, 8,
(2008) 225
A. Saccà, I. Gatto, A. Carbone, R. Pedicini, S. Maisano, A. Stassi, E. Passalacqua, Int J Hydrogen
Energy, 44, (2019) 31445
A. Saccà, I. Gatto, A. Carbone, R. Pedicini, E. Passalacqua, J. Power Sources, 163, (2006) 47
A. Saccà, R. Pedicini, A. Carbone, I. Gatto, P. Fracas, E. Passalacqua, Chem. Phys. Lett., 591, (2014)
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T. Weissbach, T.J. Peckham, S. Holdcroft, J Membr Sci 498 (2016) 94
T. Wilberforce, A. Alaswad, A. Palumbo, M. Dassisti, A.G. Olabi, Int. J. Hydrogen Energy, 41, (2016)
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R. Zeis, Beilstein J., Nanotechnol, 6 (2015) 68

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POLYSACCHARIDE-BASED POLYELECTROLYTE MEMBRANES FOR FUEL CELLS

Valeria Harabagiu

"Petru Poni" Institute of Macromolecular Chemistry, 41A, Aleea Grigore Ghica Voda
700487 Iasi, Romania
Corresponding autor: [email protected]

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ELECTROCHEMICAL IMPEDANCE SPECTROSCOPIC INVESTIGATIONS OF POROUS

AND GAS DIFFUSION ELECTRODES FOR VARIOUS APPLICATIONS

Norbert Wagner1, Maryam Nojabaee1, Martina Gerle1, Alexander Kube1,

Fabian Bienen1, Kaspar Andreas Friedrich2
1
German Aerospace Center, Pfaffenwaldring 38-40, 70569 Stuttgart, Germany
2
University of Stuttgart, Institute of Building Energetics, Thermal Engineering and Energy Storage
(IGTE), Pfaffenwaldring 31, 70569 Stuttgart, Germany
Corresponding author: [email protected]

Electrochemical impedance spectroscopy (EIS) is a powerful tool for investigating

electrochemical systems. Based on De Levie's pore model, several new models
(impedance models) and approaches to describe porous electrodes are presented. These
highly structured electrodes, thanks to their high electrochemical active surface area, are
mostly used in electrochemical systems for energy generation and storage.
The following electrochemical applications are presented as examples of EIS
investigation of gas diffusion electrodes (GDE): oxygen reduction in the Zn-air
battery and oxygen depolarizing cathode (ODC) in the chlorine alkali electrolysis,
Lithium-Sulfur battery and CO2-reduction.
Zinc based metal-air batteries have the advantage of high energy density,
because oxygen from ambient air is used without in-cell storage. As a consequence,
lighter batteries are produced with the reversible available Zinc as the only limiting
factor. However, before Znair batteries can be used as secondary elements some
obstacles have to be overcome. The low cyclability of state-of-the-art Zn-air
batteries is caused by the passivation rate and dendrite growth of zinc, carbonate
formation in the alkaline electrolytes, corrosion of cathode materials and flooding
of the cathode.
Bifunctional Ni/Co3O4 based electrodes [D. Wittmaier et al., 2019a; D.
Wittmaier et al. 2019b] were produced by the RMR technique [E. Gülzow et al.
2003] and the porous structure was varied by applying different pressures during
production of the electrodes by hydraulic hot pressing. These electrodes were used
to investigate how the electrolyte penetration depth influences the electrochemical
performance and how this behaviour can be influenced by the porous electrode
structure. In addition to the evaluation of the measured impedance spectra with
the transmission line model (TLM), the pore model based of the early work of De Levie
the distribution of relaxation times (DRT) as a new evaluation approach is used.
Distribution of relaxation times (DRT) offers a model-free approach for impedance
analysis. DRT was used to analyze a Ni/Co3O4 gas diffusion electrode (GDE) for metal-air
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batteries [I. Moussallem et al., 2008]. To identify the corresponding process for the
identified peaks, temperature, current density, gas composition, electrolyte
concentration and electrode material composition were varied. In total five processes
could be identified. Four were observed both during oxygen reduction reaction (fig. 1)
and oxygen evolution reaction (OER). A fifth could only be recognized during OER. In
particular the charge transfer coupled with an adsorption process and the porous
structure could be identified. Furthermore, it could be shown that having a bimodal
pore size distribution, consisting of two different materials, the correct calculation of
the DRT spectra is inhibited, resulting in two peaks instead of the characteristic number
of peaks that are getting smaller towards smaller time constants.

Figure 1. Current density variation of a Ni/Co3O4 electrode at 25°C in 32 wt.-% KOH, a) shows the
measured Nyquist diagram with some frequency markers, b) the calculated DRT spectra

Over the last decades, membrane chlor-alkali technology has been optimized to
such an extent that no substantial reduction of the energy demand can be expected
from further process modifications. By replacement of the hydrogen evolving cathodes
in the classical membrane cells by Oxygen Depolarizing Cathodes (ODCs) allows for
reduction of the cell voltage and correspondingly the energy consumption of up to 30%.
This replacement requires the development of appropriate cathode materials and gas
diffusion electrodes. Due to their superior long-term stability, ODCs based on silver
catalysts are very promising for oxygen reduction in concentrated NaOH solutions. Silver
is a known electro catalyst for the reduction of oxygen in alkaline fuel cell cathodes. To
enhance his catalytic activity, silver is used in a form with high specific area such as
porous electrodes where the silver particles are dispersed in the porous matrix. The
porous PTFE-bonded gas-diffusion electrodes can be prepared by a Reactive Mixing and
Rolling (RMR) production technique, first described by Winsel, later on improved by
other groups or by wet techniques using inks or suspensions, a clearly represented
overview is given in [D. Kopljar et al., 2016]. The electrodes consist of the
electrocatalytic powder (silver, Raney-silver, silver covered with PTFE (Silflon) or silver
oxide), the organic binding agent (PTFE), pore forming material (e.g. NaHCO3) and a
metal wire gauze to stabilize mechanically the electrode and to collect the current. In
gas diffusion electrodes both hydrophobic and hydrophilic pore systems are required.
The hydrophilic system allows the penetration of the electrolyte (alkaline solution) into

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the electrode and the transport of the ions to or from the reaction zone; the
hydrophobic pore system is required for the transport of the oxygen to the reaction
zone. In addition, to give the mechanical stability, the PTFE in the electrodes forms a
hydrophobic pore system, whereby the spider web of PTFE fibers in and on the
electrodes are formed during preparation.
Li-sulfur battery is a promising system, due to its high theoretical capacity (1675
mAh/gsulfur), energy density (2500 Wh/kg), the low cost and non-toxicity of sulfur.
Nevertheless, some of the drawbacks of lithium-sulfur batteries are the poor
rechargeability and high self-discharge rates. Due to the low electrical conductivity of
sulfur, electrically conductive material has to be added in order to encourage the
electrochemical reaction. Furthermore, polysulfides of high order (Li2Sn with 2 ≤ n ≤ 8)
dissolve in the electrolyte and can diffuse to the anode and react directly with lithium
metal. This so-called shuttle mechanism causes irreversible loss of sulfur.
Carbon aerogels are a highly promising material to be used as matrix for sulfur to
fabricate cathode for lithium-sulfur batteries [M. Nojabaee et al. 2021]. Resulting from
organic resorcinol-formaldehyde aerogels, carbon aerogels exhibit highly porous
structure with porosity up to 97%, high surface area about 500-3500 m²·g-1, large pore
volume about 2-3 cm³·g-1, and good electronic conductivity. Additionally, the important
advantage of carbon aerogel is its tunable porous structure and pore size distribution. In
the presentation actual results will be discussed.
To understand the underlying processes in the carbon-sulfur cathode composites a
combination of impedance spectroscopy in a symmetrical cell and UV-Vis spectroscopy,
the cathode-induced effects on the electrochemical performance of the cell are
examined. By utilizing two model systems, Ketjenblack (KB, mesoporous carbon) and
carbon aerogel (microporous carbon), the effect of infiltration, thickness, content of active
material and porosity of the cathode as well as the evolution of impedance upon
discharge and charge in the first formation cycle are comprehensively investigated. Using
a suitable transmission-line model (Fig. 2) characteristic of the porous electrodes, the bulk
and pore electrolyte, interparticles, and charge transfer resistances are defined and
quantified. In addition, the variation of charge transfer resistances on discharge/charge
and the kinetics of charge transfer as a function of infiltration method are discussed in
details.

Figure 2. Transmission-line model used for the evaluation of porous KB/Sulfur electrodes

Low-temperature electrochemical reduction of carbon dioxide to useful chemicals

can contribute to the solution of this problem by changing the role of CO2 from harmful
waste into a valuable feedstock. The electrolyzer can be operated with renewable energy
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and CO2 taken from concentrated off-gas of industrial plants. One of the main challenges
of this process is to bring gaseous CO2 in contact with the catalyst and the aqueous phase
to maintain high space-time-yields. By applying porous gas-diffusion electrodes (GDEs)
instead of plane electrodes the triple-phase-boundary - reaction zone – and gas transport
are significantly enhanced. [F. Bienen et al., 2019; F. Bienen et al., 2020] Electrochemical
impedance spectroscopy is a powerful tool to analyze the nature and velocity of single
processes occurring at the microscopic level in electrochemical devices. These insights
provide valuable information for a specific optimization of electrodes regarding
electrochemical performance and long-term stability. However, there is a lack of
knowledge which processes are displayed in the impedance spectrum during alkaline CO2
electrolysis on GDEs. This work focusses on the identification of these processes shown in
the impedance spectrum (Fig. 3) by changing experimental parameters e.g. temperature,
CO2 partial pressure & current density and analyzing the obtained response in the
spectrum. The measurements were performed in the frequency range 10 mHz to 300 kHz.

Figure 3. EIS (left side) and corresponding DRT (right side) for CO2-reduction with tin-based gas-
diffusion electrodes (GDEs) measured at different current densities and temperatures

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Key words: Electrochemical Impedance Spectroscopy (EIS), Gas Diffusion Electrodes

(GDE), Lithium-sulfur battery, CO2-reduction, Zn-air battery, Oxygen Depolarizing
Cathode (ODC)

References
F. Bienen et al., Chem. Ing. Tech., 91 (2019) 872-882 (DOI: 10.1002/cite.201800212).
F. Bienen et al. ACS Sustainable Chem. Eng. 2020, 8, 13759−13768.
E. Gülzow, N. Wagner, M. Schulze, Fuel Cells – From Fundamentals to Systems, 3 (2003) 67-72.
D. Kopljar et al., Chemical Engineering & Technology, 39 (2016) 2042-2050.
A. Kube, W. Strunz, N. Wagner, K.A. Friedrich, Electrochim. Acta, 2021 (in press).
I. Moussallem, J. Jörissen, U. Kunz, S. Pinnow, T. Turek, J. Appl. Electrochem. (2008) 1177–1194.
M. Nojabaee, B. Sievert, M. Schwan, J. Schettler, F. Warth, H. Schneider, N. Wagner, B. Milow, K.A.
Friedrich, J. Mater. Chem. A, 9 (2021) 6508-6519; DOI: 10.1039/D0TA11332H.
D. Wittmaier, S. Aisenbrey, N. Wagner, K. A. Friedrich, Electrochim. Acta, 149 (2014) 355-363.
D. Wittmaier, T. Danner, N. Wagner, K.A. Friedrich, Journal of Applied Electrochemistry, 44 (2014) 73-85.

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NANOFIBERS OF ELECTRET POLYMERS FOR TACTILE SENSING AND

WEARABLE ELECTRONICS

Ashok Vaseashta1,2
1
International Clean Water Institute Applied Research, Manassas, Virginia, USA
2
Riga Technical University Institute of Biomedical Engineering and Nanotechnologies, Riga, Latvia
Corresponding author: [email protected]

Bio-Derived Polymers exist in abundance and display diverse chemical compositions,

tunable properties, such as high k-dielectric, processability, excellent biocompatibility
and biodegradability, with no to minimum toxicity. Such features provide them with
capability for futuristic ubiquitous application in networked wearable and tactile
electronics as membranes and devices to efficiently scavenge and store operational
power from their working environment. Based on our previous work on e-textile, force
protection clothing, wearable electronics and electrospun nanofibers, we provide an
overview of the recent progress and future applications in textile, e-textile, tactile sensing
(sensors, actuators, transistors) and triboelectric devices (batteries, supercapacitors,
triboelectric nanogenerators) fabricated using bio‐derived natural materials. The diverse
structures and fabrication processes of three typical biopolymers provide sustainable
pathways that would enable viable self‐powering schemes in societally pervasive
applications. Additionally, challenges and potential research opportunities are analysed
and described.

Key words: biopolymers; tactile; triboelectric; wearable; sensors; high k-dielectric.

Figure 1. Wearable electronics in soldier suit. (inset shows tactile membrane)

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3D SELF-ASSEMBLED SrTi1-xAlxO3/FeOOH HETEROSTRUCTURES INTO COMPLEX

ARCHITECTURES WITH EFFECTIVE PHOTOCATALYTIC APPLICATIONS

Adrian Iulian Borhan, Daniel Ghercă, Alin Constantin Dîrțu, Mircea Nicolae
Palamaru, Alexandra Raluca Iordan

Faculty of Chemistry, Alexandru Ioan Cuza University of Iasi,

11 Carol I Boulevard, 700506 Iasi, Romania
Coresponding author: [email protected]

Photocatalytic overall water splitting (POWS) with suspended semiconductor

photocatalysts is one of the most promising options for carbon free generation of
hydrogen fuel from water and solar energy. Recently, high solar-to-hydrogen
efficiencies were demonstrated using Al, La and Rh co-doped SrTiO3 (Al,La,Rh:SrTiO3)
incorporated into a low-cost and scalable Z-scheme device, known as a photocatalyst
sheet [B. Moss et. al., 2021; S. Chen, et al., 2017; T. Takata et al., 2020]. However, the
unique properties that enable Al,La,Rh:SrTiO3 to support this impressive performance
are not fully understood. We want to present here the development of newly different
3D heterostructures based on FeOOH oxyhydroxide coupled to SrTi1-xAlxO3, a novel
perovskite with substitutional doping, determine their optoelectronic properties and
charge/energy transfer mechanisms and establish their potential as photocatalysts,
particularly for hydrogen production. The aim of the present study is to develop
additional synthetic routes to this important photocatalyst and to promote the
understanding of the effects of Al doping and 3D morphology on photocatalytic
activity. Moreover, we report here a novel hybrid synthesis protocol of SrTi1-xAlxO3
nanocrystals with controllable Al doping amount (max. 1 atom%) and nano-
compartimentalized into supramolecular FeOOH oxyhydroxide.

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Key words: POWS, 3D heterostructures, perovskite, FeOOH oxyhydroxide.

Acknowledgments: This work was supported by a grant of the Romanian Ministry

of Education and Research, CNCS - UEFISCDI, project number PN-III-P1-1.1-TE-2019-2037
within PNCDI III”.

References
S. Chen, et all. Nature Reviews Materials, 2017, 2, 17050.
B. Moss et. all, Nature Materials, 2021, 20, 511-517.
T. Takata et all., Nature, 2020, 581, 411–414.

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HIERARCHICAL MgO PREPARED THROUGH ONE-POT SLOW PYROLYSIS PROCESS

OF MgAl-LDH AND ITS SUPERB CADMIUM ADSORPTION PROPERTIES

Gabriela Buema, Daniel Gherca, Adrian Iulian Borhan, Nicoleta Lupu, Horia Chiriac

National Institute of Research and Development for Technical Physics,

47 Mangeron Boulevard, Iasi 700050, Romania
Corresponding author: [email protected]

INTRODUCTION AND OBJECTIVES

Cadmium has attracted the attention due to its toxicity behavior which may lead to
various diseases [Al Hamouz et al., 2017]. The adsorption process is the most
investigated method to remove Cd(II) ions from aqueous media due to its low cost and
easy operation. Experimental studies have demonstrated that Layered double
hydroxides (LDHs) represent a material that can be employed as low cost adsorbent for
Cd(II) removal due to their characteristic structure and special properties. On the other
hand, by applying the heat treatment of LDHs, the calcined LDH product is obtained.
The new material has a characteristic known as ‘memory effect’ which underlines the
fact that the new material can easily reconstruct the original layered structure [Lv et al.
2006; Teixeira et al. 2012; Zhou et al. 2015].
The main objectives of this study were: (i) the characterization of prepared material
through scanning electron microscopy (SEM), Fourier transform infrared spectroscopy
(FTIR), X-ray diffractometer (XRD); (ii) batch adsorption investigation influenced by pH,
adsorbent dose, initial Cd(II) concentration, and contact time; (iii) equilibrium and kinetic
study.

METHODOLOGY
Chemical Reagents: All the chemicals were analytical grade and were used as
received.
Preparation of the materials
Preparation of MgAl-LDH uncalcined: The preparation in detail of MgAl-LDH
uncalcined is described in our previous work (Buema et al., 2020).
Preparation of MgAl-LDH calcined: MgAl-LDH calcined, was prepared as follow:
a quantity of 2g of MgAl-LDH uncalcined was heated at 550°C for 3h. After the heat
treatment, the sample was kept in a vacuum desiccator and further used in Cd(II)
adsorption experiments.
Cd(II) adsorption study
Adsorption experiments were carried out in a batch system as a function of pH,
adsorbent dose, initial Cd(II) concentration, and contact time. Once the Cd(II) adsorption
process was completed, the supernatant was collected and analysed using a UV–vis
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spectrophotometer at 576 nm using xylenol-orange. The following formula was used to

calculate the adsorption capacity, q (mg/g):

(1)

where Ci and Cf are the initial and final Cd(II) concentrations (mg/L), q is the amount
of Cd(II) adsorbed onto MgAl-LDH calcined (mg/g), V is the total volume of solution
(L), and m is the quantity of MgAl-LDH calcined (g).

RESULTS
Material Characterization
The SEM image of MgAl-LDH calcined is similar to the data presented by
research team formed by Mokhtar et al. After calcination treatment of MgAl-LDH a
pronounced collapse in the layered structure is obtained, which may be attributed
to the removal of the interlayer anions and thermal decomposition of the hydroxide
carbonate into the corresponding metal oxides (MgAlOx) (Mokhtar et al., 2010). For
comparison, the SEM image of MgAl-LDH uncalcined was added.

Figure 1. SEM images: MgAl-LDH (left); MgAl-LDH calcined (right)

The FTIR analysis is shown in Figure 2. For MgAl-LDH calcined material, the presence
of band around 1400 cm-1 is typical of O-C-O stretching vibrations for adsorbed
carbonate anions on the surface basic sites of the MgAl-LDH calcined, after exposition
to the carbon dioxide from ambient environment [Campos-Molina et al., 2010; dos
Santos et al., 2013]. Based on the research published by Hibino et al., it can be stated
that the peaks around 844 cm-1, 679 cm-1 are attributed to the Al-O and Mg-O vibration
modes of in Mg(Al)O [Hibino et al., 1995].

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Transmittance, %

1640

1400

844
3458

679
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber, cm-1
Figure 2. FTIR analysis

Figure 3 exhibits the XRD pattern of the prepared sample. Accordingly,

crystallized MgO phase was obtained [Olsbye et al., 2002; Valente et al., 2010].

Figure 3. XRD pattern

Cd(II) adsorption study

The results regarding the capacity of the prepared material to remove Cd(II)
ions from aqueous media are listed in Figure 4.

Figure 4. The influence of working parameters

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According to Figure 4, the following conclusions can be drawn:

 The Cd(II) adsorption by MgAl-LDH calcined is influenced by the pH value of
the solution: the change of pH value from 2.5 to 5.0 shows an increase trend. The
adsorption capacity reaches 60 mg/g at pH 5 compared to 48 mg/g at pH 2.
 The influence of the MgAl-LDH calcined dose shows that the prepared
adsorbent exhibits a higher adsorption capacity using a dose of 14 mg.
 When the initial Cd(II) concentration increases from 100 mg/L to 350 mg/L,
the adsorption capacity increases substantially: from 60 mg/g to 202 mg/g.
Consequently, the changes of the initial Cd(II) concentration have a positive impact
on the adsorption capacity.
 The Cd(II) adsorption rate is very fast during the first minutes. On the other
hand, the adsorption rate becomes slow, as time passes. The equilibrium was
reached after 60 min. of contact time.
The isotherms and adsorption kinetics of Cd(II) ions on prepared material
agreed with the Freundlich model and Pseudo second order model, respectively.
The Freundlich constant, 1/n is less than 1, indicating a favourable adsorption. The
fitting to Pseudo second order model indicates a chemical adsorption.

Conclusions
In this study, MgAl-LDH calcined was synthesized.
Different characterization methods, such as: SEM, FTIR, and XRD, were used.
The influence of pH, adsorbent dose, initial Cd(II) concentration, and contact
time were investigated to explain the adsorption process.
According to the experimental results, the material proposed in this study is a
promising adsorbent for treating water containing Cd(II) ions, with a maximum
adsorption capacity of 250 mg/L.

Key words: Layered double hydroxide; Characterization; Cadmium ions; Adsorption

mechanism.

Acknowledgments: This work was supported by the Romanian Ministry of

Research and Innovation under the Nucleu programme, Project PN 19 28 01 01.

References
Buema G., Lupu N., Chiriac H., Ciobanu G., Kotova O., Harja M., (2020). Modeling of solid-fluid non-
catalytic processes for nickel ion removal. Revista de Chimie, 71, 7, 4-15.
Campos-Molina M.J., Santamaria-Gonzalez J., Merida-Robles J., Moreno-Tost R., Albuquerque
M.C.G., Bruque-Gamez S., Rodriguez-Castellon E., Jimenez-Lopez A., Maireles-Torres P., 2010.
Base catalysts derived from hydrocalumite for the transesterification of sunflower oil. Energy
and Fuels, 24(2), 979-984.

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Al Hamouz, O.C.S, Estatie, M., Saleh, T.A., 2017. Removal of cadmium ions from wastewater by
dithiocarbamate functionalized pyrrole based terpolymers. Separation and Purification
Technology, 177, 101-109.
Hibino T., Yamashita Y., Kosuge K., Tsunashima A., 1995. Decarbonation behavior of Mg–Al–CO3
hydrotalcite-like compounds during heat treatment. Clays and Clay Minerals 43 (4), 427-432.
Lv L., He J., Wei M., Evans D.G., Duan X., (2006). Factors influencing the removal of fluoride from
aqueous solution by calcined Mg–Al–CO3 layered double hydroxides. Journal of Hazardous
Materials, 133(1-3), 119-128.
Mokhtar M., Inayat A., Ofili J., Schwieger W., 2010. Thermal decomposition, gas phase hydration and
liquid phase reconstruction in the system Mg/Al hydrotalcite/mixed oxide: A comparative
study. Applied Clay Science, 50 (2), 176-181.
Olsbye U., Akporiaye D., Rytter E., Rønnekleiv M. R., Tangstad E., 2002. On the stability of mixed
2+ 3+
M /M oxides. Applied Catalysis A: General, 224 (1–2) 39–49.
dos Santos R.M.M., Gonçalves R.G.L., Constantino V.R.L., da Costa L.M., da Silva L.H.M., Tronto J.,
Pinto F.G., 2013. Removal of Acid Green 68:1 from aqueous solutions by calcined and
uncalcined layered double hydroxides. Applied Clay Science, 80-81, 189-195.
Teixeira T.P.F., Pereira S., Aquino S., Dias A., (2012). Calcined Layered Double Hydroxides for
Decolorization of Azo Dye Solutions: Equilibrium, Kinetics, and Recycling Studies.
Environmental Engineering Science, 29(7), 685-692.
Valente J.S., Hernandez-Cortez J., Cantu M.S., Ferrat G., Lopez-Salinas E., 2010. Calcined layered
double hydroxides Mg–Me–Al (Me: Cu, Fe, Ni, Zn) as bifunctional catalysts. Catalysis Today,
150 (3-4), 340-345.
Zhou Y., Hu W., Yu J., Jiao F., (2015). Effective photocatalytic degradation of methylene blue by
Cu2O/MgAl layered double hydroxides. Reaction Kinetics, Mechanisms and Catalysis, 115(2),
581-596.

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EFFECT OF THE PREPARATION CONDITIONS ON THE CATALYTIC EFFICIENCY OF

CoPt CATALYST FOR MOR

Oana-Georgiana Dragos-Pînzaru, George Stoian, Firuţa Borza, Nicoleta Lupu

National Institute of R&D for Technical Physics, Iasi, Romania

Corresponding author: [email protected]

Air pollution is currently the most important environmental risk to human

health, and it is perceived as the second biggest environmental concern at national
and international level [www.eea.europa.eu/publications/air-quality-in-europe-
2020-report]. World Health Organization (WHO) data shows that 9 out of 10 people
breathe air that exceeds WHO guideline limits containing high levels of pollutants.
Air pollution is killing an estimated seven million people worldwide every year
[www.who.int]. Pollution index in Romania gradually increased from 50.5 in 2016 to
of 58.42 in 2021 [www.statista.com/statistics/1101691/romania-pollution-index/].
In this context, the replacement of energy from fossil fuels with clean/green energy
sources is imperative, renewable energy representing a solution to many of the
world’s energy and pollution concerns.
The DMFC (Direct Methanol Fuel Cell) technology allows to produce electricity
directly from high density liquid methanol fuel trough electrochemical reactions,
working in the same time at low temperatures. The methanol is a liquid, it has an
energy density much greater than that of hydrogen in gaseous form [A.S. Aricò et
al.,2009; P. Joghee et al.,2015; G.A. Olah et al., 2009] and does not require a heavy,
bulky storage system for use in transport. One of the important advantage of the
methanol usage for fuel cells, is the possibility to use the same infrastructure
already existing for gasoline or diesel [R. Dillon et al., 2004], which can be
translated in minor costs modifications.
In DMFC, a mixture of methanol and water (methanol being completely miscible
with water [O. Dragos-Pinzaru et al., 2017a]) is directly introduced to the anode, where
the methanol is directly oxidized to carbon dioxide, via the methanol oxidation reaction
(MOR). During the MOR, two other reaction products are obtained: protons and
electrons. The protons, produced at the anode, pass to the cathode through the
electrolyte membrane, while the electrons flow from the anode to the cathode via an
external circuit. At the cathode, the electrons and the protons react with oxygen
(injected from the atmosphere) to produce water. The overall reactions process,
occurring during the acid-based DMFC are:
at anode:
CH3OH + H2O → CO2 + 6H+ + 6e- (1)
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at cathode:
O2 + 6H+ + 6e- → 3H2O (2)
overall reaction:
CH3OH + 3/2O2 → CO2 + 2H2O (3)
One of the important class of conventional materials used as catalysts for MOR
in a DMFC is represented by CoPt alloy, due to their exceptional performance in
terms of activity and selectivity
The common synthesis roots used for CoPt nanoparticles preparation are by
chemical reduction or by electrochemical deposition. The electrochemical synthesis
represents a good route to prepare materials at nanometric size, due to the fact
that it is easy to be applied, do not necessitates high vacuum and also, the growth
speed and the chemical composition of the alloy can be controlled. Also, the
electrodeposition inside the nanopores of the Anodic Aluminun Oxide (AAO)
templates, permit a good control of the nanowires shape, dimensions and aspect ratio.
The crystalline structure of as-prepared CoPt alloys is mainly FCC with soft magnetic
properties. The synthesis of tetragonal CoPt alloys having had magnetic properties,
involve a thermal treatment applied to the FCC alloy in order to change the crystalline
structure. In our previous work, we demonstrate that the crystalline structure of
electrodeposited CoPt thin films can be tuned from cubic to hexagonal, by changing the
electrodeposition conditions, the electrochemical bath’s pH or composition, respectively
[O. Dragos-Pinzaru et al., 2017a; O. Dragos-Pinzaru et al., 2017b; I. Tabakovic et al., 2016].
In this study, experiments were carried out in order to optimize the catalytic
properties of CoPt nanowires by controlling the electrodeposition parameters. The CoPt
nanowires electrodeposition occurs from a stable hexachloroplatinate solution. It will be
shown that the crystalline structure of the CoPt nanowires can be controlled by adding
saccharine like organic additives into the electrochemical bath. At the same time, it will
be demonstrated that the composition and the catalytic properties of the CoPt
nanowires arrays with a diameter of 200 nm can be tuned out by controlling the
electrodeposition potential.
CoPt nanowires were grown by electrodeposition inside anodic alumina oxide
templates (AAO), procured from Whatman. During our experiments, we used AAO
templates with a thickness of 40 µm and a nominal pores diameters of 200 nm. The
electrodeposition was performed in a 100 ml closed three electrode cell with a platinum
wire as contraelectrode, AAO templates as working electrodes, and a saturated calomel
electrode (SCE), as reference. The applied potential was controlled with a Heka
potentiostat. CoPt nanowires were prepared from the CoPt quiescent solution with and
without saccharine additive. The electrodeposition was carried out by pulse, using
different potentials ranging from -0.6 V/SCE to -1.1 V/SCE during time-on of 2.5 s and the
“rest” potential of -0.1 V/SCE during time-off. The time-off during 1 s is necessary for a
good “recovery” of the diffusion layer after the time-on.

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The nanowires morphology and composition are important parameters which

should be analysed, since the physical properties are strongly influenced by them.
In this regard, a very fine control of the synthesis parameters is necessary in order
to obtain alloys having the same properties. Fig. 1 presents an example of the cross-
section of the AAO template, filled with CoPt nanowires electrodeposited at -0.8 V
from the solution containing saccharine at pH 2.5.

Figure 1. Cross-section SEM micrograph of the AAO template filled with CoPt nanowires

The SEM images of the magnetic nanowires proves the uniform electrodeposition
inside the nanoporous template for all the samples. No modification concerning the
nanowires microstructure was found by changing the electrodeposition parameters or
the electrochemical bath characteristics. Thus, our experiments show that the Co
content of the alloy is strongly dependent of the applied potential and pH’ solution. The
magnetic element concentration in the alloy can be tuned by changing the potential
value. In this regard, by varying the applied potential from -0.6 V/SCE to -1.1 V/SCE, the
atomic % of Co increase from 0% to 90%. Fig. 2 presents the shape of the Co% function of
the applied potential for different characteristics of the electrodeposition solution: pH 2.5
and 5.5 solution with and without saccharine additive. Our results show clearly that the
nanowires composition is potential dependent.

Figure 2. Co % function of the applied potential for different electrodeposition solution: pH 2.5 (left)
and 5.5 (right) solution with and without saccharine additive

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The crystalline structure of the as prepared nanowires was determined by X-ray

diffraction. Fig. 3 presents the XRD scan of the nanowires inside the AAO template,
prepared from different solutions.
CoPt pH=2.5 without saccharin
700 CoPt pH=2.5 with saccharin
CoPt pH=5.5 without saccharin
600 CoPt pH=5.5 with saccharin

Intensity (u.a)
500

400

300

200

100

0
30 40 50 60 70 80 90
2 (degrees)

Figure 3. XRD patterns of CoPt nanowires prepared in different solutions

The XRD data show that the CoPt nanowires prepared from hexaclaroplatinate
aqueous solution without saccharine have cubic fcc structure with (111)
predominant growth direction. The CoPt nanowires prepared in presence of the
saccharine, have hexagonal, hcp predominant structure with the predominant
growth axis in the direction of (100) reflection. The crystalline structure influences
the magnetic properties of the as prepared nanowires.
In order to study the electrocatalytic properties of the CoPt nanowires as
catalysts for the MOR we have used cyclic voltammetry (CV) in aqueous solution of
2.0M CH3-OH and 0.1M H2SO4 at a scan rate of 100 mV/s. The electrodeposition of
CoPt nanowires into the AAO-template was carried out at the controlled potential
of -0.8 V/SCE, from electrochemical bats at pH 2.5 and 5.5, solutions with and
without additives.
All the synthetized CoPt nanowires present catalytic behaviour for methanol
oxidation reaction in acidic medium. The CV curves presented in Fig. 4 show an
increase of the peak current value for the samples prepared in presence of
saccharine. This result indicate that the CoPt nanowires prepared in presence of
saccharine exhibit a better catalytic activity compared with those prepared in
absence of additive. This results combined with EDS measurements show that we
can increase the catalytic activity of CoPt alloys in the oxidation of methanol, the Pt
content is decreased.

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Figure 4. CV curves for methanol oxidation on the CoPt nanowires catalysts in aqueous
solution of 2.0 M CH3-OH and 0.1 M H2SO4

In conclusion, our results clearly show that we can improve the catalytic activity
of the CoPt alloy by changing the preparation conditions.

Key words: CoPt alloy; DMFC, energy generation, electrodeposition, Methanol

Oxidation Reaction; Catalysts for fuel cells.

Acknowledgments: This work was supported by the Romanian Ministry of

Research and Innovation under the Nucleu programme, Project PN 19 28 01 01.

References
www.eea.europa.eu/publications/air-quality-in-europe-2020-report;
www.who.int
www.statista.com/statistics/1101691/romania-pollution-index/
A.S. Aricò, V. Baglio, and V. Antonucci, Direct methanol fuel Cells: History, status and perspectives in
Electrocatalysis of Direct Methanol Fuel Cells: From Fundamentals to Applications, Wiley-VCH
Verlag GmbH & Co. KGaA: Weinheim, Germany (2009) 1.
P. Joghee, J. Malik, S. Pylypenko and R. O’Hayre, A review on direct methanol fuel cells – In the
perspective of energy and sustainability, MRS Energy & Sustainability, 2, (2015) E3.
G.A. Olah, A. Goeppert, and G.K.S. Prakash, Beyond Oil and Gas: The Methanol Economy Wiley-VCH
Verlag GmbH & Co. KGaA : Weinheim, Germany, (2009).
R. Dillon, S. Srinivasan, A.S. Arico, and V. Antonucci, International activities in DMFC R&D: Status of
technologies and potential applications, J. Power Sources, 127, (1–2) (2004) 112.
O. Dragos-Pinzaru, A. Ghemes, H. Chiriac, N. Lupu, M. Grigoras, S. Riemer and I. Tabakovic, Magnetic
properties of CoPt thin films obtained by electrodeposition from hexachloroplatinate solution.
Composition, thickness and substrate dependence, Journal of Alloy. Compd., 718 (2017a) 319.
O. Dragos-Pinzaru, S. Riemer and I. Tabakovic, Composition Gradient in Electrodeposition of Thin
CoPt Films from the Quiescent Hexachloroplatinate Solutions, J. Electrochem. Soc., 164 (2)
(2017b) D30.
I. Tabakovic, J.-M. Qiu and O. Dragos, Electrodeposition of Thin CoPt Films with Very High
Perpendicular Anisotropy from Hexachloroplatinate Solution: Effect of Saccharin Additive and
Electrode Substrate, J. Electrochem. Soc., 163 (7) (2016) D287.

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SUPERCONDUCTING QUADRUPOLE LENS. DESIGN AND NUMERICAL MODELLING.

Dan Enache, Ion Dobrin, George Dumitru, Radu Pintea, Stefania Zamfir

National Institute for Research and Development in Electrical Engineering ICPE-CA Bucharest (ICPE-
CA), 313 Splaiul Unirii, District 3, Bucharest, 030138, Romania
Coresponding author: [email protected]

The beam of particles in an accelerator requires the use of quadrupole

electromagnets to control the cross section and its focusing. Increasing the energies of
accelerated particles requires increasingly intense magnetic fields and higher gradient
magnets. In this sense, a model of superconducting quadrupole lens was designed,
which consists practically in a quadrupole superconducting electromagnet HTS (High
Temperature Superconductor), generator of a magnetic field with a strong gradient of
~20 T/m.
This electromagnet consists of a four-pole iron yoke, each pole being wound with
YBCO type HTS superconducting tape [http://www.superpower-inc.com]. The poles of
the electromagnet alternate (N-S-N-S) so that a non-uniform magnetic field is generated
but with a "uniform" gradient [Jack T. Tanabe, 2005]. The HTS coil-iron yoke assembly is
maintained in a liquid nitrogen bath to cryogenic cool the coil and maintain the
superconducting state. A channel at room temperature passes through the center of the
magnet, which allows access from the outside to the magnetic field area.

Figure 1. Conceptual model of quadrupole superconducting electromagnet

The conceptual model of the quadrupole superconducting magnet has a complex

structure as shown in the diagram in figure 1 (1. Cryostat; 2. HTS superconducting
winding; 3. Iron yoke; 4. Cryogenic cooling bath of HTS winding; 5. Central channel 6.
Dewar liquid nitrogen storage; 7. Magnet power supply; 8. Liquid nitrogen level meter;
9. Temperature monitor; 10. Gaussmeter; 11. Hall probe).

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Starting from the conceptual model, numerical modeling and optimization of

the quadrupole were performed [Comsol Multiphysics www.comsol.com].

Figure 2. Computational domain

In figura 2 este prezentat modelul geometric al quadrupolului, utilizat in

modelarea numerica.

Figure 3. Magnetic flux density - full and detail - color map

Figure 3 shows the result of the numerical modeling in Comsol Multiphysics of

the magnetic flux density generated by the quadrupole, which has a maximum of
1.985 T.

Figure 4. Field gradient in the center of the quadrupole

(Ox - radius of the inner circle, Oy - field gradient [T / m])

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Figure 4 shows the result of modeling the field gradient in the center of the
quadrupole. Its maximum value is 20 T/m.

Acknowledgments: The authors acknowledge the financing of this work

through the contract PN1931030/2019 by Romanian Research Innovation and
Digitization Ministry.

References
Comsol Multiphysics www.comsol.com.
Superpower http://www.superpower-inc.com.
Jack T. Tanabe, Iron Dominated Electromagnets – Design, Fabrication, Assembly and Measurements,
Copiryght 2005 by World Scientific Publishing Co. Pte. Ltd., ISBN: 981-256-327-X, ISBN: 981-
256-381-4 (pbk).

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RESERVED TITLE

Marius Enachescu

Polytechnic University of Bucharest, Romania

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SELF-ASSEMBLED SrTiO3/NiFe2O4 /CARBON NANOTUBES AS SPONGE-LIKE

NANOHETEROSTRUCTURE FOR ENVIRONMENTAL APPLICATIONS

Daniel Gherca1,2, Adrian Iulian Borhan1,2, Mircea Nicolae Palamaru1,

Alexandra Raluca Iordan1,*
1
Faculty of Chemistry, Alexandru Ioan Cuza University of Iaşi, 11, Carol I Blvd., 700506, Iaşi, Romania
2
National Institute of Research and Development for Technical Physics,
47 Mangeron Boulevard, Iasi 700050, Romania
*
Corresponding author: Tel: +40232201341/fax: +40232201313
E-mail address: [email protected] / [email protected]

Combining nanotechnology with solar energy can lead to innovative

technologies for water purification. Hybrid nanocomposite materials are considered
to play a major role in the development of future oriented advanced functional
materials [A. I. Borhan et al., 2014a; D. Gherca, et al., 2020; A.I. Borhan et al.,
2014b]. The present
study intended to
contribute to such a
development, suppor-
ting the research in
functional materials by
the opportunity to create
new smart materials from
dufferent inorganic com-
ponents, which are
functional in wastewater
treatments. The funda-
mental idea underlying
the study, is to design,
fabricate and exploit
nanocomposite materi-als obtained by synergistically combining different types of
catalytically active NPs counterparts (SrTiO3, NiFe2O4 and Carbon nanotubes) for
photocatalytic applications, including water splitting and water remediation. Such a
unique synergistic combination of different catalytically active NPs, with peculiar
size dependent optoelectronic and catalytic properties, within highly processable
host active carbon, provides a flexible and versatile tool to access an innovative
class of multifunctional materials with superior photocatalytic properties in the UV
and visible range.
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Key words: Self-assembling, SrTiO3/NiFe2O4 composite, Carbon nanotubes,

water splitting

Acknowledgments: This work was supported by a grant of the Ministry of

Research, Innovation and Digitization, CNCS/CCCDI –UEFISCDI, project number PN-
III-P2-2.1-PED-2019-4215, within PNCDI III.

References
A.I. Borhan et al., J Taiwan Inst. Chem. E., 2014a, 45(4), 1655–1660.
A.I. Borhan et al., J. Photochem. Photobiol. A, 2014b, 279, 17–23.
D. Gherca, et al., Journal of Solid State Chemistry, 289, 2020, 121521.

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SOLID POLYMER ELECTROLYTES FOR SOLID-STATE BATTERIES

Ciprian Iacob, Radu Andrei, Silviu Badea, Irina Petreanu, Adnana Zăuleţ,
Violeta Niculescu

National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Coresponding author: [email protected]

Solid-state polymer electrolytes have received substantial attention in the

effort to revive high-energy-density Li-based batteries. In order to increase the
capacity of Li-based batteries, researchers have largely focused on new electrode
materials: regarding cathodes, Li–air and Li–sulfur batteries represent leading
frontier candidates while at anode, Li-metal can replace graphite to increase anode
energy density by approximately tenfold. Anyway, electrode advancements require
an enabling electrolyte to combat irreversible reactions and dendrite growth during
long-term charge/discharge cycling. In order to avoid these issues, solid-state
polymer electrolytes should not only provide mechanical stiffness to block
dendrites, but also should deliver safer (thermal stability without the leakage,
flammability or volatility) operation compared to liquid electrolytes. Ionic liquid gel
polymer electrolytes, made by immobilizing Li-salts dissolved in ionic liquids in a
polymer matrix or polymerized ionic liquids have received increasing attention due
to their potential applications in electrochemical devices. However, because of the
trade-off between mechanical properties and ionic conductivity, the preparation of
ionic liquid gel polymer electrolytes with both high ionic conductivity and robust
mechanical properties remains challenging. In order to achieve high ionic
conductivities in these systems, researchers have concentrated in synthesis
polymerized ionic liquids with lower glass transition temperatures; unfortunately
the higher ionic conductivity was achieved in detriment of mechanical properties.
We have recently developed a class of solid electrolytes, termed polymeric ionic
composites (PIC), composed of Li-salt dissolved in ionic liquids (IL) and a rigid-rod
polyelectrolyte, poly(2,2′-disulfonyl-4,4′-benzidine terephthalamide) (PBDT). PIC
materials, obtained through an ion-exchange process between IL and PBDT
aqueous solution, possess an unprecedented combination of high ionic conductivity
( >3 S/cm @RT), high thermal stability (stable> 150°C), low flammability, and widely
tunable tensile storage moduli (0.03−3 GPa). This PIC material fabrication platform
shows promise for safe and high-energy-density energy storage and conversion
applications, incorporating the fast transport of ceramic-like conductors with the
superior flexibility of polymer.
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Figure 1. Schematic representation of polymeric ionic composites based on PBDT preparation and
temperature dependence of ionic conductivities (𝜎0) and mechanical modulus (G’).

Acknowledgements: This work was supported by the grants of the Romanian

Ministry of Education and Research, CNCS - UEFISCDI, project number PN-III-P1-1.1-
TE-2019-1734, within PNCDI III, PN 19110204 and by a grant of the Romanian
National Authority for Scientific Research and Innovation, CCCDI – UEFISCDI, project
number ERANET-M-SMICE-Li, within PNCDI III”.

References
J.E Bostwick, CJ Zanelotti, C Iacob, AG Korovich, LA Madsen, RH Colby, Ion transport and mechanical
properties of non-crystallizable molecular ionic composite electrolytes, Macromolecules, 2020,
53 (4), 1405-1414.
C. Iacob, A. Matsumoto, H. Liu, S. Paddison, J. Sangoro, O. Urakawa, T. Inoue and J. Runt.
Polymerized Ionic Liquids: Correlation of Ionic Conductivity with Nanoscale Morphology. ACS
Macro Letters, 2017, 6, 9, 941-946.
C. Iacob and J. Runt, Charge transport of polyester ether ionomers in unidirectional silica nanopores,
ACS Macro Letters, 2016, 5, 476-480.
Atsushi Matsumoto, Francesco Del Giudice, Rachapun Rotrattanadumrong, and Amy Q. Shen,
Rheological Scaling of Ionic-Liquid-Based Polyelectrolytes in Ionic Liquid Solutions,
Macromolecules, 2019, 52, 2759-2771.

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HYDROTHERMAL FUNCTIONALIZATION OF THE CVD GROWN 3D-GRAPHENE FOAM

FOR HYDROGEN EVOLUTION REACTION IN ALKALINE ENVIRONMENT

Daniela Ion-Ebrașu1*, Radu Dorin Andrei1, Stanică Enache1, Simona Căprărescu2,

Constantin Cătălin Negrilă3, Cătălin Jianu1, Adrian Enache1, Iulian Boerașu4, Elena
Carcadea1, Mihai Varlam1, Bogdan Ștefan Vasile4
1
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
2
Inorganic Chemistry, Physical Chemistry and Electrochemistry Department, Faculty of Applied
Chemistry and Materials Science, University POLITEHNICA of Bucharest, 1-7 Polizu Str., 011061
Bucharest, Romania
3
National Institute for Materials Physics, PO BOX MG-7, Bucharest, RO-77125, Romania
4
National Research Center for Micro and Nanomaterials, Faculty of Applied Chemistry and Materials
Science, University Politehnica of Bucharest
*Correspondence author: [email protected]

Abstract: Three-dimensional graphene foam (3D-GrFoam) is a highly porous

structure and sustained lattice formed by graphene layers with sp2 and sp3
hybridized carbon. In this work, chemical vapor deposition (CVD)—grown 3D-
GrFoam was nitrogen-doped and platinum functionalized using hydrothermal
treatment with different reducing agents (i.e., urea, hydrazine, ammonia, and
dihydrogen hexachloroplatinate (IV) hydrate, respectively). X-ray photoelectron
spectroscopy (XPS) survey showed that the most electrochemically active nitrogen-
doped sample (GrFoam3N) contained 1.8 at % of N, and it exhibited a 172 mV dec −1
Tafel plot associated with the Volmer–Heyrovsky hydrogen evolution (HER)
mechanism in 0.1 M KOH. By the hydrothermal process, 0.2 at % of platinum was
anchored to the graphene foam surface, and the resultant sample of GrFoamPt
yielded a value of 80 mV dec−1 Tafel associated with the Volmer–Tafel HER
mechanism. Furthermore, Raman and infrared spectroscopy analysis, as well as
scanning electron microscopy (SEM) were carried out to understand the structure
of the samples. Four-points electrical conductivity reveled a decrease of electrical
conductivity from 1.2 S m-1 for GrFoamPt to 0.2 S m-1 for GrFoam3N sample.

Key words: graphene; chemical vapor deposition; nitrogen-doping; hydrogen

evolution reaction

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Acknowledgments: This research was funded by the Romanian Research and

Innovation Ministry-Core Program, contract number PN19110205/2019.

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COMBINED CO2 AND STEAM REFORMING OF METHANE – VIABLE WAY FOR

SYNGAS PRODUCTION

Mihaela Diana Lazăr, Monica Dan, Maria Miheţ

National Institute for Research and Development on Isotopic and Molecular Technologies – INCDTIM,
67-103 Donat Street, Cluj Napoca, Romania
Correspondence author: [email protected]

CO2 reforming of methane (usually called methane dry reforming) was

intensively studied in the last years as an alternative for valorizing excess carbon
dioxide and for providing synthesis gas for methanol or synthetic fuels production
[Jang, 2019]. The process is also important as the main components of biogas are
CH4 and CO2. By their direct catalytic reaction, synthesis gas with H2:CO ratio of 1:1
is formed (reaction 1). For methanol synthesis or Fischer-Tropsch process it is
necessary to have synthesis gas with H2:CO ratio of at least 2:1. This can be
obtained by adding water to the reformation process, in other words by implying
the steam reforming of methane (reactions 2 and 3) alongside dry reforming.

CH4 + CO2 → 2CO + 2H2 (1)

CH4 + H2O → CO + 3H2 (2)
CH4 + 2H2O → CO2 + 4H2 (3)

The resulted process is known as Combined Steam and Dry Reforming of Methane
(CSDRM) and is regarded as a more viable option to produce synthesis gas with desired
composition for its further use.
Ni based catalysts with bimodal pore structure represents a class of recently
developed materials with potentially better catalytic properties than their counterparts
with classic porous structure. The smaller pores provide higher surface area for Ni
dispersion, while the larger pores facilitate the transport of reactants and products
to/from the catalytic active sites [Bao, 2015]. The addition of CeO2 to the Ni/Al2O3
catalysts improves the catalytic properties for reformation reactions due to implication of
Ce redox process in Ni nanoparticles stabilization on the support and coke removal from
catalyst obtained surface [Dan 2015; Siang, 2017].
The dual pore size mesoporous nickel based catalysts were in a template-free
synthesis by co-precipitation of Al(NO3)3, Ce(NO3)3 (or Mg(NO3)2 or La(NO3)3) and
Ni(NO3)2 with NaOH solution followed by reflux for 24 h, filtration and drying at 100°C for
12h. The target concentration for Ni and additional oxides is 10 wt.%. The catalyst
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precursor was further calcined in Ar at 450°C for 3h and reduced in H2 at 650°C. The low
calcination temperature was selected to avoid the formation of Ni aluminate species and
the reduction temperature was estimated from H2-TPR analysis.
All catalysts were further characterized using the following methods: X-Ray
diffraction (XRD) – to establish the crystallinity of the support and the size of Ni
crystallites; N2 adsorption-desorption isotherms – to calculate the surface area using BET
method and to prove the bimodal pore structure using Dollimore-Heal model;
Temperature Programmed Reduction (TPR) – to estimate the strength of the metal-
support interaction and the optimum reduction temperature; Temperature Programmed
Desorption (H2-TPD and CO2-TPD) to estimate the type and strength of catalytic active
sites for methane and carbon dioxide activation.
The total surface area decreases by adding increasing concentrations of CeO2 to the
alumina support, but the bimodal pore size structure is preserved for all catalysts. The
catalyst precursor reducibility decreases by increasing the CeO2 content, proving the
existence of a better interaction between the NiO and the support. The results of
catalysts characterization are presented in Table 1.
The catalytic materials were tested in CSDRM at atmospheric pressure and
temperatures between 600 and 700°C. The reagents ratio was CH4 : CO2 : H2O : Ar = 1 :
0.47 : 0.8 : 5.2 which assure an oxidant to fuel ratio of nH2O+nCO2/nCH4 = 1.3. In these
conditions the carbon deposition is favored on the catalyst surface.

Table 1. The structural properties of Ni/oxide-Al2O3 materials

2 SNi
Catalyst St (m /g) 2 Rm (nm) DNi (nm) Tred (°C)
(m /g)
Ni/Al2O3(ref) 101 2 2.8 9 -
Ni/Al2O3 265 2.7 4 and 8 5.1 525
Ni/CeO2-Al2O3 200 2.8 4 and 9 5 590
Ni/MgO-Al2O3 233 2.8 4 and 9 3.8 645
Ni/La2O3-Al2O3 215 6.9 4 and 9 - 605
St – total surface area; Rm – medium pores size; DNi – nickel crystallites size (from XRD); Tred – temperature reduction peak in H2-TPR

The catalytic results, expressed as methane conversion are presented in Figure 1.

Figure 1. Variation of the methane conversion with temperature and catalyst

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The performances of Ni/Al2O3 with bimodal pores structure are net superior to
the ones obtained using a references Ni/Al2O3 catalysts with similar Ni content
deposited on a commercial support. The addition of all three additives improves the
methane conversion and catalysts stability against deactivation. The catalyst with
best performances for methane conversion is Ni/MgO-Al2O3. This behaviour can be
correlated with decrease of Ni interaction with the support and increase of
hydrogen and CO2 adsorption capacity. For Ni/La2O3-Al2O3 an important increase in
Ni dispersion was observed, but its catalytic performances, although superior to
Ni/Al2O3 is close to other two studied catalysts due to its lower capacity for CO 2
activation. Synthesis gas with the H2:CO ratio between 2.3 and 2.5 was obtained for
all the reaction conditions used in this work. The bimodal pore catalysts showed no
deactivation during CSDRM process. The minimum carbon deposition was observed
for Ni/La2O3-Al2O3

Key words: bimodal pore catalysts; syngas; biogas upgrading; combined steam
and dry reforming.

Acknowledgments: This work was supported by Ministry of Education and

Research, under NUCLEU Program, project number PN 19 – 35 02 02 and NO Grants
2014 - 2021, under Project contract no. 13/2020.

References
Z. Bao, Y. Lu, J. Han, Y. Li, F. Yu, Highly active and stable Ni-based bimodal pore catalysts for
dry reforming of methane, Appl. Catal. A General 491 (2015) 116-126
M. Dan, M. Mihet, Z. Tasnadi-Asztalos, A. Imre-Lucaci, G. Katana, M. D. Lazar, Hydrogen production
by ethanol steam reforming on nickel catalysts: Effect of support modification by CeO2 and
La2O3, Fuel, 147 (2015) 260-268
W-J. Jang, J-O Shim, H-M. Kim, S-Y. Yoo, H-S. Roh, A review on dry reforming of methane in aspect of
catalytic properties, Catal. Today 324 (2019) 15–26
T. J. Siang, H. T. Danh, S. Singh, Q. D. Truong, H. D. Setiabudi, D-V. N. Vo, Syngas Production from
Combined Steam and Carbon Dioxide Reforming of Methane over Ce-modified Silica supported
Nickel Catalysts, Chem. Eng. Trans., 56 (2017) 1129-1134

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SINGLE-STAGE SYNTHESIS OF NITROGEN-DOPED GRAPHENE OXIDE

Adriana Marinoiu, Elena Carcadea

National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Corresponding author: [email protected]

This paper highlights the ability of few-layer nitrogen-doped graphene (N/rGO)

to serve as catalytic material for oxygen reduction reaction (ORR) electrode in the
attempt to find an inexpensive alternative to platinum catalysts for use in proton
exchange membrane fuel cells (PEMFCs) [Marinoiu A., 2020]. N/rGOs have been
obtained by a one-step synthesis using microwave-irradiation process (MW). The
structure and composition of the synthesized catalysts were examined by Fourier
infrared spectroscopy, X-ray spectroscopy measurements XPS, specific surface area.
The electrocatalytic activity of the synthesized catalysts toward the ORR was
investigated by specific techniques, such as cyclic voltammetry
Nitrogen-doped graphene oxide catalysts with high ORR catalytic performance
could be one of the promising long-term solutions for the commercialization
challenge of PEMFCs. The key to answering this is to determine the contribution of
four nitrogen doping configurations, namely pyrrolic nitrogen, pyridinic nitrogen,
graphitic nitrogen, and pyridine-nitrogen oxide and to make a correlation to the
catalytic performance. A detailed comparison of physical, chemical, and
electrochemical properties of N/rGO catalysts obtained through microwave
irradiation is presented in this paper.
Few-layer nitrogen-doped graphene have been prepared using a soft
procedure, namely the microwave-irradiation process. The structural characteristics
indicated that the synergistic effect improved the electrons transportation at
nanometer-scale diffusion and also limited the resistance losses. The prepared
N/rGOs were used to investigate the potential application as ORR electrode for
PEMFC. Cyclic voltammetry (CV) measurements revealed that the prepared catalyst
has improved the catalytic activity of the commercial catalyst. The results
confirmed that the cathode modified with N/rGO can be used as a potential
support for a fuel cell electrode application. The total content of graphitic and
pyridinic nitrogen atoms is the key factor to enhance the current density in the
electrocatalytic activity for ORR. Also other electrochemical characterizations clearly
demonstrated the excellent electrocatalytic activity of N/rGO toward ORR. The
mentioned cost-effective approach opens the possibility for the synthesis of other

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nitrogen-doped materials for the development of other metal-free efficient ORR

catalysts.

Key words: graphene, nitrogen-doped graphene, microwave, fuel cells

Acknowledgments: This work was supported by Ministry of Research,

Innovation, Digitization from Romania by the National Plan of R & D, Project No. PN
19 11 02 01, and by UEFISCDI, Contract No. 460PED/2020 (Project PN-III-P2-2.1-
PED-2019-1894) and Contract No. 469PED/2020

References
Marinoiu A, Andrulevicius M, Tamuleviciene A, Tamulevicius T, Carcadea E, Raceanu M, High
performance catalytic system with enhanced durability in PEM fuel cell, International Journal
of Hydrogen Energy, 45 (17), pp. 10409-10422, 2020

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WORKING GAS INFLUENCE ON STIRLING ENGINE EFFICIENCY. A THEORETICAL

APPROACH FOR IDEAL GASES

Nicolae Aldea1, Florica Matei2, Vasile Rednic1

1
Center of Advanced Research and Technologies for Alternative Energies (CETATEA),
National Institute for Research and Development of Isotopic and Molecular Technologies,
Donat 67-103, Cluj-Napoca, Romania
2
University of Agricultural Sciences & Veterinary Medicine Cluj Napoca,
3-5 Calea Manastur St, Cluj Napoca 400372, Romania
Corresponding author: [email protected]

The indicated power and thermal efficiency are the most important features of
the Stirling engine. In the most general way, the second characteristic depends on a
set of parameters, such as the ratio between the volumes and temperatures of the
working gas in the hot and cold compartment, the ratio between the molar heat
capacities at constant volume and the constant working gas pressure; and energy
losses due to friction processes between engine components. Stirling engines can
use mono, bi or polyatomic molecules such as helium, hydrogen or carbon dioxide
as working gases. In the first part our contribution is dedicated to the elaboration of
an analytical model of thermal efficiency based on a simplified thermodynamic
cycle described in the pressure-volume diagram of two adiabatic and two isochoric
transformations. In order to verify the developed model, the technical design data
of the Stirling Genoa03 engine are used as input data for our αSETS code. The data
resulting from the code were used to estimate the thermal efficiency and the
indicated power of the considered Stirling engine. The second part of the article is
dedicated to the analytical elaboration of the adiabatic function of the working gas
for the case of a mixture consisting of two or three types of working gases at
different molar concentrations. Developed adiabatic functions are then used to
estimate thermal efficiency. It has been shown that a mixture of two or three types
of gas does not improve the thermal efficiency of the Stirling engine compared to
the use of one-component gas. The results of these models related to the Beale
relationship can be used successfully in the design process of Stirling engines.

Key words: Stirling engine; thermodynamic analysis; working gas mixture;

thermal efficiency; Beale number.

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Fe-BTC METAL-ORGANIC FRAMEWORK FOR EFFICIENT PHOTOCATALYTIC

OXIDATION OF NEUTRAL RED FROM WATER

Violeta-Carolina Niculescu, Silviu-Laurenţiu Badea, Amalia Soare, Stănică Enache,

Marius Constantinescu, Felicia Bucura, Claudia Sandru

National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Corresponding author: [email protected]

Advanced oxidation processes (AOPs) are a set of chemical treatment

procedures designed to remove organic (and sometimes inorganic) substances in
water and wastewater by oxidation through reactions with hydroxyl radicals (OH)
[Bokare and Choi, 2014; Thomas et al., 2021]. Compared with other treatment
techniques, AOPs could effectively eliminate organic compounds in the aqueous
phase, rather than accumulating or transferring pollutants into another phase.
Therefore, due to the remarkable reactivity of the •OH radical, the AOPs could be
applicable in many, if not all, scenarios where organic contaminants are to be
simultaneously removed. Among the advanced oxidation processes, an important
place is occupied by heterogeneous photocatalysis [Sadik et al., 2004; Bouchaaba et
al., 2016; Saleh and Taufik, 2019; Elshypany et al., 2021], an efficient method that
replaces alternative methods of removing organic pollutants ((e.g. phenols, dyes
[López Cisneros et al., 2002], pesticides, organic solvents, pharmaceuticals, and
household chemicals)) from wastewater, due to the ability to transform organic
pollutants into inorganic products, non-toxic to the environment, for example: CO2,
H2O and mineral acids. The textile industry is a major producer of wastewater with
a high and varied content of contaminants including dyes and one of the biggest
environmental problems is the colour removal from wastewater.
In this study the photocatalytic degradation of neutral red dye from an
aqueous solution was investigated. The metal-organic framework Fe-BTC (BTC:
1,3,5-benzenetricarboxylate) was used as catalyst to enhance the H2O2/UV system.
The Fe-BTC was synthesised by mixing the anhydrous FeCl3 with 1,3,5-
benzenetricarboxylic acid on a combined hot-plate magnetic-stirrer device at room
temperature. Various characterization techniques (elemental analysis, BET, SEM-
EDX, FTIR, Raman, XRD) shown that the synthesised Fe-BTC has similar properties
with the ones of commercial Fe-BTC.
Photocatalytic reaction of neutral red (3-amino-7-dimethylamino-2-
methylphenazine hydrochloride) was performed in an assembly in which the
neutral red solution was introduced under magnetic stirring at 300 rpm, while a UV
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lamp was fixed above the beaker. In all experiments, the starting concentration of
neutral red was 50 µM, at a solution volume of 50 mL, while various quantities (10-
100 mg) of Fe-BTC were added initially before the photocatalysis reaction. The
photo-Fenton reaction was initiated by the addition of H2O2 of 30% concentration
(in volumes from 5 to 20 mL), with the simultaneous start of the UV lamp. A control
experiment was performed by indirect photolysis of the neutral red solution in the
H2O2/UV system, in the absence of Fe-BTC. The determination of the neutral red
concentration was performed by measuring the absorbance at 530 nm using the
UV-Vis spectrophotometer. For the quantification of neutral red, a calibration curve
was drawn with five standard solutions of neutral red with concentrations between
5 and 200 µM.
In all photocatalysis experiments, neutral red degradation was observed in the
presence of the H2O2/UV system. Due to adsorption, the concentration of neutral
red decreased sharply to 26.328 µM at the beginning of the experiment, then
decreased slowly to 23.849 µM after 60 minutes. After the addition of 5 mL 30%
H2O2 and the start of photocatalysis reaction, the concentration of neutral red
decreased upon degradation to 0.191 µM after 240 minutes (fig. 1).

Figure 1. Photocatalytic degradation of neutral red (NR) (5 mL 30% H 2O2; 10 mg Fe-BTC)

Nevertheless, the results shown that, in the presence of large amounts of Fe-
BTC, the degradation of neutral red became negligible due to competitive
adsorption processes on the surface of Fe-BTC, while an increase in the amount of
H2O2 did not influence the rates of the photocatalytic reactions. It can be concluded
that this study is a step forward in studying the photocatalysis processes for dyes
removal from textile industry wastewater.

Key words: AOPs, MOF, neutral red, photocatalysis, wastewater.

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Acknowledgments: The work has been funded by the Romanian Ministry of

Research Innovation and Digitalization, NUCLEU Program-Financing Contract no.
9N/2019, under Project PN 19 11 03 01 “Studies on the obtaining and improvement
of the acido-basic properties of the nanoporous catalytic materials for application in
wastes valorization”.

References
Bokare, A.D., Choi, W., 2014. Review of iron-free Fenton-like systems for activating H2O2 in advanced
oxidation processes. J. Hazard. Mater. 275, 121–135. https://doi.org/https://doi.org/
10.1016/j.jhazmat.2014.04.054.
Bouchaaba, H., Bellal, B., Maachi, R., Trari, M., Nasrallah, N., Mellah, A., 2016. Optimization of physico-
chemical parameters for the photo-oxidation of neutral red on the spinel Co2SnO4. J. Taiwan Inst.
Chem. Eng. 58, 310–317. https://doi.org/https://doi.org/10.1016/j.jtice.2015.06.011.
Elshypany, R., Selim, H., Zakaria, K., Moustafa, A.H., Sadeek, S.A., Sharaa, S.I., Raynaud, P., Nada, A.A., 2021.
Elaboration of Fe3O4/ZnO nanocomposite with highly performance photocatalytic activity for
degradation methylene blue under visible light irradiation. Environ. Technol. Innov. 23, 101710.
https://doi.org/https://doi.org/10.1016/j.eti.2021.101710.
López Cisneros, R., Gutarra Espinoza, A., Litter, M.I., 2002. Photodegradation of an azo dye of the textile
industry. Chemosphere 48, 393-399. https://doi.org/https://doi.org/10.1016/S0045-6535(02)00117-0.
Sadik, W.A., Sadek, O.M., El-Demerdash, A.M., 2004. The Use of Heterogeneous Advanced Oxidation
Processes to Degrade Neutral Red Dye in Aqueous Solution. Polym. Plast. Technol. Eng. 43, 1675–
1686. https://doi.org/10.1081/PPT-200040069.
Saleh, R., Taufik, A., 2019. Photo-Fenton degradation of methylene blue in the presence of Au-
Fe3O4/graphene composites under UV and visible light at near neutral pH: Effect of coexisting
inorganic anion. Environ. Nanotechnology, Monit. Manag. 11, 100221. https://doi.org/10.1016/
j.enmm.2019.100221.
Thomas, N., Dionysiou, D.D., Pillai, S.C., 2021. Heterogeneous Fenton catalysts: A review of recent advances.
J. Hazard. Mater. 404, 124082. https://doi.org/10.1016/j.jhazmat.2020.124082.

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HARD CARBON DERIVED FROM WASTE BIOMASS FOR NA-ION BATTERIES

Cristina Niţă1,2,3, Biao Zhang4, Joseph Dentzer1,2, Camélia Matei Ghimbeu2,5

1
Center for Advanced Laser Technologies (CETAL), National Institute for Lasers, Plasma and Radiation
Physics (INFLPR), Magurele, Romania
2
Université de Haute-Alsace, Institut de Science des Matériaux de Mulhouse (IS2M), CNRS UMR 7361,
F-68100 Mulhouse, France
3
Université de Strasbourg, F-67081 Strasbourg, France
4
Department of Applied Physics, The Hong Kong Polytechnic University, Kowloon, Hong Kong, China
5
Réseau sur le Stockage Electrochimique de l'Energie (RS2E), CNRS FR3459, 33 Rue Saint Leu, 80039
Amiens Cedex, France
Corresponding author: [email protected]

In the recent years, the interest for eco-friendly and low-cost energy systems
has significantly increased taking into account the evolution of technology, which
comes along with a high consumption of natural resources. For the moment, Li-ion
batteries meet the market demand in terms of performance and relatively low
price, but the limited Li resources make them unsustainable for long term. In this
context, Na-ion batteries has attracted the attention of researchers from the entire
world due to the rich Na resources in the Earth’s crust which may offer a low-cost
energy system for near future [C. Nita et al., 2019]. Moreover, biomass waste is
considered one of the most interesting, renewable and cost-effective precursors to
obtain hard carbon materials with high potential as electrodes for Na-ion batteries
[C. Nita et al., 2021].
In this work, we propose new hard carbon materials based on coconut shells,
walnut shells, and corn silk biomass waste as anodes for Na-ion batteries. Their
pyrolysis at 1300oC followed by acid washing to remove inorganic impurities led to
hard carbon materials with low and similar surface areas (<10 m2g-1). Their
structures were investigated by using several complementary techniques and the
results revealed a higher degree of disorder for coconut shell HC, while for corn silk
HC, a mixture of disordered carbon and localized graphitized structure was
observed. Their different organic and inorganic compositions lead to different
carbon features and good performance in Na-ion batteries, i.e., a capacity between
293 and 315 mAh g-1 at 50 mA g-1 with good retention (87%-93%) after 100 cycles.

Acknowledgements: The authors acknowledge the financial support of this

work from University of Haute-Alsace, France, European Union's Horizon 2020
Program (project NAIADES, call: LCE10-2014, Contract no. 646433), PHC Brancusi
9BM/2019 (Bilateral project Romania-France) and PD 134/2020.
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References
C. Nita, J. Fullenwarth, L. Monconduit, L. Vidal, C. Matei Ghimbeu, Influence of carbon characteristics
on Sb/carbon nanocomposites formation and performances in Na-ion batteries, Materials
Today Energy, 13, (2019), 221-232, doi: 10.1016/j.mtener.2019.05.009.
C. Nita, B. Zhang, J. Dentzer, C. Matei Ghimbeu, Hard carbon derived from coconut shells, walnut
shells, and corn silk biomass waste exhibiting high capacity for Na-ion batteries, Journal of
Energy Chemistry, 58, (2021), 207-218, doi: 10.1016/j.jechem.2020.08.065.

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INCREASING THE ACCURACY IN DIAGNOSING THE CONDITION OF CELLULOSE

INSULATION IN TRANSFORMER UNITS THROUGH ANALYSIS AND IMPLEMENTATION
OF A NEW MARKER

Dumitru Sacerdoțianu, Ancuța-Mihaela Aciu, Cristina Maria Nițu

Research and Development Division

National Institute for Research, Development and Testing in Electrical Engineering - ICMET Craiova
Craiova, B-dul Dacia no. 118A, tel.0351 404888, e-mail: [email protected]
Corresponding authors: [email protected], [email protected],
[email protected]

High power transformers are basic components in any electric power

transmission or distribution network. The demand for electricity is constantly
increasing, resulting in a significant number of power transformers in operation and
transformers in the process of being installed. Properly built power transformers
have an average operating life of 25 to 35 years, depending on the load,
temperature and maintenance. There are cases where power transformers, with
proper maintenance, can reach an operating life of about 60 years [M. Wang et al.,
2002]. There are several high-power transformers built in the 60-70s, considered to
be near the end of their intended lifespan. From this perspective, studies were
conducted for the development of precise and safe instruments to assess and
predict the evolution of the remaining life of power transformers and to avoid the
damage to the old units, with the consequences resulting from them.
Despite the continuous progress regarding the control, automation and design
of power transformers, the general configuration of high-power transformers,
including their components and materials, remains almost unchanged from the first
commercial versions.
The insulation system of high-power transformers consists of the oil and solid
insulating material (impregnated in insulating oil) complex. The electrical insulating
oil is generally mineral oil, and the solid insulation is based on cellulose (especially
Kraft paper, pressboard and thermally improved kraft paper/TUK). An assessment
of their degradation condition consists in monitoring both sides of the insulation
system.
Several factors (electrical, mechanical and thermal stresses) influence the
operating life of power transformers. These factors interfere with the components
of the insulation system, therefore accelerating the normal ageing of oil and paper.
Fortunately, the oil can be reclaimed or possibly replaced when necessary, without
shutting down the transformer.
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The solid part of the insulation system (paper and pressboard) cannot be
monitored or changed once the transformer is built. Therefore, the operating life of
transformers is determined by the life of the cellulose insulation. Then, it is very
important to periodically check the condition of the cellulose insulation, in order to
apply mitigation techniques at the right time.
The most important parameter for the assessment of the aging condition of
the cellulose in transformers is its degree of polymerization (DP). The degree of
polymerization (DP) was measured according to IEC 60450. This physico-chemical
analysis provides some data on the mechanical property of cellulose. The DP value
of a new cellulose-based material is approximately 1200, while the final lifetime
criterion is approximately 200 [L. Lundgaard et al., 2007]. However, the drawback of
this method is the inapplicability of the cellulose samples in operating condition. In
order to take the samples necessary to determine the DPv, the transformer must be
switched off or sampling must be carried out during repair or reconditioning. For
this reason, methods have been developed to indirectly monitor the ageing process
and condition of the insulation paper, and hence the condition of high-power
transformers. The determination of an oil-soluble by-product of cellulose
degradation, also known as a chemical marker, is thus essential for the electrical
industry.
The first studies covered the relation between the amount of carbon oxides,
CO and CO2, in oil and the degree of polymerization (DP) of the insulating paper.
Carbon oxides, including carbon monoxide (CO) and carbon dioxides (CO 2) are
measured by using the dissolved gas analysis (DGA) through gas chromatography
(GC) techniques. In the case of free-breathing transformers, the level of carbon
dioxide can be considerably influenced by ingress from the atmosphere [L.
Lundgaard et al., 2007].
The application of the CO2 and CO ratio as an indicator of the health of paper is
unreliable due to the long-term oxidation effect of oil or it could occur as a result of
free air ingress due to leakage [R. Gilbert et al., 2010]. To overcome this problem,
additional tests, such as the furan analysis.
Another current technique is the analysis of furan compounds, a group of
chemical compounds formed by the oxidation, hydrolysis and pyrolysis of cellulose.
After a complex process, the glucose molecule, which is not soluble in oil degrades
into different types of furan derivatives. Some of them are available for use as
chemical markers based on their polarity and solubility in oil.
2-furfuraldehyde (2-FAL) has been shown to have a high degree of generation
and better stability than the other furan compounds and can be extracted from oil
and used to characterize the thermal decomposition of the electroinsulating paper.
A high concentration of 2-FAL indicates a high level of paper degradation.
The constructive differences of transformers, such as the amount of solid
insulating material or the type of design (e.g. shell-type vs. core-type transformers)
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limit the interpretation of 2-FAL and the determination of the typical threshold values.
Also, several physico-chemical parameters, such as temperature, moisture, oxygen
concentration, etc. influence 2-FAL concentration in transformer oil [J. Kachler and I.
Höhlein, 2005a; J. Kachler and I. Höhlein, 2005b; J.A. Lapworth et al., 2007].
To overcome these drawbacks, several alternative chemical markers have been
studied for the determination of the degradation of solid insulation in oil-immersed
transformers. Of these markers, methanol (MeOH) showed the greatest stability at
different temperatures. For these reasons, methanol is of particular interest for
paper depolymerization monitoring and is useful for transformer health condition
diagnostic [IEC 60450:2007; IEC 61198:1993].
Due to the fact that methanol is a new marker used in determining the aging of
insulation, there is no standardized method. To efficiently determine this marker, the
following method was presented in the literature: Head Space/Gas Chromatography/
Mass Spectrometry (HS/GC/MS), [J. Jalbert et al., 2012a; A. Schau et al., 2011; J. Jalbert
et al., 2012b]. HS allows the vaporization of molecules, then GC separates different
molecules and finally MS analyzes and quantifies the molecules.

Figure 1. HS/GC/MS equipment diagram

Methanol [IEC 60450:2007] has lately been used as a paper degradation

marker because it has been found that this marker has the following advantages:
– It can be applied in different types of mineral oils (uninhibited and
inhibited);
– It is generated by all types of cellulose-based paper, including paper with
improved thermal properties, even at low temperatures;
– There is a direct relationship between the number of cleavages of glycosidic
bonds in the cellulose chains and methanol generation over time;
– The increase in methanol concentration is directly proportional to the
decrease in the degree of polymerisation;
– MeOH recovery time, after processing the oil of a given transformer is half
the time necessary for 2-FAL recovery.
A study presented in [J.A. Lapworth et al., 2007] specified that, in addition to
MeOH, ethanol (EtOH) also has a special behavior, acting as a chemical hotspot
marker for cellulose insulation. This is due to the fact that, at temperatures above
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250°C, the main by-product is levoglucosan, which further decomposes to generate

a high amount of EtOH.
Therefore, such a behavior of alcohols provides the possibility to distinguish
between normal and abnormal cellulose insulation aging, thus distinguishing the
area of moderate aging from a small area of accelerated aging of the solid
insulation. Therefore, based on MeOH levels, the condition of the insulation can be
tracked from the initial aging to the end. Recent research has confirmed that MeOH
can be used as a chemical marker to detect the beginning of the decomposition of
cellulose insulation, showing a good correlation with the DP, in contrast with the 2-
FAL marker which can be used for the severe degradation of cellulose insulation.
ICMET Craiova (National Institute for Research, Development and Testing in
Electrical Engineering) designed and developed a distributed and open monitoring
system, which can be completed with acquisition modules in accordance with the
most complex requirements.
The monitoring system is provided with sufficient inputs and outputs so as to
allow monitoring and processing of all quantities specified in the Technical
Specification and in the requirements of the beneficiary.
The monitoring system (according to Figure 2) consists of transducers, among
the most efficient and reliable acquisition modules currently available on the
market, each device in itself being purchased from suppliers recognized for both
operating and monitoring the transformer units.
The architecture of the monitoring system allows a close interconnection
between the equipment and the possibility of centralizing the information on the
monitor of a monitoring-dedicated computer as well as the integration into SCADA
of the monitored quantities on Modbus TCP/IP.

Figure 2 - Transformer units monitoring system architecture

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The online monitoring system allows the analysis of the parameters that
influence the condition of:
- oil;
- solid insulation;
- bushings;
- windings;
- core;
- on-load tap changer;
- cooling system.
According to the new pursuits in determining the level of insulation aging, a
sensor is intended to be implemented in the system presented above, to allow the
determination of methanol concentration of in transformer oil.
Thus, after the implementation of the sensor, the proposed monitoring system
will allow the acquisition, processing and display of data on transformer health
condition, but also their storage in the database
During the accelerated aging of the paper samples umder laboratory
conditions, the partition phenomenon plays an important role in the concentration
of methanol in oil. This phenomenon explains the way in which changes in
parameters such as temperature, internal pressure, humidity, type of paper and oil,
etc. can shift the migration of methanol, generated by cleavages of cellulose chains,
to oil. Therefore, methanol can be used as a marker to assess the actual condition
of the solid insulation over time and in terms of tensile strength.
The experimental research studies presented and discussed in this paper have
shown that MeOH is a promising marker for the evaluation of aging of all cellulose-
based materials (standard Kraft paper, pressboard and thermally upgraded paper
(TUK) and can be applied in different types of minerals oils (inhibited and
uninhibited). The correlation between the degree of polymerization (DP) and the
generation of MeOH is well determined, however, it should be taken into
consideration that the prior detection of MeOH, compared to 2-FAL, is of particular
importance for an efficient technique of monitoring and assessing the condition of
degradation of the solid insulation in the transformer.

Key words: insulating paper, ageing, degree of polymerization, chemical markers,

methanol.

References
R. Gilbert, J. Jalbert, S. Duchesne, P. Tétreault, B. Morin, and Y. Denos, "Kinetics of the production of
chain-end groups and methanol from the depolymerization of cellulose during the aging of
paper / oil systems. Part 2: Thermally-upgraded insulating papers ", Cellulose, vol. 17, pp. 253-
269, 2010;

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IEC 60450:2007 - Measurement of the average viscometric degree of polymerization of new and
aged cellulosic electrically insulating materials
IEC 61198:1993 - Mineral insulating oils. Methods for the determination of 2-furfural and related
compounds.
J. Jalbert, E.M. Rodriguez-Celis, O.H. Arroyo-Fernández, S. Duchesne, B. Morin, “Methanol Marker
for the Detection of Insulating Paper Degradation in Transformer Insulating Oil”, MDPI Energies
2019, 12, 3969; doi:10.3390/en12203969
J. Jalbert et al., “Robust and sensitive analysis of methanol and ethanol from cellulose degradation in
mineral oils,” in Journal of Chromatography A, vol. 1256, pp. 240-245, Nov. 2012a;
J. Jalbert, R. Gilbert, Y. Denos, P. Gervais, 2012b, “Methanol: a novel approach to power transformer
asset management”, IEEE Trans. on Power Delivery, Vol. 27, No. 2, pp. 514-520;
J. Kachler and I. H hlein, “Aging of Cellulose at Transformer Service Temperatures, Part 1. Influence
of Type of Oil and Air on the Degree of Polymerisation of Pressboard, Dissolved Gases and
Furanic Compounds in Oil ”, IEEE Electr. The island. Mag., Vol. 21, No. 2, pp. 15-21, 2005a;
J. Kachler and I. Höhlein, “Aging of Cellulose at Transformer Service Temperatures, Part 1. Part 2:
Influence of Water content and Temperature on Degree of Polymerization and Formation of
Furanic Compounds in Free-Breathing Systems ”, IEEE Elect. The island. Mag., Vol. 21, No. 5,
pp. 20-24, 2005b;
J.A. Lapworth, RJ Heywood, PN Jarman and C. Myers, “Transformer Insulation: Towards more
reliable residual life assessments ”, Cigre A2-D1 Colloquium in Brugge, 2007;
L. Lundgaard, D. Allan, I. Hohlein, R. Clavreul, M. Dahlund, H.-P. Gasser, et al., "Aging of cellulose in
mineral-oil insulated transformers", Cigre Brochuer No. 323, 2007;
A. Schaut, S. Autru, S. Eeckhoudt, 2011, “Applicability of methanol as a new marker for paper
degradation in power transformers”, IEEE TDEI, Vol. 18, n°2, p. 533-540;
M. Wang, AJ Vandermaar, KD Srivastava, "Review of condition assessment of power transformers in
service", Electr. The island. Mag. IEEE, vol 18, no. 6, pp. 12-25, 2002;

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HIGH TEMPERATURE OXIDATION OF ALTERNATIVE BOND COAT MATERIALS AS

PART OF THERMAL BARRIER COATING SYSTEMS

Amalia Soare1, Ioana Csaki2, Cristina Oprea3, Ioan Costina4

1
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
2
University Politehnica Bucharest, Romania
3
SC TENSOR SRL Bucharest, Romania
4
Institute for High Performance Microelectronics – IHP, Frankfurt am Oder, Germany
Coressponding author: [email protected]

Thermal Barrier Coating (TBS) systems are complex systems used in gas
turbines that is the reason why the research of alloys with higher melting point and
better mechanical properties have been carried out lately.
An important part of this system is represented by the Bond Coat (BC) which is
the buffer layer. The BC is thought to be responsible for the failure of the entire
system by partial buckling and subsequent spallation of the coating from the alloy.
This work is proposing new Ru-based materials which seem to be a promising
alternative to the more traditional (Ni,Pt)Al alloys.
RuAl alloys were prepared by induction melting and by Spark Plasma
Sputtering (SPS) in an attempt to obtain stoichiometric RuAl alloys. They were
oxidised in air at 1100C for 10h and 100h and also subjected to cryogenic
temperatures (liquid N2) in air for 1h and 2h.
The results are encouraging in case of Ru Al alloys prepared by induction
melting where the team managed to get an alumina layer free of Ru and other
impurities.

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IONIC CONDUCTIVITY AND DIELECTRIC RELAXATION OF NASICON

SUPERIONIC CONDUCTORS AT THE NEAR-CRYOGENIC REGIME

Athanasios Tiliakos1,2, Mihaela Iordache1, Adriana Marinoiu1

1
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
2
National R&D Institute for Laser, Plasma and Radiation Physics (INFLPR),
409 Atomiştilor Street, Măgurele, 077125, Romania
Coressponding author: [email protected]

With a crystal lattice structure firstly characterized in the 1970s, NASICON

sodium-based superionic conductors have recently found renewed interest as solid
electrolytes in sodium-ion and seawater flow batteries due to their exceptional
ionic conductivity being on the same scale as liquid electrolytes. Since sodium ions
in the crystal lattice move among interstitial positions through site-specific
bottlenecks, the overall conductivity is strongly dependent on the NASICON
composition. In this work, we report on the synthesis protocols and processing
parameters of Na3Zr2Si2PO12 prepared from Na2CO3, SiO2, ZrO2, and NH4H2PO4
precursors by the conventional solid-state reaction (SSR) route. We critically
evaluate important observations made in the extended literature on the topic,
including: i) the importance of precursor particle size concerning the SSR synthesis,
focusing on effective ball-milling protocols; and ii) the onset of excess zirconia
contamination, expanding on the effects of both thermal and pressure processing –
the latter often overlooked in the available literature. In approaching the cryogenic
regime, the dataset availability concerning ionic conductivity and dielectric
permittivity measurements for NASICON is extended, starting from elevated
temperatures at 200°C and reaching into the very low temperature zone at -100°C.

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CAPACITY ABSORBANCE OF BIODEGRADABLE MATERIAL USED TO REMOVE

HYDROCARBONS

Sanda Voinea1,*, Cornelia Nichita1,2, Iulia Armeanu1, Bianca Şolomonea1,

Cornelia Diac1, Paul Dogaru1
1
University of Bucharest, Faculty of Physics, 405 Atomiștilor Street, 077125, Măgurele, Romania
2
National Institute for Chemical – Pharmaceutical Research and Development, 112 Vitan Avenue,
031299, Bucharest, Romania
Corresponding author: [email protected]

Abstract. The primary aim of the present paper is to provide an alternative

solution in case of accidental water pollution with different types of oil. The main
element used is an absorbent based on Sphagnum moss, a biodegradable material
which plays an important role in ecology. Using both usual experimental devices
and modern laboratory equipment, the study supports environmental protection by
analyzing the capacity of this natural absorbent to remove hydrocarbons from
contaminated water. Also, we investigated the physical and chemical properties of
the clean water, as well as the soil, in order to have an overview of absorbent
capacity for their treatment.

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METALLIC-NANOPARTICLES ON MESOPOROUS SILICA STRUCTURES

Monica Dan, Oana Grad, Maria Miheţ, Gabriela Blăniţă, Diana Lazăr

National Institute for Research and Development of Isotopic and Molecular Technologies,
67-103 Donath. Str. 400293 Cluj-Napoca, Romania
Corresponding author: [email protected]

Carbon dioxide and methane are the mainly components of greenhouse gases
(GHGs) emitted by power production and burning of fossil fuels. There is a need to
reduce their presence in atmosphere and developing of an efficient technology to
transformed them into valuable products is a very attractive solution. Recently,
combined steam and CO2 reforming of methane (CSCRM) has gain attention and
has been considered as a better promising technique for syngas production due to
the direct control of the H2/CO2 ratio by adjusting the feed ratio of carbon dioxide
and steam. The synthesis gas is used for selective synthesis of various chemicals and
oxygenated fuels.
Generally, the catalysts used in CSCRM are based on Ni. There are very few
studies published regarding the using of mesoporous silica structures as catalyst
support in the CSCRM process. The present work reports the preparation and
characterization of the new catalysts obtained by confinement of Ni nanoparticles
(NPs) within the pores of ordered mesoporous silica structures. The mesoporous
silica structures namely MCM-41 (hexagonal structure) and MCM-48 (cubic
structure) were prepared by a sol gel method at low temperature under
hydrothermal conditions. This method of preparation favoured the obtaining of
silica supports with large surface area and ordered mesoporous structure, which
can contribute to the homogeneous confinement of Ni NPS within their pores. The
Ni clusters have been embedded into mesoporous silica supports by different
approaches: (i) impregnation and (ii) double solvent method.
The prepared mesoporous supports and their subsequent Ni-based catalysts
were characterized from structural, textural and morphological point of view.

Key words: Ni nanoparticles; ordered mesoporous silica; nanoconfinement;

combined steam and CO2 reforming of methane.

Acknowledgments: The authors acknowledged the research grants from EEA

(European Economic Area) – Norway, project RO-NO-2019-0379.

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DEVELOPMENT OF NOVEL NASICON CERAMIC ELECTROLYTE MEMBRANE FOR

SEAWATER BATTERIES WITH HIGH RATE OF CONDUCTIVITY

Simona Borta, Mihaela Iordache, Dorin Schitea, Ioan-Sorin Sorlei, Cătălin Capriş,
Adriana Marinoiu
1
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Corresponding author: [email protected]

The new requirements for energy storage systems are very different from
electric vehicles or energy consumption systems and varies greatly depending on
factors such as the location of the installation or its size [Kim, Jae-Kwang et al.,
2014]. A reasonable and practical strategy is to meet the various requirements of
each application with different alternative battery systems. While a Li-ion battery
that has a high volumetric energy density may be an appropriate choice for storing
energy in densely populated areas, other new battery systems may become more
competitive and offer optimal solutions [Goodenough J. B., 2013; Lin D. et al., 2017;
Ko M. et al., 2016; Lu L. et al., 2013]. Recently, the development of aqueous Na-ion
rechargeable batteries has emerged as a promising alternative energy storage
solution [Kim, Haegyeom et al., 2014; Shin Jaeho, 2020; Bin Duan et al., 2018].
In general, Na-ion batteries are less expensive than Li-ion batteries, and the
use of aqueous electrolytes is beneficial to the environment than non-aqueous
electrolytes [Kundu D. et al., 2015; Vaalma C. et al., 2018]. Also, aqueous
electrolytes have higher ionic conductivities, are safer and cheaper [Kim H., et al.,
2014; Bin D., et al., 2018].
A major disadvantage of Na-ion batteries is the relatively low voltage of the cell
and which is inevitably restricted by the water reduction and oxidation potentials.
However, if the benefits of rechargeable Na-ion batteries can be achieved on a
large scale, they would exceed the limitations described above and make new
seawater batteries a viable candidate for ESS's.
The cell consists of two compartments, an anode and a cathode, which are
separated by a NASICON ceramic electrolyte [Han J. et al., 2018]. One of the
promising solid electrolytes for Na+ ions migration is the NASICON (Na Super Ionic
Conductor, Na1+xZr2P3-xSixO12 (0 ≤ x ≤ 3)).
The structure of Na1+xSixZr2P3−xO12 (x = 0–3) is composed of three-dimensional
linked network of ZrO6 octahedra and PO4 or SiO4 tetrahedral as oxidized
compounds. Na+ ions are located in the interstitial sites in this framework (Fig. 1).

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The oxygen corners of silicate or phosphate tetrahedral structures shared with six
oxygen molecules of ZrO6 octahedral structure. It means that each tetrahedral and
octahedral component is linked by oxygen molecules. In this way, the infinite loops
of structures are formed along the c-xis. The basic mechanism of transportation of
Na+ ions is the migration of Na+ ions through 3D structure holes designated
“bottlenecks” of the structure. The bottleneck area is interstitial sites between ZrO6
octahedral and Si(P)O4 tetrahedral structure [Hueso K. B. et al., 2012]. As Na+ ions
migrate through the bottleneck sites with small activation energy (hopping
mechanism), the energy barrier of Na+ ions diffusion would be influenced by the
size of the bottleneck area [Losilla E. R. et al., 1998].
The main objective of this paper is to produce substantially higher ionic
conductivities, with improved morphology and higher density of NASICON
membrane produced from nano-powder precursors for solid-state sodium-ion
batteries.

Figure 1. (a) Crystal structure of monoclinic Na3Zr2Si2PO12 consisting of ZrO6 octahedra (in green) and
SiO4/PO4 tetrahedra (in pink) with its Na1 ↔ Na2 transport path
(b) and Na1 ↔ Na3 transport path (c)

The high ion conducting monoclinic Na3Zr2Si2PO12 phase transformed to

rhombohedral phase at higher temperatures due to the shear deformation of the
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unit cell [Jolley A. G. et al., 2015]. They obtained higher ionic conductivity for 5 wt%
of additive material which acts as a melt-pool along the grain boundary area to
enhance the Na-ion mobility. However the simultaneous use of excess wt% of Na
and P content in Na3Zr2Si2PO12 using 10 wt% excess Na3PO4 precursors showed
lower conductivity value than that of the Na3Zr2Si2PO12 with excess Na only as the
former case created non-conducting impurities at the grain boundaries [Narayanan
Sumaletha et al., 2019]. Khakshour et al. used both micro and nano-sized
precursors for the preparation of Na3Zr2Si2PO12 material by the solid-state reaction
route and reported the best room temperature conductivity value (1.16 × 10 –3 S
cm–1 vs. 0.62 × 10–3 S cm–1) of the same material prepared using nanocrystalline
precursors at similar sintering conditions [Jalalian-Khakshour A. et al., 2020]. The
improvement in conductivity value was attributed to the improved morphology
with the higher density.
In this study, the potential advantages of using nanoscale precursor particles
for NASICON ceramic electrolyte synthesis by solid state reaction are analysed by
direct comparison with macroscopic scale precursors and fixed processing
parameters. A major interest is given by the way it affects the microstructure,
crystal structure and impurities and, at the same time, the electrical performance.
The effect that the precursor size has on the properties of the powder before the
final sintering step is analysed in terms of particle size distribution and
microstructure. NASICON pellets are then prepared from powders, at a range of
sintering times (10 h) with microstructure, crystal structure, density and electrical
performance analysis.

Key words: seawater batteries, NASICON membrane, ion conductivity, solid-

state reaction

Acknowledgments: This work is supported by Ministry of Research, Innovation,

Digitization from Romania by the National Plan of R & D, Project No. PN 19 11 02 01
and by UEFISCDI, Project PN-III-P2-2.1-PED-2019-2079 (Contract No. 469PED/2020).

References
Bin Duan, et al. Progress in aqueous rechargeable sodium‐ion batteries. Advanced Energy Materials,
2018, 8.17: 1703008.
Goodenough John B., Park Kyu-Sung. The Li-ion rechargeable battery: a perspective. Journal of the
American Chemical Society, 2013, 135.4: 1167-1176.
Han Jinhyup, et al. Development of coin-type cell and engineering of its compartments for
rechargeable seawater batteries. Journal of Power Sources, 2018, 374: 24-30.
Hueso Karina B.; ARMAND, Michel; ROJO, Teófilo. High temperature sodium batteries: status,
challenges and future trends. Energy & Environmental Science, 2013, 6.3: 734-749.

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Jalalian-Khakshour A., et al. Solid-state synthesis of NASICON (Na 3 Zr 2 Si 2 PO 12) using

nanoparticle precursors for optimisation of ionic conductivity. Journal of Materials Science,
2020, 55.6: 2291-2302.
Jolley Adam G., et al. Structural Investigation of Monoclinic‐Rhombohedral Phase Transition in
Na3Zr2Si2PO12 and Doped NASICON. Journal of the American Ceramic Society, 2015, 98.9:
2902-2907.
Kim Haegyeom, et al. Aqueous rechargeable Li and Na ion batteries. Chemical reviews, 2014, 114.23:
11788-11827.
Kim Jae-Kwang, et al. Rechargeable seawater battery and its electrochemical mechanism.
ChemElectroChem, 2014, 2.3.
Ko Minseong, et al. Scalable synthesis of silicon-nanolayer-embedded graphite for high-energy
lithium-ion batteries. Nature Energy, 2016, 1.9: 1-8.
Kundu Dipan, et al. The emerging chemistry of sodium ion batteries for electrochemical energy
storage. Angewandte Chemie International Edition, 2015, 54.11: 3431-3448.
Lin Dingchang, Liu Yayuan, Cui Yi. Reviving the lithium metal anode for high-energy batteries. Nature
nanotechnology, 2017, 12.3: 194-206.
Losilla Enrique R., et al. Understanding Na mobility in NASICON materials: a Rietveld, 23Na and 31P
MAS NMR, and impedance study. Chemistry of materials, 1998, 10.2: 665-673.
Lu Languang, et al. A review on the key issues for lithium-ion battery management in electric
vehicles. Journal of power sources, 2013, 226: 272-288.
Narayanan Sumaletha, et al. Sintering temperature, excess sodium, and phosphorous dependencies
on morphology and ionic conductivity of NASICON Na3Zr2Si2PO12. Solid State Ionics, 2019,
331: 22-29.
Shin Jaeho, Choi Jang Wook. Opportunities and reality of aqueous rechargeable batteries. Advanced
Energy Materials, 2020, 10.28: 2001386.
VaalmaChristoph, et al. A cost and resource analysis of sodium-ion batteries. Nature reviews
materials, 2018, 3.4: 1-11.

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DESIGN AND APPLICATIONS OF ROTATING FEEDTHROUGH

BASED ON MAGNETIC FLUIDS

Marian Curuia, Cătălin Brill

National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
Corresponding authors: [email protected]

Rotating feedthroughs are used on large scale in applications where is

necessary to move or adjust the position of some components inside the vacuum
chamber. Magnetic fluids represent one of the best and modern solution for sealing
in these cases. The advantages of rotating feedthrough based on magnetic fluids
are long lifetime, hermetic sealing without contaminating, high-speed, smooth
running and simple maintenance. The design of such type of feedthrough is
presented in the paper. Also, the following design issues related to performance
maximizing of rotational feedthrough and the resistance at differential pressure are
discussed: ferrofluid properties and the dimensioning of the permanent magnet,
the number of the sealing stages and the air gap between shaft and polar pieces.

Key words: magnetic fluid, rotating feedthrough, high and ultrahigh vacuum,
cryogenic applications.

References
T. Borbat et. al., Applications of magnetic nanofluids in rotating seals, Romanian Academy
Publication House, Bucharest 2006, pg. 200-210
T. Borbat et. al., Magnetic nanofluids and magnetic composite fluids in rotating seal systems,
Published in Engineering Conferences Online, 2010
S.A. Novopashin, M.A. Serebryakova, and S.Ya. Khmel, Methods of magnetic fluid synthesis,
Thermophysics and Aeromechanics, 2015, Vol. 22, No. 4
S. Odenbach, 2009, Colloidal Magnetic Fluids, Springer
K. Raj, s.a., Recent Advances in Magnetic Liquid Sealing, 26th Annual Design Engineering Show and
Conference May 7-10, Chicago, Illinois
C. Scherer and A. M. Figueredo Neto, Ferrofluids: Properties and Applications, Brazilian Journal of
Physics, vol. 35, no. 3A, September, 2005

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SUSTAINABLE LABORATORY METHOD FOR PGM RECOVERY FROM SPENT

AUTOMOTIVE CATALYTIC CONVERTORS

Monica Dan, Oana Grad, Maria Miheţ, Angela Kasza, Diana Lazăr

National Institute for Research and Development of Isotopic and Molecular Technologies, 67-103
Donat, 400293 Cluj-Napoca, Romania
Corresponding authors: [email protected]; [email protected]

Due to their excellent proprieties such as: thermoelectric stability, corrosion

resistance, high electrical conductivity, catalytic activity the platinum group metals
(PGMs), which includes Platinum (Pt), Palladium (Pd), Rhodium (Rh), Osmium (Os),
Iridium (Ir) and Ruthenium (Ru) are widely used in various applications. Therefore,
many industries depend on PGMs sustainability and availability. The automotive
industry use PGMs as catalytic converters (Three-Way-Catalyst (TWC) or Diesel-
Oxidation Catalyst (DOC), Figure 1. The primary PGMs sources are strongly
geographically limited and scarce, which makes the spent automotive catalysts the
biggest secondary PGM resource. As, there is growing demand for the metals and
also taking into account the negative impact of these spent catalyst on the
environment, the recycling of PGMs from automotive catalysts is indispensable. The
recovery of PGMs from the spent catalyst is a complex process due to the presence
of different components in the catalytic support and also due to the alteration of
the initial catalyst structure during many hours of usage.

Figure 1. Catalytic auto converter

[https://engineeringlearn.com/what-is-catalytic-converter/]

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The objective of this study was to establish an efficient and eco-friendly

laboratory method for recovering the PGMs from the spent auto catalysts by
employing different experimental conditions. The studied samples came from a
spent automotive catalyst that had become deactivated under real traffic
conditions. The autocatalytic converter was crushed in a planetary ball mill and the
obtained powder was used further in our study. The spent automotive catalyst
samples were characterized using different characterization techniques such as:
powder diffraction (XRD), spectrophotometric analysis (XPS), thermogravimetric
analysis (TGA). The PGMs recovery process consist in a succession of steps: (i) metal
leaching with an H2O2+ HCl solution and (ii) metal recovery from solution. For a high
degree of recovery in the dissolving step we have varied different parameters like:
leaching agent concentration, the temperature and the extraction time.
Furthermore, different precipitation techniques were employed in order to
separate the individual ions from the leaching solution and to obtain high yield and
purity for recovered PGMs.

Key words: recovery, platinum, catalytic converters, environment

Acknowledgments: This work was supported by a grant of CNCS/CCCDI –

UEFISCDI; project PN-III-P2-2.1-PTE-2019-0606, Contract nr. 33 PTE/2020,
Implementation of the platinum group metals recovery technology from car
catalytic converters – AutoCat.

References
https://engineeringlearn.com/what-is-catalytic-converter/

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ADVANCED ELECTRODE BASED ON ZINC OXIDE AND VANADIUM OXIDE-

GRAPHENE FOR SODIUM-ION BATTERY: INFLUENCE OF MORPHOLOGY AND
DOPING

H. Ghannam1, 2, M. Buga3, C. Ungureanu3, A. A. Zăuleţ3, A. C. Galca 1, M. Y. Zaki1, E.

Matei1, I. Stavarache1, C. C. Negrilă1, G.E. Stan1, M-C. Bartha1, M. Baibarac1, T.
Tite1,*, A. Chahboun2,*
1
National Institute of Materials Physics, RO-077125 Magurele, Romania
²Abdelmalek Essaadi University, FSTT , Thin Films and Nanomaterials Lab., 90000 Tangier, Morocco
3
National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
Corresponding authors: [email protected];
[email protected]/[email protected]

Access to reliable energy electricity is nowadays the backbone of our modern

economy, our social life and comfort. With the expansion of decentralized electrical
energy production, the inclusion of energy storage systems (ESS) involving intermittent
renewable sources (e.g. solar, wind, tidal) has been found extremely promising.
However, the climate change issue is contentious. By considering our greed for energy
consumption, batteries and supercapacitors represents nowadays our best advanced
technologies for ESS (e.g. power plants), in particular, in off-grid interconnected areas.
Lithium-ion batteries (LIBs), while first commercially developed for portable electronics
are now ubiquitous in our daily life, in increasingly diverse applications (e.g. smart
watches, electric cars, medical devices, drones). However, despite its great success,
LIBs used raw elements which are not sustainable (e.g. Lithium, Cobalt), and still need
improvements in energy density, cost, and safety (e.g. considering flammable
electrolyte). As such, there is a massive ongoing effort to improve LIBs by replacing the
commercial cathode (e.g. LiCoO2) and to design new batteries without lithium. In this
context, Sodium-ion batteries (SIBs) are regarded as potential alternative to LIBs due to
the sustainability and low price of sodium, and a possibly easier manufacturer
assembling procedure [S. Fang et al., 2020]. Notably, one aspect is common for all
approaches – the design of the appropriate electrodes. The choice of raw material and
electrode composition plays a crucial role to enhance the energy storage. Among new
materials investigated in the literature, carbonaceous materials (e.g. graphene) and
layered metal oxides (LMO) (e.g. zinc oxide (ZnO) and vanadium oxide (VOx)) have shed
new promises for future generation of electrodes for energy storages devices in
regards to their unique physico-chemistry properties [B. Park, et al., 2016; M. Jing, et
al., 2019]. For example, graphene has a considerable interest in energy storage because
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of its large surface areas, high electronic conductivity, and excellent capability. It is
commonly used as an anode for SIBs, with a moderate capacity of ~350 mAh/g [A. K.
Thakur et al., 2021]. On the other hand, ZnO offers a high theoretical capacity of 685
mAh/g corresponding to its sodiated for SIBs [F. Xu et al., 2016]. However, the
combination of carbonaceous and metal oxides materials seems to be an interesting
solution to prevent the capacity fading upon cycling of metal oxide provided from the
inherent poor electrical conductivity and large volume expansion, and thus improve the
electrochemical performance of SIBs [J. Liu et al., 2009].
In the present work, Metal oxide (e.g. ZnO and VOx)-graphene material is
studied as anode and cathode material for SIBs. Indeed, ZnO was successfully
electrodeposited on graphene Aluminum surface. The effect of ZnO morphology
and Mg-doped ZnO on electrochemical performance of ZnO-graphene and
ZnO/VOx-graphene electrode was studied. The findings are discussed and analyzed
through the morphological, structural, and chemical results. The electrochemical
performance of electrode synthetized surfaces was measured by using cyclic
voltammetry, impedance and galvanostatic charge-discharge methods performed in
0.1 M aqueous Na2SO4 solution.
Key words: Electrodeposition, Zinc oxide, Graphene, Vanadium oxide, Doping,
Sodium-ion battery.

Figure 1. SEM images of (Al-graphene-ZnO) surface electrode.

Figure 2. Cyclic voltammetry performance of Al, Al-graphene, and Al-graphene-ZnO at

different scan rates in 0.1M aqueous Na2SO4 solution.
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Acknowledgments: The authors thank “Agence universitaire de la Francophonie”

for the Eugen Ionescu research scholarship (H.G), and CNCS-UEFISCDI for the financial
support in the framework of grants PN-III-P2-2.1-PED-2019-4519.

References
S. Fang, D. Bresser and S. Passerini, Transition Metal Oxide Anodes for Electrochemical Energy
Storage in Lithium- and Sodium–Ion Batteries, Adv. Energy Mater., 2020, 10, 1902485.
M. Jing, F. Li, M. Chen, F. Long, T. Wu, Binding ZnO nanorods in reduced graphene oxide via facile
electrochemical method for Na-ion battery, Applied Surface Science, 2019, 463, 986-993.
J. Liu, Y. Li, R. Ding, J. Jiang, Y. Hu, X. Ji, Q. Chi, Z. Zhu andX. Huang, Carbon/ZnO nanorod array
electrode with significantly improved lithium storage capability, J. Phys. Chem. C, 2009, 113,
5336–5339.
B. Park, S. M. Oh, Y. K. Jo, S. J. Hwang, Efficient electrode material of restacked Na–V2O5–graphene
nanocomposite for Na-ion batteries, Materials Letters, 2016, 178, 79-82.
A. K. Thakur, M. S. Ahmed, G. Oh, H. Kang, Y. Jeong, R. Prabakaran, M. Ponrajan Vikram, S. W.
Sharshir, J. Kim and J. Y. Hwang, Advancement in graphene-based nanocomposites as high capacity
anode materials for sodium-ion batteries, J. Mater. Chem. A, 2021, 9, 2628-2661.
F. Xu, Z. Li, L. Wu, Q. Meng, H. L. Xin, J. Sun, B. Ge, L. Sun and Y. Zhu, In situ TEM probing of
crystallization form dependent sodiation behavior in ZnO nanowires for sodium-ion batteries,
Nano Energy, 2016, 30, 771–779.

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SOLID STATE ELECTROLYTE (Na3Zr2Si2PO12) WITH IMPROVED IONIC CONDUCTIVITY

Mihaela Iordache, Simona Borta, Claudia Sişu, Thanos Tiliakos, Adriana Marinoiu

National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
Corresponding author: [email protected]

That's why, rechargeable batteries play an important role in energy storage as

they efficiently store energy from renewable sources and are used on request
[Narayanan S., 2019]. Although lithium-ion batteries were fully developed and widely
applied in various energy storage systems, the limitation of lithium resources restricts
their magnitude applications. Currently use of lithium ion-battery technology is
extensive and consumption will certainly limit its availability in nature. Thus, as an
alternative, there is a need for developing new electrolytes based on other mobile ions,
particularly Na+ ion-based systems, to replace/complement Li+ ion-based electrolytes. It
is essentially due to the huge availability of sodium in nature and its low cost [Guin M.,
2016; Dinachandra Singh M., 2019; Ruan Y., 2019; Jalalian-Khakshour A. 2020]. Due to
the abundant distribution and low-cost Sodium ion, the electrochemical cells and
systems that use it are considered to be more competitive than lithium-ion devices in
the field of stationary terrestrial energy applications. However, the energy density of
Sodium ion electrochemical cells is much lower than that of the lithium-ion ones [Ruan,
Y., 2019; Jalalian-Khakshour, A., 2020].
It is known that NASICON (Na+ Super Ionic Conductor) has a high ionic conductivity
and a relatively high chemical stability. Na3Zr2Si2PO12 (NZSP) was first proposed by Hong
and Goodenough in 1976. This material has the highest ionic conductivity of Na1+
xZr2Si2P3-xO12(0 <x <3) for x = 2 and it corresponded to a monoclinic structure [Fuentes
R.O., 1999; Fuentes R. O., 2001; Guin M., 2016; Park H., 2016; Naqash S., 2017; Jalalian-
Khakshour A., 2020]. NZSP has been considered a very promising solid-state electrolyte
that can be used in membranes for electrochemical applications. However, in order to
obtain good performance of solid-state sodium membranes, both the ionic conductivity
and interfacial resistance reduction of NZSP must be improved. Ionic conduction occurs
when Na+ moves from one site to another by "blockages" formed by oxygen ions.
Furthermore, the total electrical conductivity strongly depends on the density and the
nature of the granule boundaries. Microstructure of samples is usually affected by the
method of preparation [An J., 2019]. One of the primary methods described in literature
of NZSP synthesis is the solid-state reaction at high temperature. However, high
temperature can lead to the formation of secondary phases. So far, the reported
conductivity achieved using this method ranges from 0.092 to 1.2 mS cm–1 at 25°C [Guin
M., 2016; Jalalian-Khakshour A., 2020].
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The purpose of this paper is to make a solid - state electrolytic material based on
sodium (NASICON membrane), with the best possible conductivity for use in
electrochemical devices. In this work, we report on the synthesis protocols and
processing parameters of Na3Zr2Si2PO12 prepared from Na2CO3, SiO2, ZrO2, and
NH4H2PO4 by solid-state reaction (SSR) synthesis. Material characterization has been
conducted by optical microscopy, granulometry (dynamic light scattering, DLS),
porosimeter (BET/BJH), and X-ray diffractometry (XRD). Electrical properties, i.e., dc
(electrical) and ac (ionic) conductivity, have been evaluated by impedance
spectroscopic methods over the temperature range of 100°C to -100°C. Particular
attention has been focused on monitoring the role of NASICON composition and the
applied processing parameters (i.e., sintering temperature and pellet-forming isostatic
pressure) on the measured electrical properties. In-lab prepared samples have been
compared with commercial NASICON pellets, which served as reference for controlling
the electrical properties of the synthesized materials.
Surface area analysis was conducted using BET analysis (Fig. 1). Nitrogen
adsorption is caused by the existence of intrinsic surface energies. The pre-sintered
powder indicated a BET surface area of 1.6 m2/g. The nitrogen adsorption/desorption
isotherms were measured at 77 K. The obtained curves indicated a hysteresis loop in
the adsorption-desorption isotherms, suggesting the presence of mainly a mesoporous
structure. XRD analysis (Fig. 2) was conducted to investigate the crystal structure of the
NZSP materials, after calcination and after sintering, and were compared to the
commercial reference sample.

Figure 1. BET (left) and BJH (right) analysis of surface porosity for pre-sintered NZSP powders.

Figure 2. XRD spectra of NASICON samples before and after sintering

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The in-lab NASICON, produced by stoichiometric ratios of the precursor

materials, sintered at 1100oC, and assembled into pellet form by applying the
pressure load of 3500 kg, reached the same level of ionic conductivity as the
commercial reference samples. Our work serves as an initial stepping stone for
furthering our ongoing research into ceramic superionic conductors and their
possible applications in energy generation and storage.

Key words: NASICON membrane, solid-state reaction, electrolytic material,

conductivity.

Acknowledgments: This work is supported by Ministry of Research, Innovation,

Digitization from Romania by the National Plan of R & D, Project No. PN 19 11 02 01
and by UEFISCDI, Project PN-III-P2-2.1-PED-2019-2079 (Contract No. 469PED/2020).

References
An, J., Oh, S., He, L., Plewa, A., Morita, M., Zhao, Y., Sakamoto, T., Song, X., Zhai, W., Zeng, K., Lu, L.,
+
2019. Composite NASICON (Na3Zr2Si2PO12) Solid-State Electrolyte with Enhanced Na Ionic
Conductivity: Effect of Liquid Phase Sintering.
Dinachandra Singh, M., Dalvi, A., Phase, D.M., 2019. Electrical transport in PEO-NaI-NASICON
nanocomposites: An assessment using impedance and X-Ray absorption spectroscopy. Mater.
Res. Bull. 118. https://doi.org/10.1016/j.materresbull.2019.05.010
Fuentes, R.O., Marques, F.M.B., Franco, J.I., 1999. Cerámica y Vidrio Synthesis and properties of
nasicon prepared from different zirconia-based precursors, Bol. Soc. Esp. Cerám. Vidrio.
Fuentes, R. O., Figueiredo, F.M., Marques, F.M.B., Franco, J.I., 2001, Influence of microstructure on
the electrical properties of NASICON materials, Solid State Ionics 140, 173-179.
Guin, M., Tietz, F., Guillon, O., 2016. New promising NASICON material as solid electrolyte for
sodium-ion batteries: Correlation between composition, crystal structure and ionic
conductivity of Na3+xSc2SixP3-xO12. Solid State Ionics 293, 18–26.
Narayanan, S., Reid, S., Butler, S., Thangadurai, V., 2019. Sintering temperature, excess sodium, and
phosphorous dependencies on morphology and ionic conductivity of NASICON Na3Zr2Si2PO12.
Solid State Ionics 331, 22–29, https://doi.org/10.1016/j.ssi.2018.12.003.
Naqash, S., Ma, Q., Tietz, F., Guillon, O., 2017. Na3Zr2(SiO4)2(PO4) prepared by a solution-assisted
solid state reaction. Solid State Ionics 302, 83–91.
Park, H., Jung, K., Nezafati, M., Kim, C.S., Kang, B., 2016. Sodium Ion Diffusion in Nasicon
(Na3Zr2Si2PO12) Solid Electrolytes: Effects of Excess Sodium. ACS Appl. Mater. Interfaces 8,
27814–27824. https://doi.org/10.1021/acsami.6b09992.
Ruan, Y., Guo, F., Liu, J., Song, S., Jiang, N., Cheng, B., 2019. Optimization of Na3Zr2Si2PO12 ceramic
electrolyte and interface for high performance solid-state sodium battery. Ceram. Int. 45,
1770–1776. https://doi.org/10.1016/j.ceramint.2018.10.062.

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STEP-BY-STEP DESIGN PROCESS OF A LIQUID HYDROGEN TANK

Anca Mihaela Istrate, Valeriu Drăgan, Raluca Maier, Romică Stoica, Andrei
Mandoc, Alexandra Despa

Romanian Research and Development Institute for Gas Turbine COMOTI,

220D Iuliu Maniu Av., Bucharest, Romania
Corresponding author: [email protected]

Dependence on fossil fuels is an acute problem in the process of industrial

evolution on short and medium term. Therefore, global efforts are being made to
make the transition to renewable energy. The main objectives are to drastically
reduce the level of pollutant emissions and, on the other hand, to find sustainable
solutions, with energy performance close to the fuels currently used.
The transition to hydrogen seems to be the answer to these problems. This
subject has been studied intensively for about 20 years. [Wright, 2000] Regarding
hydrogen storage, the proposed solutions vary depending on the quantity stored
and the applications concerned. [Rivard, 2019]
This paper addresses the issue of liquid hydrogen storage in cryogenic tanks.
Liquid hydrogen might be a feasible solution in terms of volumetric and gravimetric
efficiency, given that 5 kg of liquid hydrogen can be stored in a 75 liter tank,
compared to 5 kg of hydrogen gas which requires a 125 liter tank if it is compressed
to 700 bar. [Fisher, 2005]
This paper aims to formulate a design process for a liquid hydrogen tank,
taking into account geometry, thermo-mechanical stresses and operational
requirements. Moreover, the obtained design is subjected to numerical analyses to
determine the temperature distribution, hydrogen phase distribution, and also the
fluid velocity.
Regarding the cryogenic tank design process, this paper presents a step-by-
step method of dimensioning and sizing. First of all, the liquid hydrogen load
needed for operational service has to be determined. Besides this load, additional
mass has to be taken into account for an unusable quantity of fluid. This extra mass
is given by the expulsion efficiency and by the boil-off phenomenon which depends
on the time that the liquid hydrogen needs to be stored and on the heat flow from
the environment. If the liquid hydrogen is warmed up by the external heat it boils.
The resulting vapours increase the pressure inside the tank, and once the maximum
allowed pressure is reached, venting is necessary, therefore the total mass of liquid
hydrogen is decreasing. Once the total mass of fluid and the internal pressure are
established, the liquid hydrogen volume is determined. The total cryogenic tank
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volume depends on the liquid hydrogen volume, other subassemblies volume and
on the ullage volume which is the unfilled space inside the tank that allows the fluid
to increase its volume due to thermal expansion. The next step of the designing
process is the shape and material selection. The selection of the material is closely
related to the operational requirements of the tank. This paper addresses the
majority of the risks encountered by the materials in the use of liquid hydrogen
tanks, such as: the density and the crystallinity of the material, chemical
compatibility, permeability, weight, cost etc. After choosing the materials
architecture, the tank wall thickness shall be determined. It is strongly related to
the chosen internal pressure and to the safety factors provided by the standards. A
preliminary value of the tank wall thickness is determined in order to proceed the
design process. Of course these steps can be reiterated in order to optimise the
design. In addition to the steps mentioned above, the paper also addresses various
materials and technologies for the cryogenic tank thermal insulation.
Finally, based on the obtained results, an advanced composite materials
architecture is proposed for manufacturing by means of specific technologies. A
literature review is performed in order to identify suitable materials and processes
for manufacturing liquid hydrogen storage tanks.

Key words: liquid hydrogen tank, composite materials, design process,

numerical analysis.

References
Timothy S. Fisher, Jinsong Zhang, A Review of Heat Transfer Issues in Hydrogen Storage
Technologies, Journal of Heat Transfer, Vol. 127, December 2005
Etienne Rivard, Michel Trudeau, Karim Zaghib, Hydrogen Storage for Mobility: A Review, MDPI –
th
Materials Journal, 19 June 2019
R. J. Wright, G. M. Roule, LH2 Tank Composite Coverplate Development and Flight Qualification for
the X-33, 2000

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IRON OXIDE NANOPARTICLES SYNTHESIZED BY LASER PYROLYSIS FOR

ONCOLOGICAL APPLICATIONS

Iulia Ioana Lungu1,2, Simona Nistorescu1, Mihaela Balas1, Ecaterina Andronescu2,

Florian Dumitrache1, Athanasios Tiliakos3
1
National Institute of Laser, Plasma and Radiation Physics, 409 Atomistilor Street, 077125 Magurele,
Ilfov, Romania;
2
Faculty of Applied Chemistry and Materials Science, University Politehnica of Bucharest, 1-7 Gh.
Polizu Street, 011061 Bucharest, Romania;
3
National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
Corresponding author: [email protected]

Iron oxide nanoparticles (NPs) are used in a wide variety of applications,

ranging from energy storage to biomedicine, due to their unique properties,
especially their capacity to be controlled by means of an external magnetic field.
However, one crucial aspect when it comes to their final structural or magnetic
properties is the synthesis method, with different results coming from chemical,
mechano-chemical, hydrothermal, and sol-gel methods. Laser pyrolysis presents
an alternative option, where the synthesis is conducted on the intersection
between a focused continuous wave of high-power CO2 laser radiation and a
streaming flow consisting of reactant, sensitizer, and inert sheath gases. The main
advantages of using laser pyrolysis for iron oxide NP synthesis include the low
degree of contamination, as well as the control over size distribution and
morphology – the latter extending to the selection between different iron oxide
allotropes, from α-Fe2O3 hematite to γ-Fe2O3 maghemite and Fe3O4 magnetite.
Herein we report on the laser pyrolytic synthesis of γ-Fe2O3 NPs with controllable
size distribution, using iron pentacarbonyl as the iron precursor and ethylene as
the energy transfer agent and their biological testing, as potential agents from
oncological applications.

Acknowledgments: This research was funded by grants of the Ministry of

Education and Research and UEFISCDI, contract no. 63PCCDI/2018(PN-III-P1-1.2-
PCCDI-2017-072), 460PED-2020(PN-III-P2-2.1-PED-2019-1894) and Nucleu
Programme, ctr. No. 16N/08.02.2019.

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References:
Lungu, I., Nistorescu, S., Badea, M., Petre, A., Udrea, A., Banici, A., Fleacă, C., Andronescu, E.,
Dinischiotu, A., Dumitrache, F., Staicu, A. and Balaș, M., 2020. Doxorubicin-Conjugated Iron
Oxide Nanoparticles Synthesized by Laser Pyrolysis: In Vitro Study on Human Breast Cancer
Cells. Polymers, 12(12), p.2799.
Lungu, I.I., Technologies based on controlled magnetic nanostructures with oncological applications:
early diagnosis and targeted delivery, PhD thesis, Politehnica University of Bucharest, Romania,
to be available in 2022.

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SYNTHESIS AND CHARACTERIZATION OF BROMINATED POLY(2,6-DIMETHYL

PHENYLENE OXIDE) POLYMER

Elena Marin, Anişoara Oubraham, Simona Borta, Violeta Niculescu,

Adriana Marinoiu

National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
Corresponding author: [email protected]

Anion exchange membranes based on poly(2,6-dimethyl-1,4-phenylene oxide)

(PPO) were used as polymer electrolyte membrane for fuels cell application. PPO as
a membrane material offers several advantages over other aromatic polymers.
PPO has strong hydrophobicity, high strength and modulus and high hydrolytic
stability. Poly(2,6-dimethyl-1,4-phenylene oxide) can be readily modified in both
aryl- and benzyl-position by electrophilic or radical substitution reactions. [K.H.
Gopi, 2014]
Also, PPO has a number of advantages: reactivity of methyl groups; good
solubility in the usual solvents used in the preparation of membranes; good
resistance to contact with various chemical agents and to mechanical stresses. [D.
Garganciuc, 2008]
N-bromosuccinimide (NBS) and azobisisobutyronitrile (AIBN) were added to a
stirred solution of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) in chlorobenzene.
[V. Yadav, 2017]. The mixture was stirred under refluxing condition for some hours.
The obtained solution was washing with ethanol, filtrated and dried under vacuum
to get final Br-PPO. [R. D. Noble, 2005]
In this paper we will present the preparation and characterization of Br-PPO.
The structure, morphology and properties will be characterized using: Scanning
Electron Microscopy (SEM) with Energy Dispersive X-Ray Analysis (EDX), analyses
for specific surface area & pore size, vapor adsorption & chemisorption (BET),
nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy
(FTIR).

Key words: poly(2,6-dimethyl-1,4-phenylene oxide), synthesis, characterization,

chlorobenzene, N-bromosuccinimide.

Acknowledgments: This work is supported by Ministry of Research, Innovation,

Digitization from Romania by the National Plan of R & D, Project No. PN 19 11 02 01
and by UEFISCDI, PN-III-P2-2.1-PED-2019-2079 (Contract No. 469PED/2020).
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References
D. Garganciu, G. Batranescu, G. Nechifor, M. Olteanu, Materiale Plastice, 2008, 45, 1, 2008
K.H. Gopi, S.G Paera, all, Journal of Hydrogene Energy, 39, 2014, 2659‐2668
R. D. Noble, R. Agrawal, Industrial and Engineering Chemistry Research, 44, 2005, 2887.
V. Yadav, P. Sharma, V. Kulshrestha, International Journal of Hydrogene Energy, 42, 2017, 26511-
26521

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SINGLE-STAGE SYNTHESIS OF GRAPHENE OXIDE FUNCTIONALIZED WITH

PLATINUM-COBALT-CERIA

Adriana Marinoiu, Amalia Soare

National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
Corresponding author: [email protected]

Proton exchange fuel cells (PEMFCs) are considered as efficient, zero-emission

power sources. The performance of PEMFCs decreases very quiqly as a function of
potential cycling and a corrosive operating environment, during the electrochemical
aging. Most of the performance degradation can be assigned mainly to the limited
durability of the electrocatalyst, especially on the cathode side where the
electrocatalysts are exposed to extremely harsh oxidative conditions.
The development of highly active and stable oxygen reduction reaction (ORR)
catalyst to reduce/replace platinum-based catalysts are still considered the major
challenges in the research dedicated to PEMFCs. The graphene-based materials are
the present challenges to be applied in fabrication of electrodes, mainly due to the
very well-known 2 D proprieties (such as specific surface area, high conductivity).
On the one-hand, the bimetallic platinum-cobalt (Pt-Co) catalyst exhibited
better stability than Pt/C in acidic media, since the metal dissolution and
redeposition were considered to be the most important degradation mechanism for
Pt-based fuel cell electrocatalysts [Marinoiu A. et al., 2020]. On the other hand,
ceria (CeO2) nanoparticles displayed enhanced electrochemical oxygen reduction
activity with a 4e− process similar to commercial Pt/C but with much higher stability
and durability properties.
Herein we report platinum-cobalt-ceria supported on reduced graphene oxide
(Pt-Co-CeO2/rGO) as a promising electrocatalyst with competent ORR kinetics
mainly through a four-electron reduction pathway, and good stability and excelent
durability. The Pt-Co-CeO2/rGO catalyst was obtained by a facile single-step
microwave process. The as-synthesized Pt-Co-CeO2/rGO nanocomposites were
characterized and evaluated as electrode by specific electrochemical methods.
The process, according to this study, presents an original approach: a fast and
cost-effective way to prepare Pt-Co-CeO2/rGO, starting from commercial graphene
oxide and salts sources of Pt, Co and Ce. The electrochemical performance was
investigated using a commercial workstation. The electrodes were prepared and
tested accordingly with typical procedures developed in Group of Materials for
Hydrogen Energy from ICSI Energy [Marinoiu A. et al., 2020]. The prepared
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electrodes based on Pt-Co-CeO2/rGO demonstrated good stability and remarkable

durability during ORR reaction, main criterions used in development of different
architectures of electrocataysts for PEMFC.

Key words: graphene, platinum-doped graphene, microwave, fuel cells

Acknowledgments: This work was supported by Ministry of Research,

Innovation, Digitization from Romania by the National Plan of R & D, Project No. PN
19 11 02 01, and by UEFISCDI, Contract No. 460PED/2020 (Project PN-III-P2-2.1-
PED-2019-1894) and Contract No. 469PED/2020

References
Marinoiu A., Andrulevicius M., Tamuleviciene A., Tamulevicius T., Carcadea E., Raceanu M., High
performance catalytic system with enhanced durability in PEM fuel cell, International Journal
of Hydrogen Energy, 45 (17), pp. 10409-10422, 2020

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SINGLE-STAGE SYNTHESIS OF GRAPHENE OXIDE DOPED WITH IODINE

Adriana Marinoiu, Elena Marin, Amalia Soare, Violeta Niculescu, Felicia Bucura,
Anca Zaharioiu, Marius Constantinescu

National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
Corresponding author: [email protected]

With various technology upgrades to achieve a low cost and reliable fuel cell,
there is still a pressing need for increasing of the catalytic stability and durability.
Among others advances, the graphene-based materials are considered to be
applied within membrane electrode assembly, due to the specific proprieties such
as specific surface and potential low manufacturing cost. Between these materials,
the reduced graphene oxide (rGO) has been investigated intensively as support for
low temperature fuel cell catalysts.
The doping of rGO by physical adsorption is promising, since it can increase the
concentration of charge carriers without affecting their mobility, as in the case of
adsorbed chemical dopants, where the covalent bond can sometimes cause
crystalline defects and irreversibly alter the structure of electrons. Doping of
heteroatoms in carbon lattice can change the both chemical and physical
proprieties. Among them, the halogen-doped graphene and particularly iodine
demonstrated promising performances for oxygen reduction reaction (ORR)
Within this paper, the results of an ongoing national project, which is intended
to implement graphene-based electrodes for the PEM fuel cells manufacturing line
from ICSI Energy department are shown and discussed. This stage of the project
was focused onto synthesis methodology through a facile and low-time consuming
procedure and comprehensive characterization.
The process, according to this study, presents an original approach: a fast and
cost-effective way to prepare iodine-doped graphene, starting from commercial
graphene oxide, various sources of iodine (elemental iodine, hydrochloric acid,
various organic salts such as potassium iodide, so on) and a reducing agent (e.g.
sodium borohydride). The electrochemical performance was investigated using a
commercial workstation. The electrodes were prepared and tested accordingly with
typical procedures developed in Group of Materials for Hydrogen Energy from ICSI
Energy [A. Marinoiu, 2020]. The elementary composition of the prepared graphene
materials was achieved by X-ray photoelectron spectroscopy measurements. The
graphene materials obtained starting from different sources of iodine were
evaluated and compared and it was found that the graphene material
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functionalized with iodine, starting from hydroiodic acid, gave the highest
concentration of doping. The prepared MEA based on iodine doped graphene oxide
demonstrated excellent stability and remarkable performance for ORR reaction,
attributes which are ideal for practical PEMFC applications.

Key words: graphene, iodine-doped graphene, microwave, fuel cells

Acknowledgments: This work was supported by Ministry of Research,

Innovation, Digitization from Romania by the National Plan of R & D, Project No. PN
19 11 02 01, and by UEFISCDI, Contract No. 460PED/2020 (Project PN-III-P2-2.1-
PED-2019-1894) and Contract No. 469PED/2020

References
A. Marinoiu et al. Appl Surf Science 504 p. 144511 (2020)

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MEMBRANE ELECTRODE ASSEMBLIES FOR PEMFCS INCLUDING FULLY

INTEGRATED GRAPHENE-BASED ELECTRODES PREPARED BY LASER AND
MICROWAVE METHODS

Adriana Marinoiu, Anişoara Oubraham, Mihaela Iordache,

Simona Borta, Athanasios Tiliakos

National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
Corresponding author: [email protected]

This work capitalizes on the expertise of the Materials for Hydrogen Energy
group of ICSI ENERGY to produce a laboratory-based proof of concept: monolithic
graphene-based electrodes for membrane electrode assemblies (MEAs),
encompassing both microporous and macroporous layers and doubling as catalyst
supports by bearing integrated catalytic layers, for anodes and cathodes, realized
by laser or microwave methods. These may potentially replace the time-consuming
and costly pyrolytic methods that currently dominate the industrial manufacturing
of nanocarbonic materials for FC, offering a competitive advantage to the national
initiative for a hydrogen economy.
Laser-based manufacturing of graphene-based electrodes is realized by laser
pyrolysis (photothermal) of solid polymeric substrates, specifically commercially
available polyimides (PI), performed on CO2 laser CNC engravers operating in pulsed
mode. The method has been extensively researched, proven to result in the
production of a highly porous and conductive graphene-based 3D foam of
controllable physical and chemical properties, generally referred to as Laser-
Induced Graphene (LIG) [Tiliakos, 2016]. The integration of LIG-embedded
nanoparticles of either pure platinum catalysts, alternative non-platinic metal
catalysts, or non-metal co-catalysts is realized by mixing metal acetylacetonates
(bearing a wide selection of transition metals as coordination groups) into the
polymeric matrix of the PI precursor, polyamic acid (PAA). The resulting complex
mixtures are dried and annealed to imidize into PI films, and laser pyrolyzed into
catalyst-bearing LIG monoliths with controllable properties. These are transferred
on Nafion membranes via a low-temperature decal transfer method specifically
designed and tested for the fabrication of LIG-based MEAs [Tiliakos, 2019].
Another strategy focuses on preparing noble or non-noble nanoparticles
supported on reduced graphene oxide (rGO), by using a fast and efficient one-step
microwave-assisted method – current efforts are focused on optimizing operating
parameters, such as microwave power, temperature, and process duration
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[Marinoiu, 2020]. Microwave irradiation secures the uniform and prompt heating of
reaction mixtures, thereby allowing the simultaneous reduction of graphene oxide
(GO) and metal ions, resulting in the rapid formation of metal nanoparticles with a
narrow size distribution (2-5 nm). Moreover, defect sites generated by removal of
functional groups on GO during the reduction process serve as anchoring sites for
the adhesion of nanoparticles. Dopant, catalytic, and co-catalytic precursors
introduced in the reactor during the reduction stage include: chloroplatinic acid
(H2PtCl6), chloroauric acid (HAuCl4), cobalt chloride (CoCl2), hydroiodic acid (HI), and
urea (CH4N2O).

Key words: membrane electrode assembly, graphene, laser, microwave, fuel cells

Acknowledgments: This work is supported by UEFISCDI Contract No.

460PED/2020.

References
Marinoiu A., et al., Appl. Surf. Science 504, 144511 (2020)
Tiliakos A., et al., J. Anal. Appl. Pyrol. 121, 275 (2016)
Tiliakos A., et al., Appl. Surf. Science 504, 144096 (2019)

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.SYNTHESIS OF GRAPHENE-BASED MATERIALS FUNCTIONALIZED WITH AZULENE

AND PEMFC FUNCTIONALITY TESTING WITH INNOVATIVE ELECTRODES

Adriana Marinoiu1, Irina Petreanu1, Mihaela Iordache1, Simona Nica2,

Claudia Sişu1, Sorin Sorlei1, Cătălin Capriş1, Elena Carcadea1
1
National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
2
"C D. Nenitzescu" Institute of Organic Chemistry -CCO, Splaiul Independentei 202 B, Bucharest,
Romania
Corresponding author: [email protected]

This work is focused on new synthesis method of azulene-functionalized graphene.

This includes a simple working methodology by using a 1,3-dipolar cyclo-addition after
a Prato reaction with sarcosine and 1-formyl azulene and rGO dispersed in DMF, under
mild reaction conditions (atmospheric pressure, temperature 145 C) for five days.
According to the proposed method, the process is simple, it does not present
technological difficulties, the activities of operation, exploitation and control are easy
to execute during the whole process, the process is economical and the reagents and
materials used are easily accessible and less expensive.
A process has been developed for the synthesis of graphene materials with a non-
benzenoid hydrocarbon, keeping intact the basic structure of the initial graphene and,
in addition, covalently grafting azulene residues which can improve the properties of
the obtained material. Thus, starting from a relatively cheap carbon material (rGO),
through a special process designed by chemical synthesis, graphene covalently
functionalized are obtained, with physico-chemical, morphological and structural
properties, which facilitate use in various electrochemical devices.
1-Azulencarboxaldehyde was prepared by the Vilsmeyer reaction (Figure 1).

Figure 1. Synthesis of 1-formyl azulene by the Vilsmeier method

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Figure 2. Reaction scheme for the synthesis of nanohybrid graphene material, covalently
functionalized with azulene by a 1.3 dipolar cycloaddition reaction

The materials were obtained at the Center for Organic Chemistry Nenitescu in
collaboration with ICSI Rm Valcea. The following table will indicate: graphene raw
materials and their main characteristics, as well as the synthesis process used.

Table 1. Azulene-functionalized graphene materials: name and main

characteristics of the raw materials used
rGO,
(furnizor
Sample rGO characteristics Synthesis method
Abalonix,
Norway)
rGO/Az_1 Reduced rGO, partly reduced. Carbon Substitution reaction in a classic laboratory
Graphene content: 85% atomic/80% wt. installation in a round bottom flask and magnetic
Oxide stirring
rGO/Az_2 Graphene GO-powder, C/O atomic Substitution reaction in a classic laboratory
Oxide ratio=2.5 - 2.6 installation in a round bottom flask and magnetic
stirring
rGO/Az_3 Fully reduced rGO fully reduced. Carbon Substitution reaction in a classic laboratory
content:98.5-99.5% wt installation in a round bottom flask and magnetic
stirring
rGO/Az_1’ Reduced rGO, partly reduced. Carbon 1-Azulencarboxaldehyde and 1-formyl azulene
Graphene content: 85% atomic/80% wt were classically prepared in the reaction flask.
Oxide The covalent functionalized nanohybrid
graphene material with azulene was prepared in
the microwave field
rGO/Az_2’ Graphene GO-powder, 1-Azulencarboxaldehyde and 1-formyl azulene
Oxide C/O atomic ratio = 2.5-2.6 were classically prepared in the reaction flask.
The covalent functionalized nanohybrid
graphene material with azulene was prepared in
the microwave field
rGO/Az_3’ Fully reduced rGO fully reduced. Carbon 1-Azulencarboxaldehyde and 1-formyl azulene
content: 98.5-99.5% wt were classically prepared in the reaction flask.
The covalent functionalized nanohybrid
graphene material with azulene was prepared in
the microwave field
rGO/Az_MW Fully reduced rGO, fully reduced. Carbon Substitution reactions were performed
content 98.5-99.5% wt exclusively in the microwave field

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Results-selection
The FTIR spectrum of graphene oxide (rGO) is almost uncharacteristic, with weak
skeletal vibrations of aromatic domains around 2922 cm–1. The absence of oxygen-
containing functional groups in the initial rGO is consistent with the absence of
stretching vibration around the 1700 cm–1 region. For the functionalized material, some
bands are observed, which are characteristic of azulene. These are consistent with the
aromatic nature of azulene observed at 1574 and 1646 cm-1 as strong bands, due to C-C
stretches in the aromatic rings. The disappearance of the aldehyde stretch band,
centered at 1700 cm– 1 (found in the IR spectrum of 1-formyl azulene - used as starting
aldehyde) in functionalized material is consistent with the reaction of aldehyde groups
and therefore the covalent attachment of azulene. The absorption bands in the region
2847–2916 cm–1, attributed to the C - H tensile vibrations of the aromatic rings, further
confirm the existence of azulene bonds on rGO.

Figure 3. Infrared spectrum (FTIR) for rGO / Az_1

The results on PEMFC Functionality Testing with Innovative Electrodes were

provided by the cyclic voltammetry, obtained in the electrochemical system with 3
electrodes. For the manufacture of the electrode, the procedure is as follows: a
catalytic ink is prepared, which contains the material to be tested by CV, Nafion
solution and isopropyl alcohol for the dispersion of graphene powder. 10 μL of ink
was deposited onto the working electrode, dried at 40 C for 2-4 h, then introduced
in the test cell and test by scanning the current in the potential range -0.8 - 0.8 V.
The dependence of the maximum peak currents indicating the electrocatalytic
activity is linear and is a function of the scanning speed, indicating a limited
diffusion reaction in the composite material. The figures presented below show the
behavior of graphene materials functionalized with azulene in the potential range
from 0.0 to 0.8 V. All graphene materials functionalized with azulene possess a
good electrochemical stability at over 100 cycles (in 1 M KOH electrolyte, potential -
0.8 + 0.8 V), keeping over 95% of their electrochemical activity. It can be mentioned

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an improved cycle stability for composite materials, concluded based on these

results, and the differences between composite materials are quite small.

Scan rate 50 mV/s – 10 cycles

Scan rate 75 mV/s – 10 cycles Scan rate 100 mV/s – 10 cycles

Scan rate 50 mV/s – 50 cycles Scan rate 50 mV/s – 100 cycles

Figure 4. Functionality testing with innovative electrodes- cyclic voltammetry results

Key words: graphene, azulene, electrode, fuel cells

Acknowledgments: This work was supported by Ministry of Research,

Innovation, Digitization from Romania by the National Plan of R & D, Project No. PN
19 11 02 01

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BIO-SUPERCAPATTERY’S MODIFIED ELECTRODES BASED ON HIGH CONTENT

BACTERIA-SECRETED ELECTRON SHUTTLES BIOFILMS

Robert Ducu, Cristina Obreja, Andreea Culcea, Mihai Iordoc

National Institute for Research and Development in Electrical Engineering ICPE-CA, 313 Splaiul Unirii,
030138, District 3, Bucharest, Romania, EU
Corresponding author: [email protected]

Supercapatteries represent the future most promising energy storage and

conversion devices, being the last generation of supercapacitors. This unique
combination leads to the formation of such device that can deliver high energy density
with no compromise on the power density. The SUPERFILM project consists of
developing a novel asymmetric supercapattery with high power density, high energy
density, environmentally friendly, low cost, long cycle life and harmless in use, based on
functional electrode materials made of vertically aligned graphene sheets decorated
with transition metals and conducting biofilms and redox-mediated gel-type electrolyte.
The hybridization of the material could be at electrode materials level or device
level. Vertically aligned graphene alone is a well-known capacitive material that stores
charges electrostatically at its surface and pores. This vertically aligned graphene can be
combined with battery-grade material such as niobium oxide to form hybrid material.
This hybrid material can offer a high specific capacity compared to vertically aligned
graphene and high-power density and life cycle compared to niobium oxide. In this
approach, the focus is on the synthesis route, design, and nanoarchitecture of the
hybrid material. Individual battery and capacitive electrodes are combined to form the
hybrid device. This approach looks facile but practically is quite a challenging task to
combine the unmatching performance electrodes in a single device.
The living biofilm is grown on the vertically aligned graphene and is “freezed” by
destroying the living cells with gamma radiation and keep the non-living metabolic
products 3D network and electron shuttles only. During the gamma radiation exposure,
the 3D bacterial network is decorated with in-situ reduced niobium nanoparticles.
Electron shuttles - (or redox mediators) are essential components in intracellular
electron transfer, while microbes also utilize self-produced and naturally present
compounds for extracellular electron transfer. These compounds assist in microbial
energy metabolism by facilitating electron transfer between microbes, from electron-
donating substances to microbes, and/or from microbes to electron-accepting
substances. Riboflavin (RF) and flavin mononucleotide (FMN), were the mostly
documented electron shuttles. RF is produced as the precursor for flavin adenine
dinucleotide (FAD) synthesis in cytoplasm. Phenazines generated by a diverse of
bacteria, particularly Pseudomonas species, were also intensively studied as intrinsic
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electron shuttles. All these aspects lead to a breakthrough innovation in terms of

research in the field of supercapacitors. Thus, obtaining an asymmetric supercapattery
with a power density exceeding 2 W/g, a life cycle of hundreds of thousands of
charge/discharge cycles with the electrochemical stability above 90%, a higher energy
density than 40 Wh/kg and a specific capacity greater than 200C/g, is an absolute
novelty and create prerequisites for a future large-scale study.

Ragone plot of different energy storage devices and the position of

hybrid device (supercapattery) [Chen, 2017]

Schematic diagram of (A) ELDC, (B) pseudocapacitor, and (C) supercapattery

[Numan, 2021]

The main goal of this work is the development and optimization of capacitor-type
modified electrode (negative electrode as power source in supercapattery), based on
vertically aligned graphene covered with gamma radiation reduced transitional metal
(Nb, Ta) nanoparticle decorated conductive biofilm.

Key words: biosupercapattery, biofilm, electron shuttle, modified electrode,

bacteria.

References
Chen G.Z., Int. Mater. Rev. 62 (4), (2017), 173-202.
Numan A. Advances in Supercapacitor and Supercapattery, Elsevier, (2021), pp 45-61.
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FUNCTIONALIZATION OF THE POLY(2,6-DIMETHYL PHENYLENE OXIDE)

POLYMER WITH BROMINE

Anişoara Oubraham, Elena Marin, Simona Borta, Violeta Niculescu, Amalia Soare,
Adriana Marinoiu

National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
Corresponding author: [email protected]

Poly(2,6-dimethyl phenylene oxide) (PPO) is one of the most important classes

of the aromatic polymers containing aryl and benzyl groups. Nowadays as a base
material, PPO has been extensively studied for their versatile electrochemical
applications such as electro-dialysis, fuel cells, batteries, diffusion dialysis,
electrolysis and electro deionization due to its easily modiable structure with robust
stability [M. Monohar, D. Kim, 2020].
The bromination reaction is present in the following scheme:

Figure 1. The scheme of PPO bromination reaction

Polymer is prepared from PPO and N-bromosuccinimide (NBS) in chlorobenzene

solvent, in presence of azobisisobutyronitrile (AIBN) initiator (reaction with homeolitic
mechanism, with substitution at methyl groups of polymeric chain). The brominating
reaction is conducted to obtain a brominating product. [M. Georgescu et al., 2010; D.
Garganciu et al., 2008]
The product Br-PPO will be characterized using: Scanning Electron Microscopy
(SEM) with Energy Dispersive X-Ray Analysis (EDX), analyses for specific surface area
& pore size, vapor adsorption & chemisorption (BET), nuclear magnetic resonance
(NMR) and Fourier transform infrared spectroscopy (FTIR).

Key words: polymer aromatic, aryl, benzyl, N-bromosuccinimide, chlorobenzen

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Acknowledgments: This work is supported by Ministry of Research, Innovation,

Digitization from Romania by the National Plan of R & D, Project No. PN 19 11 02 01
and by UEFISCDI, PN-III-P2-2.1-PED-2019-2079 (Contract No. 469PED/2020)

References
D. Garganciu, G. Batranescu, G. Nechifor, M. Olteanu, Materiale Plastice, 2008, 45, 1, 2008
M. Georgescu, M. Radu, B. Albu, L. Pasare, D. Rata, M. Georgescu, ICAMS 2010 – 3rd International
Conference on Advanced Materials and Systems;
M. Monohar, D. Kim, RSC Adv., 2020, 10, 3670;

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AMINO-FUNCTIONALISED SILICA NANOPARTICLES – SYNTHESIS AND

CHARACTERIZATION

Irina Petreanu, Amalia Soare, Stănică Enache, Ciprian Iacob

National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
Corresponding author: [email protected]

Silica nanoparticles with pendant aminopropyl moieties bound on the surface

were synthesized by co-precipitation of the two silica precursors: tetraethoxysilane
(TEOS) and 3-triethoxysilylpropylamine (APTES). The synthesis product was
characterised using elemental analysis, Raman spectroscopy, electronic microscopy
(SEM) and thermal gravimetric analysis (TGA). The presence of amino group was
emphasized into Raman spectra [Hiraoui et al.] (Fig. 1) and proved by elemental
analysis and thermal gravimerty. SEM image show the morphology of spherical
silica nanoparticles. Amino-functionalised silica nanopaticles can be used directly or
after additional functionalization via amino group in different application fields, one
of the interests being nanocomposite polymers for energy devices.

Figure 1. Overlapped Raman Spectra of silica (MS II) and

amino-functionalised silica nanoparticles (MS-NH2)

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Key words: Silica nanoparticles, amino-functionalised, Raman spectroscopy,

SEM, Thermal Gravimetric Analysis.
Acknowledgments: The authors acknowledge the financial support of the
Project PN 19 11 02 04, Dezvoltarea de electroliti solizi cu conductivitate ultra-
ridicata si electrozi cu stabilitate ciclica imbunatatita pentru baterii solid-state, by
the Ministry of Scientific Research and Innovation.

References:
M. Hiraoui, M. Guendouz, N. Lorrain, A. Moadhen, L. Haji, M. Oueslati, Spectroscopy studies of
functionalized oxidized porous silicon surface for biosensing applications, Materials Chemistry
and Physics 128 (2011) 151–156.

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ANTIOXIDANT AND UV PROTECTION EFFECT OF SELECTED TYPES OF BERRIES

Claudia-Valentina Popa1,2*, Sorin Avrămescu2, Eliza Oprea2, Mihai Coman3, Maria

Marinescu2, Irina Mirela Pietreanu4, Ciprian Iacob4
1
„Cantacuzino” National Military Medical Institute for Research and Development, 103 Splaiul
Independenței, 050096, Bucharest, Romania
2
University of Bucharest, Faculty of Chemistry, 90-92 Panduri Street, 050657, Bucharest, Romania.
3
Research Institute for Fruit Growing, 402 Marului Street, Pitesti-Maracineni, 117450, jud. Arges,
Romania.
4
National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
*Corresponding authors: [email protected]; [email protected]

The berries, due to the presence of bioactive components (especially polyphenols,

vitamins), exhibit a strong antioxidant capacity, but also antimicrobial and therapeutic
(gastroprotective, hepatoprotective, antiproliferative, anti-inflammatory) activities etc.
[Jurikova T., 2017; Golba M., 2020; Paredes-Lopez O., 2010]
In this work, antioxidant activity and UV protection effect of fruits belonging to the
species: Aronia melanocarpa (Michx) Elliott. (Rosaceae, chokeberry), Lonicera caerulea
L. (Caprofoliaceae, honeysuckle), and Sambucus nigra L. (Adoxaceae, elderberry) were
studied.
Alcoholic extracts from these berries were obtained by Soxhlet, maceration,
ultrasounds and microwaves methods. The content of antioxidants from obtained
extracts was evaluated by HPLC-DAD method [Ghinea I.O., 2021]. Antioxidant
activity was determined by DPPH free radical scavenging method [Lungu L., 2010].
Protection effect against harmful UV rays was evidence.
Values of antioxidant activity determined by spectrophotometric method were
reported us equivalents (µg /mL extract) caffeic acid, gallic acid, morin, quercetin,
rutin, Trolox, ascorbic acid and curcumin and are in concordance with the results of
chromatographic method.
Extraction methods do not influence significantly the antioxidant activity of
extracts. The experimental results have shown that analyzed fruit extracts have the
highest antioxidant activity. Extracts from mentioned berries can be used in
different pharmaceutical formulations with potential UV protection effect.

Key words: berries, polyphenol compounds; antioxidant activity, UV protection.

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References
Ghinea I.O., Mihaila M.D.I., Blaga (Costea) G.V., Avramescu S.M., Cudalbeanu M., Isticioaia S.F.,
Dinica R.M., Furdui B., HPLC-DAD polyphenolic profiling and antioxidant activities of Sorghum
bicolor during germination, Agronomy 2021, 11, 417.
Golba M., Sokol-Letowska A., Kucharska A.Z., Health properties and composition of Honeysuckle
berry Lonicera caerulea L. An update on recent studies, Molecules, 2020, 25, 749.
Jurikova T., Mlceka J., Skrovankova S., Sumczynski D., Sochor J., Hlavacova I., Snopek L., Orsavova J.,
Fruits of Chokeberry Aronia melanocarpa in the prevention of chronic diseases, Molecules,
2017, 22, 944.
Lungu L., Popa C.V, Savoiu M., Danet A.F., Dinoiu V., Antioxidant Activity of Brassica oleracea L.,
Allium cepa L. and Beta vulgaris L. Extracts, Rev. Chim (Bucharest), 60, 10, 2010.
Paredes-Lopez O., Cervantes-Ceja ML, Vigna-Perez M, Hernandez-Perez T. Berries: improving human
health and healthy aging, and promoting quality life--a review. Plant Foods Hum Nutr. 2010,
65(3), 299.

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ADVANCED ELECTRODE MATERIALS: ELECTROCHEMICAL

AND MECHANICAL PERFORMANCES

S. Rada1, 2, M. Unguresan2, M. Zagrai1, S. Macavei1

1
National Institute for Research and Development of Isotopic and Molecular Technologies, 400293,
Cluj-Napoca, Romania
2
Physics and Chemistry Department, Technical University of Cluj-Napoca, 400020, Romania
Corresponding author: [email protected]

ABSTRACT
Lead acid batteries have the largest market share among all the rechargeable
chemical power sources both in terms of the sales value and the maximum
cumulative capacity [K. Kopcznski e al., 2019]. Lead is the main raw material in the
fabrication of automotive batteries and cannot be replaced with other material.
Lead-based batteries will remain by necessity the most widespread energy storage
system in automotive applications. Their low cost and unparalleled ability to start
the engine at cold temperatures sets them apart in conventional and basic
microhybrid vehicles, and as auxiliary batteries in all other automotive applications.
The car battery called scientifically the automobile accumulator has real advantages
in terms of cost, recycling and current efficiency. Battery performance can be
increased by going deeper into the phenomena that occur on electrodes and
choosing the design features of the electrodes in order to optimize their
performance.
In this paper the structural, electrochemical and mechanical properties of the
vitreous system in the 0.15MnO2⸱0.85[(100-x)PbO2⸱xPb] composition where x = 0 –
100 mole% Pb were investigated, in order to find the most suitable lead content in
the matrix host that offers significantly superior optimized performance as
advanced electrode of the lead battery [S. Rada et al., 2015].
X-ray diffractograms for the prepared system having the 0.15MnO2⸱0.85[(100-
x)PbO2⸱xPb] where x = 0 – 50 mole% Pb are shown in Fig. 1. XRD data analysis
indicates in all cases vitroceramic structures consisting of four crystalline phases:
metallic Pb with cubic structure, PbO2 with orthorhombic structure, PbO with
orthorhombic structure and Mn3O4 with tetragonal structure.
The electrochemical performance of materials prepared as working electrodes
for car batteries has been demonstrated by cyclic voltammetry and linear scanning
voltammetry measurements. The prepared materials were tested as a working
electrode in the 5M sulphuric acid solution and further, were subjected to the
Vickers hardness measurements. A thorough knowledge of the structure of
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electrode materials is essential to understand the defects or microcracks that may

occur after their introduction into the sulfuric acid solution. Micro- and macrocracks
in the material are important factors that influence the evolution of hardness
values and the life cycle of the electrode.

Figure 1. X-ray patterns of the vitreous system in the

0.15MnO2⸱0.85[(100-x)PbO2⸱xPb]composition where x = 0 – 50 mole % Pb.

Figure 2. Cyclic voltammograms of prepared materials in the 0.15MnO2⸱0.85[(100-x)PbO2⸱xPb]

composition with x = 70 mole% Pb as the working electrode in a electrolyte solution of
5M sulphuric acid at different scan rates.

Measurements of cyclic voltammetry and linear scanning voltammetry for the

PbO2-Pb-MnO2 materials in the composition 0.15MnO2⸱0.85[(100-x)PbO2⸱xPb] with
x = 0–100 mole% Pb as working electrodes, in an electrochemical cell that
simulation the behaviour of the car battery, were investigated using an AUTOLAB
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PGSTAT 302N potentiostat/galvanostat using NOVA 1.11 software. A three-

electrode electrochemical cell was used to simulate the behaviour of the electrode
in the car battery. The reference electrode was the calomel electrode of
Hg/Hg2Cl2/KCl type. As the working electrode - the sample prepared from lead and
doped with manganese dioxide was used - and for the counter electrode was used
a platinum electrode, immersed in a 5M sulfuric acid solution.
Cyclic voltamograms for the studied electrode materials (see Fig. 2) indicate
the presence of oxidation processes involving the formation of a layer of lead oxide,
lead hydroxides and lead sulfate in the cathodic region, respectively, which lead to
electrode inhibition [S. Rada et al., 2020]. By the Pb doping, the intensity of these
oxidation peaks decreases in the following descending order for x: 50% > 60% >
40% > 70% > 80% > 10% > 30% > 100% Pb. This oxidation peak has low intensity for
samples with x = 10%, 30% and 100% Pb and is undetectable in the cyclic
voltammogram for samples with x = 20 and 90% Pb.
Measurements of the Vickers hardness by the indentation method for the
PbO2-Pb-MnO2 materials in the composition 0.15MnO2⸱0.85[(100-x)PbO2⸱xPb] with
x = 10–100 mole% Pb were performed using a kit Micro-Vickers Nova 130, equipped
with a microscope and software.

Figure 3: Microscopic images and traces with the pyramidal contour obtained after indentation for
electrode materials after being tested in the 5M sulfuric acid solution.

Microscopic analysis of the surface of the studied samples (see Fig. 3) shows
that their microstructure is dependent on the lead content. For samples with x = 10
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and 20 mole% Pb, the samples show microcracks and heterogeneous areas. For
samples with x = 30, 40 and 90 mole% Pb, the crystallinity is slightly higher and
some cracks were appeared. The microscopic image of the sample with x = 50
mole% Pb shows a metallic phase dispersed between two heterogeneous zones.
The surface of the samples with x ≥ 60 mole% is heterogeneous with structural
defects at the microscopic level.
The lowest value of the Vickers hardness would be found in the samples with
x = 100 mole% Pb, because it has only lead in its composition and lead is a soft
metal. The samples with x = 10 and 20 mole% Pb also have a low values of Vickers
hardness due to the fact that have a microstructure with larger blocks of crystallites
and well-defined shapes that are delimited by the areas with lower crystallinities.
These compositional evolutions may be due to cracks in the sample structure with
x = 20 mole% Pb. The micro- and macro-cracks in the material result in a decrease
in the hardness of the material, leading over time to the appearance and
accentuation of the wear process of the battery electrode.
In conclusion, the mechanical properties of the studied electrode materials are
dependent on the structure, shape and size of the crystallites as well as on the
physical and chemical influence of the environment (sulphuric acid environment) in
which they are, correlated with those that occur during stress.
Therefore, measurements of cyclic voltammetry, Vickers hardness and trace of
the pyramidal contour obtained after indentation (this did not produce to the
cracks) recommend the sample with x = 90 mole% Pb as most suitable electrode
material in car battery applications, both from the point in view of the
microstructure, as well as its electrochemical and mechanical properties.

Key words: PbO2-Pb-MnO2, electrode, battery, XRD, cyclic voltammetry,

Vickers.

Acknowledgments: This paper was financially supported from the Nucleus

project with the number PN 19350101.

References
K. Kopcznski, A. Gabryelczyk, M. Baraniak, B. Legoz, J. pernak, E. Jankowska, W. Rzeszutek, P.
Kedzior, G. Lota, Positive electrode material in lead acid car battery modified by protic
ammonium ionic liquid, J. Energy Storage 26 (2019) 100996.
S. Rada, L. Rus, M. Rada, E. Culea, N. Aldea, S. Stan, R. C. Suciu, A. Bot, Synthesis, structure, optical
and electrochemical properties of the lead sulfate-lead dioxide-lead glasses and vitroceramics,
Solid State Ionics 274 (2015) 111-118.
S. Rada, M. Unguresan, M. Rada, C. Tudoran, Jiaou Wang, E. Culea, Performance of the recycled and
copper-doped materials from spent electrodes by XPS and Voltammetric characteristics, J.
Electrochem. Soc. 167 (2020) 090548-090554.

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INFLUENCE OF THE THERMAL STRESS REGIME ON THE PROPERTIES OF C25/30

CONCRETE USED FOR NUCLEAR BUILDINGS

Irina Maria Sturzeanu

Institute for Nuclear Research, Campului Street, No.1, Mioveni, Arges, Romania
Corresponding author: [email protected]

The main extreme environmental conditions at which a structure with impact

on nuclear safety can be exposed, without taking into account events such as
earthquakes or severe accidents that may have consequences on the structural
integrity of the nuclear power plant, are high temperatures and pressure and
irradiation. Heat gradients are important for concrete structures because they can
affect the compressive strength (load-bearing capacity) and the stiffness (structural
deformations and loads that can develop).
Since the containment of the reactor is one of the five physical barriers of the
defence in depth concept, it is important to know the effects of its degradation,
caused by various factors - including high temperatures, on the integrity and
reliability of the functions for which was designed.
The paper aims to analyse the influence of the type of thermal stresses on
which the concrete structures of a nuclear power plant can be exposed, on the
macro structural properties, thus assessing the degree of degradation. For this
purpose, C25/30 concrete samples, prepared according to the Task Book used at
Cernavoda NPP for nuclear buildings, were subjected to continuous and cyclic
thermal treatments, for ~1 year, in wet and dry environment, at a temperature
level permitted in the normal operation of the reactor. At the end of the thermal
treatments, the samples were subjected to specific tests, according to standardized
methods, in order to determine the permeability, compressive strength and
elasticity of the samples.
The obtained results indicate a decrease of the three parameters monitored,
after applying the thermal treatments. Regarding the permeability and modulus of
elasticity, the lowest decreases was observed for the cyclic treatment in wet
environment, followed by the dry treatment. In case of compressive strength, the
lowest loss was observed for the cyclic treatment in dry environment, followed by
the continuous treatment. The recorded variations, although indicates decreases,
are not significant in terms of the durability of the concrete.
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Through this study, it was observed that, after the applied stresses, the
followed properties continued to maintain within the limits imposed by the Task
Book for this class of concrete, thus indicating the maintenance of an increased
degree of nuclear safety, through the concrete buildings.

Key words: C25/30 concrete, thermal stress, durability, nuclear safety

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COMPARISON OF PRODUCING PLATINUM ON REDUCED GRAPHENE OXIDE

NANOSHEETS OBTAINED UNDER MICROWAVE IRRADIATION,
USING REDUCING AGENTS

Felicia Vasut, Anisoara Oubraham, Amalia Maria Soare, Adriana Marinoiu,

Daniela Ion-Ebrasu, Mirela Dragan, Stanica Enache, Ramona Ionela Zgavarogea

National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
Corresponding author: [email protected]

Graphene is a material with a high potential for a wide range of applications. It

has excellent physical and chemical properties including mechanical strength and
strain, high thermal conductivity, electron mobility and chemical inertness. It is an
ideal support material for noble metal. Also, carbon-based supports with Pd, Au, Ag
or Pt nanoparticles have already been demonstrated to exhibit high efficiencies for
different processes (hydrogen storage, CO oxidation, oxygen reduction or in fuel
cell applications, hydrogen peroxide detection, lithium-ion batteries).
The microwave-assisted techniques have been demonstrated as a rapid and
high effective strategy for preparation of graphene-based materials. The microwave
heating has been used for exfoliation of graphite, reduction of GO (graphene oxide)
and preparation of graphene-based hybrid materials. Microwave-assisted
techniques ensures a high local temperature and pressure and the energy is
transferred directly into the graphene oxide. The heat and the pressure are
produced by the interaction of the irradiation with the polar bonding of the
functional groups containing oxygen from the surface and from the edge of the
graphene oxide sheets.
The hydrophobic catalyst is considered an essential element for increasing the
tritium separation performances and in minimizing LPCE (Liquid Phase Catalytic
Exchange) column sizes, facilitating tritium transfer from tritiated vapor water to
deuterium. Worldwide were prepared and tested more than 100 catalysts at
laboratory scale. ICIT Ramnicu Valcea developed his own catalyst for removing
tritium from heavy water. Until now, the catalytic efficiency of the catalyst has been
satisfactory, but there are possibilities to improve the characteristics, with
improving the catalytic efficiency.
The catalyst uses platinum-like active metal placed on charcoal, and PTFE for
hydrophobicity. For this type of material, Pt is found as agglomerates that leading
to an increase of hydrophilicity in the final catalyst and also, to a low number of

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functional groups for isotopic exchange. In order to avoid these drawbacks, another
type of platinum-based material was considered, with a higher platinum dispersion
on the surface which would lead to an increase number of functional groups for the
isotopic exchange process. Platinum on graphene was considered in order to
improve platinum distribution on the catalyst.
The paper presents the effect of the reducing agents on the morphological and
structural properties of the platinated graphene oxide. NaBH4 and KOH were used
as both reductive and dispersing agents for deposition of Pt nanoparticles on sheets
of graphene oxide, sample prepared with ethylene glycol being used like reference.
The aim of the research is to obtain a platinum concentration in graphene higher
than 10% (this is the concentration of platinated charcoal), using a faster method
(microwave irradiation) than the classical one (Hummers method). A diagram of the
preparation process is presented in figure 1.

There are different methods to synthesize Pt on graphene composites, but

using microwaves involves advantages like fewer stages and shorter time to
produce. The obtaining method uses reduction of H2PtCl6 in the presence of
ethylene glycol and other reducing agents (NaBH4 and KOH) and graphene oxide
suspension. Samples were then microstructurally investigated using SEM, BET, X-ray
diffraction, RAMAN and TGA.

Key words: Platinated graphene; Catalyst; Physical-structural characterization;

Reducing agents

Acknowledgments: This work was supported by Core Programme of Ministry of

Research and Innovation from Romania, Project No. 19 11 01 03.

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NITROGEN-DOPED GRAPHENE CATALYSTS EFFICIENT IN OXYGEN REDUCTION

REACTION IN ALKALINE MEDIA

Adriana Vulcu, Camelia-Berghian Grosan, Monica Dan, Alin Sebastian Porav

National Institute for Research and Development of Isotopic and Molecular Technologies, 67-103
Donat St., Cluj-Napoca, Romania
Corresponding author: [email protected]

Tremendous interest is paid to the development of electrocatalysts with high

catalytic performance and low material costs for oxygen reduction reaction (ORR).
The ORR is an important reaction in fuel cells which occurs at the cathode and
involves the transfer of four electrons and four protons. Platinum – based catalysts
have proved to be the best electrocatalysts for ORR, but platinum catalysts are
expensive and have poor durability. In this context, it is vital to develop low cost,
highly active and stable catalysts to replace the platinum-based materials for large
scale applications [Y. Zhan et al., 2018; Y. Qian et al., 2016]. Recently, carbon
materials doped with nitrogen have been identified as promising electrocatalysts
for ORR, owing to their large surface area, good conductivity, durability and
relatively low cost. Special attention have been paid to N-doped graphene catalysts
which can efficiently electrocatalyze the ORR via four-electron pathway in alkaline
fuel cells and possess better catalytic activity and stability than Pt/C [P.J. Kulesza et.
al., 2018; Y. Zhao et al., 2017; R. Ma et al., 2019]. The N-doped graphene can be
synthetized by means of various methods, such as chemical vapour deposition
(CVD), thermal annealing, hydrothermal or solvothermal treatment. These methods
present drawbacks like high production cost, complicated manipulation, low
production and cannot be used for large scale production and application in fuel
cells [Y. Zhao et al., 2017]. To overcome these issues the development of facile
approaches for N-doped graphene synthesis are demanded. A promising approach
for N-doped graphene synthesis is the mechanical ball milling method which is a
green and economical method and allows the preparation of advanced
electrocatalysts for fuel cells [Y. Xue et al., 2015].
In this paper, the ball milling method was employed to prepare N-doped
graphene from graphite and melamine as nitrogen source. This green procedure
allows the synthesis of large quantities of N-doped graphene materials which can
be used as electrocatalysts in ORR. The as prepared materials were characterized by
X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman
spectroscopy, thermogravimetric analysis (TGA), transmission electron microscopy

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(TEM), scanning electron microscopy (SEM) and energy dispersive X-ray analysis
(EDX). The ORR performance investigation of the N-doped graphene, obtained by
the ball milling procedure, has been performed using cyclic voltammetry and
rotating disk electrode protocols.

Key words: nitrogen-doped graphene, oxygen reduction reaction, alkaline media,

ball milling.

Acknowledgments: This research leading to these results has received funding

from the Norway Grants 2014–2021, under Project contract no. 29/2020 and Ministry
of Education and Research, Romania ,through Core Program PN 19 35 02 02.

References
J. Kulesza, J.K. Zak, I.A. Rutkowska, B. Dembinska, S. Zoladek, K. Miecznikowski, E. Negro, V. Di Noto,
P. Zelenay, Curr. Opin. Electrochem, 9, (2018), 257
R. Ma, G. Lin, Y. Zhou, Q. Liu, T. Zhang, G. Shan, M. Yang, J. Wang, NPJ Comput. Mat., 5, (2019), 78
Y. Qian, P. Du, P. Wu, C. Cai, D.F. Gervasio, J. Phys. Chem. C, 120, (2016), 9884
Y. Xue, H. Chen, J. Qu, L. Dai, 2D Materials, 2, (2015), 044001
Y. Zhan, F. Xie, H. Zhang, Z. Lin, J. Huang, W. Zhang, X. Sun, Y. Zhang, J. Chen, H. Meng, J.
Electrochem. Soc., 165, (2018), J3008
Y. Zhao, C. Zhang, T. Liu, R. Fan, Y. Sun, H. Tao, J. Xue, Int. J. Electrochem. Sci., 12, (2017), 3537

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ISOTOPES IN ENVIRONMENTAL STUDIES AND LIFE QUALITY

APPLICATIONS

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MULTISENSORY SYSTEMS BASED ON ELECTROCHEMICAL SENSORS AND

BIOSENSORS USED IN THE ANALYSIS AND MONITORING OF NATURAL WATERS
QUALITY

Constantin Apetrei

”Dunarea de Jos” University of Galati, Faculty of Science and Environment, Department of Chemistry,
Physics and Environment, 47 Domneasca Street, RO-800008, Galati, Romania
Corresponding author: [email protected]

Over the years, many rivers, streams, lakes and coastal waters around the
world have been affected by pollution. Livestock farms can be a major source of
pollution, as fertilizers, manure and pesticides periodically reach rivers and lakes.
Used on agricultural surfaces, they stimulate crop growth, but in water they can
lead to excessive algae multiplication. As a result, the amount of oxygen in the
water decreases, and fish and other creatures risk suffocation. That is why there are
rigorous controls to determine which chemicals to spread on agricultural areas and
when. Chemicals used to destroy unwanted parasites or plants can also have a
disturbing effect on plants and living things in the water. This is why aerial spraying
is prohibited and the watercourses are protected by buffer zones. Certain sectors of
industry produce substances that are harmful to the environment and human
health, but the existence of strict laws and the emergence of greener technologies
have reduced water pollution caused by industry. Most wastewater is treated to
remove organic matter, and some of it is disinfected or treated to remove
nutrients. And people can be a direct source of pollution. For example, unused
pharmaceuticals, if not disposed of properly, can get into the soil, rivers and lakes,
with harmful consequences for plants and animals [Mora et al., 2021; Hosseiny et
al., 2021].
For the analysis of environmental samples in order to determine the degree of
pollution, different standardized instrumental methods are used for the specific
analysis of the chemical compounds of interest. Of these, chromatographic
methods are the most widely used [Menger et al., 2020]. In recent years, systems
based on electrochemical sensors and biosensors for the determination of analyts
of interest in natural water pollution have had a special development. These
systems have the advantage that they are portable, can perform on-site analyses,
do not require chemical reagents or solvents and have a relatively low cost [Hossain
& Mansour, 2019; O’Grady et al., 2021].
This work will present the development and characterization of new
electrochemical sensors and biosensors based on screen-printed electrodes
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modified with different nanomaterials, electron mediators and biological

recognition elements used in the analysis of various environmental samples. Two
viable strategies will be addressed in the analysis of environmental samples, the
qualitative and quantitative analysis of chemical pollutants and the global analysis
of the quality of environmental samples, which is based on the use of multisensory
systems and the analysis of multivariate data.

Key words: sensor; voltammetry; nanomaterial; data analysis; water quality.

References
Hossain S. M. Z., Mansour N., Biosensors for On-Line Water Quality Monitoring – a Review. Arab
Journal of Basic and Applied Sciences 2019, 26 (1), 502–518.
Hosseiny H., Cao H., Smith V., Xu W., Unraveling the Transport and Fate of Polycyclic Aromatic
Hydrocarbons Through Coupling Fluvial Geomorphic Modeling and Measured Data. Front.
Water, 2021, 3, 705694.
Menger F., Gago-Ferrero P., Wiberg K., Ahrens L., Wide-Scope Screening of Polar Contaminants of
Concern in Water: A Critical Review of Liquid Chromatography-High Resolution Mass
Spectrometry-Based Strategies. Trends in Environmental Analytical Chemistry, 2020, 28,
e00102.
Mora A., García-Gamboa M., Sánchez-Luna M. S., Gloria-García L., Cervantes-Avilés P., Mahlknecht
J., A Review of the Current Environmental Status and Human Health Implications of One of the
Most Polluted Rivers of Mexico: The Atoyac River, Puebla. Science of the Total Environment,
2021, 782, 146788.
O’Grady J., Zhang D., O’Connor N., Regan F., A Comprehensive Review of Catchment Water Quality
Monitoring Using a Tiered Framework of Integrated Sensing Technologies. Science of The Total
Environment, 2021, 765, 142766.

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POLLUTANTS IN THE AQUATIC ECOSYSTEMS OF THE LOWER DANUBE AND

NORTH WESTERN BLACK SEA BASINS

Carmen Lidia Chiţescu1, Antoaneta Ene2*, Irina Elisabeta Geana3, Aida Mihaela
Vasile4 and Corina Teodora Ciucure3
1
Dunarea de Jos University of Galati, Faculty of Medicine and Pharmacy, 35 A.I. Cuza Street, 800010
Galati, Romania; [email protected]
2
Dunarea de Jos University of Galati, INPOLDE research center, Faculty of Sciences and Environment,
47 Domneasca Street, 800008 Galati, Romania; [email protected]
3
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
[email protected] ; [email protected]
4
Dunarea de Jos University of Galati, Faculty of Food Science and Engineering, 111 Domneasca
Street, 800201 Galati, Romania; [email protected]
*
Corresponding author: [email protected]

The tremendous impact of natural and anthropogenic organic and inorganic

substances, continuously released into the environment requires a better understanding
of the chemical status of aquatic ecosystems. Water contamination monitoring studies
have been performed for different classes of substances, in different regions of the
world. Reliable analytical methods and exposure assessment approaches were employed
for better management of water resources.
Due to the location, climatic and historical conditions, Lower Danube and Black Sea
basins constitute a unique ecosystem [Covaci et al., 2006]. In the Eastern Europe, rapid
development of small industry, tourism activities and urban area, together with a
decrease of the intensive farming, led to the frequent changes in a pollutant profile. High
industrial pollution inputs from tributaries and poor control of the discharges significantly
affected the Lower Danube water quality [Gasparotti, 2014].
A systematic search in Web of Science (Clarivate Analytics) and Google Scholar for
papers published between 2010 and 2021 on the monitoring studies in the Lower
Danube and North West Black Sea basins aquatic environment of regulated and
unregulated persistent and emerging pollutants was performed in order to provide
policy-relevant data.
A number of 78 studies describing sampling campaigns, seasonal monitoring,
temporal monitoring or spatial monitoring were identified concerning contaminants
classes such as pharmaceuticals (PhACs), personal care products (PCPs), endocrine
disruptors (EDs), polar pesticides (organophosphorous, carbamates, triazines), persistent
organic pollutants (POPs) such as polychlorinated biphenyls (PCBs), organochlorine

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pesticides (OCPs) or polycyclic aromatic hydrocarbons (PAHs), but also heavy metals and
microbial pollution in matrices such as groundwater, surface water, sediments and biota.
The literature on monitoring programs of organic and inorganic pollutants published
during 2010-2021, shows that this research area has been extended in the last year (Fig.
1), due to the higher concern of political entities and, on the other hand, the
development of more sensitive analytical techniques.

15
14
Number of publications

13
12
11
10 PhACs
9
8
7 metals
6
5
4 POPs
3
2
1
0
2010 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020
Publication year
Figure 1. Frequency of reports by year (2010-2020), dealing with monitoring of the pollutants

The most frequently reported contaminants of emerging concern in the study

area for the target period of time including those on referred by the Watch List of
Decision 2018/840/EU were: pharmaceuticals (carbamazepine, sulfamethoxazole, and
diclofenac, trimetoprim and caffeine), bisphenol A, estrogens, caffeine, pesticide
(atrazine, carbendazim, metolachlor) and PCPs like triclosan (Fig. 2).

Figure 2. Frequency of the detection of certain CECs reported in the monitoring campaigns on Lower
Danube and Nord-Western Black Sea basins, published between 2010-2021
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Among POPs, PAHs were investigated in 10 studies, PCBs in 5, OPCs in 11.

Studies were focused on the analysis of sediment or top soil, surface water and fish.
The concentrations of Σ16PAHs (US EPA PAHs) in the sediment samples from the
Lower Danube basin were higher than those reported for Upper Danube [Nagy et
al., 2014]. The reported metals, in the following decreasing order of concentration
were: Fe>Zn>Cu>Pb>Cr>Ni>As>Cd>Hg.
Untreated and inadequate treated waste water was demonstrated as being the
main source of organic pollution in the low Danube basin. The metals pollution is
associated with industrial and municipal sources. Seasonal variations were reported
for all contaminants classes, probable due to the temperature related processes of
biotransformation and absorption.
Apart from study related to The Joint Danube Surveys, 6 studies concerning
microbiological pollution on the Lower Danube basin were identified. A total of 32
different sites of MONITOX network were selected in the Lower Danube region and
Romanian Black Sea coast for a recent study conducted in June 2019 and June-July
2020, concerning microbiological pollution in the Black Sea Basin [Ene, 2020].
Comparison between faecal and organic pollution of water samples from the Black
Sea area, Romania and water samples from the Aegean Sea, Kavala, Greece were
presented by Vasile et al. in 2020 [Vasile et al. 2020]. Higher values of faecal
indicators were measured in Black Sea compared to the Aegean Sea coast.
The pollution level in the Lower Danube basin are in agreement to other big
European rivers such as the Rivers Elbe (Germany) [Wiegel et al., 2004], Lis
(Portugal) [Paíga et al., 2016] or Po (Italy) [Ferrari et al., 2011].

Key words: pharmaceuticals, endocrine disruptors, persistent organic pollutants,

metals, microbiological contamination, monitoring survey.

Acknowledgments: This research was performed in the frame of the project

with code BSB 27 –MONITOX (2018-2021), financed through the Joint Operational
Programme Black Sea Basin 2014-2020 of European Union. The Irina Elisabeta
Geană and Corina Teodora Ciucure work was supported by the Romanian Ministry
of Research and Innovation, grant number PN 19110303 "Advanced techniques for
identifying sources of contamination and biochemical reactions in aquatic
ecosystems"

References
Covaci A., Gheorghe A., Hulea O., Schepens P., Levels and Distribution of Organochlorine Pesticides,
Polychlorinated Biphenyls and Polybrominated Diphenyl Ethers in Sediments and Biota from
the Danube Delta, Romania. Environ. Pollut. 2006, 140, 136-149
Ene A., Vasile M.A., Bahrim G., Study of Microbiological Contamination Level of Surface Water in
MONITOX Network Areas before and after COVID-19 Pandemic. Analele Univ. ”Dunărea Jos”
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Din Galați Fasc. II Mat. Fiz. Mec. Teor. Ann. ”Dunarea Jos” Univ. Galati Fascicle II Math. Phys.
Theor. Mech. 2020, 43, 75-81.
Ferrari F., Gallipoli A., Balderacchi M., Ulaszewska M.M., Capri E., Trevisan M., Exposure of the Main
Italian River Basin to Pharmaceuticals. J. Toxicol. 2011, 2011, e989270.
Gasparotti C., The Main Factors of Water Pollution in Danube River Basin. EuroEconomica 2014,
1(33), 91-106.
Nagy A.S., Simon G., Szabó J., Vass I., Polycyclic Aromatic Hydrocarbons in Surface Water and Bed
Sediments of the Hungarian Upper Section of the Danube River. Environ. Monit. Assess. 2013,
185, 4619-4631
Paíga P., Santos L.H.M.L.M., Ramos S., Jorge S., Silva J.G., Delerue-Matos C., Presence of
Pharmaceuticals in the Lis River (Portugal): Sources, Fate and Seasonal Variation. Sci. Total
Environ. 2016, 573, 164-177.
Vasile M.A., Ene A., Bahrim G., Microbiological Quality and Contamination Level of Water of Black
Sea and Northern Aegean Sea. Conference paper. "Environmental Toxicants in Freshwater and
Marine Ecosystems in the Black Sea Basin" Kavala, Greece, 8-11 septembrie 2020. Available
online: https://ibn.idsi.md/vizualizare_articol/115635.
Wiegel S., Aulinger A., Brockmeyer R., Harms H., Löffler J., Reincke H., Schmidt R., Stachel B., von
Tümpling W., Wanke A., Pharmaceuticals in the River Elbe and Its Tributaries. Chemosphere
2004, 57, 107-126.

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ION MOBILITY-MASS SPECTROMETRY: PRINCIPLES AND APPLICATIONS

Karel Lemr, Lucie Borovcová, Marianna Nytka

Department of Analytical Chemistry, Faculty of Science, Palacky University,

17.listopadu 12, 771 46 Olomouc, Czech Republic
Corresponding author: [email protected]

Stand-alone ion mobility (IM) spectrometry is an important tool, e.g., in safety

control at airports or in the pharmaceutical industry. Its coupling to mass
spectrometry is of interest to analytical chemists too. It is dated to 1960, but more
widely available commercial instruments have been introduced during the last 15
years. Mass spectrometry separates ions according to mass to charge ratio, but ion
mobility is also influenced by the shape of molecules [Ewing, Glover and Clemmer,
2016; Gabelica and Marklund, 2018; Lapthorn Pullen and Chowdhry, 2013;
Wintrode, 2013]. It adds selectivity to mass spectrometric analysis. In ion mobility
spectrometry, ions drift through a mobility cell filled with buffer gas. Their mobility
depends on their charge, mass, and collision cross-section that are characteristic of
a given ion. Mobility separation can be accomplished in time, space, and using
confinement with the selective release [Kliman, May and McLean, 2011; May and
McLean, 2015; Morrison and Clowers, 2018; Ridgeway et al., 2018]. Different
mobility cell designs are used. Mobility separation can be performed using a drift
tube, traveling wave IM, asymmetric field IM, differential IM, and trapped IM [Li,
Delafield and Li, 2020]. Separation is characterized by resolving power and some
improvement was achieved using non-conventional techniques including cyclic
traveling wave ion mobility. Separation is influenced by analyte properties but also
by instrumentation or buffer (drift) gas and its pressure. The choice of buffer gas
can significantly improve separation, e.g., separation of protomers [Gabelica and
Marklund, 2018; Kurulugama et al., 2015; Warnke et al., 2015].
The coupling of ion mobility to mass spectrometry provides: 1) the reduction of
chemical noise; 2) the separation of ions into families; 3) the separation of isomers,
isobars, and conformers; 4) collision cross-section as another identifier. Many
examples can be found in the literature, e.g., the reduction of chemical noise in
mass spectra of peptides (Guevremont 2004) and background in chromatograms of
ibuprofen metabolite (Smith et al. 2013), the separation of N-linked glycans into
families (Harvey et al. 2013) and the separation of protein conformers [Pritchard
O’Connor and Ashcroft, 2013]. The discrimination of various isomers was also
demonstrated, e.g., alditols [Zhu et al., 2009] and hyaluronan-derived
oligosaccharides [Hermannová et al., 2015; Borovcová et al., 2017]. Finally, collision
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cross-section is useful in identification. Experimental values can be compared with

calculated ones [Gabelica and Marklund, 2018] which can provide more detailed
insight into molecular structures [Kurulugama et al., 2015, Moss, 2012; Zhou Tu and
Zhu, 2018, Liu et al., 2021]. In our laboratory, a new Select Series Cyclic ion
mobility-mass spectrometer, Waters, [Giles et al., 2019] was installed in December
2019. The instrument is equipped with traveling wave ion mobility similarly to
Synapt, Waters, but a cyclic mobility cell is used instead of a linear one. It offers
resolving power 400 or higher and IMn. It enables us to achieve or to improve
mobility separation of new designer drugs, oligosaccharides, and dyes.
It can be concluded that ion mobility improves selectivity and provides useful
structural information, but it can also decrease ion transmission and influence the
duty cycle of an instrument.

Key words: ion mobility, mass spectrometry, collision cross-section, resolving

power, isomeric separation, buffer gas

Acknowledgments: The authors are grateful to the ERDF project OA ITI –

ARTECA (CZ.02.1.01/0.0/0.0/17_048/0007378) of the Ministry of Education, Youth
and Sports of the Czech Republic.

References
Borovcová L., Hermannová M., Pauk V., Šimek M., Havlíček V., Lemr K.: Simple area determination of
strongly overlapping ion mobility peaks, Anal. Chim. Acta, 981 (2017) 71.
Ewing M.A., Glover M.S., Clemmer D.E.: Hybrid ion mobility and mass spectrometry as a separation
tool, J. Chromatogr. A, 1439 (2016) 3.
Gabelica V., Marklund E.: Fundamentals of ion mobility spectrometry, Curr. Opin. Chem. Biol., 42
(2018) 51.
Giles K., Ujma J., Wildgoose J., Pringle S., Richardson K., Langridge D., Green M.: A cyclic ion mobility-
mass spectrometry system, Anal. Chem., 91 (2019) 8564.
Guevremont R.: High-field asymmetric waveform ion mobility spectrometry: a new tool for mass
spectrometry, J. Chromatogr. A, 1058 (2004) 3.
Harvey D.J., Scarff C.A., Edgeworth M., Crispin M., Scanlan C.N., Sobott F., Allman S., Baruah K.,
Pritchard L., Scrivens J.H.: Travelling wave ion mobility and negative ion fragmentation for the
structural determination of N-linked glycans, Electrophoresis, 34 (2013) 2368.
Hermannová M., Iordache A.M., Slováková K., Havlíček V., Pelantová H., Lemr K.: Arrival time
distributions of product ions reveal isomeric ratio of deprotonated molecules in ion mobility–
mass spectrometry of hyaluronan-derived oligosaccharides, J. Mass Spectrom., 50 (2015) 854.
Kliman M., May J.C., McLean J.A.: Lipid analysis and lipidomics by structurally selective ion mobility-
mass spectrometry, Biochim. Biophys. Acta, 1811 (2011) 935.
Kurulugama R.T., Darland Ed., Kuhlmann F., Stafford G., Fjeldsted J.: Evaluation of drift gas selection
in complex sample analyses using a high performance drift tube ion mobility-QTOF mass
spectrometer, Analyst, 140 (2015) 6834.

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Lapthorn C., Pullen F., Chowdhry B.Z.: Ion mobility spectrometry-mass spectrometry (IMS-MS) of
small molecules: Separating and assigning structures to ions, Mass Spectrom. Rev., 32 (2013)
43.
Li G., Delafield D. G., Li L.: Improved structural elucidation of peptide isomers and their receptors
using advanced ion mobility-mass spectrometry, TrAC, Trends Anal. Chem. 124 (2020) 115546.
Liu Y., Liu Y., Nytka M., Huang S. R., Lemr K., Tureček F.: Probing D- and L‑Adrenaline Binding to
β2‑Adrenoreceptor Peptide Motifs by Gas-Phase Photodissociation Cross-Linking and Ion
Mobility Mass Spectrometry, J. Am. Soc. Mass Spectrom. 32 (2021) 1041.
May J.C., McLean J.A.: Ion mobility-mass spectrometry: time-dispersive instrumentation, Anal.
Chem., 87 (2015) 1422.
Morrison K.A., Clowers B.H.: Contemporary glycomic approaches using ion mobility-mass
spectrometry, Curr. Opin. Chem. Biol., 42 (2018) 119.
Moss C.L., Chamot-Rooke J., Nicol E., Brown J., Campuzano I., Richardson K., Williams J.P., Bush M.F.,
Bythell B., Paizs B., Turecek F.: Assigning structures to gas-phase peptide cations and cation-
radicals. An infrared multiphoton dissociation, ion mobility, electron transfer, and
computational study of a histidine peptide ion, J. Phys. Chem. B, 116 (2012) 3445.
Pritchard C., O’Connor G., Ashcroft A.E.: The role of ion mobility spectrometry-mass spectrometry in
the analysis of protein reference standards, Anal. Chem. 85 (2013) 7205.
Ridgeway M.E., Lubeck M., Jordens J., Mann M., Park M.A., Trapped ion mobility spectrometry: A
short review, Int. J. Mass Spectrom., 425 (2018) 22.
Smith R.W., Toutoungi D.E., Reynolds J.C., Bristow A.W.T, Ray A., Sage A., Wilson I.D., Weston D.J.,
Boyle B., Creaser C.S.: Enhanced performance in the determination of ibuprofen1-β-O-
acylglucuronide in urine by combining high field asymmetric waveform ion mobility
spectrometry with liquid chromatography-time-of-flight mass spectrometry, J. Chromatogr. A,
1278 (2013) 76.
Warnke S., Seo J., Boschmans J., Sobott F., Scrivens J.H., Bleiholder C., Bowers M.T., Gewinner S.,
Schöllkopf W., Pagel K., von Helden G.: Protomers of benzocaine: solvent and permittivity
dependence, J. Am. Chem. Soc., 137 (2015) 4236.
Wintrode P.: Mass spectrometry in structural biology, Biochim. Biophys. Acta, Proteins Proteomics,
1834 (2013) 1187.
Zhou Z., Tu J., Zhu Z.J.: Advancing the large-scale CCS database for metabolomics and lipidomics at
the machine-learning era, Curr. Opin. Chem. Biol., 42 (2018) 34.
Zhu M., Bendiak B., Clowers B., Hill H. H., Jr.: Ion mobility-mass spectrometry analysis of isomeric
carbohydrate precursor ions, Anal. Bioanal. Chem., 394 (2009) 1853.

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APPLICATION OF STABLE ISOTOPE RATIO ANALYSIS FOR THE CHARACTERIZATION

OF PHARMACEUTICALS, COSMETICS AND SUPPLEMENTS

Matteo Perini

Fondazione Edmund Mach, via Mach1, 38010, S. Michele all’Adige, Italy

Corresponding author: [email protected]

Stable isotope ratio analysis of bio-elements (hydrogen, carbon, nitrogen,

oxygen and sulphur) has been used since the 1990s to check food authenticity and
traceability of a wide variety of food commodities [Rossmann, 2001]. In the last few
years, examples of applications also in the pharmaceutical and cosmetic field have
been reported [Pellati et al., 2013; Perini et al., 2017, 2021; Perini, Paolini, et al.,
2019; Perini, Pianezze, et al., 2019]. The use of stable isotope analysis for products
authentication purposes is possible thanks to isotopic fractionation occurring in
several processes and reactions (biological, biochemical, physical, chemical etc.)
which generates unique isotopic signatures. For this reason, the application of this
technique on the bulk samples as well as on specific components (e.g. aroma
compounds) can be used to detect the origin of an ingredient (synthetic or natural),
the substitution of one ingredient for another, as well as the geographical and/or
botanical origin of the products.
The widespread and well-known technique based on the coupling between
elemental analyzer and mass spectrometer (EA-IRMS) is now flanked by liquid
chromatography (LC-IRMS) and gas chromatography (GC-IRMS). Today it is
therefore possible to analyze not only the bulk of the matrices but also their
individual components.
The δ13C and δ2H values of vanillin can determine whether the product is
natural (deriving from the expensive CAM plant Vanilla), biotechnologically derived
or synthetic [Perini, Pianezze, et al., 2019]. Moreover, the δ13C values of specific
components of Rosa damascene mill., one of the most expensive essential oils in
the market world, can indicate the fraudulent addition of cheaper oil from a C4
plant (e.g. Cymbopogon martinii, palmarosa) [Pellati et al., 2013].
In pharmaceutical and cosmetic formulations, δ13C analysis is a suitable tool to
discriminate between squalene and squalane from shark (illegal) and from olive oil
(expensive) [Camin et al., 2010] as well as between monacolin K (contained in the
fermented dietary supplement red yeast rice) and the commercially marketed
statin, lovastatin [Perini et al., 2017] .The L-theanine extracted from Camellia

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Sinensis is easily distinguishable from that obtained biosynthetically [Perini et al.,

2021].
It is possible to combine different isotopic signatures to guarantee the natural
origin of curcumin, caffeine [Ding et al., 2019], tartaric acid and its derivatives.
These examples demonstrate that the isotopic fingerprint represent an
effective tool for the authenticity assessment of economically important
pharmaceutical, cosmetic and supplement products.

Key words: stable isotope analysis, pharmaceuticals, cosmetics, supplements

References
Camin, F., Bontempo, L., Ziller, L., Piangiolino, C., & Morchio, G. (2010). Stable isotope ratios of
carbon and hydrogen to distinguish olive oil from shark squalene-squalane. Rapid
Communications in Mass Spectrometry: RCM, 24(12), 1810-1816.
Ding, B., Zeng, G., Wang, Z., Xie, J., Wang, L., & Chen, W. (2019). Authenticity determination of tea
drinks in the Chinese market by liquid chromatography coupled to isotope ratio mass
spectrometry. Microchemical Journal, Devoted to the Application of Microtechniques in All
Branches of Science, 144, 139-143.
Pellati, F., Orlandini, G., van Leeuwen, K. A., Anesin, G., Bertelli, D., Paolini, M., Benvenuti, S., &
Camin, F. (2013). Gas chromatography combined with mass spectrometry, flame ionization
detection and elemental analyzer/isotope ratio mass spectrometry for characterizing and
detecting the authenticity of commercial essential oils of Rosa damascena Mill. Rapid
Communications in Mass Spectrometry: RCM, 27(5), 591-602.
Perini, M., Carbone, G., & Camin, F. (2017). Stable isotope ratio analysis for authentication of red
yeast rice. Talanta (Vol. 174, pp. 228–233). https://doi.org/10.1016/j.talanta.2017.05.057
Perini, M., Paolini, M., Pace, R., & Camin, F. (2019). The use of stable isotope ratio analysis to
characterise saw palmetto (Serenoa Repens) extract. Food Chemistry, 274, 26-34.
Perini, M., Pianezze, S., Strojnik, L., & Camin, F. (2019). C and H stable isotope ratio analysis using
solid-phase microextraction and gas chromatography-isotope ratio mass spectrometry for
vanillin authentication. Journal of Chromatography. A, 1595, 168-173.
Perini, M., Pianezze, S., Ziller, L., & Camin, F. (2021). Characterization of L-theanine in tea extracts
and synthetic products using Stable Isotope Ratio Analysis. Journal of Food and Drug Analysis,
Vol. 29, Issue 2, pp. 312-319. https://doi.org/10.38212/2224-6614.3349
Rossmann, A. (2001). Determination of Stable Isotope Ratios in Food Analysis. Food Reviews
International, Vol. 17, Issue 3, pp. 347-381. https://doi.org/10.1081/fri-100104704

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LARGE-SCALE ATMOSPHERIC CIRCULATION PATTERNS EMBEDED IN THE STABLE

ISOTOPE COMPOSITION OF PRECIPITATION

Aurel Perșoiu1,2
1
Emil Racoviță Institute of Speleology, Romanian Academy, Clinicilor 5, Cluj-Napoca, Romania
2
Ștefan cel Mare University, Universității 13, Suceava, Romania
Corresponding author: [email protected]

South-Eastern Europe is experiencing an intensification of the frequency and

duration of summer heat waves, leading to increased stress on the scarce water
resources. Rainfall variability in the region is modulated by the interplay of Atlantic,
Mediterranean and Black Sea sources and regional climatic influences that result in
complex patterns of water availability. Further, climatic models are showing that
the expected warming will result in a complex alteration of the moisture bearing
atmospheric flows, resulting in more erratic rainfall patterns in terms of frequency,
duration and intensity of the events, amount and seasonal distribution. In order to
cope with these challenges, we need 1) a clear understanding of the source and
path of moisture reaching the region, and 2) a long-term perspective on the
interplay between climatic changes and stable isotope variability in rain. In this
context, our study aims to investigate the stable isotope composition of
precipitation along several paths from moisture sources (Atlantic Ocean,
Mediterranean and Black Sea) to Eastern Europe.
Between March 2012 and December 2020 we have collected monthly
precipitation samples for stable isotope analyses at 21 stations in Romania and
Republic of Moldova. The location of the stations was chosen to reflect the
different climatic conditions in Romania (Fig. 1) and also to span the largest
latitudinal (2°30’), longitudinal (6°30’) and altitudinal (1500 m) gradients. The water
was collected continuously using tube-dip-in 5 L water collectors. At the end of
each month, a 22 ml aliquot was collected from the container and stored (in HDPE
scintillation vials) until analysis at 4 °C. In winter, snowfall samples were collected in
10 L (40 cm deep) plastic containers, allowed to melt at room temperature at the
end of each month, and stored similarly to the liquid water samples. Water samples
were analysed for their stable isotopic composition at the Stable Isotope
Laboratory, Ștefan cel Mare University (Suceava), using a Picarro L2130-I CRDS
analyser coupled to a high precision vaporizing module. Prior to analyses, the
samples were filtered through 0.45 μm nylon membranes. The raw values were
normalized on the SMOW-SLAP scale using two internal standards calibrated
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against the primary VSMOW2 and SLAP2 standards provided by IAEA. The stable
isotope values are reported using the standard δ notation. Based on repeated
measurements of an internal standard, the precision of the measurements is
estimated to be better than 0.16 ‰ for δ18O and 0.7 ‰ for δ2H, respectively.
Our results show that the study area is fed by precipitation derived from
several moisture sources located in the North Atlantic Ocean, the Mediterranean
and the Black seas, with a complex interplay between these, modulated by large-
scale atmospheric circulation patterns. Analyses of correlation between air
temperature and the main teleconnection indices show a positive relationship with
North Atlantic Oscillation (NAO), the East Atlantic pattern (EA), the East
Atlantic/Western Russia pattern (EA/WR), the Atlantic Multidecadal Oscillation
(AMO) and the Arctic Oscillation (AO) and negative correlations with the
Polar/Eurasia pattern (POL) and the Scandinavian pattern (SCA). In winter, the
climatic conditions in the Central and Eastern part of Romania (CEE) are influenced
by the NAO, the main mode of climatic variability in the Northern Hemisphere,
which in turn is influenced by the EA pattern that has an important role in the
location and strength of NAO dipole. The positive phase of NAO (when the
atmospheric pressure is below average in Iceland and above it in the Azores) is
associated with higher than normal temperatures in CEE and Southern Europe and
the precipitation source is predominantly Atlantic. Conversely, the negative phase
of the NAO is linked to low temperatures in CEE and a southward displacement of
the westerlies, carrying moisture from North Atlantic towards CEE and the
Mediterranean Sea. In summer, the action of atmospheric pressure centres on
temperature and moisture sources is more complex than in winter, due to blocking
structures and highly dynamic Rossby waves meandering over Europe. High
temperatures are associated with a stationary anticyclonal structure over CEE in
which the Rossby waves act in the convergence areas and the moisture sources is
predominantly from the eastern part of Europe.
These modes of climate variability are affecting the δprec differently, with the
EA, NAO and AO pattern having a stronger influence during winter, while during
summer, δprec shows a strong correlation with the AMO and EA.
Positive temperature anomalies are associated with a high pressure system
over the whole eastern part of Europe and flanked by a low pressure system on the
left and right. In general, these kind of blocking situations are associated with
heatwaves and droughts over the eastern part of Europe, like the exceptionally dry
and warm summer of 2010.
These differences are clearly discernible when identifying the moisture sources
based on the analysis of deuterium excess (d-excess) values of precipitation water. D-
excess values in precipitation are an indication of changes in conditions at the moisture
sources (or changes of the moisture sources), recycling processes along the moisture
tracks or reorganization of the atmospheric circulation. Our data shows that during
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spring and autumn most of the moisture east of the Carpathian Mountains is coming
along eastern trajectories or is locally recycled, with the Atlantic Ocean contributing
significantly during spring and summer. The Mediterranean and Black Seas are less
important as moisture sources, with the highest percentage influence during winter
and spring as mobile cyclones penetrate farther north. Relatively low contributions of
Atlantic Ocean and Mediterranean Sea derived moisture are due to the orographic
barrier effect of the Carpathians. Comparatively, stable isotopes data from the western
flanks of the Carpathian Mts. Have shown the strong influence of both the Atlantic and
the Mediterranean sources.
Climatic models show that, besides general warming, a yet poorly understood
change in the position of the moisture tracks and pressure changes is expected for
Europe, with areas where various centers of action interact (e.g., SE Europe) being
most affected. In order to improve the ability of these models to predict such
changes, a better understanding of present day conditions is required.

Key words: stable isotopes, precipitation, atmosphere, large-scale circulation,

Europe

Acknowledgments: The IAEA partly supported the stable isotope collection and
analysis in the framework of CRP F33021 (Application and development of isotope
techniques to evaluate human impacts on water balance and nutrient dynamics of
large river basins, contract 18452/RO) and CRP F31006 (Isotope variability of rain
for assessing climate change impacts, contract 23550/RO) research contracts. This
work was supported by a grant of the Romanian Ministry of Education and
Research, CNCS – UEFISCDI, project number PN-III-P4-ID-PCE-2020-2723.

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BIODEGRADATION OF PENTACHLOROPHENOL BY SPHINGOBIUM

CHLOROPHENOLICUM DSM 7098 AND DETECTION OF ITS METABOLITES BY
UHPLC-Q-ORBITRAP HRMS

Silviu-Laurentiu Badea, Elisabeta-Irina Geana, Corina Ciucure,

Violeta-Carolina Niculescu, Radu Tamaian, Roxana-Elena-Ionete

National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, 240050 Râmnicu Vâlcea, Romania
Corresponding author: [email protected]

This study aimed to investigate the aerobic biodegradation of pentachlorophenol

(PCP) by Sphingobium Chlorophenolicum DSM 7098, as a model compound for the class
of polyhalogenated phenols, in order to elucidate its biodegradation pathways into
aquatic environments, but also as a strategy for remediation of industrial sites
contaminated with PCP and with other chlorophenols [McCarthy et al., 1997;
Hlouchova et al., 2012; Bosso and Cristinzio, 2014].
The biodegradation experiments were carried out in sterile 600 mL Erlenmeyer
flasks covered with metal caps [Khessairi et al., 2014]. 500 mL of sterile DSMZ No. 1
culture medium (containing 5 g/L peptone and 3 g/L meat extract) was inoculated
with 40 mL of Sphingobium chlorophenolicum DSM 7098 pre-culture. In parallel,
500 mL of sterile DSMZ culture medium No. 1 was transferred to the second
Erlenmeyer flask which was kept as a control. PCP was spiked in both flasks using a
stock solution of acetone to final aquatic concentrations of about 4.9 µg/mL. The
biodegradation experiment was performed on an incubator for 9 days at 30 ºC and
125 rpm. The culture growth was monitored by taking 3 mL of culture medium
using a plastic syringe and by measuring its optical density at 600 nm using a
SPECORD 200 PLUS UV-VIS spectrophotometer. At the beginning of the experiment
and at every 24 hours, 13 mL of medium were sampled from both flasks using
plastic syringes for UHPLC-MS-MS analysis.
The above-mentioned samples were treated with 0.5 mL 37% HCl to stop the
biodegradation of PCP and extracted for 12-36 h with 2 mL pentane containing
pentabromophenol (PBP) as internal standard. The organic extract was collected
using Pasteur pipettes and transferred to 16 mL vials, where it was dried on
anhydrous sodium sulfate. The dry organic extracts were transferred to glass tubes
and evaporated to dryness under a stream of nitrogen. The resulting residues were
re-dissolved in 2 mL of acetonitrile, then filtered through a 0.45 PTFE filter
membrane into 2 mL vials for injection in UHPLC-MS-MS. The measurements were

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performed with a Dionex UltiMate 3000 ultra-high pressure liquid chromatograph

with DAD detection coupled with a quadrupole-Orbitrap high-resolution mass
spectrometer (UHPLC-Q-Orbitrap HRMS type). Separation of the analytes was
performed on a Syncronis C18 analytical column (50 mm × 2.1 mm, 1.7 μm) under
the following gradient: ultrapure water with 0.1% formic acid and 5 mM ammonium
formiate (A) and methanol with 0.1% formic acid and 5 mM ammonium formiate
(B), at a flow rate of 0.3 mL/minute. The mass spectrometer was configured in ESI
ionization mode (negative), at an applied voltage of 3.0 kV. Mass spectral data were
recorded in the scanning range of m/z 100–1000, with full scan resolution of 70
000. Data quantification was performed by the internal standard method, in a
linearity range of 1-50 μg/mL.
Pentachlorophenol (PCP) was dehalogenated by Sphingobium chlorophenolicum
DSM 7098 in a 9 days experiment. The concentration of PCP decreased from 4.0 μg/mL
at the beginning of the experiment to 0.88 μg/mL after 6 days of biodegradation (Fig. 1).
In the control flaks, the PCP concentration varied between 4.5 μg/mL at the beginning of
the experiment and 3.7 μg/mL after 6 days, indicating no significant variation of the PCP
concentration.
PCP concentration (mg/mL)

0 1 2 3 4 5 6 7
Time (days)
Figure 1. Variation of pentachlorophenol (PCP) concentration (●) during aerobic biodegradation by
Sphingobium chlorophenolicum DSM 7098 and evolution of PCP concentration in the control flask (■).

The main metabolites detected by HRMS (negative ionization mode) were 2,3,5,6-
tetrachlorophenol (TCP) detected at the retention time of 12.33 minutes,
tetrachlorohydroquinone (TCHQ) detected at 13.35 minutes, and 2,6-
dichlorohydroquinone (2,6-DCHQ) detected at 0.57 minutes. These three metabolites
detected by UPLC-MS-MS are similar to the metabolites detected in previous studies
involving aerobic biodegradation of PCP [Dai et al., 2003; Hlouchova et al., 2012].

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Preliminary results of this biodegradation study shown the potential of high-

resolution mass spectrometry (HRMS) in performing the suspect screening of PCP
metabolites. In the same time, the study shown the potential of Sphingobium
chlorophenolicum DSM 7098 culture in the biodegradation of PCP over a wide range of
aqueous concentrations. Future experiments with Sphingobium chlorophenolicum DSM
7098 culture will contribute to the elucidation of the aerobic biodegradation
mechanism of PCP using high resolution mass spectrometry (HRMS).

Key words: Biodegradation, Pentachlorophenol, Metabolites, HRMS.

Acknowledgments: This research was performed within the project PN

19110303 entitled “Advanced techniques for identifying sources of contamination
and biochemical reactions in aquatic ecosystems” financed by the Ministry of
Research, Innovation and Digitalization.

References
Bosso L, Cristinzio G. A comprehensive overview of bacteria and fungi used for pentachlorophenol
biodegradation. Reviews in Environmental Science and Bio/Technology, 2014; 13: 387-427.
Dai M, Rogers JB, Warner JR, Copley SD. A previously unrecognized step in pentachlorophenol
degradation in Sphingobium chlorophenolicum is catalyzed by tetrachlorobenzoquinone
reductase (PcpD). Journal of bacteriology, 2003; 185: 302-310.
Hlouchova K, Rudolph J, Pietari JM, Behlen LS, Copley SD. Pentachlorophenol hydroxylase, a poorly
functioning enzyme required for degradation of pentachlorophenol by Sphingobium
chlorophenolicum. Biochemistry, 2012; 51: 3848-60.
Khessairi A, Fhoula I, Jaouani A, Turki Y, Cherif A, Boudabous A, et al. Pentachlorophenol
Degradation by <i>Janibacter</i> sp., a New Actinobacterium Isolated from Saline Sediment of
Arid Land. BioMed Research International ,2014; 2014: 296472.
McCarthy D, Claude A, Copley S. In vivo levels of chlorinated hydroquinones in a pentachlorophenol-
degrading bacterium. Applied and Environmental Microbiology, 1997; 63: 1883-8.

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ISOTOPIC MODELS FOR DETECTING FOOD AND BEVERAGE AUTHENTICITY

Oana Romina Botoran, Diana Costinel, Roxana Elena Ionete

National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
Corresponding author: [email protected]

The worldwide spread of agricultural products and their availability on the

market as Protected Designation of Origin (PDO), Products Geographical Indication
(PGI), traditional specialty guaranteed (TSG), or organic products has received a
tremendous attention as a key element influencing consumer behaviour. However,
maintaining and strengthening such production requires not only the introduction
of initiatives to protect against unfair competition, but also quality products [Dias
and Mendes, 2017; Creydt et al., 2018]. The most ubiquitous example is
represented by the unregulated imported agricultural products of lower quality that
are promoted as "local" or coming from certain geographical locations [Chae and
Kim, 2016]. In addition to the false declaration of the geographic origin of the
product, frauds regarding different food products and beverages include other
several aspects, such as substitution of an expensive constituent with a cheaper
one (e.g., botanical origin), undeclared sugar addition, lowering the content of
valuable constituent by dilution, use of technologies not allowed by legislation,
mislabelling, incorrect or insufficient description and fraudulent imitations of
products (fig. 1).

Figure 1. Types of food products and beverages frauds

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The importance of traceability applies not only to regional foods, the quality of
which is closely related to both a specific geographic area and traditional
production methods, but has also draw the attention of consumers in all food
products, especially following recent food crises such as outbreaks of bovine
spongiform encephalopathy, avian and swine influenza, and foot-and-mouth
disease [Amaral, 2021; Hassoun et al., 2020]. Quality and safety are influenced
throughout the entire production chain. Improving the traceability process for
agricultural products, which will become final food products as such or as a result of
technological processes, is an essential element of quality management systems in
the food industry. Furthermore, it is often irrelevant whether a fraudulent act was
involved in the labelling of a product, enough to adversely affect both the consumer
and the legitimate manufacturer. The latter suffer damage because they are
deprived of valuable business and the established reputation of their products is
damaged. As a result, it is necessary to protect both buyers and sellers by
developing analytical protocols that can be used to identify the origin of food.
Methods for proving authenticity and providing analytical data for traceability
require robust analytical techniques that can be used by various regulators [Camin et
al., 2017]. Therefore, it is not surprising that studies on food authentication are
increasing the number of certified traditional products such as cheese [Fontenele et al.,
2017], wine vinegar [Paneque et al., 2017; RíosReina et al., 2017], vegetables [Novak et
al., 2019; Drivelos et al., 2016; Mir-Marqués et al., 2016], fruits [Dasenaki and
Thomaidis, 2019), meat [Marchetti et al., 2020], lard [Chiesa et al. al., 2016] or saffron
[Senizza et al., 2020; Cagliani et al., 2015]. Food authentication is based on unique
markers or groupings of markers identification that may be used to characterize the
authenticity of food or potential adulterants/contaminants and to solve authenticity
issues. From food authenticity testing benefits more than just customers; it also
benefits food manufacturers who want to ensure their goods' labelling and branding
conformity. Also, regulatory agencies are requesting a more comprehensive and up-to-
date list of analytical procedures for confirming the authenticity of food products and
assisting law enforcement. Therefore, the accuracy of food authenticity markers, as
well as the assessment of factors that influence them, are critical for making the best
judgment about product authenticity or adulteration.
Traditionally, chemical approaches to food authentication have required assessing
a product's many ingredients, physical or chemical properties, or relying on a single
"ideal marker" of either authenticity or adulterant presence. The use of dedicated
chromatographic and spectroscopic techniques to determine "fingerprints" of
substances such as aroma compounds, oligosaccharides, or the near infrared spectrum
as quick, non-destructive screening procedures has also showed tremendous promise.
Also, organoleptic testing is a reasonably simple and time-efficient method, but
particularly in the case of more expensive goods like wine, spirits, and olive oil, where
an objective assessment of whether the product looks, smells, and tastes as a standard
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product, specific techniques are needed. This is the most difficult aspect of developing
analytical procedures for traceability, identifying a marker (or markers) that are unique
to the food, its geographical origin, or production process, and are related to a legal
requirement, standard, or guidance, with minimal natural fluctuation, multi-element
stable-isotope ratio (SIR) analysis being shown to be particularly useful for this purpose.
Light isotopic forms of compounds that contain elements such as nitrogen, carbon,
hydrogen and oxygen are more volatile, reactive, disperse faster and participate more
rapidly in natural biochemical reactions. This leads to isotopic differentiation in physical
and biological processes, allowing particular isotopic ratios to be used as authenticity
markers for biological and chemical samples. This is a relatively new technique that was
first successfully applied to the authenticity of wine originating from Europe [Epova et
al., 2020; Dinca et al., 2016, Geana et al., 2016] but it now provides information on the
geographical origin of a variety of other foods and beverages, including fruit juices
[Perini et al., 2018; Botoran et al., 2017], olive oil [Camin et al., 2017], and honey
[Geana et al., 2020; Dinca et al., 2014]. Animal products, such as milk and dairy
products, lamb, pork, beef, and chicken meat, have recently been the subject of
research to determine their geographical origins and dietary histories [Zhao et al.,
2020, Vinci et al 2013]. Observing that any animal or plant has its own intrinsic isotopic
composition, which can only be modified by metabolic turnover, every tissue will result
in a “fingerprint” or “isotopic signature”. In addition to selecting the most appropriate
method for food and beverage authenticity determination, another important factor is
related to data interpretation, specifically multivariate statistical analysis application. It
is frequently necessary to match a large number of variables derived from various
analytical techniques in order to classify 'similar' products of the same origin: analytical
parameters that are markers of geographical origin, chemical characteristics of the
food correlated with similar characteristics measured in the area, and markers linked to
the composition and transformation processes. As a result, the employment of
mathematical models and their validation is an essential technique. There are
sometimes more than ten factors in origin assignment, with no evident difference
between the isotopic fingerprints; this complexity prevents the use of simpler
univariate tests (ANOVA or t-test). The main statistical data analysis preferred for
performing multivariate data analysis and exploratory and predictive analyses with the
purpose of identifying origin based on isotope data used in food authentication are
traditionally represented by principal component analysis (PCA), discriminant analysis
(DA), and cluster analysis (CA). Such multivariate approaches imply a homogeneous
sample distribution per group and must be treated with attention, especially regarding
measurement uncertainty inclusion. Lately, there is an increasing emphasis to use
machine learning algorithms, such as artificial neural network, k-nearest neighbours
(kNN), decision tree (DT), support vector machine (SVM) and soft independent
modelling by class analogy for stable isotopes data classification in food authenticity,

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because these strategies can extract information from data itself and better reflect
data's natural process.
The use of statistical data assessment tools has simplified the treatment of vast
amounts of data with numerous variables, but their application is often suboptimal or
might lead to inaccurate findings if not assessed by specialists in the field, leaving the
fundamental issue of creating reference data banks as an international accepted
strategy.

Key words: stable isotopes, authenticity, chemometrics, food products and

beverages

Acknowledgments: This work is part of the project PN 19 11 03 02 part of the

Research Program „ICSI 4EE” financed by the Romanian Ministry of Research,
Innovation and Digitalization and the CNCS – UEFISCDI, project PN-III-P1-1.1-PD-
2019-0325, within PNCDI III (acronym ISO-TECH), ctr. PD 146/2020.

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Fontenele M. A., Bastos M. D. S. R., dos Santos K. M. O., Bemquerer M. P., do Egito A. S. (2017). Peptide
profile of coalho cheese: A contribution for Protected Designation of Origin (PDO). Food Chemistry,
219. http://dx.doi.org/10.1016/j.foodchem.2016.09.171
Geana E. I., Popescu R., Costinel D., Dinca O. R., Ionete R. E., Stefanescu I., Artem V., Bala C. (2016).
Classification of red wines using suitable markers coupled with multivariate statistic analysis. Food
chemistry, 192, 1015–1024. https://doi.org/10.1016/j.foodchem.2015.07.112
Geană E.-I., Ciucure C.T., Costinel D., Ionete R.E. (2020) Evaluation of honey in terms of quality and
authenticity based on the general physicochemical pattern, major sugar composition and δ13C
signature. Food Control 109:106919
Hassoun A., Måge I., Schmidt W. F., Temiz H. T., Li L., Kim H. Y., Nilsen H., Biancolillo A., Aït-Kaddour A.,
Sikorski M., Sikorska E., Grassi S., Cozzolino D. (2020). Fraud in Animal Origin Food Products: Advances
in Emerging Spectroscopic Detection Methods over the Past Five Years. Foods (Basel, Switzerland),
9(8), 1069. https://doi.org/10.3390/foods9081069
Novak V., Adler J., Husted S., Fromberg A., Laursen K. H. (2019). Authenticity testing of organically grown
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M. (2019). Identification of phenolic markers for saffron authenticity and origin: An untargeted
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ENVIRONMENTAL RADIOCARBON AND CO2 LEVEL IN THE ATMOSPHERE OF

RAMNICU VALCEA, ROMANIA

Ionut Faurescu1, Octavian Duliu2, Carmen Varlam1, Denisa Faurescu1, Diana

Bogdan1, Diana Costinel1
1
National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
2
Geological Institute of Romania, Caransebes 1, RO-012271 Bucharest, Romania
Corresponding author: [email protected]

Radiocarbon (14C) natural production takes place at high altitude in the

atmosphere due to the nuclear reaction of thermal neutrons, generated by cosmic
rays, with 14N nuclei. 14C thus formed oxidizes to carbon dioxide and results in a flux
of 14CO2 in the troposphere where it is incorporated into plants through
photosynthesis, as well as in the meteoric and ocean waters through CO 2 exchange
reactions. However, anthropogenic impacts on the environment are a major cause
of significant change in the isotopic composition of carbon in the atmosphere. This
paper describes our sample preparation procedures for radiocarbon measurements
by direct absorption method and liquid scintillation counting (LSC) in order to
establish the radiocarbon level in the atmosphere of Ramnicu Valcea, Romania. The
validation of routine procedure for radiocarbon measurement was obtained by an
intercomparison exercise on environmental samples with IFIN-HH laboratory that
uses the accelerator mass spectrometry (AMS). We also compare our specific
results with 14CO2 observations at Jungfraujoch high altitude research station in the
Swiss Alps conducted to monitor the background 14CO2 level over Europe and
define the reference for regional estimates of fossil fuel CO2 (Hammer et al. 2017).
Radiocarbon measurements on biological samples (control sample) were done in
order to see if the 14C level in wild vegetation (WV), grapes and tree leaves was
comparable with the 14C level in the atmosphere.
The samples were collected in the vicinity of the Experimental Pilot Plant for
Tritium and Deuterium Separation (PESTD) from the Institute of the Cryogenics and
Isotopic Technologies (ICSI) placed about 10 km south from the Ramnicu Valcea city
(Romania), in the Govora industrial area. This facility is an experimental project in
the national nuclear energy research program, which has the aim of developing
technologies for tritium separation from heavy water. It should be noted that in the
Govora industrial area operates a 315MW coal-fired thermoelectric power plant
and two chemical plants. In order to determine radiocarbon activity in the
atmosphere, samples were collected monthly by absorption of CO2 into sodium
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hydroxide (NaOH) at Ramnicu Valcea. In addition, control materials (tree leaves,

wild vegetation, and grapes), known activity standards, and process blanks (marble)
were analysed.
The method used for determining 14C concentration was the direct
absorption method followed
by LSC [Leaney et al., 1994; Varlam et al., 2006]. This consists of measuring 14C
contained in a known quantity of carbon, as carbon dioxide, obtained from a
sample, standard and background material, counted in an ultra-low level liquid
scintillation counter Quantulus™ 1220. The procedure applied in our laboratory has
three steps. The first step is the preparation of the homemade liquid scintillation
cocktail, which contains an amine (CarbonTrap, Meridian Biotechnologies Ltd),
fluorescence substances (PPO and bis-MSB, PerkinElmer) and solvents (methanol
and toluene). The second stage of the procedure is obtaining and purification of
CO2. For air samples, the obtained Na2CO3 by active absorption of atmospheric CO2
into sodium hydroxide (NaOH) has been acidified with HCl in order to obtain pure
CO2. The pure CO2 was collected in a gas bag, which then was connected to the
bubbling system containing a pump, a purification system, a flowmeter and the
bubbler with scintillation cocktail. The CO2 from the gas bag is then bubbled
through the liquid scintillation solution with a flow rate of about 0.2 L/min for 10
min to ensure saturation of amine with the CO2 as carbamate. Biological samples
were dried into the oven at 60°C to constant weight and then ground and
combusted in an oxygen atmosphere (17 atm.) in a Parr 1121 combustion vessel
[Moghissi et al., 1975] in order to obtain CO2. After combustion the gas mixture was
purified in the same way as described above and then bubbled through the liquid
scintillation solution with a flow rate of about 0.2 L/min for 10 min. The results of
the radiocarbon measurements are reported in Δ14C [Stuiver and Polach, 1977]. The
effect of isotope fractionation has been taken into account in the data evaluation,
and therefore the results of 14C activity are corrected for δ13C. The δ13C ratio was
measured by isotope ratio mass spectrometry on a Delta V IRMS on small aliquots
of sodium carbonate resulted from the absorption of CO2 into sodium hydroxide
and dried control samples.
In order to validate the LSC radiocarbon measurement was organized an
intercomparison regarding the determination of C-14 concentration in
environmental samples by liquid scintillation and accelerator mass spectrometry
(AMS). The LSC measurements were performed at ICSI Rm. Valcea, and the AMS
measurements by at IFIN-HH. The comparison was made on five environmental
samples (thuja leaves, Thuja occidentalis L.) that were collected monthly. The
results were satisfactory and showed that radiocarbon measurements by LSC
provide reliable values although the LSC uncertainties are much higher than that of
the AMS measurements.

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Figure 1 shows the atmospheric Δ14C data measured on the Ramnicu Valcea
samples (grey line) during the period from August 2012 to January 2018 and Δ 14C
data set for Jungfraujoch location (black line) during the period August 2012 to
February 2016. The long-term decrease of Δ14C in atmospheric CO2 observed since
the 1960s has continued during the studied period. For the Ramnicu Valcea
location, the measured Δ14C levels varied between –57‰ and 62‰, with a
minimum value in October 2014 and a maximum value in November 2015. The
mean of Δ14C for the studied period was around 0‰. The results have a decreasing
trend, but due to local influence caused by the continuous production of fossil CO 2,
we cannot observe Δ14C seasonal variations. By comparison with Jungfraujoch, the
Δ14C values for the Ramnicu Valcea location are lower due to the major impact of
the coal-fired thermoelectric power plant in the immediate vicinity of the sampling
location of the CO2 atmospheric samples. Radiocarbon levels for the biological
samples are shown in Figure 2. The mean of Δ14C values for control samples (wild
vegetation [WV], grapes, and tree leaves) was 11‰. The maximum value was
observed in grapes (42‰) while the minimum value was found in the wild
vegetation in the autumn (–42‰).

14
Figure 1. Variation of the Δ C for collected atmosphere samples in Ramnicu Valcea and
14
Δ C for Jungfraujoch (2012–2016). The dashed line represents the linear trend
line for the Ramnicu Valcea values.

The observed values for our control samples were in the same range as those
observed for the atmosphere. These kinds of samples do not necessarily reflect the
radiocarbon level in the atmosphere at the time of collection, but rather these are time
integrated samples that allow evaluating emissions over a longer period of time.

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14
Figure 2. Variation of the Δ C for collected control samples.

In conclusion the monitored site is a particular one due to the Suess effect
caused by the continuous production of fossil CO2 by a coal-fired thermoelectric
power plant. By comparison with Δ14C values recorded at Jungfraujoch and other
undisturbed locations, our values were smaller. Also, seasonal variations could not
be highlighted. Δ14C values for wild vegetation, grapes, and tree leaves were in the
same range as those observed for the atmosphere. In the future, we want to
monitor locations similar to those studied, but also undisturbed locations or close
to nuclear facilities.

Key words: atmosphere, radiocarbon, LSC, direct absorption method.

Acknowledgments: This work was supported by project PN 18 12 03 04, part of

Core Program ICSI 4E supported by the Romanian Ministry of Research and
Innovation, by a grant of Ministry of Research and Innovation, CNCS - UEFISCDI,
project number PN-III-P1-1.1-PD-2016-0532, within PNCDI III and monitoring
program of Tritium Removal facility PESTD.

References
14
Hammer Samuel, Levin Ingeborg, 2017. Monthly mean atmospheric Δ CO2 at Jungfraujoch and
Schauinsland from 1986 to 2016. https://doi.org/10.11588/data/10100, heiDATA, V2.
Leaney F., Herczeg A., Dighton J., 1994. New developments for the direct CO2 absorption method for
radiocarbon analysis. Quaternary Science Reviews, 13(2):171-178.
Moghissi A.A., Bretthauer E.W., Whittaker E.L., McNelis D.N., 1975. Oxygen bomb combustion of
environmental and biological samples for tritium analysis. International Journal of Applied
Radiation and Isotopes, 26(6–7):339-342.
14
Stuiver M., Polach H , 1977. Discussion: reporting of C data. Radiocarbon, 19(3):355-363.
14
Varlam C., Stefanescu I., Varlam M., Faurescu I., Popescu I., 2006. Optimization of C concentration
measurement in aqueous samples using the direct absorption method and LSC. In: Chalupnik S,
Schoenhofer F, Noakes J, editors. LSC 2005: Advances in liquid scintillation spectrometry.
Tucson (AZ): Radiocarbon, p. 423-428.

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THE DEVELOPMENT OF A FOOD SUPPLEMENT WITH ANTIOXIDANT PROPERTIES

Adina Frum1*, Cecilia Georgescu1, Felicia Gligor1, Carmen Dobrea1, Maria

Muresan1, Diana Stegarus2, Ovidiu Tita1
1
“Lucian Blaga” University of Sibiu, 9 Victoriei Avenue, Sibiu, Sibiu County, Romania
2
National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
Corresponding author: [email protected]

An adequate and varied diet could provide, under normal conditions, all the
necessary nutrients for a normal development and a healthy life, in quantities that
correspond to those established and recommended by the generally accepted
scientific data. This ideal situation, unfortunately, is not the real one because of
different lifestyles or other reasons, thus allowing consumers to choose to
supplement the intake of certain nutrients with food supplements [Directive
2002/46/EC 2002].
The aim of this study is to develop a food supplement that contains bioactive
compounds that possess antioxidant activity and that can provide health benefits to
consumers.
The raw materials used for the formulation of the food supplement consisted
of dried powders of two berries and two types of fermented, red pomaces. The
mixed powders were analyzed regarding their particle size distribution estimation
by analytical sieving and flow properties. After the obtaining of the capsules, the
final product was analyzed regarding the uniformity of mass of single-dose
preparations and disintegration [Ph. Eur., 2019]. Spectrophotometrical assays were
performed for the analysis of total polyphenols, and for the assessment of the
antioxidant activity of the raw materials and food supplement capsules. A high-
performance liquid chromatography analysis was performed in order to identify
and quantify several bioactive compounds ((+)-catechin, caffeic acid, cinnamic acid,
chlorogenic acid, ferulic acid, gallic acid, syringic acid, resveratrol, rutin and
quercetin) from both, raw materials and food supplement capsules [Frum et al.,
2018].
Results show that the raw material was a gross powder with good flow
properties. The developed capsules met the requirements regarding the uniformity
of mass of single-dose preparations, thus falling into the ±7,5% deviation from the
average mass of the capsules. The disintegration of the analyzed capsules was
performed in less than 3 minutes, thus rendering the capsules compliant with the
quality requirements of the 10th edition of the European Parmacopoeia.
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From the total of phenolic compounds analyzed, a percentage larger than 15%
was determined for chlorogenic acid, rutin and ferulic acid and the amount per
capsule determined, was larger than 100 µg phenolic compound/capsule for these
substances. The total polyphenolic content was greater than 6,5 mg/capsule and it
was consistent with the result of the antioxidant activity, thus confirming that the
food supplement developed could possess antioxidant properties.
The developed food supplement meets the quality requirements in order for it
to be commercialized and the content in bioactive compounds that possess
antioxidant properties could provide health benefits to consumers.

Key words: antioxidant activity, bioactive compounds, food supplements,

polyphenols

References
th
*** Council of Europe. European Pharmacopoeia, 10 edition, Strasbourg: France, 2019.
***Directive 2002/46/EC of the European Parliament and of the Council of 10 June 2002 on the
approximation of the laws of the Member States relating to food supplements. The European
Parliament and the Council of the European Union, 2002, L 183/51.
Frum A., Georgescu G., Gligor F.G., Lengyel E., Stegarus D.I., Dobrea C.M., Tita O., Identification and
quantification of phenolic compounds from red grape pomace, Scientific Study and Research –
Chemistry and Chemical Engineering, Biotechnology, Food Industry, 2018, 19(1), 45-52.

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THE DISTRIBUTION OF PERSISTENT ORGANIC POLLUTANTS (POPS) IN THE

ENVIRONMENT-PLANT CHAIN ‒ BAIA SPRIE AND COPȘA MICA CASE STUDY

Elisabeta-Irina Geana1, Corina Teodora Ciucure1, Constantin Nechita2,*

1
National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
2
National Institute for Research and Development in Forestry "Marin Drăcea" Calea Bucovinei, 73 bis,
725100, Câmpulung Moldovenesc, Romania
Corresponding authors: [email protected]; [email protected]

INTRODUCTION
Environmental pollution is one of the world's concerns [Manisalidis et al., 2020],
showing adverse biological effects on natural resources (plants, ecosystems) and
population through direct or indirect toxic actions by acidifying the trophic c]hain. The
primary sources of air pollution are (i) stationary (e.g., power plants, industrial
platforms, oil refineries); (ii) mobile (e.g., cars, buses, trucks, trains, and planes); (iii)
surface (e.g., municipalities, rural localities or agricultural areas), and (iv) natural (wind-
blown dust, forest, vegetation fires or volcanic eruptions). The particulate matter
(including PM10 and PM2.5 fractions) has origin mainly from anthropogenic sources,
including coal power generation, industrial activities (heating, iron industry, coal coking,
metallurgy), motor vehicle emission [Francová et al., 2017], biomass burning [Johnston
al., 2019], and dust resuspension [Wang et al., 2021]. Air pollutants are a mixture of
toxicological compounds, including heavy metals and persistent organic pollutants
(POPs), such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls
(PCBs), but also polychlorinated dibenzo-p-dioxins (PCDDs), and dibenzofurans (PCDFs).
These contaminants are present in the environment mainly due to anthropogenic
activities [Vitali et al., 2019]. European Union recommends monitoring air pollution to
assess regional variability of pollution on ecosystems and promote two methods of
sampling environmental contaminants. First, the active sample collection from the air
environment using pumps passes through a filter. The second passive sampling
involves using diffusion and absorption mechanisms of living organisms to trap
contaminants in the sampling matrix. Passive air samples (bio-indicators) involving
living organisms (vegetation and insects) are very effective in simultaneously
monitoring numerous air pollutants [Pegoraro & Wannaz, 2019]. Thus, (trees, mosses,
lichens, etc.) can be used effectively as bio-monitors of environmental pollution. The
determination of organic and inorganic contaminants in plants has been for many years
an alternative, easy and efficient way to conduct ecological research both in the urban
reference as well as in the highly polluted industrial regions [Odabasi et al., 2016].
This study aimed to investigate two classes of POPs, namely PAHs and PCBs in
different environmental matrices (vegetation, soil, water, and sediments) collected from
two industrial areas of Romania: (1) Copșa Mică, an area with a history in industrial
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activity for the production of carbon black from methane gas (Carbosin SA) and the
production of Pb and Zn from mining concentrates, accompanied by the recovery of
other metals (Sb, Bi, Ag, Au) (Sometra SA) and (2) the mining area Baia Sprie, known for
toxic metal pollution in Cd, Cu, Pb, Zn and As ore processing plants (Cupro SA,
Romplumb SA).

RESULTS AND DISCUSSIONS

The 16 EPA PAHs (naphthalene - Nap, acenaphthene - Ace, fluorine - Fl,
phenanthrene - Phe, anthracene - Ant, fluoranthene - Flu, pyrene - Py, benzo (a)
anthracene - BaA, crysene - Chr, benzo(b)fluoranthene –B(b)F benzo(k)fluoranthene –
B(k)F, benzo(a)pyrene - BaP, dibenzo(a,h)anthracene - DahA, benzo(g,h,i)perylene -
BghiP, indeno(1,2,3-cd) pyrene - Ind and fourteen PCBs (PCB 18, PCB 31, PCB 28, PCB
52, PCB 44, PCB 101, PCB 149, PCB 118, PCB 153, PCB 138, PCB 180, PCB 170, PCB 194,
PCB 209) were determined in vegetation, including leaves, fruits (core and peel) and
vines for different species of trees (pedunculate oak, beech, poplar, acacia), leaves and
fruits of shrubs (maces, blackberries), but also spontaneous grassy vegetation using a
HPLC-FLD method for PAHs analysis and a GC-ECD method for PCBs analysis, after the
microwave assisted solvent extraction method and SPE purification.
The analyzed PAHs expressed as ∑PAH varied according to vegetation type, the
plant's organs, and the region. The highest concentrations of PAHs were observed in
the aerial parts of plants (leaves and fruits), which indicates that the mode of
penetration of PAHs in plants is by atmospheric deposition of particles loaded with
pollutants on the plant surface (Fig. 1a). We also noted significant PAH concentrations
in beech leaves, mushrooms, needles (Taxus baccata L. and Pinus sylvestris L.,
Cupressus macrocarpa Hartw.), and surface soil (Fig. 1b and 1c).

a) b)

c)
Figure 1. The content of PAHs in different environmental matrices collected from:
a), b) Copșa Mică area, and c,) Baia Sprie region

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Figure 2a highlights that most of the collected samples from the Copsa Mica area
had the ratios of BaA/ (BaA + Chr) between 0.2 and 0.35 indicating a mixed
contribution (petrogenic and pyrogenic). Other samples in Copsa Mica had the ratio
IcdP/(IcdP + BghiP) between 0.2 and 0.5, showing a pyrolytic source (oil combustion).
Finally, for the remaining samples, the IcdP/(IcdP + BghiP) were below 0.5, reflecting a
pyrolytic source (burning solid fuels like biomass and coal). Similar contribution sources
were also identified for the samples collected from the Baia Sprie area (Fig. 2b).

a) b)
Figure 2. Plots of diagnostic ratios BaA/(BaA+Chr) against IndP/(IndP+BghiP) for
a) Copsa Mica and b) Baia Sprie

Principal component analysis (PCA) of the quantitative data for each PAH
indicates that the distribution of individual PAHs corresponds with highly
contaminated environmental matrices. The best bio-indicators of environmental
PAH pollution were oak trees, including leaves, fruits, braches. Significant
contaminant values were also archived in the needles of Cupressus macrocarpa
Hartw., Pinus sylvestris L., and different mushrooms species (Fig 3).

Figure 3. PCA analysis of different environmental matrices and distribution of PAHs,

highlighting pollution bio-indicators in the investigated areas: Copșa Mică (blue) and Baia Sprie (red)

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Regarding PCB investigations, except PCB 118, PCB 194, and PCB 209, which
were not detected or detected in a small number of samples, the other congeners
were observed in most of the collected samples, demonstrating ubiquitous
contamination by PCBs mainly in location 1 from Copsa Mica (Fig. 4a). Higher
amounts of PCBs were identified in Cupressus macrocarpa Hartw., followed by
Pinus sylvestris L., needles, and Quercus robur L. leaves (Fig. 4b). The interpretation
is that the PCBs originated from atmospheric deposition, especially on surfaces with
a high lipid content and large surface area.

a) b)
Figure 4. The content of PCBs in different environmental matrices collected from
a) Copșa Mică and b) Baia Sprie

CONCLUSIONS

This study report concentration of PAHs and PCBs in different environmental

matrices (vegetation, soil, sediments) collected from the high contaminated
industrial areas, Copsa Mica and Baia Sprie from Romania. Through comprehensive
analysis using diagnostic ratios, combustion of petroleum, coal, and biomass were
the primary sources of PAHs in the environmental compartments of the study area.
Principal component analysis indicates that Cupressus macrocarpa Hartw., Taxus
baccata L. and Pinus sylvestris L., needles, Quercus robur L. leaves, and mushrooms
and fruits are the most suitable environmental matrices used as bio-monitors of
environmental contamination.

Key words: bio-indicators, environmental contamination, vegetation, polycyclic

aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs)

Acknowledgments: This work was funded by The Ministry for Research, Innovation
and Digitization, Core Framework, Contract No. PN 9N/2019, PN 19110302 "Research on
the variation trends specific to stable isotopes in different tree species: deepening the
fractionation mechanisms and the chemical processes interconnected on the soil water-
plant chai" and Contract No. 12N/2019, PN 19070502 "Evaluation by transdisciplinary

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techniques of the oak trees decline affected by actual environmental changes in the
extra-Carpathian area – adaptation, mitigation and risks".

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Odabasi, M., Tolunay, D., Kara, M., Ozgunerge Falay, E., Tuna, G., Altiok, H., … Elbir, T. (2016).
Investigation of spatial and historical variations of air pollution around an industrial region
using trace and macro elements in tree components. Science of the Total Environment, 550,
1010–1021. https://doi.org/10.1016/j.scitotenv.2016.01.197
Pegoraro, C. N., & Wannaz, E. D. (2019). Occurrence of persistent organic pollutants in air at
different sites in the province of Córdoba, Argentina. Environmental Science and Pollution
Research, 26(18), 18379–18391. https://doi.org/10.1007/s11356-019-05088-z
Tahir, S. N. A., Rafique, M., & Alaamer, A. S. (2010). Biomass fuel burning and its implications:
Deforestation and greenhouse gases emissions in Pakistan. Environmental Pollution, 158(7),
2490–2495. https://doi.org/10.1016/j.envpol.2010.03.017
Vitali, M., Antonucci, A., Owczarek, M., Guidotti, M., Astolfi, M. L., Manigrasso, M., … Protano, C.
(2019). Air quality assessment in different environmental scenarios by the determination of
typical heavy metals and Persistent Organic Pollutants in native lichen Xanthoria parietina.
Environmental Pollution, 254, 113013. https://doi.org/10.1016/j.envpol.2019.113013
Wang, B., Tang, Z., Li, Y., Cai, N., & Hu, X. (2021). Experiments and simulations of human walking-
induced particulate matter resuspension in indoor environments. Journal of Cleaner
Production, 295, 126488.

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APPLICATION OF STABLE ISOTOPE ANALYSIS IN FORENSIC ANTHROPOLOGY

George Cristian Curcă, Dr. Güner Gemai, Dr. Mariana Roșu

National Institute of Legal-Medicine “Mina Minovici” Bucharest, Romania

Corresponding author: [email protected]

Isotopes are ubiquitously present in the world we live in, but the balance
between different isotopes of the same element varies among different substances
and eco-systems. Our body incorporates from the food we eat and the water we
drink, stable isotopes in a specific ratio. As we advance in age, our tissues
continually renew themselves, however the clearance time in the body for every
isotope and their ratio is different depending of the tissue.
Stable isotope analysis of the bio-elements has provided a novel approach in
forensic anthropology. These subtle, but significant ratio variations may be
analyzing and quantified giving a body isotope fingerprint which is able to localize
geographically the person on an isotope landscape: with these new advances,
forensic anthropology emerges from individual identification to personal
identification.
More application highlights: diet, water and food origin, historical recovery of
anthropologic sites, geographic area of living and nationality origin, identification of
unknown persons, missing person’s cases, immigration and human rights, etc.
This presentation will underline general characterist.ics of this pilot study in
Romania, in collaboration with The National Research and Development Institute
for Cryogenics and Isotopic Technologies - ICSI Rm. Valcea as an interinstitutional
and interdisciplinary cooperation, aim, scope, short-term and long-term objectives,
main methods applied, and will highlight some of the above forensic applications.

Key words: forensic anthropology, stable isotopes, forensic applications

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CLIMATE CHANGE SHIFTS THE TREND OF METALLOID CONTENT IN THE

LAST TWO DECADES

Andreea Maria Iordache1, Cezara Voica2, Constantin Nechita3*

11
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
2
National Institute for Research and Development of Isotopic and Molecular Technologies, 67-103
Donat St., Cluj-Napoca, 400293, Romania
3
National Institute for Research and Development in Forestry "Marin Drăcea" Calea Bucovinei, 73 bis,
725100, Câmpulung Moldovenesc, Romania.
Corresponding author: [email protected]

The contamination of lakes by heavy metals has raised concerns worldwide with
regard to increasing pollution and its negative impacts on ecosystem health. The
possible relationship between metal levels in the Olt River ecosystem in southern
Romania (measured during seven monitoring periods, with 1064 sediment and water
samples) and daily climate data from 1950-2019 was explored to assess the need for
targeted mitigation strategies, source identification, and risk assessment. The
occurrence of atypical weather in 2018 and 2019 was demonstrated using indices of
the extreme climate and the European Climate Assessment and Dataset. The results
indicated the significant impact of climate warming on intramountain ecosystems. The
As, Pb, Cd, and Hg contents in sediments and the As and Pb concentrations in water
varied significantly between 2018 and 2019 (two-sample t-test of means, p<0.001). In
2018, there was a strong relationship between the sediment Pb, As, Cd, and Hg
contents and temperature (r>0.8, p<0.001). Mercury in sediments had a positive
correlation with precipitation, and Hg in the water had a positive correlation with
minimum temperature in May 2018 (p<0.01). In July 2019, heavy metals were
positively correlated with precipitation and negatively correlated with temperature.
The highest correlation coefficients were obtained when analyzing the relationships of
these metals with the minimum and maximum temperatures. The significant but weak
correlation between the elemental contents in 2018 (low in June and October) and in
2019 (very high in May) emphasized the intermetal association caused by natural
changes in the physicochemical characteristics of water and sediments as a result of
increasing temperatures. Hierarchical component analysis, principal component
analysis, and canonical correspondence analysis indicated that the heavy metal levels
were influenced by anthropogenic activities. The statistical analysis showed strong
relationships between heavy metal levels and climatic factors and attributed the
discrepancies in elemental concentrations between 2018 and 2019 to climate
warming and changes in the physicochemical characteristics of the water.

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Climate-trace element relationships

The daily climate parameters investigated emphasized atypical weather
conditions for the two extreme sites, #1, Cornetu Lake (316 m altitude), and #12, the
Danube River upstream of the Olt River (27 m altitude), in 2018-2019 (Fig. 1a,b).
Contrary to the pattern in 2018, the combined effect of summer days (SD)>25
intervals and increased TX mean value shifted in 2019 (Fig. 1a), which increased the
variability of temperature and the occurrence of extreme events.

Figure 1. Climate data for the extreme sites Cornetu lake (#1) and Danube River - upstream the Olt
River (#12). a) Digital daily minimum (TN) and maximum (TX) temperature; b) The sum of daily
precipitation (RR) for #1 (blue) and #12 (red) in 2018 and 2019; dark bars indicate the sampling
periods; SD – summer days

The historical perspective of climate reconstruction for more than two centuries
(Harris, 2014) demonstrated significant changes in precipitation anomalies for many
years, but the 2018-2019 period was not found to be extreme (Fig. 2). The summer of
2018 was the third-warmest summer recorded for the studied areas (Fig. 2e) and
belonged to the fourth warmest global record since 1880. The summer of 2018 was
the third-warmest summer recorded for the studied areas (Fig. 2e) and belonged to
the fourth warmest global record since 1880 [Blunden, 2019; Cheng, 2019]. We
observed significant differences (p<0.001, two-tailed hypothesis) between mean
extreme site values for TM, TN, TX, and RR (t-values = -14.50, -15.19, -14.89, and
6.34, respectively) in the time interval between 1960 and 2019. Consecutive dry days
(CDDs) have decreased in Cornetu Lake since the 1980s, but for the Danube River
upstream of the Olt River, no trend was observed. This indicated that climate change
effects at intramountain sites are stronger than those at lower altitudes (Fig. 2f).
Since 1980, the extreme temperature intensity indices (TXx, TNx, TXn, and TNn) have
shown a significant positive trend, similar to those in other geographical regions
[Lobell, 2011]. The percentile-based indices TN10p (cold nights) and TX10p (cold
days) significantly decreased after 2000, while the frequency of warm nights (TN90p)
and warm days (TX90p) increased since 1984 (Fig. 2a-d).
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Our study area exhibited a significant increasing trend for extreme temperatures
in the past, but only in summer and winter. The warm spell duration index (WSDI)
showed a sharp increase starting at the beginning of the 1990s, with a maximum for
the Cornetu Lake (2018 indices ranked third) and Danube River upstream of the Olt
River (2019 ranked fifth) sites (Fig. 2e). The highly wet days (Rx5day) index increased
only at intramountain sites. However, it did not exhibit a consistent statistically
significant trend (within the 1 SD range), instead showing a positive anomaly for #1 in
2018 and a negative anomaly for #1 in 2019 and negative values for #12 in both years
(Fig. 2h). The incremental tendency of extreme precipitation indices is less spatially
consistent and strongly correlated with elevation, indicating future risk for
intramountain sites.

Figure 2. Normalized values for extreme climate indices in extreme sites Cornetu lake (#1 – blue line)
and Danube River – upstream the Olt River (#12 – red line): a) TN10p – the annual percentage of
days when TN<10th percentile; b)TX10p – the annual percentage of days when TX<10th percentile;
c) TN90p – the annual percentage of days when TN>90th percentile; d) TX90p – the annual
percentage of days when TN>90th percentile; e) WSDI – the annual number of days contributing to
events where six or more consecutive days experience TX>90th percentile; f) CDD – the maximum
annual number of consecutive dry days (when precipitation <1.0 mm); g) RRX5day – maximum 5-day
precipitation total; h) RR20mm – annual number of days when precipitation ≥20 mm; j) RR90p – the
annual percentage of days when TX>90th percentile

Intermetal relationships and factor loadings

The hierarchical dendrogram resulting from the HCA approach shows that trace
elements were categorized into two distinct clusters. The first homogeneous group
consisted of As, Cd, Pb, and Hg in sediments and Hg in water. The second formed a
single branch consisting of the As, Pb, and Cd in water, indicating anthropogenic

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drivers of the HM and trace elements analyzed. In the plot, the y-axis shows similarity
with a circular orientation (Fig. 3a). The trace elements formed three groups, with the
first containing those from sediments and Hg in water, the second containing Pb, and
third containing the Cd in water, indicating different origins of these elements (Fig.
3b). The cumulative percentage of inertia presented by the first two factorial axes
explained 94% of the variance in 2018 (Fig. 3c) and 81% in 2019 (Fig. 3d). Trace
elements with a significant contribution to the orientation of the two primary
factorial axes were Pb in sediments and As in water in 2018 (Fig. 3e,f). The overall
conclusion is that human-derived sources are dominant in trace element origins. The
CCA using the first two axes explained 98-95% of the trace element variance based on
climate (TM, TN, TX, and RR daily data) in 2018‒2019, corresponding to 55-75% of
the inertia. The Olt River is not the most polluted water body in Romania, but it has
contributed significantly to the enrichment of HM pollution in Danube River
sediments. The water pollution in Romanian lakes appears to be less impressive than
that in sediments.

Figure 3. The multivariate statistical results for heavy metals and climate data; a) dendrogram of
hierarchical cluster analysis (HCA) based on similarities; b) principal component analysis (PCA) to provide
a grouping of variables; canonical correspondence analysis (CCA) indicate significant dependence of trace
elements on daily climate data, different in c) 2018 and d) 2019; non-symmetrical correspondence
analysis (NSCA) e) demonstrated high variability of data in 2018 and f) insignificant for (p<0.001) in 2019

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Climate-induced elemental increasing trend in the last two decades

Impressive amounts of HMs in lake sediments and quasi-static environments
with a low velocity of flow that progressively accumulated deposits and pollution
were noted in the last two decades. Also, the results highlight the predisposition of
the western and southern regions of the country to the occurrence of exceptional
HM pollution events; these regions are also expected to be exposed to increasing
climate extremes according to future projections.

Key words: heavy metals, ICP-MS extreme climate in 2018-2019, ecological risk
assessment

Acknowledgments: This work was supported by the Romanian National Authority for
Scientific Research and Innovation, Contract Contract No. 9N/2019, PN 19110303, No.
12N/2019, PN 19070502, and 36N/2019, PN 19350202.

References
Harris, I.P.D.J., Jones, P.D., Osborn, T.J., & Lister, D.H. Updated high‐resolution grids of monthly
climatic observations–the CRU TS3. 10 Dataset. Int. J. Climatol. 34(3): 623‒642 (2014)
Blunden, J., & Arndt, D.S. A look at 2018: Takeaway points from the State of the Climate supplement.
Bull. Am. Meteorol. Soc. 100(9): 1625–1636. (2019)
Cheng, L. et al. 2018 continues record global ocean warming. Adv. Atmos. Sci. 66: 249–252 (2019)
Lobell, D.B., Schlenker, W., & Costa-Roberts, J. Climate trends and global crop production since 1980.
Science. DOI: 10.1126/science.1204531 (2011).

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THE USE OF FRESHWATER BRYOZOANS AS EMERGING BIOINDICATORS FOR

WATER POLLUTION IN DANUBE DELTA

Ira-Adeline Simionov1*, Ștefan-Mihai Petrea2, Alina Mogodan2,

Aurelia Nica2, Victor Cristea1
1
MoRAS Research Center, “Dunarea de Jos” University of Galati, Domnească Street,
No 47, Galați, Romania
2
Faculty of Food Science and Engineering, “Dunarea de Jos” University of Galați,
Domnească Street, No 47, Galați, Romania
*
Corresponding author: [email protected]

Water pollution with heavy metals is a persistent and hazardous issue, due to
the metals incapacity to decompose and its tendency to accumulate in biota. The
lentic aquatic environments of Danube Delta are subjected to anthropogenic
pressures, due to intensive agriculture, intense tourism, and the lack of sewage
systems. The influence of global warming, through increase water temperature, has
allowed alien species development in the waters of Danube Delta, such as
Pectinatella magnifica. Therefore, the aim of the present study was to use the
bryozoan as bioindicator for heavy metal pollution in Barcaz Lake, Danube Delta.
Water and biota samples were collected in previously decontaminated flasks and PE
bags, in September 2020, from Barcaz Lake and transported to the laboratory. The
quantification of Cd, Pb, Ni, Cr, Cu, Fe and Zn in samples was determined by using
the technique HR-CS-GF-AAS and Analytik Jena Contraa 700 equipment. Also, the
pollution index for each metal was calculated. Pearson coefficient was applied for
the correlation analysis of water and biota results. The maximum registered values
for the analyzed metals in the water matrix were as it follows: 5.87 µg/L Cd, 0.91
µg/L Pb, 4.07 µg/L Ni, 0.32 µg/L Cr, 3.98 µg/L Cu, 0.12 mg/L Fe, 0.06 mg/L Zn. All
studied metals did not exceed the maximum permitted level by the national
regulation of surface waters, except for Cd, which exceeded the value of 5 µg/L and
it is specific to quality class V waters. The following average accumulation trend was
identified in the water matrix: Fe>Zn>Cu>Ni>Cd>Pb>Cr.

Key words: Danube Delta, bryozoan, heavy metals.

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THE INFLUENCE OF AN ALTITUDINAL GRADIENTON THE CONIFER-SOIL

RELATIONSHIP IN A TEMPERATE FOREST OF ROMANIA

Anca Maria Zaharioiu1,2, Roxana Elena Ionete1, Claudia Sandru1 , Silviu Laurentiu
Badea1 , Marius Gheorghe Miricioiu1, Oana Romina Botoran1
1
National Research and Development Institute for Cryogenic and Isotopic Technologies—ICSI Rm.
Valcea, Uzinei Street, No. 4, P.O. Box 7 Raureni, 240050 Valcea, Romania
2
Faculty of Agricultural Sciences, Food Industry and Environmental Protection, “Lucian Blaga”
University of Sibiu, 7-9 I. Ratiu Str., 550012 Sibiu, Romania
Corresponding author: [email protected]

INTRODUCTION

Today, the Earth is facing continuous climate changes. Climate change

mitigation can be achieved both anthropically by controlling human activity, but
also by nature, forests which are the most important terrestrial ecosystems that
can mitigate climate change (Bonan, 2008). Forests cover about 30% of the total
area of the Earth, representing 75% of the earth's gross primary production and
about 45% of the earth's carbon [Beer, 2010; Pan, 2013]. The carbon stock in forest
biomass is the help the Earth needs to fight climate change [Dixon, 1994; Lal, 2005;
Pan, 2011]. The ecosystem undergoes a complex process to accumulate this carbon
stock and depends on several interacting factors: climate, soil community and
decomposition [Triadiati, 2011; Innangi, 2015; Bradford, 2016]. Approximately half
of the carbon storage is contained in soils of global forests. The strategy for climate
change is considered to be the conservation and promotion of the storage of
organic carbon in the soil. Given the importance of forest ecosystems for C cycle,
afforestation and reforestation is a common practice today [Noble, 2000]. This
study investigated changes in carbon (C) and nitrogen (N) concentrations in the
three components of the forest ecosystem (leaves, bark and soil) along an
altitudinal gradient in the temperate forests of Romania.
Sustainable forest management has become a dominant concept for global
forestry, currently being linked only to timber production, but embracing the
functions of the entire ecosystem and there is an intense demand for measuring
and monitoring models and processes at the global level in forest ecosystems. A
typical terrestrial ecosystem (forest) composed of biotic factors (plants, animals and
microorganisms) and abiotic factors (air, water, rocks), is an integrated system
ofliving organisms and inorganic environment (non-living). Like all systems,

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ecosystems are a combination of interconnected parts that form a unitary or

functional group subjected to various scientifical investigations.
The nutrient cycle is one of the major aspects of the relationship between
plants and soil, representing principal elements that most clearly define the
boundaries of ecosystems and express the nature of ecosystems. These
components are not separate entities, but rather a constantly unified system
associated with each other. An ecosystem perspective is fundamental in predicting
the forest's response to environmental conditions. Plants need nutrients from the
soil to grow (Fig. 1). Soils play a major role in supporting stand productivity and
forest value by regulating nutrient cycles. Soil fertility is maintained when nutrients
are efficiently recycled through the soil food web and the soil-plant system.
Understanding soil nutrient controls remains a vital question in determining the
stock of nutrients available for plant absorption. The variability of soil nitrogen
availability with climate may be a more important growth factor than the variability
in climate physiology of trees.

Figure 1. The effects of tree species on the nutrient cycle and soil biota:
a feedback mechanism that promotes species coexistence

RESULTS AND DISCUSSION

These present investigationsfocused on understanding the fate of nutrients

deposited in terrestrial ecosystems, representing a key approach for predicting
their impact, as the study of long-term nutrient cycle processes applied in forest
ecosystems is still quite limited.This study determined the concentrations and ratios
of C and Nin four key ecosystem components (fresh leaves, forestfloor litter,
mineral soil and soil microbial biomass) along a 1500-m altitudinal gradient (from
500 mto 1554 m a.s.l.) in the central-southern part of the Carpathians (Cozia
mountain). Our principalhypothesis was that this nutrient concentration would
change along the gradient and that the pattern of change coulddiffer depending on
the ecosystem component and the nutrient measure.

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The relationship between soil element composition and vegetation along an

altitudinal gradient(from 500 m to 1550 m a.s.l.) was investigated using the
principal component analysis (PCA – fig. 2), observing that samples taken from
spruce forests at high altitudes in the Cozia area, are characterized by relatively
high concentrations of C and N, especially the soil samples from a depth of 20-40
cm and forest floor litter. A relatively high concentration of C in the leaves was
identified at an altitude of 1102 m. These results can be explained by a potential
increase in transpiration with altitude when there is an lower average rate than the
ambient temperature. This results from the higher total radiation absorbed by the
leaves, the increase in the diffusion coefficient of water vapor in the air at low
barometric pressure and the increased density gradient of H2O vapor from the leaf
to the ambient air.

Figure 2. Diagram of the main components 1 and 2 regarding the distribution of the elemental
composition from the soil and vegetation samples

Moreover, exposure to conditions that induce high rates of perspiration can

consume the available water. These processes induce the stomataclosure and
therefore the reduction of photosynthesis and can also lead to a more xeromorphic
composition of plant species.The availability of these elements could also be
decreased in the surface soil due to precipitation, resulting in leaf and soil nutrients
not being significantly correlated. Leaf and litternutrients as well as litter and soil
nutrients were significantly correlated, indicating that litter is a link betweenplants
and soil and demonstrating the coupling among leaf, litter, and soil nutrients.

CONCLUSION

The main conclusions that emerge from this stage are that the stoichiometric
nutrient ratios and nutrient stock were significantly different for different

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components, and the C and N elements are closely related between plants, forest
floor litter and soils in secondary mixed forest ecosystems. All plants allocated more
N and C to the leaves. The N and C soil content can be related to the type of forest
due to the difference in concentration of nutrients in the vegetation.This study
showed that soil organic C and total N concentrations significantly increased with
altitude, likely because low temperature limits the cycling of organic matter at high
altitudes, but a comprehensive analysis regarding the effects of altitude on plants
should also include radiation and other weather conditions during the day and
growing season.

Key words: forest ecosystem, altitude, nutrients, soil.

Acknowledgments: The work has been supported by NUCLEU Program, Project

PN 19 11 03 02"Research on variation trends specific to stable isotopes in different
tree species: deepening of fractionation mechanisms and interconnected chemical
processes on the soil-water-plant chain".

References
Beer C., Reichstein M., Tomelleri E., Ciais P., Jung M., Carvalhais N., Rödenbeck C.,Arain M.A.,
Baldocchi D., Bonan G.B., Bondeau A., Cescatti A., Lasslop G.,Lindroth A., Lomas M., Luyssaert,
S., Margolis H., Oleson K.W., Roupsard O.,Veenendaal E., Viovy N., Williams C., Woodward F.I.,
Papale D., 2010. Terrestrialgross carbon dioxide uptake: global distribution and covariation
with climate. Science, 329, 834-838.
Bonan G.B., Forests and climate change: Forcings, feedbacks, and the climate benefits of forests.
Science, 2008, 320, 1444-1449.
Bradford M.A., Berg B., Maynard D.S., Wieder W.R., Wood S.A., Understanding the dominant
controls onlitter decomposition. J. Ecol. 2016, 104, 229-238.
Dixon R.K., Brown S., Houghton R.A., Solomon A.M., Trexler M.C., Wisniewski J., Carbon pools and
fluxof global forest ecosystems. Science, 1994, 263, 185-190.
Innangi M., Schenk M.K., D’Alessandro F., Pinto S., Menta C., Papa S., Fioretto A., Field and
microcosmsdecomposition dynamics of European beech leaf litter: Influence of climate, plant
material and soil withfocus on N and Mn. Appl. Soil Ecol., 2015, 93, 88-97.
Lal R., Forest soils and carbon sequestration. For. Ecol. Manag. 2005, 220, 242-258. Forests, 2017, 8,
240 13.
Noble I., Bolin B., Ravindranath N.H., Verardo D.J., Dokken D.J., Land Use, Land Use Change, and
Forestry, Cambridge University Press: Cambridge, UK, 2000.
Pan Y., Birdsey R.A., Fang J., Houghton R.A., Kauppi P.E., Kurz W.A., Phillips O.L., Shvidenko A.,Lewis
S.L., Canadell J.G., et al., A Large and Persistent Carbon Sink in the World’s Forests. Science,
2011, 333,988-993.
Pan Y., Birdsey R.A., Phillips O.L., Jackson R.B., 2013. The structure, distribution, andbiomass of the
world's forests. Annu. Rev. Ecol. Evol. Syst. 44, 593-622.
Triadiati S., Tjitrosemito B., Guhardja E., Sudarsono I., Qayim I., Leuschner C., Litterfall production
andleaf-litter decomposition at natural forest and cacao agroforestry in Central Sulawesi,
Indonesia. Asian J. Biol. Sci. 2011, 4, 221-234.

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GEOLOGICAL AND GEOPHYSICAL CONSIDERATIONS REGARDING THE MINERAL

AND GEOTHERMAL WATERS FROM THE RAMNICU VALCEA - GOVORA AREA

Laurentiu Asimopolos1, Natalia-Silvia Asimopolos1, Violeta Carolina Niculescu2

1
Geological Institute of Romania, 1st Caransebeş Street, 012271 – Bucharest, Romania.
2
National Research and Development Institute for Cryogenic and Isotopic Technologies—ICSI Rm.
Valcea, Uzinei Street, No. 4, P.O. Box 7 Raureni, 240050 Valcea, Romania
E-mail address of presenting author: [email protected]
Corresponding author: [email protected]

ABSTRACT
The Govora hydrothermal deposit is located in the area of the Oltenia
Subcarpathians, in the basement of the Hința valley basin, and partially in that of
the Gătejești brook. The sub-Carpathian relief is characterized locally by a hilly
relief, with altitudes between 200 and 500 m. From a geological point of view, the
area of Govora resort is part of the Getic Depression and is located in the western
part of the Ocnele Mari - Govora Anticlinal, with E-W orientation.
The boreholes indicated the existence of Miocene formations, alternating
Sarmatian sands and marls, marls, sands, Badenian salt levels and Swiss conglomerate,
sandy and marly horizons.
The major structural character of the area is given by the presence of the Govora
anticline, having a general E-V development, with a slight inflection to the SE near the
resort.
The axis of the anticline consists of deposits belonging to the Helvetian, and the
flanks are formed by Badenian and Sarmatian deposits.
Important from the point of view of mineral waters is the fact that this major
structure is fragmented into hydrodynamic units through the Blidari longitudinal fault,
which affects its southern flank, and through a series of NE-SW oriented fault faults
[Pricăjan, 1972, Blaga 1975, 1977, 1979, 1984].
Mineral waters differ hydrodynamically in two categories related to structural
tectonic conditions, namely: sulfurous, related to the fissure systems of Sarmatian, and
chloride-sodium-bromide-iodide, stored in aquifers and cracks in Swiss deposits.
The first have total mineralizations between 1435 and 44398 mg/l, and those
in the second category between 31024 and 87337 mg/l. It should be mentioned
that in sulfurous waters the H2S content reaches a value of 26 mg/l, and in
chlorosodium waters, iodine has maximum values of 58 mg/l [Pricăjan, 1972].
From a genetic point of view, sulfurous waters are considered to come from
the mixture of surface waters with reservoir waters, in a long process of formation,
which gives them a mixed chlorurosodium, bicarbonate and sodium character in

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which crude oil impregnations, deposits are observable. of sulfur and the release of
gaseous hydrocarbons.
The sources belonging to this genetic type are grouped on the right slope of the
Hința brook located on the southern flank of the Govora Anticlinal. The second genetic
type, that of high concentration waters, which accompany the hydrocarbon deposits
are chlorinated-sodium-calcium-magnesium-iodinated-brominated and have been
identified in wells especially in the northern flank of the Govora Anticlinal.
Sulfur mineral waters were identified in catchment wells no. 1-7, and
chlorosodium mineral waters, through the group of wells no. 606 and 606bis,
respectively no. 617 and 618.
In addition to the mineral waters of the resort, in the spa cure is also used the
therapeutic mud accumulated in the collapsed spaces of the old salt mines from
Ocnele Mari [Roanghes-Mureanu, 2012, 2013].
In figure 1 is a part of geological map 1:200000, L-35-XXV with legend of age
(from archive of Geological Institute of Romania, https://www.igr.ro).

Figure 1. Part of geological map 1:200000, L-35-

XXV with legend of age

In extended paper we will present

gravity map (Bouguer anomaly, Free Air
anomaly) with data from International
Gravimetric Bureau [https://bgi.obs-mip.fr/]
and magnetic map with data from archive
of Geological Institute of Romania,
[https://www.igr.ro].

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For the analyzes performed for the Govora hydromineral deposit, were taken
into account wells, springs and running waters from the perimeter of Govora resort.
Two main groups of sources were distinguished. The first group was
characterized both by high values in deuterium (between -5.2 ‰ and -30.2 ‰) and
in salts (between 70771 mg/l and 27270 mg/l). The other group included the other
sources with lower values for both deuterium (between -51.4 ‰ and -72.6 ‰) and
for the salt content (between 307 mg/l and 29478 mg/l).
In the first group, wells from deep depths entered exclusively. Due to their high
deuterium content, as well as salts, they were considered as fossil (deposit) waters.
This type of water does not participate in the current meteoric circuit. In the second
group entered waters, which, in one form or another, participate in the current
meteoric circuit.
The distribution of δD values and overall salt content (Δd) can be followed in
the table below (Table 1). All values in the table represent average values for one
year of observation [Papp, D.C. 2014].

Table 1. The distribution of δD values and overall salt content (Δd)

Source δD (‰) ∆d (mg/)
1 Drilling 100ISPG -22.86 46608.00
2 Drilling 601 -10.68 38256.21
3 Drilling 606 -8.67 29950.80
4 Drilling 600bis -14.58 58992.92
5 Drilling 608 -12.68 29044.69
6 Drilling 2PG -10.89 30838.29
7 Wells no. 1 -64.69 5940.33
8 Wells no 2 -63.72 11567.00
9 Wells no. 3 -65.89 9634.07
10 Wells no 4 -61.70 2792.08
11 Wells no 5 -59.98 2324.71
12 Wells no 6 -61.75 2360.00
13 Wells no 7 -63.50 13672.79
14 Spring no. 23_AUG. -62.94 1560.50
15 Spring no. 30 DEC. -63.03 1384.71
16 Spring no. SLF1 -63.75 5683.00
17 Spring no. SLF2 -58.49 4332.00
18 The well -65.23 510.17
19 The well -60.09 952.33
20 The well -64.27 395.75
21 Stream -58.81 1387.36
22 Stream Viorel -62.08 479.60
23 Stream Hința -60.46 759.29
24 Stream Vila 9 -64.75 559.43
25 Stream -61.38 407.73
26 Stream -56.80 1146.75

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Most of the water sources tested within the Govora deposit show seasonal
variations typical of meteoric water. Waters characterized by high values of deuterium
concentration and overall salt content from great depths have a major component of
reservoir water and therefore seasonal variations are very small.
For the waters in the meteoric circuit the seasonal variations of the δD values are
between the same limits for all the studied sources, but the minimum and maximum
sequences differ from one source to another. ΔD values are at their maximum in the
warm months due to intense evaporation in the warm periods. The values decrease
with the melting of the snow.
The highest Δd values appear in the autumn-winter months when the contribution
of precipitation and infiltration water is low. During the spring months, the infiltration
of water from melting snow produces a dilution of groundwater. As already
mentioned, within the Govora resort, two main groups of sources were distinguished:
(1) waters characterized by high values of deuterium and salts and (2) waters
characterized by lower values both for the content in deuterium as for the salt content.
However, for all mineral water sources in this resort a positive correlation was
obtained between the δD values and the overall salt content, with statistical
significance (r = 0.89) suggesting the existence of a unique underground mixing system
of these two groups of mineral waters.
In Govora resort there are two genetic types of water, completely different from
each other: - deuterium and salt salts (fossils), - waters from the meteoric circuit. The
waters of the meteoric circuit can in turn be divided into two subgroups: - waters from
local infiltrations with relatively low salt concentrations (wells 4, 5 and 6); - waters
mainly from winter infiltrations or from high altitudes which are strongly loaded in salts
and have the lowest values in deuterium. The influence of reservoir waters on the
waters of the meteoric circuit is proved by the definition on the correlation diagrams
between the average values of δD and Δd of some mixing lines that include both
genetic types.

Key words: hydrothermal deposit, hydrogeological structures, geochemical data,

isotopic research.

Acknowledgments: We thank for support by the Ministry of Research for financing

of the project “The realization of 3D geological/geophysical models for the
characterization of some areas of economic and scientific interest in Romania”, with
Contract no. 28N/2019.

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References
Blaga L., Blaga M.L., Ciobotaru T., Feurdean V., Studiu bazat pe măsurători de concentrație a
deuteriului din apele mineral din zona Călimănești - Căciulata”, raport la contractul de
cercetare ITIM Cluj-Napoca nr. 780/1977 si nr. 366/1979.
Blaga L., Blaga M.L., Ciobotaru T., Feurdean V, Bindea C., Florian M., Studiu bazat pe determinări de
concentrație a deuteriului din apele termominerale, freatice si de suprafață din perimetrul
stațiunii Olănești”, rapoarte la contractul de cercetare ITIM Cluj-Napoca nr. 767/1977-1978-
1979.
Blaga L., Blaga M.L., Ciobotaru T., Feurdean V., Studiu bazat pe măsurători de concentrație a
deuteriului din apele termominerale din zona stațiunilor balneo-climaterice ale județului
Vâlcea, raport la contractul de cercetare ITIM Cluj-Napoca nr.593/1975.
Blaga L.M., Florian M. 1984. Contribuţii la studiul hidrogeologic al zăcământului hidromineral
Olăneşti cu ajutorul izotopilor stabili, St. tehn. econ. Inst. Geol. Geof., Seria E, 14, p. 63-84, Inst.
Geol. Geof., Bucureşti.
Papp D.C. 2014. Caracteristici izotopice ale apelor minerale din zona subcarpatica (Călimănești –
Căciulata, Olănești, Govora), Raport de cercetare la proiectul: PN 09 21 03 06: Interpretarea
datelor izotopice pentru stabilirea originii și dinamicii subterane a apelor minerale din zona
Harghita-Covasna. Comparatii cu alte zone carpatice (Faza 14), arhiva I.G.R.
Pricajan A., 1972. Apele minerale şi termale din România, Editura Tehnică, Bucureşti.
Roanghes-Mureanu, A-M., 2012. The Environmental Impact of Tourist Activities Performed in the
Spa Resorts of Vâlcea Subcarpathians, Analele Univ. Buc., Geografie, LXI, 147-157.
Roanghes-Mureanu, A-M., 2013. The impact of tourism on the environment in the drainage Basin of
the Olănești river, Riscuri şi catastrofe, nr. XII,vol.13, nr.2/2013.
https://www.igr.ro
https://bgi.obs-mip.fr/

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GEOLOGICAL STUDY ABOUT THE HYDROMINERAL AND GEOTHERMAL DEPOSIT

CĂLIMĂNEȘTI – CĂCIULATA

Natalia-Silvia Asimopolos1, Violeta Carolina Niculescu2,

Laurentiu Asimopolos1, Delia Cristina Papp1
1
Geological Institute of Romania, 1st Caransebeş Street, 012271 – Bucharest, Romania
2NationalResearch and Development Institute for Cryogenic and Isotopic Technologies—ICSI Rm.
Valcea, Uzinei Street, No. 4, P.O. Box 7 Raureni, 240050 Valcea, Romania
E-mail address of presenting author: [email protected]
Corresponding author: [email protected]

ABSTRACT

The Călimănești - Căciulata hydromineral deposit is located in the southern part

of the Southern Carpathians, at their contact with the Getic Depression. Within the
resort there are two types of relief: a mountainous one with altitudes between 800-
1200 m made up of metamorphic rocks and another of sub-Carpathian hills made
up of sedimentary deposits. The Olt crosses both types of relief [Pascu 1981;
Pricajan 1972]. The geological composition of the area includes: (1) the crystalline
foundation composed of Shiites, Paragnais, Gnaises and Micassists and (2)
sedimentary deposits of Cretaceous and Eocene age, arranged transgressively and
discordantly over the foundation. The Cretaceous appears up to date on the course
of the Olt in the form of the Turnu Layers formed predominantly of conglomerates
and the Căciulata Layers, with a predominantly marly-sandy character. The Eocene,
found in boreholes, is represented by conglomerates and sandstones (Fig. 1). Over
these formations, on both banks of the Olt, there are deposits of the two terraces
that can reach thicknesses of several tens of meters (Jiblea area). Between the
crystalline formations of Cozia and the sedimentary of the Getic depression that
includes the hydromineral deposits of the resort, there is a major tectonic
dislocation [Airinei, 1980] highlighted by the two contrasting relief planes, the
mountainous and the hilly, from which downstream the sediment acquires a
thickness. very big. It is an SSE-oriented monocline with falls of only 10-35°, locally
disturbed by small anticlines and a series of faults on which mineral springs usually
appear.

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Figure. 1. Geological profile between Cozia and Govora (after Feru, in Pricăjan, 1985) 1-Sarmatian; 2-
Badenian; 3-Helvetian; 4-Acvitanian-Burdigalian; 5-Oligocene; 6-Eocene (conglomeratic horizon,
marly horizon); 7-Cretaceous (a-upper, b-lower, c-undifferentiated); 8-Jurassic; 9-crystalline; 10-
faults; 11-deep drilling; 12-mineral springs; 13-probable directions of rise of reservoir water and
gaseous hydrocarbons

Depending on their lithological constitution, the formations present in the

geological structure of the region have the following hydrogeological characteristics
[Pricăjan, 1972; Blaga, 1975, 1977, 1979, 1984; Papp, 2014]:
- the lens, due to the strong tectonization, has a network of faults and cracks,
and on the surface has a blanket of alteration, favoring the circulation of
groundwater;
- Cretaceous deposits (Senonian) consist predominantly of sandstones and
conglomerates with an accentuated fissure, favored by the presence of numerous
tectonic micro-accidents; in the cracks of Senonian detrital deposits it is possible to
accumulate significant amounts of groundwater;
- pelitic intercalations do not always constitute screen surfaces, the waters
having favorable circulation conditions;
- Eocene deposits allow the accumulation of groundwater in the fissures of the
two conglomerate horizons, basal and upper. The medium marly, impermeable
horizon has a role of screen in the way of the expansion of the underground waters
from the basal horizon;
- Oligocene deposits, predominantly marly, represent an impermeable
package;
- the mineralized springs, which appear from the Eocene conglomerates at
Călimănești, are arranged near the contact with the medium marly horizon, being
ascending springs.
Mineral water sources are represented by springs or boreholes. The mineral
waters from Călimănești-Căciulata are cold or thermal waters, chlorosodic or
bicarbonate, alkaline, calcium, magnesium, sulfurous, sometimes bromoiodinated.
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In the Călimănești area there are two groups of springs, some located on the right
bank of the Olt River inside the resort, and others on the Glodu brook. In the resort, the
best known are: Spring no. 7 (sulfurous water, bicarbonate, calcium, oligomineral),
Spring no. 14 (weakly sulfurous water, sodium bicarbonate, calcium, magnesium,
oligomineral), Source no. 6 (sulfurous, brominated, iodinated, chlorinated, sodium
water), Source no. 4 (sulfurous, brominated, iodinated, chlorinated, sodium water) and
Spring no. 3 (sulphurous, brominated, iodinated, chlorinated, sodium water). A number
of 14 mineral springs appear in the Glodul Valley area.
In the Căciulata area can be mentioned the sources: Spring no. 1 (sulphurous,
brominated, iodinated, chlorinated, sodium, oligomineral water), Drilling 1004
(sulphurous, brominated, iodinated, chlorinated, sodium thermomineral water, having
a temperature of approximately 45°C) and Drilling 1003 (sulphurous, brominated,
iodinated thermomineral water, chlorinated, sodium, having a temperature of about
50°C).
In the Cozia area there are several drillings: Drilling no. 1 (sulfurous, brominated,
iodinated, chlorinated, sodium water), Drilling no. 2 (sulfurous, brominated, iodinated,
chlorinated, sodium, tonic thermomineral water), Drilling no. 3 (sulfurous water,
weakly brominated, sodium chloride with low concentration), Drilling no. 4 (water
similar to Drilling no. 3) and Drilling no. 5 (sulfurous, brominated, iodinated,
chlorinated, sodium thermomineral water, having a temperature of about 43°C).
In the Păușa area the most important sources are Spring no. 1 and Spring Nr. 2,
both flowing sulfurous mineral waters, weakly brominated, iodinated, chlorinated,
bicarbonate, sodium.
For the Călimănești - Căciulata deposit, the analyzed samples come from
mineral water springs, wells and boreholes, as well as from surface waters in the
area. The distribution of δD values and the overall salt content (Δd) can be followed
in the table below (Table 1). All values in the table represent average values for one
year of observation.

Table 1. Distribution of δD values and the overall salt content (Δd)

Source δD (‰) ∆d (mg/)
Stream Păușa -64.20 329.80
Spring no.1 Păușa -71.62 1181.65
Spring no.2 Păușa -64.42 921.70
Spring no. 6 Călimănești -53.44 12395.95
Spring no. 4 Călimănești -65.55 1733.00
Spring no. 5 Călimănești -63.30 5557.00
Spring no. 7 Călimănești -62.85 388.85
Spring no. 8 Călimănești -61.87 5821.48
Spring no. 9 Călimănești -61.64 7161.50
Spring no. 10 Călimănești -60.35 7448.40
Spring no. 11 Călimănești -58.27 10618.00

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Spring no. 12 Călimănești -54.47 14528.17

Spring no. 12bis Călimăneși -56.72 13440.00
Spring no. 13 Călimănești -61.83 4908.20
Spring no. 14 Călimănești -62.51 357.63
Stream Caciul -62.60 310.00
Spring no. 1 Caciu -61.49 2931.90
Spring no. 2 Caciu -75.58 1452.78
Drilling 1003 -68.76 4832.77
Drilling 1004 -73.10 2736.37
Drilling 1005 -54.40 13497.52
Drilling H1 -71.68 2999.50
Drilling H2 -70.73 3700.43
Drilling H3 -69.77 3750.86
Drilling H4 -75.10 1765.25
Drilling H5 -75.50 1087.00
Drilling H6 -74.86 1729.33
Spring no. Bolnt -64.95 429.57
Drilling 1 Cozia -70.56 3646.23
Drilling 2 Cozia -65.68 794.60
Drilling 3 Cozia -73.44 3318.82
Drilling 4 Cozia -73.28 3856.68
Drilling 5 Cozia -70.06 4411.81
Drilling 1 Arutel -70.63 3423.35
Drilling 2 Arutel -73.12 2504.12
Spring no. 1 GLOD -58.74 7941.40
Spring no. 2 GLOD -58.49 8751.00
Spring no. 3 GLOD -62.71 4172.33
Spring no. 4 GLOD -59.05 8178.25
Spring no. 1 MUERS -64.11 5211.00
Spring no. 3 MUERS -78.31 979.50
Spring no. Cabana Cozia -63.75 67.56
Spring Stana -61.25 57.33
Stream Olt Călimănești -73.57 293.86
Lotru -72.29 67.50
Lotrișor -58.74 73.75
Lotrița -69.40 149.00
Stream MACIE -66.80 84.00
Stream MANAI -73.60 94.00

The range of variation of δD values for groundwater sources is between -54.4 ‰

and -75.5 ‰, and overlaps the range of surface water variation in the studied area
(-53 ‰ ÷ -76 ‰), suggesting that the waters underground belong to the meteoric
cycle. In the case of surface water, due to the evaporation produced during the
summer months which causes an enrichment in both deuterium and salts, there is a
positive correlation between the values δD and Δd. If there are relationships with
groundwater, correlation coefficients are low or even negative.
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For different water sources in the Călimănești-Căciulata area (average values),

there is a good correlation between the values of deuterium concentration and global
salt content. Regarding the seasonal variations, the general behavior of the
groundwater in the Călimănești - Căciulata area is typical for the waters from the
meteoric circuit, both according to the average values of the deuterium concentrations
and according to their variations in time. For most water sources, the lowest δD values
were recorded in July, while the highest values appear in September - November. Some
mineral springs have high values in the spring months.
The lowest salinity values appear in April - June. In general, seasonal variations in
groundwater suggest as supply areas water infiltrations from rainfall at higher altitudes
(mountain area) mixed with local infiltrations. For Probe 1005, the presence of a minor
component of reservoir water can be admitted, which is less affected by temperature
variations.

Key words: hydromineral, geothermal, hydrogeological structures, geochemical

data.

Acknowledgments: We thank for support by the Ministry of Research for financing

of the project “The realization of 3D geological / geophysical models for the
characterization of some areas of economic and scientific interest in Romania”, with
Contract no. 28N/2019.

References
Airinei I., 1980. Radiografia geofizică a subsolului României, Ed. științifică și enciclopedică, București.
Blaga L., Blaga M.L., Ciobotaru T., Feurdean V., „Studiu bazat pe măsurători de concentrație a
deuteriului din apele mineral din zona Călimănești-Căciulata”, raport la contractul de cercetare
ITIM Cluj-Napoca nr. 780/1977 si nr. 366/1979.
Blaga L., Blaga M.L., Ciobotaru T., Feurdean V., Studiu bazat pe măsurători de concentrație a
deuteriului din apele termominerale din zona stațiunilor balneo-climaterice ale județului Vâlcea,
raport la contractul de cercetare ITIM Cluj-Napoca nr.593/1975.
Blaga L.M., Florian M. 1984. Contribuţii la studiul hidrogeologic al zăcământului hidromineral
Olăneşti cu ajutorul izotopilor stabili, St. tehn. econ. Inst. Geol. Geof., Seria E, 14, p. 63-84, Inst.
Geol. Geof., Bucureşti.
Papp D.C. 2014. Caracteristici izotopice ale apelor minerale din zona subcarpatica (Călimănești-
Căciulata, Olănești, Govora), Raport de cercetare la proiectul: PN 09 21 03 06: Interpretarea
datelor izotopice pentru stabilirea originii și dinamicii subterane a apelor minerale din zona
Harghita-Covasna. Comparatii cu alte zone carpatice (Faza 14), arhiva I.G.R.
Pascu M., 1981. Apele subterane din Romania. Ed. Tehnica, Bucuresti.
Pricajan A., 1972. Apele minerale şi termale din România, Editura Tehnică, Bucureşti.
Roanghes-Mureanu A-M., 2012. The Environmental Impact of Tourist Activities Performed in the Spa
Resorts of Vâlcea Subcarpathians, Analele Univ. Buc., Geografie, LXI, 147-157.
Roanghes-Mureanu A-M., 2013. The impact of tourism on the environment in the drainage Basin of
the Olănești river, Riscuri şi catastrofe, nr. XII,vol.13, nr.2/2013.

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CARBON ISOTOPES IN EVERGREEN PLANTS AS CLIMATIC MARKERS

Oana Romina Botoran, Marius Gheorghe Miricioiu, Diana Costinel,

Roxana Elena Ionete

National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
Corresponding author: [email protected]

Knowing the mechanism by which organisms functionally vary enables

scientists to predict community structure and ecological processes, explain
variables impacting the distribution of species, and provide an understanding of
why mechanisms such as the nutrient cycling and plant productivity differ between
systems [Betz et al., 2020]. Plant species along abiotic gradients can be selectively
filtered in most ecosystems by the environment. Many community- and ecosystem-
level variables respond similarly to altitude across differing gradients because their
responses to elevation are frequently driven by variations in temperature and
precipitation [Liang et al., 2019]. By studying plant life patterns in alpine mountains
often provides a global image of the community processes and ecosystem
responses to global climate change at much greater spatial and temporal scales
than traditional ecological experiments can, providing golden opportunities for
ecological research. In investigating the potential impacts of climate change on
carbon (C) cycle in forest systems, rapid and accurate analytical techniques, such as
isotopic analyses, have been used to understand mechanisms of plant adaptation.
The result of the fractionation processes occurring during C ecosystem exchange
are represented by variations in the stable isotopic composition of C (δ13C) in plants
and soils. Thus, 13C can be used as a valuable indicator regarding the ecosystem
state and provide useful insights on how these systems respond to biotic and
abiotic factors [Badea et al., 2020]. In such a context, the Cozia Mountain region
located in the central-southern part of Carpathians, Romania, offers the rare
opportunity to investigate a diverse range of natural ecosystems under varied land
use management intensities and climatic circumstances. The Cozia region hosts a
large variety of semi-natural and manage ecosystems as a result of the strong
elevational and land-use gradient.

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Figure 1. δ C values of leaves, bark, leaf litter and soils in the natural broadleaf stands at
altitudes of 744, 1102, 1399, and 1554 m in the Cozia Mountain.

In this study, we examined the variation of δ13C in fresh plant leaves, litter, and
semi-decomposed and soil humic substances in order to characterize soil carbon
dynamics at a local or regional scale in Cozia Mountain. The specific objectives were
to: (i) determine the patterns of δ13C variation in dominant plant species (spruce -
Picea abies) and soil with altitude, (ii) investigate how soil δ13C varies with soil
depth at different altitudes, and (iii) examine the effects of climatic factors on plant
and soil δ13C along the elevation gradient in Cozia Mountain.
The evergreen tree leaf δ13C at 1554 m a.s.l. was -28.4‰ significantly enriched
than evergreen trees at lower altitudes (-30.5‰ to -29.67‰) (Figure 1). A similar
δ13C - altitude relationship was also evident in leaf litter and also in mineral soil
layers at 0-20 cm, 20-40 cm. Comparatively, fresh leaves had depleted δ13C than
leaf litter or bark. The δ13C soil enrichment was higher with the increase of the soil
depth for all altitudes. The absolute enrichment factor (AF) generally increased
from the leaves to the soil collected from 20 cm, and then decreased and remained
stable in the deeper soil at higher altitudes. The relative enrichment factor (FR) was
generally higher in the soil layers from the surface (0-10 cm) (1.49% to 4.43%) and
10-20 cm (0.93% to 1.76%) than in the deeper layers.

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Figure 2. Latitudinal and longitudinal trends in δ Csoil variation

Temperature is a direct, well-known factor in litter decomposition, and litter

mass loss rates are often higher at lower levels due to warmer conditions (Figure 2),
potentially boosting the supply rates of nutrients available from the soil. However,
precipitation, which can also promote decomposition rates of plant debris [Canessa
et al., 2021], may play a more prominent role than temperature relative to
elevation gradients in temperate ecosystems. For example, decomposition rates
increase toward colder, but wetter, higher elevations in northern Arizona in the
United States. Moreover, in the Himalayas, monthly precipitation was the best
abiotic predictor of monthly litter mass loss, while annual temperature and
evapotranspiration were the best predictors of annual litter mass loss, suggesting
that different climatic variables or which interact, which covariate with height, can
cause decomposition at different time scales [Maxwell et al., 2018]. However, both
changes in the quality of litter with elevation and the role of waste quality in
transforming mass and nutrient loss rates as a function of elevation gradients can
vary greatly both within plant species and between these. Consequently, even
when some characteristics of the leaves and litter change to values usually
associated with low litter quality at high levels, these traits are not always the same
as those that actually cause the decomposition of the litter [Salinas et al., 2011;
Sundqvist et al., 2011].
Our findings support the prediction that the relative importance of plant
functional features for litter decomposition increases as the trait values covered by
the species evaluated vary. This is a significant finding because the range of traits
evaluated can influence whether climate or traits are more essential in influencing
decomposition dynamics. In other words, it's difficult to accurately determine the
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drivers of decomposition when inter- and intraspecific diversity in litter features of

a specific plant community is not well represented, which may have contributed to
the prevailing climate-control paradigm in the past. Also, this study demonstrates
the importance of understanding how basic factors like soil parent material and
species composition interact with anthropogenic ones like air pollution and climatic
regime alterations to influence forest ecosystems' principal functions. Climate and
atmospheric changes have been demonstrated to affect the distribution of
important primary producers along altitudinal gradients, making montane forests
extremely vulnerable. Such changes can have a domino effect on biodiversity,
putting at a high-risk sensitive water resources that are typically thought to be slow
to adapt to climate change.

Key words: climate, stable isotopes, elevation, forest ecosystem

Acknowledgments: This work is part of the project PN 19 11 03 02 part of the

Research Program „ICSI 4EE” financed by the Romanian Ministry of Research,
Innovation and Digitalization and the CNCS – UEFISCDI, project PN-III-P1-1.1-PD-
2019-0325, within PNCDI III (acronym ISO-TECH), ctr. PD 146/2020.

References
Badea, S.L., Ionete, R.E., Costinel, D., Nechita, C., Botu, M., Botoran, O.R., 2020. Changes of carbon-isotope
ratios in soil organic matter relative to parent vegetation and site specificity. Not. Bot. Horti Agrobot.
Cluj-Napoca 48. https://doi.org/10.15835/nbha48412138
Betz, O., Srisuka, W. & Puthz, V. Elevational gradients of species richness, community structure, and niche
occupation of tropical rove beetles (Coleoptera: Staphylinidae: Steninae) across mountain slopes in
Northern Thailand. Evol Ecol 34, 193–216 (2020). https://doi.org/10.1007/s10682-020-10036-2
Canessa, R, van den Brink, L, Saldaña, A, et al. Relative effects of climate and litter traits on decomposition
change with time, climate and trait variability. J Ecol.; 109: 447– 458 (2021)
https://doi.org/10.1111/1365-2745.13516
Liang S, Peng S, Chen Y. Carbon Cycles of Forest Ecosystems in a Typical Climate Transition Zone under
Future Climate Change: A Case Study of Shaanxi Province, China. Forests. 2019; 10(12):1150.
https://doi.org/10.3390/f10121150
Maxwell, T. M., Silva, L., & Horwath, W. R. (2018). Integrating effects of species composition and soil
properties to predict shifts in montane forest carbon-water relations. Proceedings of the National
Academy of Sciences of the United States of America, 115(18), E4219–E4226.
https://doi.org/10.1073/pnas.1718864115
Salinas N, Malhi Y, Meir P, Silman M, Roman Cuesta R, et al. 2011. The sensitivity of tropical leaf litter
decomposition to temperature: results from a large-scale leaf translocation experiment along an
elevation gradient in Peruvian forests. New Phytol. 189:967–77
Sundqvist MK, GieslerR,Wardle DA. 2011. Within- and across-species responses of plant traits and litter
decomposition to elevation across contrasting vegetation types in subarctic tundra. PLoS ONE
6(10):e27056

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A NEW METHOD FOR HELIUM ISOTOPES SEPARATION BY GAS

CHROMATOGRAPHY

Gheorghe Bulubaşa, Alina Niculescu, George Ana, Ciprian Bucur, Iulia Stefan

National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
Corresponding author: [email protected]

Helium, in general, and Helium 3, in particular, are increasingly used gases and
difficult to recover from various gaseous mixtures. An efficient method for helium-3
recovery is a chromatographic method. The helium 3 isotope is produced by beta
disintegration of tritium. An important source of helium 3 is the cover gas used in
the moderator circuit at Cernavoda NPP. Also, it can be extracted from tritium
storage units where it accumulates following the beta disintegration [1].

where is the beta particle (electron) and ̅ - antineutrino

The aim of this paper is to propose a new method for the investigation and
evaluation of the separation and recovery of helium isotopes by gas chromatographic
method. The chromatographic column used for this study is a 5 meters long, packed
column filled with 5A molecular sieve, using hydrogen as carrier gas. The column is
operated at 77K and different carrier gas flow rates in the range of 20-90sccm.
We calculated the separation parameters (retention time, retention factor, full
width at half maximum, selectivity, resolution) in order to establish the operating
conditions for the separation and recovery optimization.

Key words: gas chromatographic separation, helium isotopes, tritium.

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MULTICLASS ORGANIC CONTAMINANTS RESIDUES IN FISH MUSCLE TISSUE OF

DIFFERENT SPECIES COLLECTED FROM MIDDLE AND LOWER COURSE OF THE OLT
RIVER, ROMANIA

Corina Teodora Ciucure1, Carmen Lidia Chiţescu2, Elisabeta-Irina Geana1,*

1
National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
2
Dunarea de Jos University of Galati, Faculty of Medicine and Pharmacy, 35 A.I. Cuza Street, 800010
Galati, Romania
Corresponding author: [email protected]

INTRODUCTION

A huge number of chemicals are produced, marketed and used by modern

society and can be released into the environment through various means. The
continuous emission of these chemical residues into rivers, lakes or other
environmental compartments may pose a risk to ecosystems and humans, although
the exposure concentrations of individual substances may be in the range of ng/L to
μg/L (in water) [Hollender et al., 2019]. Thus, the presence of toxic residues of
organic contaminants in edible aquatic organisms is a real and important concern
for human health, as fish consumption is an irreplaceable component of a balanced
human diet. This aspect led government authorities and international organizations
such as the European Union (EU) and Codex Alimentarius to set maximum residue
levels (MRLs) for organic contaminants in different foods [Garlito et al., 2019].
Given the fact that, the new regulatory frameworks require sensitive and very
specific methods for measuring pesticide residues, such as high-resolution LC and
GC analytical techniques, but also safe and efficient methods of extracting organic
contaminants from complex matrices, such as muscle tissue and various fish organs
[Belenguer, Martinez-Capel, Masiá, & Picó, 2014]. Until recently, research has
focused on the analysis of persistent organic contaminants such as organochlorine
pesticides (OCP), polychlorinated biphenyls (PCBs) and polycyclic aromatic
hydrocarbons (PAHs) in fish in correlation with agricultural and industrial activities
and less information has been available on other groups of organic contaminants
such as polar pesticides, furan, dioxins, etc. Even though they were long-term used
in the past in agriculture, their use being banned today [Ajiboye, Kuvarega, &
Onwudiwe, 2020], organochlorine pesticides (OCPs) are a permanent concern due
to their high toxicity but also their resistance to biotic and abiotic degradation
processes [Hinojosa-Garro, Burgos Chan, & Rendón-von Osten, 2016]. The
widespread expansion of agricultural techniques based on the application of
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pesticides has led to an increase in the use and disposal of pesticide residues in
aquatic environments worldwide. The chemical diversity of pesticides has evolved
in recent decades, and the pesticides used today are generally more polar and less
persistent [Han & Sapozhnikova, 2020].
The present study aims to investigate the distribution of organic contaminants
in different species of fish (catfish - Silurus glanis, crucian - Carrassius gibelio, perch
- Perca fluviatilis, slug - Rutilus rutilus, bream - Abramis brama) taken in the period
2019 - 2020 from the middle and lower course of Olt River, in the localities of
Cornet, Strejești and Izbiceni, in order to investigate the impact of pollution with
organic contaminants on the aquatic ecosystem of the Olt River. For that, target
analytical methods were applied in order to quantify organophosphorus,
organophosphates, triazines, carbamates and acid herbicide pesticides by UHPLC-
MS/MS, OCP and PCB by GC-ECD, but also a non-specific UHPLC-MS/MS screening
method to identify other classes of emerging organic contaminants. The extraction
of organic contaminants from fish muscle tissue was performed according to
QuEChERS - Quick, Easy, Cheap, Effective, Rugged, and Safe protocol.

RESULTS AND DISCUSSIONS

The profile of the polar pesticides investigated in the analyzed fish samples
illustrates that organophosphate pesticides are the majority class of polar pesticides
identified in the analyzed samples (Fig. 1), with maximum values of 5.72 ng/g for
dimethoate, 8.57 ng/g for fampur, 22.05 ng/g for thionazine (zinofos), 41.97 ng/g for
tetraethyl dithiopyrophosphate and 3292.11 ng/g for phorate. The main
organophosphorus pesticides identified in the analyzed fish samples were fosdrin
(mevinfos) with values between 3.35-11.85 ng/g, dichlorvos (0.44-31.90 ng/g),
etoprofos (0.44-95.10 ng/g), tetrachlorvinphos (2.39-262.01 ng/g), chlorpyrifos (2.26-
72.76 ng/g), while carbamates were detected in a concentration range between n.d. in
the case of methiocarb and 77,43 ng/g for aldicarb sulphoxide, and maximum
concentrations of triazine pesticides were detected between 0,67 ng/g for atraton and
10,55 ng/g for ametryn.

Figure 1. Profile of the main classes of polar pesticides in the muscle tissue of different fish species
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Pesticides accumulate in different fish muscle tissue, depending on the species,

size, age, but also exposure to aquatic environments with high concentrations of
pollutants. It was observed that, triazine pesticides, carbamates, organophosphorus
pesticides and acid herbicides accumulate mostly in slugs (Rutilus rutilus, which are
a species of fish that live in stagnant or slow-flowing waters with a muddy or sandy
bottom, as are accumulation lakes on the Olt River, while organophosphate
pesticides accumulate the most in the muscle tissue of catfish and plaice, fish
species that prefer deep places with mud and turbid waters (Fig.2).

Figure 2. Profile of pesticide classes quantified in the muscle tissue of different fish species

Regarding the spatial distribution of the investigated polar pesticides in the

muscle tissue of the fish species in the study area, the highest concentrations of
pesticides were observed in the samples taken from the Strejești location (S2 and
S2 bis, C1 (2)) and Izbiceni (P2 and P3) which represent specific agricultural areas
for legume and maize crops (Fig. 3).

Figure 3. Spatial distribution of pesticides in fish in the study area - the middle and lower basin of the
Olt River (C - Cornet, S - Strejești, I - Izbiceni)

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Non-specific UHPLC-MS/MS screening analysis revealed that the number of

organic contaminants identified in the analyzed fish samples varied depending on
the species, most organic contaminants being identified in crucian, a fatty fish
species, faties facilitating the accumulation of organic contaminants in muscle
tissue, but also in organs.

Figure 4. The number of organic contaminants by UHPLC-MS/MS screening

analysis

Regarding the spatial distribution of organochlorine pesticides in the fish

species in the study area, the highest concentrations of pesticides were observed in
the samples taken from Izbiceni location (sample P2 - bream) and location Strejești
(sample C1 (1) - caras), on average the OCP content in the studied fish species being
approximately the same (Fig 5a). Significant amounts of congeners PCB 31, PCB 28,
PCB 44, PCB 149 and PCB 118 were detected in the fish samples from the Izbiceni
location which represents the end point of the Olt river, before the discharge into
the Danube, where the PCB is accumulated mainly from the industrial activities
present along the Olt River (Fig. 5b).

Sampling locations
Figure 5. Spatial distribution of: a) OCPs and b) PCBs in muscle tissue of fish from the study area

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Conclusions
This study completes the monitoring of organic contaminants in the water-
sediment-biota chain from the middle and lower section of the Olt river, as part of an
ongoing project. Such studies are important for assessing the quality of ecosystems,
assessing environmental factors, and at the same time are valuable tools for
environmental education, for society's awareness of the negative impact on the
environment due to industrial, agricultural and domestic activities. The results showed
some exceedances of the OCP content in the muscle tissue of the fish. Given the
associated risks to human health and the wider potential implications for the
environment, clear legislation is needed for each contaminant in different
environmental matrices. The study will continue by tracking the impact of POP
pollution on the aquatic ecosystem in heavily contaminated areas, such as the Strejești
and Arcești reservoirs on the Olt River, affected by industrial pollution in the area.

Key words: polar pesticides, organochlorine pesticides (OCP), polychlorinated

biphenyls (PCBs), UHPLC-MS/MS, GC-ECD, fish muscle tissue

Acknowledgments: This work was funded by The Ministry for Research,

Innovation and Digitization, Core Framework, grant numbers: PN 9N/2019 (Project
PN 19110303 "Advanced techniques for identifying sources of contamination and
biochemical reactions in aquatic ecosystems"

References
Ajiboye, T. O., Kuvarega, A. T., & Onwudiwe, D. C. (2020, September 1). Recent strategies for environmental
remediation of organochlorine pesticides. Applied Sciences, MDPI AG(Switzerland).
https://doi.org/10.3390/APP10186286
Belenguer, V., Martinez-Capel, F., Masiá, A., & Picó, Y. (2014). Patterns of presence and concentration of
pesticides in fish and waters of the júcar river (eastern spain). Journal of Hazardous Materials, 265,
271–279. https://doi.org/10.1016/j.jhazmat.2013.11.016
Garlito, B., Ibáñez, M., Portolés, T., Serrano, R., Amlund, H., Lundebye, A. K., … Hernández, F. (2019). LC-
MS/MS method for the determination of organophosphorus pesticides and their metabolites in
salmon and zebrafish fed with plant-based feed ingredients. Analytical and Bioanalytical Chemistry,
411(27), 7281–7291. https://doi.org/10.1007/s00216-019-02104-6
Han, L., & Sapozhnikova, Y. (2020). Semi-automated high-throughput method for residual analysis of 302
pesticides and environmental contaminants in catfish by fast low-pressure GC–MS/MS and UHPLC-
MS/MS. Food Chemistry, 319, 126592. https://doi.org/10.1016/j.foodchem.2020.126592
Hinojosa-Garro, D., Burgos Chan, A. M., & Rendón-von Osten, J. (2016). Organochlorine Pesticides (OCPs) in
Sediment and Fish of Two Tropical Water Bodies Under Different Land Use. Bulletin of Environmental
Contamination and Toxicology, 97(1), 105–111. https://doi.org/10.1007/s00128-016-1828-1
Hollender, J., van Bavel, B., Dulio, V., Farmen, E., Furtmann, K., Koschorreck, J., … Tornero, V. (2019). High
resolution mass spectrometry-based non-target screening can support regulatory environmental
monitoring and chemicals management. Environmental Sciences Europe, 31(1), 1–11.
https://doi.org/10.1186/s12302-019-0225-x
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ASPECTS REGARDING THE TRANSPORT OF WATER WITH DIFFERENT H-O

CONCENTRATIONS FROM SOIL TO PLANTS

Diana Costinel, Roxana Elena Ionete, Oana Romina Botoran

National Research and Development Institute for Cryogenics and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street no. 4, PO Box Râureni 7, 240050, Râmnicu Vâlcea, Romania
Corresponding author: [email protected]

The aim of this study was to provide a complex investigation on the variation of
Oxygen 18 (18O) and Deuterium (2H) concentration in roots, stems and leaves of
plants in various stages of vegetation, subjected to watering with waters having
different deuterium content, as well as characterizing the H-O isotopic profile of
water extracted from soil.
Field experiments: An evaluation of the isotopic profile of the water extracted
from the soils irrigated with waters having different deuterium content was
performed (sampling after and before watering) in a first stage. In the second stage,
the isotopic fingerprint of the water extracted from the plants (at various stages of
vegetation) was compared to the isotopic composition of the irrigation water as
well the water extracted from the soils where the plants developed. To reduce the
isotopic exchange between the soil and the laboratory environment as much as
possible, we used narrow and deeper alveoli (length-width-depth: 5x5x15 cm).
Two varieties of salad, namely Lettuce lollo bionda (LLB) and Lactuca sativa (LS),
were used as biological materials. Three different types of water have been
considered for watering: (i) tap water (TW), with a composition of -9.63‰ for δ18O,
and -67‰ (~145 ppm of Deuterium, calculated after Hagemann et al., 1970) for
δ2H; (ii) deuterium depleted water (DDW), with a stable isotope fingerprint of -
139‰ for δ18O and -840‰ for δ2H (~ 25 ppm Deuterium content, calculated using
water dilution techniques); and (iii) deuterated water (DW), having +22.30‰ for
δ18O and +155‰ for δ2H (with a Deuterium concentration of ~ 180 ppm). The plants
were watered every two days with an amount of 5 ml of water. As a growing
substrate, BioFlo universal soil was chosen, being composed of a mixture of brown
and red peat with a moderate organic matter content. During the experiment, the
temperature of the plant growth medium was set at 21°C, excepting 2 days (after
the salad samples reached maturity) in which it was modified, by increasing it with
4°C, in order to observe the plants responses to stress due to growing conditions.

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Figure 1. Plants evolution in time; the experiment was performed in laboratory conditions

Sampling and Sample Preparation: During the entire experiment, the water
extraction from plants and soils was made by using the lyophilization method
(Figure 2).

Figure 2. Lyophilisation system from LIS laboratory

Analysis Technique: Hydrogen and oxygen stable isotopes analysis from water
samples was performed using a GasBench II (Thermo Electron) equilibration system
coupled with a Continuous Flow Isotope Ratio Mass Spectrometer (CF-IRMS) Delta
V Plus (Thermo Electron, Bremen-Germany). The Deuterium and Oxygen 18 isotopic
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composition from water was obtained after the isotope exchange between the
sample and equilibration gas mixture (Coplen T.B., 1994).
Results and discussions: Initially, the water from soil was extracted before
watering, representing the “zero point”: the soil humidity was 54 % and the water
isotopic fingerprint was -95‰ for δ2H (~ 141 ppm content in Deuterium) and -
12.00‰ for δ18O. After watering, humidity increased with approximatively 5 % for
all soils. For two days, the soils sampling was performed at intervals of 1, 4, 7 and
24 hours after watering. For practical reasons, the sampling rates of soils was
changed to weekly, especially when the plants entered in the vegetation stage (e.g.,
the amount of soil in the vessel had to remain approximately constant after
sampling, in order not to affect the plant evolution).
After the isotopic measurements, we found different isotopic exchanges
between soil surface and environment, strongly dependent to the type of water
used for irrigation. For soils watered with DDW, after one hour, the deuterium
content decreased with approximatively 30 ppm and increased slowly with 13 ppm
until the 24 hours sampling. For the next watering with DDW, the deuterium
concentration decreased from the zero point with 43 ppm and increased slowly
with 11 ppm in 24 hours. For that soil sample, the decrease in Deuterium content
continued, the values registering a similar trend to those from the vegetation
period of the plants, observing an approximately constant average value of 72 ppm
Deuterium content (± 3 ppm between samplings). Similar variations were observed
for oxygen 18 (range between -100 ‰ to -87 ‰).
For the soils watered with TW, the Deuterium content increase with
approximatively 1 ppm after one hour, followed by a slow increase with 4 ppm in
24 hours. After a new watering with TW, the Deuterium content increased from
zero point by 1 ppm, followed by a slow increase with 2 ppm in 24 hours. For that
soil sample, during the whole experiment, was calculate an average value of
approximately 146 ppm (± 1 ppm between sampling). The measured ranges for
oxygen 18 were between -6 ‰ to -4 ‰. Regarding the soil watered with deuterated
water, the Deuterium content increase with approximatively 11 ppm after one
hour, followed by a decrease with 1 ppm from the level reached after one day. For
the next 24 hours, after a new watering, the Deuterium content increased from
zero point with 13 ppm, followed by slowly decrease at this level with 2 ppm. For
that soil, for the vegetation period of the plants, was calculate an average value of
approximately 167 ppm (± 2 ppm between sampling). The measured ranges for
oxygen 18 were between +12 ‰ to +17 ‰.
The experiment's second phase focused on the isotopic fingerprint of water
extracted from plants, observing a significant enrichment in heavy isotopes of
water from plants watered with DDW: the Deuterium content for young plants was
69 ppm, increasing to 109 ppm for mature plants, a higher level of enrichment
being registered in leaves than in roots and stem (see Figure 3). Heavy isotopes
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were concentrated when the plants entered in the vegetation, a significant increase
being observed in the leaves. This behavior can be attributed to the adaptation /
acclimatization of plants in response to the abiotic factor, namely the water
depleted in deuterium. The use in the irrigation process of a water with a low
deuterium content has positively influenced the plants evolution (Figure 1).
Although, the germination of LS plants was much faster than of LLB plants, at the
end of the experiment we calculated a difference of 14 ppm Deuterium content in
the LLB leaves compared to LS leaves. In the period of plants growing under
temperature stress, were observed changes in the isotopic fingerprint of the water
extracted from all plants (Figure 3) - an increase in the heavier isotopes content,
followed by a slight decrease, then continuing the normal trend.

Figure 3. Variation in time of the H-O isotopes signature in water extracted from the leaves
watered with deuterium depleted water, tap water and deuterated water

Figure 4. Deuterium content (ppm) calculated in water extracted from the leaves of plants
and soils watered with different types of water (tap water TW, water depleted in deuterium DDW
and deuterated water DW) (Hagemann, 1970)

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Conclusions: Enrichment or depletion in the heavy stable isotopes of hydrogen

and oxygen in water extracted from plants and soils, compared to the initial
fingerprint of water used for irrigation, occurs differently, depending on several
factors: type of water used for irrigation, type of plant, phase of plant vegetation,
and environmental conditions. Both biological materials presented a poor
development in the presence of deuterated water, but were positively influenced
by depleted water, which contributed to the earlier formation of plant roots and
stems.

Key words: deuterium, oxygen 18, tap water, deuterium depleted water, soil.

Acknowledgment: This work is part of the project PN 19 11 03 02 part of the

Research Program „ICSI 4EE” financed by the Romanian Ministry of Research,
Innovation and Digitalization and the CNCS – UEFISCDI, project PN-III-P1-1.1-PD-
2019-0325, within PNCDI III (acronym ISO-TECH), ctr. PD 146/2020.

References
Butnaru G, Dobrei A, Stefanescu I, Costinel D, Titescu G, Boleman A, The associate effect of depleted
water and magnetic particles on Vitis Vinifera (L) organogenesis, Progress in Cryogenics and
Isotopes Separation, 2009 (12), pp.94-105.
Costinel D, Ionete RE, Popescu R, Stefanescu I, Dinca OR, Butnaru G, Stable isotopic fingerprint of
water from Vitis Vinifera L. plants growing in different environmental conditions, Book of
abstract at International Symposium on Isotope Hydrology: Revisiting Foundations and
Exploring Frontiers IAEA, Water Resources Programme - CN225, 2015.
Finnigan GasBench II 2004 - Operating Manual Revision A 111 8342, September-09.
Coplen T.B. 1994. Reporting of stable hydrogen, carbon, and oxygen isotopic abundances. Pure Appl.
Chem. 66: 273-276.
Coplen T B, Wildman J and Chen J 1991 Anal. Chem. 63 910-2
Hagemann, R., Nief, G. and Roth, E. 1970. Absolute isotopic scale for deuterium analysis of natural
waters. Absolute D/H ratio for SMOW. Tellus 22: 712-715

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ELECTROCHEMICAL DETECTION OF GLYPHOSATE BASED ON MOLECULARLY

IMPRINTED POLYPYRROLE-MODIFIED GOLD ELECTRODE AND DISPERSED GOLD
NANOPARTICLES ON REDUCED GRAPHENE OXIDE

Elisabeta-Irina Geana1, Corina Teodora Ciucure1, Amalia Soare1, Stanica Enache1,

Livia Alexandra Dinu2
1
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
2
National Institute for Research and Development in Microtechnologies (IMT Bucharest), 077190
Voluntari (Ilfov), Romania
Corresponding authors: [email protected]; [email protected]

INTRODUCTION
In the agriculture global sector, the herbicides market is growing and
competitive. Gly [(N-phosphonomethyl) glycine] is a nonselective and broad-spectrum
herbicide and is widely used to control weeds in grain crops. The overuse of Gly has
induced issues, such as contamination of surface water, decreased soils fertility,
adverse effects on soil microbiota and possible incorporation in food chains [Singh,
2020]. Herbicides, such as Gly, have been classified as “priority hazardous substances”
in the European Water Framework Directive (WFD) #2000/60/EC. Chronic exposure of
Gly is associated with many human health hazards that include: endocrine function
disruption, colitis, diabetes, heart disease or obesity. The maximum residue limit (MRL)
of glyphosate is established at the very low concentration, especially for drinking water
(0.1μg/L or 0.6 nM, in European countries) [Dolan, 2013]. Legislative bodies, local
authorities and industries, all require frequent water quality monitoring, and this is
time and labor intensive, and an expensive undertaking. For this purpose, there is an
urgent need for a sensitive, selective and fast responsive monitoring method [Valle,
2019]. In recent years, as valuable alternatives to the standard chromatographic
detection methods, in particular coupled with mass detection (HPLC-MS and GC-MS),
the electrochemical sensors have been intensively studied in the last years [Duffy,
2017]. In this work two types of materials have been used to develop electrochemical
sensor for Gly detetction. The gold nanoparticles (AuNPs) modified graphene (Gr)
nanomaterials showing high sensitivity as non-enzymatic material for sensor
modification, while the molecularly-imprinted polymer (MIP) showing both high
sensitivity and high selectivity towards the detection of Gly in synthetic water samples.

RESULTS AND DISCUSSIONS

Screen-printed carbon and gold electrodes (SPCE and AuSPE) have been used as
electrochemical transducers for the development of Gly sensors. Two AuNPS-Gr
nanomaterials, synthesized in different ways, using electrochemical (Dinu Gugoasa,
2021) and eco-friendly microwave-assisted chemical method (Marinoiu, 2020), have
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been employed to design the working area of the SPCE for sensitive detection of Gly. For
the first designs of the sensors, AuNPs-Gr has been either dispersed in DMF, or in water
containing nafion and isopropanol solution. These modified sensors have been
electrochemically characterized using cyclic voltammetry (CV) and electrochemical
impedance spectroscopy (EIS), showing a larger active area (AA) and a low charge
transfer resistance (Rct) for the sensors modified with AuNPs-Gr/SPCE, compared to the
Gr/SPCE and bare SPCE.
Taking into consideration that Gly is not an electroactive compound, the procedure
for sample preparation included a freshly prepared electroactive compound, potassium
ferricyanide (K3Fe(CN)6), that has to be added to the working solution. In this case, the
electrochemical behavior of the redox couple Fe2+/Fe3+ is evaluated. So, the peak current
intensity of the AuNPs-Gr/SPCE is decreasing with the increase of the Gly concentration
(Fig. 1a). During the electrochemical detection, Gly molecules get adsorbed on the
AuNPs-Gr films (fig. 1b), and because of this, the quantification limit of Gly remains high.
To overcome this aspect, Nafion was used in the preparing of dispersed AuNPs-Gr,
instead of dimethylformamide (DMF), to limit the fouling effect produced by Gly. The
AuNPs-Gr-Nafion/SPCE has been tested in the presence and absence of Gly (Fig. 1c)
showing that Gly is affecting the electron transfer of the redox couple by a recording a
decreased current intensity. The limit of detection for AuNPs-Gr-Nafion/SPCE was lower
(LOD=8.3 ng/L) than AuNPs-Gr/SPCE (LOD=0.3 µg/L), proving the efficacy of using Nafion
for the sensors design.

a) b)

c) d)
Figure 1. CVs recorded using: a) AuGr-DMF / SPCE in phosphate buffer containing different
concentrations of Gly; b) Repetitive CV measurements for AuGr-DMF/SPCE in phosphate buffer
containing 1 ppb Gly; c); AuGr-Nafion / SPCE in 1mM K3FeCN6 (0.2M KCl), in the presence of Gly
(blue) and in absence of Gly (orange) d); AuGr-Nafion/ SPCE in solutions containing different
concentrations of Gly in 1mM K3FeCN6 (0.2M KCl).

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Since the non-enzymatic sensor based on AuNPs-Gr nanomaterials have not shown
a reliable selectivity towards the detection of Gly, a high-selectivity material is required.
For this purpose, molecularly imprinted polypyrrole (MIPPy) has been employed for the
modification of the WE of the AuSPE. The molecularly imprinting technique generates
robust synthetic molecular recognition materials with antibody-like ability to bind and
discriminate between molecules. The preparation procedure is presented in Fig. 2a.
Morphological characterization of the imprinted surface from the top surface area of the
sensor has been presented in Fig 2b. and Fig. 2c. The evaluation of different
concentrations of Gly has been performed in synthetic solutions containing the same
electroactive compound (K3Fe(CN)6) with a known redox behavior. The signal was
recorded in the absence and presence of Gly (Fig. 2d). A signal drop and a potential shift
has been observed in the presence of Gly, due to the fact that Gly is hosting the
imprinted cavities of the MIP-sensor. The PPy-MIP based electrochemical sensor has
been tested for standard glyphosate solution obtaining a linear concentration range from
5.0-50.0 ng/L and a limit of detection of 1.6 ng/L.

a) b) c)

d) e)
Figure 2. a) Schematic representation of the design of the MIPPy/AuSPE and the experimental
procedure to detect Gly; b) SEM characterization of the MIPPy/AuSPE; c) AFM characterization of
the MIPPy/AuSPE; d) CVs recorde using MIPPy/AuSPE in 1mM K3FeCN6 (0.2M KCl), in the presence of
Gly (orange) and in absence of Gly (blue); e) CVs recorded using the MIPPy/AuSPE in solutions
containing different concentrations of Gly in 1mM K3FeCN6 with 0.2M KCl and (inset) the calibration
curve of the MIP sensor.

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CONCLUSIONS

Several electrochemical sensing designs were constructed using state-of-the-art

materials, such as AuNPs-Gr nanomaterials and polypyrrole conducting polymer on
screen printed electrodes. The combination of such miniaturized electrochemical
transducers, cheap and portable electrochemical instruments, sensitivity provided by
the large active area of the nanomaterials (e.g. AuNPs-Gr) and the selectivity ensured
by the antibody-like materials (eg imprinted molecular polymers - MIP), are generally
ideal for on-site environmental applications. The AuNPs-Gr/SPCE, AuNPs-Gr-
Nafion/SPCE and MIPPy/AuSPE have been investigated for Gly detection from synthetic
water samples. From the three proposed sensors, the MIPPy/AuSPE showed the lowest
LOD and functional concentration range, while AuNPs-Gr-Nafion/SPCE covers the
concentration range required for Gly detetion from water samples.

FUTURE PERSPECTIVES

The use of electrochemical sensors in the field of the environment is still

limited compared to medical and food applications. Most commercial sensors are
for medical applications, while only a few are adapted for environmental
monitoring. Thus, there is a permanent challenge for the development of improved
and more reliable devices that allow sensitive and selective detection of organic
contaminants from different environmental matrices.

Key words: electrochemical sensor, glyphosate, molecularly imprinted polymer,

gold nanoparticles, graphene, screen printed electrode

Acknowledgments: This work was funded by The Ministry for Research,

Innovation and Digitization, Core Framework, grant numbers: PN 9N/2019 (Project
PN 19110303 "Advanced techniques for identifying sources of contamination and
biochemical reactions in aquatic ecosystems" and PN 14N/2019 (MICRO-NANO-SIS
PLUS).

References
Dinu Gugoasa L.A., Pogacean F., Kurbanoglu S., Barbu Tudoran L., Serban A.B., Kacso I., Pruneanu S.,
Graphene-Gold Nanoparticles Nanozyme-Based Electrochemical Sensor with Enhanced
Laccase-Like Activity for Determination of Phenolic Substrates, J Electrochem. Soc., 2021, 168,
067523
Dolan T., Howsam P., Parsons D.J., Whelan M.J., Is the EU drinking water directive standard for
pesticides in drinking water consistent with the precautionary principle? Environ. Sci.
Technol. 2013, 47, 4999–5006.

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Duffy G., Regan F., Recent developments in sensing methods for eutrophying nutrients with a focus
on automation for environmental applications, Analyst, 2017,142, 4355-4372.
Marinoiu A., Andrei R., Vagner I., Niculescu V., Bucura F., Constantinescu M., Carcadea E., One Step
Synthesis of Au Nanoparticles Supported on Graphene Oxide Using an Eco-Friendly Microwave-
Assisted Process, Materials Science (Medžiagotyra), 2020, 26(3), 249-254.
Singh S., Kumar V., Datta S. et al., Glyphosate uptake, translocation, resistance emergence in crops,
analytical monitoring, toxicity and degradation: a review. Environ Chem Lett 18, 663–702
(2020).
Valle A.L., Mello F.C.C., Alves-Balvedi R.P., Rodrigues L.P., Goulart L.R., Glyphosate detection:
Methods, needs and challenges. Environ. Chem. Lett. 2019, 17, 291-317

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OVERVIEW OF IoT PARADIGM FOR THE SUSTAINABLE CONSTRUCTION SECTOR

Nicoleta Cobîrzan1, Maria Simona Raboaca2,*, Raluca A. Felseghi1,3,

Simona Stanca1
1
Faculty of Civil Engineering, Civil Engineering and Management Department, Technical University of
Cluj-Napoca, Constantin Daicoviciu street, No.15, 400020 Cluj-Napoca, Romania;
2
National Research and Development Institute for Cryogenic and Isotopic Technologies—ICSI Rm.
Valcea, Uzinei Street, No. 4, P.O. Box 7 Raureni, 240050 Valcea, Romania;
3
Faculty of Electrical Engineering and Computer Science, Ștefan cel Mare University of Suceava,
Universităţii Street, No.13, 720229 Suceava, Romania.
Corresponding author: [email protected] author

The Internet of Things (IoT) have been widely implemented in various activities
of today's modern life, and at an accelerated rhythm, more and more intelligent IoT
services and applications are developed. The Internet of Things offers substantial
opportunities to increase the quality of products, services and technologies in the
construction sector.
This paper aims to provide an overview of IoT tools such as Building
Information Modeling, Radio-frequency identification, sensor, Location Services
(Waze, Google Map and GPS), smart communication, Big Data, Augmented Reality,
Remote Operation, that have applicability in construction projects, providing
increased performance for Project Management, Site monitoring, Construction
Safety, Fleet Management, Machine Control.
Among the key benefits offered by the implementation of IoT in the
management of construction sites can be listed the following: better use of time;
business intelligence; energy, fuel, and power savings; environmental monitoring;
health monitoring of structures; identification of flaws in construction phases;
improved projects handling with minimum human effort; improved supply chain
management; maintenance of machinery and equipment promptly; minimised
project delay by taken preventive measures; compliance, productivity, profitability;
remote operation of activities in worksite; up-to-date information for better
decision making; waste management.

Key words: construction sector; Internet of Things; project management

digitalization; sustainability indicators; smart management of construction site.

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13
C NMR INVESTIGATIONS OF RADICAL SCAVENGING ACTIVITIES OF ASCORBIC
ACID AND RESVERATROL USING 1,1-DIPHENYL-2-PICRYLHYDRAZYL

Vicol Crina, Gorincioi Elena*1, Duca Gheorghe

Institute of Chemistry, 3 Academiei st., Chisinau, Republic of Moldova

1
Tiraspol State University, 5 Iablocikin str., Chișinău, Republic of Moldova
Corresponding author: [email protected]

INTRODUCTION

Resveratrol (3,5,4'-trihydroxy-trans-stilbene, Res) is a member of the stilbene family

of natural phenolic compounds. It is a well-known stress metabolite found at different
concentrations in all parts of Vitis plants [Amalfitano, 2000]. The oxidative
dehydrogenation-condensation process of Res leads to the formation of Res oligomers –
viniferins [Amalfitano, 2000; Muhammad, 2014]. Res and viniferins are commonly found
in many food products, the red wine being the most notable dietary source of these
natural metabolites [Fernández-Mar, 2012]. Over the last few decades, it has been
found that Res is the key to the origins of many bioactivities related to human health,
e.g. anti-tumor, antioxidant and anti-platelet aggregation [Mao, 2015].
L-Ascorbic acid (AA) is one of the most studied water soluble natural antioxidants.
It possesses very strong antioxidant activity against different types of free radicals,
being a primary scavenger of radical species. Thereby, it is commonly used as a
reference compound when studying the antioxidant activity of other active
biomolecules. In wines, AA is mostly present from adding it during the wine-making
process, as long as its contribution is known to be positive for the quality of the
beverage, and respectively, to the total antioxidant capacity of wines [Badea, 2015].
For many years, nuclear magnetic resonance (NMR) spectroscopy remains one of
the analytical methods that are essential for wine authentication (Solovyev, 2020).
Recent papers have shown the use of 13C NMR for clarifying the molecular mechanisms
of the radical scavenging activities of antioxidants in tea [Sawai, 1998; Sawai, 2000;
Sawai 2005] and fruits [Lopez-Martinez, 2015].
In the present work, an analytical approach based on the use of 13C NMR is
presented, describing some attempts to model and elucidate the plausible interactions
between two wine antioxidants – Res and AA. The free radical scavenging abilities of
the mentioned wine antioxidants were studied by using 1,1-diphenyl-2-picrylhydrazyl
radical (DPPH).

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MATERIALS AND METHODS

Commercial standards of resveratrol (TCI Europe nv, Belgium), L - ascorbic acid,

DPPH (Sigma-Aldrich, Germany) L - dehydroascorbic acid (Sigma-Aldrich, Switzerland);
acetone-d6 and methanol-d4 (Sigma-Aldrich, USA) were used for all experiments. NMR
spectra were recorded on a Bruker AVANCE 400 spectrometer equipped with a 5-mm
broadband reverse probe with field z gradient, operating at 400.13 and 100.61 MHz for
1
H and 13C nuclei, respectively.

RESULTS AND DISCUSSION

Scheme 1 depicts the general processes for scavenging the DPPH radicals by AA
and Res.

Scheme 1. Annihilation the DPPH radicals by AA and Res

Villano et al. employed the UV-Vis spectrophotometric technique to determine the

radical scavenging abilities of many wine polyphenols, reporting the following total
reaction stoichiometries: the value 2.6 for interaction of AA with DPPH and 1.0 for
interaction of Res with DPPH [Villano, 2007]. Numerous scientific papers regarding the
molecular mechanisms of antioxidant activity of AA are reported, while mechanistic
pathways involving Res as antioxidant are still under discussion. Thus, according to
theoretical calculations of Caruso et al., the p-4′-OH in Res is more acidic compared to
the other two m-OH groups [Caruso, 2004]. They consider H-atom transfer to be the
dominant mechanism by which Res intercepts free radicals. Hussein et al. propose a
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mechanism of Res antioxidant activity that involves the quinone-structure formation

[Hussein, 2011]. Obtaining the catechin quinone as the oxidation product of (+)-catechin
under reaction with DPPH was reported by Sawai et al. [Sawai, 1998; Sawai, 2000]. They
presented the appearance of the carbonyl signals of (+)-catechin oxidation products in
the 13C NMR spectra. With regard to the Res – DPPH reaction, the literature describes
various Res oligomers as final products of Res oxidation [Shang, 2009; Mei, 2014; Mao,
2015].
In our experiments, the reactions of AA and Res with DPPH were carried out in the
mixture of deuterated solvents acetone-d6-methanol-d4 in the NMR tube. The AA : Res :
DPPH (1:1:2.6) molar ratios were mainly analyzed, being compared with the data
obtained from the experiments with the free radical deficiency AA : Res : DPPH (1:1:1).
Two approaches of performing the reactions were followed: I) mixing antioxidants and
free radical (reaction time-1 hr), NMR analysis; II) Mixing Res and free radical (reaction
time-1 hr), then adding AA (reaction time-15'), NMR analysis. In order to facilitate the
analysis of the 13C NMR data and to avoid signal overlapping, the following characteristic
peaks has been chosen by us for identification: AA- 64.3 ppm, dehydroascorbic acid
(DAA)- 89.9 ppm, Res-117.1 ppm, DPPH-H- 122.1 ppm, Res oligomer- 58.9 ppm (Fig. 1).
It is interesting to mention, that no carbonyl signals characterizing the Res-
quinone (approx. at 180 ppm) were present in the 13C NMR spectra, neither for Res–
DPPH reaction (Fig. 1, case 1), nor for the other examined reactions (Fig. 2, cases A, B
and C). Instead, the signal (58.9 ppm) in the typical region for the described Res
oligomers (Shang, 2009; Mao 2015; Liu, 2013) was found in the spectrum (Fig. 2, case
A), but not in experiences depicted in Fig. 2, cases B and C.

13
Figure 1. C NMR spectra: 1) reaction of Res with DPPH free radical, 1:1 molar ration, r.t., 1hr., in
acetone-d6; 2) Res in acetone-d6; 3) AA in methanol-d4; 4) DAA in methanol-d4.

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In the light of the obtained data, some primary considerations can be pointed
out: 1) no Res-quinone has been detected, upon the interaction of Res with DPPH;
2) Res oligomerisation occurred when the 1:1:2.6 molar ratio (AA : Res : DPPH) was
employed and Res was left to react with DPPH one hr. before adding AA (Figure 2,
case A), IInd approach; 3) this molar ratio is insufficient for the total oxidation of
both used antioxidants (see: peak of AA, along with that of DAA in the spectrum,
Figure 2, case A); 4) peaks close to 117.1 ppm also attest the existence of Res
oligomer species (Shang, 2009; Mao 2015; Liu, 2013).

13
Figure 2. C NMR spectra: A) AA : Res : DPPH (1:1:2.6) molar ratio, II-nd approach of conducting the
reaction; B) AA : Res : DPPH (1:1:2.6) molar ratio, I-st approach of conducting the reaction; C) AA :
Res : DPPH (1:1:1) molar ratio, II-nd approach of conducting the reaction.

Moreover, the experience with the same 1:1:2.6 molar ratio (AA : Res : DPPH), but
with the changed mode of interaction of reagents (Ist approach) additionally confirmed the
data on AA as antioxidant of reference: AA scavenged all DPPH- no peaks of AA, but that of
DAA are present in the spectrum, potent peak of untransformed Res being also attested.
Comparison between the reaction- AA : Res : DPPH =1:1:2.6 (Figure 2, case B) and the
reaction performed under conditions of free radical deficiency (AA : Res : DPPH =1:1:1,
Figure 2, case C), when antioxidants were mixed with DPPH, has corroborated the above-
mentioned observations.
The reported herein preliminary results, focused on the use of 13C NMR offer some
insights into the perspectives of wine antioxidant interactions and other studies are in
progress.

Key words: NMR, resveratrol, resveratrol oligomers, ascorbic acid, DPPH

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Acknowledgments: This work was supported by state program no.

20.80009.5007.27, of the National Agency for Research and Development of Moldova.

References
Amalfitano, C., Evidente, A., Mugnai, L., Tegli, S., Bertelli, E., Surico, G. Phytopathologia
Mediterranea, 2000, 1000-1006.
Badea, G., Antoce, A. Scientific Papers. Series B, Horticulture, 2015, 59, 123–140.
Caruso, F., Tanski, J., Villegas-Estrada, A., Rossi, M. Journal of Agricultural and Food Chemistry,
2004, 52(24), 7279-7285.
Fernández-Mar, M. I., Mateos, R., Garcia-Parrilla, M. C., Puertas, B., Cantos-Villar, E. Food
Chemistry, 2012, 130(4), 797-813.
Hussein, M. A. International Journal of Phytomedicine, 2011, 3(4), 459.
López-Martínez, L. M., Santacruz-Ortega, H., Navarro, R. E., Sotelo-Mundo, R. R., González-Aguilar,
G. A. PloS one, 2015, 10 (11), e0140242.
Liu, W. B., Hu, L., Hu, Q., Chen, N. N., Yang, Q. S., & Wang, F. F. Molecules, 2013, 18(6), 7093-7102.
Mao, Q. The synthesis and antioxidant capacities of a range of resveratrol and related phenolic
glusides, Doctoral dissertation, Univeristy of Adelaide, 184 pag., 2015.
Mei, Y. Z., Liu, R. X., Wang, D. P., Wang, X., Dai, C. C. Biotechnology Letters, 2015, 37(1), 9-18.
Muhammad, N., Din, L. B., Ibrahim, N., Zakaria, Z., Yaacob, W. A. In The Open Conference
Proceedings Journal, 2014, 5(1).
Sawai, Y., Moon, J. H. Journal of Agricultural and Food Chemistry, 2000, 48(12), 6247-6253.
Sawai, Y., Moon, J. H., Sakata, K., Watanabe, N. Journal of Agricultural and Food Chemistry,
2005, 53(9), 3598-3604.
Sawai, Y., Sakata, K. Journal of Agricultural and Food Chemistry, 1998, 46(1), 111-114.
Shang, Y. J., Qian, Y. P., Liu, X. D., Dai, F., Shang, X. L., Jia, W. Q., Zhou, B. The Journal of Organic
Chemistry, 2009, 74(14), 5025-5031.
Solovyev, P. A., Fauhl‐Hassek, C., Riedl, J., Esslinger, S., Bontempo, L., Camin, F. Comprehensive
Reviews in Food Science and Food Safety, 2020, 20(2), 2040-2062.
Villaño, D., Fernández-Pachón, M. S., Moyá, M. L., Troncoso, A. M., García-Parrilla, M. C. Talanta,
2007, 71(1), 230-235.

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WATER CHEMISTRY AND O-H-N STABLE ISOTOPES PATTERN AS TOOLS FOR

TRACING SOURCES OF CONTAMINATION

Roxana Elena Ionete, Diana Costinel, Oana Romina Botoran, Claudia Şandru,
Mihaela Iordache, Andreea Maria Rădulescu
1
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Corresponding author: [email protected]

Due to growing human activity, which has resulted in a high demand for water
resources and contamination, tracing contaminant sources in surface and groundwater
remains a significant concern. According to the World Health Organization,
contaminated water is responsible for almost two-thirds of all ailments. Since nitrate is
one of the water quality criteria that must be monitored, determining the source and
biogeochemical changes of nitrogen is typically of great relevance for water resource
management [Segal-Rozenhaimer et al., 2004; Aggarwal, Gat and Froehlich, 2005;
Hoefs, 2009]. Upstream discharge of high nitrate or ammonium sewage effluents,
leaching from agricultural land during high precipitation, discharge of farm or industrial
effluents, and/or seasonal influences can all contribute to increased inorganic nitrogen
concentrations in surface waters [Ging, Lee and Silva, 1996; Popescu et al., 2015].
Stable isotopes are a useful tool for determining the source of pollution. Environmental
isotopes (O-H-N-O) were proved as excellent tracers for the physical processes that
affect water, and are used to determine the source, path and history of a water source.
Meteorological changes, in particular, impact stable water isotopes (18O and 2H), that
provide a unique fingerprint of their origin, which is critical for determining the source
of water [Clark and Fritz, 1997]. Since isotopic values differ from source to source, the
stable isotopes of nitrogen and oxygen in nitrate (15N and 18O) are also essential for
determining the sources of nitrate contamination [Xue et al., 2009]. In this work, some
preliminary investigation on the main tributary of the Danube in Romania, the Olt
River, is presented, in terms of chemical and stable isotope composition. The major
goal was to discover the main pollution sources and examine the seasonal and spatial
isotope trends of the waters.
The Olt River stretches over 615 km from its source in the Eastern Carpathian
Mountains, to its mouth at the Danube River, draining relief units with different
physical and geographical conditions (30% mountains, 53% hills and 17% plain). Our
study refers to the middle and inferior watershed of the Olt River, passing through
Valcea, Olt and Teleorman counties, crossing them from north to south. For the study,

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water samples were collected during March 2018 – February 2019, from 21 locations
(18 accumulation lakes, 1 point from the Olt River before spilling into the Danube River
and 2 points in the Danube River (upstream and downstream of the Olt River)), namely
P1 – Cornetu, P2 – Lotru. P3 – Turnu, P4 – Calimanesti, P5 – Daesti, P6 – Ramnicu Valcea,
P7 – Govora, P8 – Babeni, P9 – Ionesti, P10 – Zavideni, P11 – Dragasani, P12 – Strejesti,
P13 – Arcesti, P14 – Slatina, P15 – Draganesti, P16 – Frunzaru, P17 – Rusanesti, P18 –
Izbiceni, P19 – Islaz, P20 – Danube - Upstream the Olt River, P21 – Danube – Downstream
the Olt River.
Colorimetric method was used to determine the nitrate, nitrite and ammonium
concentrations in water; calcium and magnesium was carried out by flame atomic
absorption spectroscopy, and chloride ions were determined by titrating the water
samples against a standard solution of AgNO3 using potassium chromate as an
indicator. The δ18O, δ2H and δ15N measurements were made by continuous flow-
isotope ratio mass spectrometry.
Increased values and a wide range of concentrations were recorded in the cold
months for nitrates and ammonium (January and February). To warmer months
(March - October), both the concentrations and variation were lower (Figure 1). This
behavior is explained by a lower microbial activity in cold months, more active
biological conditions during the warm months, leading to faster transformations of
nitrogen compounds in water.

2000 3200

2800
P1

1500 2400
RWQC II

N-NH4+ (mgN/L)
N-NO3- (mgN/L)

2000 RWQC III

1000 1600
RWQC I

1200
RWQC III
500 800
P18
P14 P13 RWQC II
P2 P2 400 P14 P9
P1 P10 P8
RWQC I
0 0
Mar-18 May-18 Jun-18 Oct-18 Jan-19 Febr-19 Mar-18 May-18 Jun-18 Oct-18 Jan-19 Febr-19

+
Figure 1. Variation of nitrate (N-NO3ˉ) and ammonium (N-NH4 ) in the Olt River waters,
during the study period

2H of the river water varied from -84.54 ‰ to -59.86 ‰, with an average of -
70.68 ‰ and 5.95 ‰ standard deviation. 18O had values between -11.61 ‰ and -
8.67 ‰, within a range of 2.94 ‰, with an average of -10.06 ‰ and 0.72 ‰
standard deviation. For both 2H and 18O, the values were higher in June and
October, than in January, February, March and May. The regression line
associated with the basin water (BWL) was found to be close to the local meteoric
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water line of precipitation from 2018 (LMWL 2018) – obtained by collected

precipitation samples on the ICSI Rm. Valcea site, but slightly enriched (situated
on a lower slope) – see Figure 2.

Figure 2. H-O stable isotopes patterns of the Olt River waters and
precipitation during the study period

Over the observed period, 15N in the Olt river waters showed little
variations, from -1.6 ‰ to 0.62 ‰, with a mean value of -1.11 ‰ (Figure 3). The
highest value (0.62 ‰) was found in June at a sampling location in the Danube,
upstream the Olt River, followed by two locations on the Olt River, near Rm.
Valcea town (Daesti and Rm. Valcea dam), in March, and one location in
Calimanesti, in October. The total concentration of inorganic nitrogen (Ntotal) from
the studied samples, which mainly depends of nitrate concentration (N-NO3)
varied between 0.78 and 5.63 mg/L, with an average of 2.49 mg/L.

Figure 3. Correlation of  N with Ntotal and N-NO3ˉ concentrations in the Olt river waters,
15

during the study period (sampling locations: P4 – Calimanesti, P5 – Daesti, P6 – Rm. Valcea, P20 –
Danube (upstream by the Olt River spill in the Danube River))

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Samples with slightly enriched values for δ15N were those from the locations: (i)
P4 (Olt River) in October 2018 (-0.38 ‰), (ii) P5 and P6 (Raul Olt) in March 2018 (-
0.26 ‰, respectively -0.2 ‰), and (iii) P20 (Danube River) in June 2018 (0.62 ‰).
The depleted values recorded for the δ15N may reflect for the inorganic nitrogen
both an agricultural source (chemical fertilizer - δ15N: -6 to 6‰) and atmospheric
precipitation (δ15N: -13 to 13‰), but also soil organic-derived nitrate (δ15N: 0 to
8‰) [Flipse and Bonner, 1985; Kendall, 1998].
NH4 fertilizer, NO3 fertilizer and urea are (in)organic fertilizers produced by fixation
of atmospheric N2 and present little differences in δ 15N content as a result of small
fractionation during subsequent processing of the fixed N. Studies have shown that
following its application, the fertilizer nitrogen becomes intimately involved with
biological transformations in the soil-plant system, and in many cases thereby loses its
isotopic identity by exchange with the large amount of soil organic nitrogen [Flipse and
Bonner, 1985; Heaton, 1986]. In our case, rainfall could also have played a role in
carrying away recently applied fertilizer, due to the low δ15N and N-NO3ˉ values.
A process was assigned as naturally occurring if for a decrease of the total nitrogen
concentration the δ15N enriched, while for an increase of the total nitrogen the δ15N
depleted [Heaton, 1986; Aggarwal, Gat and Froehlich, 2005]. For that a mixing
calculation has to be performed for each sampling month in order to determine the
processes that took place along the Olt River, taking into consideration the flows of the
surface waters and the mean precipitation amounts.
Also, to narrow the sources, a correlation between the δ 15N values and δ18O
in the nitrate ion has to be performed as future work.

Keywords: stable isotopes; inorganic nitrogen species; surface water; pollution

source.

Acknowledgments
This work was supported by the Romanian Ministry of Research, Innovation and
Digitization, grant number PN 19110303 "Advanced techniques for identifying
sources of contamination and biochemical reactions in aquatic ecosystems".

References
Aggarwal P.K., Gat J.R., Froehlich K.F., 2005. Isotopes in the Water Cycle: Past, Present and Future of
a Developing Science. Springer, (2005) 67.
Clark I.D., Fritz P., Environmental Isotopes in Hydrogeology, 2st ed.; CRC Press: New York, NY, USA,
1997; pp. 13–168
Flipse Jr W.J., Bonner F.T., Nitrogen‐isotope ratios of nitrate in ground water under fertilized fields,
Long Island, New York. Groundwater 23.1 (1985): 59-67. https://doi.org/10.1111/j.1745-
6584.1985.tb02780.x
Ging P.B., Lee R.W., Silva S.R., 1996. Water chemistry of Shoal Creek and Waller Creek, Austin Texas,
and potential sources of nitrate. US Geological Survey WRIR 24, (1996) 4196
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Heaton, Tim HE. Isotopic studies of nitrogen pollution in the hydrosphere and atmosphere: a
review. Chemical Geology: Isotope Geoscience Section 59, (1986): 87-102.
https://doi.org/10.1016/0168-9622(86)90059-X
Hoefs J., Stable Isotope Geochemistry. Springer, Berlin (2009).
Popescu R., Mimmo T., Dinca O.R., Capici C., Costinel D., Sandru C., Ionete R.E., Stefanescu I., Axente
D., Using stable isotopes in tracing contaminant sources in an industrial area: A case study on
the hydrological basin of the Olt River, Romania, Science of the Total Environment, 533, (2015)
17. https://doi.org/10.1016/j.scitotenv.2015.06.078
Segal-Rozenhaimer M., Shavit U., Vengosh A., Gavrieli I., Ferger E., Holtman R., Mayer B., Shaviv A.,
Sources and transformation of nitrogen compounds along the lower Jordan River, Journal of
Environmental Quality, 33, (2004) 1440. https://doi.org/10.2134/jeq2004.1440
Xue D., Botte J., De Baets B., Accoe F., Nestler A., Taylor P., Van Cleemput O., Berglund M., Boeckx
P., Present limitations and future prospects of stable isotope methods for nitrate source
identification in surface and groundwater. Water Resources, 2009, 43, 1159-1170.
https://doi.org/10.1016/j.watres.2008.12.048

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USING ISOTOPIC PROFILE OF FRUITS TO DIFFERENTIATE BOTANICAL

ORIGIN – PRELIMINARY DATA

Roxana Elena Ionete, Oana Romina Botoran, Diana Costinel

1
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Corresponding author: [email protected]

Fruit composition is a result of interactions between various factors such as fruit

class/varieties and growing conditions in terms of local climatic influences (e.g.,
temperature, precipitation, insolation), geographic (e.g., altitude, latitude, distance to sea,
slope - for hilly regions) and geological (e.g., soil type, water, water retention in soil, soil
drainage) features. During physical-chemical and biological processes like photosynthetic
fixation, significant fractionation of heavy to light stable isotopes can occur in biological
materials. Plants have enzyme(s) that select against the less abundant and heavier 13C
isotopes relative to 12C isotopes. Temperature, plant type (e.g., C3 versus C4), and the
environment [Costinel et al., 2011; Magdas et al., 2012; Dinca et al., 2014] all have a role in
stable carbon isotope fractionation, therefore plant 13C/12C ratios can vary based on
latitude, location/altitude, and climate (e.g., plants in humid areas take in more CO2 and
develop a lower ratio of 13C to 12C than in arid ones). Furthermore, throughout fruit
growth, hydrogen and oxygen stable isotopes in fruits reflect the plant's environmental
conditions as well as the isotopic composition of the plant's source water [Ionete et al.,
2018]. As a result, stable isotopes have been intensively studied for use in confirming
origin claims. The hypothesis of this study is that classification of grapes, plums, apples,
pears, strawberries, cherries, sour cherries and apricots, in terms of variety origin, year of
production and harvest period, can be improved using stable isotope (D/H by SNIF-NMR,
δ18O and δ13C by CF-IRMS) information fused with 1H and 13C NMR profiles (Fig. 1).

Figure 1. Vintage discrimination of fruits based on isotopic data

18 13 1 13
(D/H - SNIF-NMR, δ O and δ C - CF-IRMS, and H and C-NMR)
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The pooled data from 170 fruit samples from different regions of Romania were
analysed using various multivariate statistical approaches, including principal
component analysis (PCA), discriminant analysis (DA), factor analysis (FA), and analysis
of variance (ANOVA). As part of our preliminary investigations, a separate discriminant
analysis of stable isotope ratios as well as 1H and 13C-NMR spectra was carried out for
all samples analysed in order to obtain specific models to differentiate between types
of fruits, harvest and harvest period. (Fig. 2).

18 13 1 13
Figure 2. Discrimination of fruits by genus – fused information: D/H, O, C and H/ C- NMR data

This approach would be the most appropriate, since it would allow to provide
a clearly differentiation of a fruit sample based on its main characteristics.
However, this first statistical modelling suggestion conduct us to the conclusion
that the variations within the data sets (1H-,13C-NMR spectra and stable isotope
data) are too important to be considered in one vector diagram regarding these
major parameters. The uniqueness of each fruit sample should be examined along
with its main characteristics, such as variety, harvest season (summer, autumn)
and year of production, as the data are influenced by the specificity of the sample.
Expansion of this type of profiling research includes the addition of more
geographic areas, other agronomic practices (organic vs. conventional), and
additional types of fruit.

Keywords: fruits; stable isotopes; NMR.

Acknowledgments: This work is part of the project PN 19 11 03 02 part of the

Research Program „ICSI 4EE” financed by the Romanian Ministry of Research and
Innovation.

References
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Dinca O.R., Ionete R.E., Popescu R., Costinel D., Radu G.L. Geographical and Botanical Origin
Discrimination of Romanian Honey Using Complex Stable Isotope Data and Chemometrics,
Food Analytical Methods, 2014, 8(2):401-412.
Costinel D., Tudorache A., Ionete R.E., Vremera R., The impact of grape varieties to wine isotopic
characterization, Analytical Letters, 2011, 44(18), p 2856-2864.
Ionete RE, Costinel D, Popescu R, Botoran OR, Stable isotope ratio of O‐ H‐C bioelements and its
nd
applicability in verifying the origin of wine, XXII Conference “New Cryogenic and Isotope
Technologies for Energy and Environment” 24–26 October 2018, Băile Govora, Romania, Book
of Abstracts, pp. 211-212.
Magdas D.A., Cuna S., Cristea G., Ionete R.E., Costinel D. Stable isotopes determination in some
Romanian wines, Isotopes in Environmental and Health Studies, 2012, 48(2), p 345-353.

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BRINGING TOGETHER QUANTUM SIEVING PROCESS AND METAL-ORGANIC

FRAMEWORKS TO DEVELOP A NEW HYDROGEN ISOTOPE SEPARATION
TECHNOLOGY

Adriana Marinoiu1, Simona Nica2, Marian Curuia1, Mihai Varlam1

1
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
2
"C D. Nenitzescu" Institute of Organic Chemistry -CCO, Splaiul Independentei 202 B, Bucharest,
Romania
Corresponding author: [email protected]

This work is focused onto bringing together the existing expertise of the
research groups (ICSI Rm Valcea and CCO Bucharest) in hydrogen isotope
separation technologies, cryogenics and metal-organic frameworks (MOF) synthesis
and investigation, in order to develop a laboratory based proof concept for
deuterium gas production, based on an in house developed cryogenic thermal
desorption mass spectrometer.
The scope of this work was to develop a sustainable technology of hydrogen
isotope separation using an adsorbent porous metal-organic framework (MOF).
Although the isotope effect on physical adsorption has been known for many
years, the idea of quantum sieving D2 from H2 was first introduced by Beenakker [J.
J. M. Beenakker, 1995]. The separation is achieved through the difference in the
quantum zero-point energy of the adsorbed isotopologues. Recently, porous
crystalline metal–organic frameworks (MOFs) have emerged as a promising
candidate for H2 purification and isotope separation owing to their designable
porosity and functionality, which affect their molecular sieving effect and the
kinetic and/or chemical affinity quantum sieving effects.
Starting from the original model consisting of a hard sphere potential in a
cylindrical well, various other models were developed such as microporous carbons,
carbon nanotubes or graphene and hexagonal boron nitride based membranes with
improved H2/D2 separation factor [M. Lozada-Hidalgo, 2016]. In this context, metal-
organic frameworks (MOFs) immediately emerge as a superior class of materials for
isotopes separation. They exhibit some of the largest pore volumes and highest
surface areas with permanent porosity and high thermal stability.

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Schematic illustration of cryogenic thermal desorption mass spectrometer (left) and the
in-house existing cryogenic thermal desorption mass spectrometer that is used to develop the new
isotope separation technology on gas phase.

The rational design and synthesis with a judicious choice of metal ions and
organic ligands provide the desired properties and functionality, resulting in a
controlled structural topology, pore size, shape, and surface polarity.
In ICSI group, the low temperature thermal desorption spectroscopy is provided by
a home-built cryogenic thermal desorption mass spectrometer. Basically, this is a
system based on thermal desorption spectroscopy (TDS), obtained as an integration of
low-temperature cryogenic cryo-cooler and of quadrupole mass spectrometer. This is a
versatile set-up for low-temperature TDS since was extended down to very low
temperatures (of about 20-70 K). The technique is capable to measure quantitatively
the desorption of molecular hydrogen storage, which typically exhibits a small enthalpy
of adsorption. This technique was developed to study the interaction between weakly
adsorbed H2 molecules and porous materials.
This work is intended to provide a comprehensive understanding of the
fundamental theories and strategies for MOF-based H2 separation and purification,
including hydrogen isotope separation with representative examples. A key property of
MOFs-based materials for this target is well organized between the two different
materials with different porosities. Furthermore, the specific surface area and the ratio
of MOFs in the matrix are all design considerations for these materials.

Key words: quantum sieving, isotope, porous metal-organic framework, ligand

Acknowledgments: This work was supported by UEFISCDI Contract No.

469PED/2020

References
J. J. M. Beenakker, V. D. Borman, S. Y. Krylov, Chem. Phys. Lett., 1995, 232, 379
M. Lozada-Hidalgo, S. Hu, O. Marshall, A. Mishchenko, A. N. Grigorenko, R. A. W. Dryfe, B. Radha, I.
V. Grigorieva, A. K. Geim, Science, 2016, 351, 68.
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CHEMICAL AFFINITY SEPARATION (CAQS) FOR THE MOF STUDY IN ISOTOPIC

EXCHANGE SEPARATION – TRIAZOLATE-BASED LIGAND SYNTHESIS FOR THE
PRODUCTION OF THE MFU-4L MOF

Adriana Marinoiu1, Simona Nica2, Gheorghe Ionita1

1
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
2
"C D. Nenitzescu" Institute of Organic Chemistry -CCO, Splaiul Independentei 202 B, Bucharest,
Romania
Corresponding author: [email protected]

Currently, H/D separation can be achieved by cryogenic distillation of molecular

species, or by the Girdler-sulfide process. Both processes require high energy costs,
being recognized as one of the most expensive separation methods in the chemical
industry. A possibility with low energy consumption is the use of membranes: (i)
metallic, which ensure mechanical strength as well as selective permeability, being
known Pd membranes and its alloys, eg with Ag, Cu; (ii) porous materials. The use
of porous materials involves 2 mechanisms: sequestration/confinement in small
pores (separation mechanism by quantum-kinetic effect-QS) and chemosorption on
specific centers (separation mechanism by quantum effect by chemical affinity-
CAQS).
Metal-organic network (MOF) materials have a porous structure that can
incorporate transition metals, a structure that can provide the simultaneous
realization of both properties. Copper is considered a key element in the design of
these networks.
To date, only a few experimental studies based on MOF have been reported,
although more promising theoretical and simulation work has been developed on
the quantum-kinetic separation mechanism. Almost all previous experiments on
D/H selectivity were limited to the equilibrium adsorption of pure gas, ie the ratio
n(D2)/n(H2), due to the absence of the direct method for measuring mixtures,
resulting in only a selectivity estimated by kinetic separation (QS).
To elucidate quantum effects, well-designed MOFs should be investigated by a
method that allows direct determination of selectivity after exposure to a mixture
of isotopes under cryogenic conditions (eg at 20-80 K, low pressure). The quantum-
kinetic separation mechanism - the separation of isotopes into nanopores may be
possible when the difference between pore size (d) and molecular size (σ) becomes
comparable to the Broglie wavelength of molecules (λ) when molecules are
restricted in transverse motion in -a given space.
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The first experimental results for the separation of hydrogen and deuterium
using MOF, showed that the diffusivity for D2 was higher than that for H2 at 77 K in
MOF-1 (a mixed Zn-MOF with a bimodal aperture) and attributed this to quantum
effects. However, the diffusivity difference of D2 and H2 at 77 K was quite small
[Kapelewski M.]. In addition, from the analysis of the H2 and D2 isotherms, the
surface interactions with D2 were slightly stronger than the surface interactions
with H2, due to the difference in vibration energy levels.
In quanto-kinetic separation, pore size really plays an important role in
determining diffusion kinetics and therefore separation. Correlation between
isotope separation efficiency and pore hole diameter in four architectures -
different networks of imidazole and MOF type zeolites (COF-1 and COF-102)
showed that the tendency to reach a maximum molar ratio (n D2/n H2) is then when
the opening diameter has been reduced to 3.4 Å. The results obtained on these
MOF systems suggest that the optimal diameter of the holes, for quantum
separation, should be between 3.0 Å and 3.4 Å [Kapelewski M.]. Despite numerous
experimental investigations on KQ, almost all porous networks architectures
showed only physiosorption properties, and the isotopic separation factors were
relatively low.
Alternatively, the chemical affinity separation mechanism for MOF study
(CAQS) has recently been used instead of isotopic. In this respect, MOFs are
excellent candidates for CAQS due to their versatile functionality (ie open metal
sites) produced by incorporating a large number of coordinating unsaturated metal
sites into the network structure.
The behaviour of CAQS in MOF containing an exceptionally high density of
exposed metal cations has recently been explored. A family of types of MOF-74-M
structures (M = Fe, Co, Ni) was used, which have the highest hydrogen adsorption
enthalpies recorded for porous physosorptive materials. Isotherms were measured
over a temperature range of 77-150 K and indicated a significantly higher initial
heat of adsorption of D2 than H2, the largest difference being 1.4 kJ mol-1 (Ni-MOF-
74). The selectivity for D2 was estimated at 77 K, 87 K, 100 K, 120 K and 150 K,
indicating an increase in selectivity from 1.5 to 150 K to 5.0 to 77 K. Infrared
measurements on different types of MOF-74, showed a strong correlation between
the selectivity and the frequency of the translation mode of the adsorbed molecule,
and from here it was confirmed that the separation is predominant even at high
temperatures, due to the difference of zero point energies of isotopes adsorbed at
these related sites [Hyunchul O., 2016].
Although, at the current level of development, many of the practical challenges
remain to be solved, quantum separation by MOFs will be a very efficient way to
separate hydrogen isotopes. The challenges of this stage will obviously be related to
the use of information obtained from the KQS and CAQS study in the field of
isotope separation to create new and efficient porous networks (architectures). In
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particular, porous materials that have both effects (KQS and CAQS) would be
beneficial for the very efficient separation of hydrogen isotopes. For example, a
cleverly designed porous material could be a core-shell MOF with sufficiently flexible
holes and numerous open metal sites (inner part). Therefore, a flexible opening would
increase the absorption of D2 from H2, resulting in an enriched deuterium concentration
inside the MOF. Then, strong binding sites would selectively capture deuterium, leading
to increased selectivity. In this stage, the synthesis strategies regarding the obtaining of
porous networks type MOF will be presented.
D/H separation is a difficult task because the dimensions shape and
thermodynamic properties of isotopes are similar. Quantum-kinetic separation (QS)
and quantum separation by chemical affinity (CAQS) will be explored for the separation
of hydrogen isotopes using MOF structures due to orifices precisely adjusted the
morphology and functionality of these porous networks. This new class of porous
networks has recently opened up new avenues for the efficient separation of hydrogen
isotopes. The correlation between the molar ratio D/H and the pore size of the
different types of MOF shows that the molar ratio is strongly dependent on the pore
size, pressure and temperature at which it determines the separation.
MOF structures possess strong binding sites (10-14 kJ mol-1 for hydrogen on
open metal sites) and showed a significantly higher adsorption enthalpy for D 2 over
H2 at the open metal site (approx. 1-2 kJ mol). The strong attraction between
unsaturated metal centers and hydrogen isotopes keep these sites occupied at
relatively high temperatures (even above 77 K). Therefore, the strongly bound sites
lead to large differences in the adsorption enthalpy between the isotopes, which in
turn cause high separation factors at temperatures above 77 K. The highest
reported separation efficiency of a D2/H2 equimolar mixture in MOF by CAQS, it
showed a selectivity of 11.8 at temperatures of 60 K and pressure of 30 mbar.
Moreover, the selectivity showed a rather high value of SD2/H2 ≈6.3 even above the
temperature of liquid nitrogen (80 K and 30 mbar) [Weinrauch I., 2017].
The use of MOFs in CAQS presents encouraging prospects with high selectivity
at relatively high operating temperatures to achieve efficient separation of
hydrogen isotopes. Moreover, CAQS with MOF showed that deuterium can be
easily enriched in a temperature range from 80 to 110 K. These results demonstrate
the high potential of MOF for application in the separation of hydrogen isotopes.

Triazolate-based ligand synthesis for the production of MFU-4l MOF

According to recent literature, MOF-type porous structures are suitable for
hydrogen isotope separations. The detailed analysis of the specialized articles
highlights the fact that the most versatile MOF type structures are those built from
benzobistriazole type derivatives and [Zn5Cl4]6+ type units.
These porous structures have high thermal stability, but also hydrolytic
stability. Due to the cavity of about 2.5 A, these structures are selective for the
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adsorption of small molecules such as H2 and, consequently, can be used as

"molecular sieving", a property less common in other porous structures.
MOF-4l (arge) type structures constructed using bridges bis (1H-1,2,3-triazolo
[4,5-b], [4',5'-i]) dibenzo [1,4] dioxin (H2-BTDD) leads to isoreticular structures that
can be used to store hydrogen by physisorption phenomena.

Objective 2021: to synthesize the structure of MOF-4l.

The organic ligand type bis (1H-1,2,3-triazolo [4,5-b], [4',5'-i]) dibenzo [1,4]
dioxin (H2-BTDD) was synthesized starting form dibenzo [1,4] dioxin (commercially
available). This is done on a laboratory scale, through a sequence of three organic
reactions with the isolation, purification and characterization of each reaction
product of this sequence.

Short description:
In a first stage, the nitration reaction of dibenzo [1,4] dioxin is carried out with a
mixture of fuming nitric acid / trifluoroacetic anhydride in order to carry out the
nitration reaction in all positions with the obtaining of 2,3,7,8- tetranitrodibenzo
[1,4] dioxin with an estimated yield of about 73%.

In order to achieve the cyclization reaction to obtain the proposed triazole

derivative, this compound 2,3,7,8-tetranitrodibenzo [1,4] dioxin will be reduced
with Sn/HCl, a versatile hydrogenation reagent to reduce aromatic nitroderivatives
to the corresponding amines.

2,3,7,8-tetraaminodibenzo [1,4] dioxin obtained previously is subjected to

diazotization in acid medium to give bis (1H-1,2,3-triazolo [4,5-b], [4',5'-i]) dibenzo
[1,4] dioxin (H2-BTDD) in yields above 65%.

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MFU41 can now be obtained either by solvothermal reactions or by microwave

by the reaction between bis (1H-1,2,3-triazolo [4,5-b], [4',5'-i]) dibenzo [1,4] dioxin
and zinc chloride in dimethylformamide.
MFU-4l is described as a microcrystalline powder with crystal sizes between 1
and 5 μm.

Key words: chemical affinity separation, MOF, triazole derivative microwave

Acknowledgments: This work was supported by Ministry of Research, Innovation,

Digitization from Romania by the National Plan of R & D, Project No. PN 19 11 01 03

References
Kapelewski M. T., S. J. Geier, M. R. Hudson, D. Stuck, J. A. Mason, J. N. Nelson, D. J. Xiao, Z. Hulvey, E.
Gilmour, S. A. FitzGerald, M. Head-Gordon, C. M. Brown, J. R. Long, J. Am. Chem. Soc., 136,
2014, 12119-12129
Hyunchul Oh, Michael Hirscher, Quantum Sieving for Separation of Hydrogen Isotopes Using MOFs,
Eur. J. Inorg. Chem., 2016, 4278-4289
Weinrauch I., I. Savchenko, D. Denysenko, S.M. Souliou, H.-H. Kim, M. Le Tacon, L.L. Daemen, Y.
Cheng, A. Mavrandonakis, A.J. Ramirez-Cuesta, D. Volkmer, G. Schutz, M. Hirscher, T. Heine,
Nat. Commun., 8, 2017, 14496

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INTERPRETATION OF ISOTOPIC DATA FOR GROUNDWATERS IN THE OLĂNEȘTI

AREA COMPARISONS WITH OTHER CARPATHIAN ZONES.

Delia Cristina Papp1, Laurentiu Asimopolos1,

Violeta Carolina Niculescu2, Natalia-Silvia Asimopolos1
1
Geological Institute of Romania, 1st Caransebeş Street, 012271 – Bucharest, Romania.
2
National Research and Development Institute for Cryogenic and Isotopic Technologies—ICSI Rm.
Valcea, Uzinei Street, No. 4, P.O. Box 7 Raureni, 240050 Valcea, Romania
E-mail address of presenting author: [email protected]
Corresponding author: [email protected]

ABSTRACT
The research activities consisted in the inventory of isotopic and geochemical
data for mineral and geothermal waters belonging to the Olanesti resort, in order
to define their origin, genetic relationships and underground dynamics in the
geological context of the Getic Depression. Comparative study with other
Carpathian zones (i. e. Harghita – Covasna, Apuseni Mountains, Pannonic Basin,
Transylvanian Basin, and External Flysch) has also been performed.
Mineral springs, boreholes and surface water in the area are the main types of
water taken into consideration. The database includes measurements of deuterium
concentration (δD (‰)) and total salt content (∆d (mg/l)), expressed as the
difference in density between a standard distilled water and the water sample. For
the mineral waters from the Olănești resort, the database also includes chemical
analyzes of Li, Na, K, Mg, Ca, and Sr. The analyzes were performed by the National
Research and Development Institute for Isotopic and Molecular Technologies, Cluj-
Napoca [Blaga et al., 1975, 1977, 1978, 1979; Blaga & Florian, 1984], and detailed
statistical analyses was performed within the PN 09 21 03 06 project [Papp, 2014].
In the Getic Depression, the hydromineral deposits genetically belong to the
Eocene and Miocene formations. Mineral waters have a predominant sulfurous and
chlorosodic character [Pricăjan, 1985]. The mineral waters have allowed the
development of several spas, of which the most important are those on the Olt Valley,
respectively Căciulata, Călimănești, Olănești and Govora [Roanghes-Mureanu, 2012].
The main features that define the hydrogeological conditions of the Getic
Depression are [Pascu, 1981]: the development of coarse detrital rocks in the
Badenian - Villafranchian stratigraphic interval; moderate relief energy; the absence
of eruptive formations; the absence of post-volcanic manifestations; a quiet
tectonic framework, with anticlines and synclines in the northern-central area, and
a monoclinal style in the rest of the depression; the existence of areas of
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neotectonic subsidence, which have led to the occurrence of hydrographic

convergences: widespread of alluvial cone deposits; in some areas, where rivers
flow on Pliocene sands or Cândești gravels, they lose part of their flows, and
sometimes dry out completely; Pliocene deposits contain important reserves of
groundwater under pressure; locally, the presence of evaporites determines high
mineralization of groundwater; due to the presence of hydrocarbon deposits,
associated waters with very high mineralization, as well as thermal waters occur.
The main types of hydrogeological structures (Fig. 1) in the Getic Depression
are: alluvial structures, including terraces and alluvial cone deposits; hydro-
structures, fed by the discharge of hydrocarbon structures and from the
hydrographic network; deep hydro-structures in Miocene - Pliocene granular
formations (waters under pressure having an artesian character).
The Olănești hydrothermal deposit is located in the Olănești river basin, at the
morphostructural contact between the Căpățânii Mountains and the sub-
Carpathian hills of Oltenia (Olănești hills). It currently functions as one of the most
important spas in the Getic sub-Carpathian area [Oprea, 2009]. From a geological
point of view, the resort is located in the Getic Depression, consisting of monoclinal
sedimentary formations of Upper Cretaceous, Eocene and Oligocene over the
metamorphic formations of the Southern Carpathians. The mineral waters in the
area are accumulated in the Eocene and Oligocene conglomerates, as well as in the
Senonian sandstones (Pricăjan, 1985). Groundwater circulation took place on the
fault system, as well as on the stratification surfaces, and its ascent is favored by
the presence of gases, mainly methane. In the Olănești area, the hydromineral
deposit is exploited through over 30 springs and several drillings.

Figure 1. Geological map of Romania, scale 1:200000 showing the study area
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The main types of mineral waters are [Pricăjan, 1972]: sulphurous, bicarbonate,
sulphated, sodium, calcium, magnesium waters with a total mineralization of 500 -
1000 mg/l and H2S content between 0.1 and 9 mg/l; sulfurous, chlorinated,
bicarbonate, sodium waters with a total mineralization of 1300 mg/l; sulfurous,
chlorinated, brominated, iodinated, sodium, calcium, magnesium waters, found in
most boreholes in the area, with a mineralization between 1500 and 3000 m/l and an
H2S content varying between 5 and 20 mg/l.
Hydrogeological, hydrochemical and isotopic studies [Blaga et al., 1977, 1978, 1979]
showed that the mineral waters from Olănești are of deep origin, such as formation
waters, in different stages of dilution with surface waters. The formation waters, highly
mineralized (sulfurous, chloro-sodium, bromo-iodinated, ammoniacal, with low sulfate
content) is mixed in different proportions with water of meteoric origin, accumulated in
the Eocene conglomerates or Senonian sandstones with increased sulphates content.
Based on δD data, three components have been identified: local infiltration waters,
especially from the Olăneşti Valley, waters from high altitudes, and deep formation
waters. The presence of H2S is an important characteristic of the mineral waters from
Olănești. The H2S is considered of organic origin, resulting from the reduction of sulfates
by specific anaerobic bacteria in the presence of hydrocarbons.
The mean values of D and total salt content of groundwater from Olănești
area as compared to groundwaters from different Carpathian areas are ploted in Fig 2
(data from Papp, 2014). It shows that the groundwater in the East Carpathians
(Harghita - Covasna and Sângeorz Băi area) are characterized by the lowest D values
(between -77 ‰ and -75 ‰) compared to other Carpathian areas, suggesting that
these waters originate mainly from infiltrations at high altitudes. The total salt content
is between 1778 mg/l and 2374 mg/l. Groundwater in the Pădurea Craiului Mountains
area and those in the Pannonian Basin (Băile-Felix Oradea) are characterized by slightly
higher D values (-72 ‰ and -67 ‰) but have much lower salinities (<1700 mg/l).
Groundwater in the deposits of the Pannonian Basin (Oradea-Satu Mare), the Getic
Depression (Olănești, Călimănești-Căciulata, Govora) and the External Flysch (Slănic
Moldova) show D values for waters from the meteoric cycle (-66 ‰ to - 60 ‰), and
the total salt content of this waters is high (> 3100 mg/l).

Figure 2. Plot of the mean values of D and total salt content of groundwater in
different Carpathian areas

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Fossil waters differ in terms of isotopic composition and total salt content from
one area to another (Fig. 3). The formation waters from Bazna (Transylvanian Basin)
display the highest D values and of total salt content (δD = -8.7 ‰ and Δd =
39800.3 mg/l). These values are typical values for formation waters, unaltered or
altered in a very small proportion by the mixture with surface waters. The salt
waters from the Transylvanian Basin, whose salinity comes from the dissolution of
salt deposits, display total salt content values similar to those from Bazna, but their
δD values are lower, falling within the variation range of other formation waters in
the the Getic Depression, Eastern Carpathians (Harghita - Covasna, Sângeorz Băi),
and the Pannonian Basin (δD = -43.5 ‰ ÷ -33.5 ‰).
The application of isotopic and geochemical methods in the study of
groundwater and in particular of mineral and geothermal waters, as well as the
unitary interpretation of results in a geological, hydrogeological and geothermal
context brings important clarifications regarding the origin and genesis of waters,
input zones and recharge mechanisms, determination of residence times and
underground flow rates, as well as estimation of mixing relationships between
different adjacent aquifer systems. From a genetic point of view, groundwater is a
mixture in varying proportions between two basic components. The origin of these
two components is markedly different; on the one hand there is the syngenetic
component, such as formation water or fossil water, and the current component
represented by the infiltration into the ground of some waters with an isotopic
composition similar to the surface waters of meteoric origin. As such, knowledge of
the isotopic composition of surface water and those from precipitation is
indispensable in assessing the replenishment of groundwater aquifers.

Figure 3. Plot of the mean values of D and total salt content of formation
water in different areas from Romania

Key words: hydrothermal deposit, hydrogeological structures, geochemical

data, isotopic research

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Acknowledgments: We thank for support by the Ministry of Research for

financing of the project “The realization of 3D geological / geophysical models for
the characterization of some areas of economic and scientific interest in Romania”,
with Contract no. 28N / 2019.

References
Blaga, L., Blaga, M.L., Ciobotaru, T., Feurdean, V., „Studiu bazat pe măsurători de concentrație a
deuteriului din apele mineral din zona Călimănești - Căciulata”, raport la contractul de
cercetare ITIM Cluj-Napoca nr. 780/1977 si nr. 366/1979.
Blaga, L., Blaga, M.L., Ciobotaru, T., Feurdean, V, Bindea, C., Florian, M., „Studiu bazat pe determinări
de concentrație a deuteriului din apele termominerale, freatice si de suprafață din perimetrul
stațiunii Olănești”, rapoarte la contractul de cercetare ITIM Cluj-Napoca nr. 767/1977-1978-
1979.
Blaga, L., Blaga, M.L., Ciobotaru, T., Feurdean, V., Studiu bazat pe măsurători de concentrație a
deuteriului din apele termominerale din zona stațiunilor balneo-climaterice ale județului
Vâlcea, raport la contractul de cercetare ITIM Cluj-Napoca nr.593/1975.
Blaga, L.M., Florian, M. 1984. Contribuţii la studiul hidrogeologic al zăcământului hidromineral
Olăneşti cu ajutorul izotopilor stabili, St. tehn. econ. Inst. Geol. Geof., Seria E, 14, p. 63-84, Inst.
Geol. Geof., Bucureşti.
Oprea, M. 2009. Băile Olănești. Studiu de geografia turismului. Teza de doctorat, Univ. de Vest,
Timișoara.
Papp, D.C. 2014. Caracteristici izotopice ale apelor minerale din zona subcarpatica (Călimănești-
Căciulata, Olănești, Govora), Raport de cercetare la proiectul: PN 09 21 03 06 (Faza 14), arhiva
I.G.R.
Pascu, M. 1981. Apele subterane din Romania. Ed. Tehnica, Bucuresti.
Pricajan A. 1972. Apele minerale şi termale din România, Editura Tehnică, Bucureşti.
Roanghes-Mureanu, A-M., 2012. The Environmental Impact of Tourist Activities Performed in the
Spa Resorts of Vâlcea Subcarpathians, Analele Univ. Buc., Geografie, LXI, 147-157.

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DETERMINATION OF PESTICIDE RESIDUES IN HONEY: A PRELIMINARY STUDY

FROM VARIOUS ROMANIAN HONEY PRODUCERS

Diana Popescu (Stegarus)1, Corina Ciucure1, Cristea (Iancu) Ramona2, Ecaterina

Lengyel2, Violeta Niculescu1
1
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI
Ramnicu Valcea, 4th Uzinei Street, 240050 Ramnicu Valcea, Romania
2
Lucian Blaga University of Sibiu, 9th Victoriei Street, 550024, Sibiu, Romania;
Corresponding author: [email protected]

Pesticides, used for bees care or in crop fields in the neighborhoods, can have
negative effects on the health of bees and humans, inducing a decrease of the
antimicrobial properties of the honey. Pesticide residues should be lower than the
maximum residue level. For that reason, investigation of pesticides in honey is vital,
since the use of chemical solutions has “rise up” significantly, due to the increased
demand for food production. [Calatayud-Vernich P. et al., 2016] Our aim was to
investigate the level of pesticides from various honey types (α-HCH, β-HCH, δ-HCH,
aldrin, dieldrin, endrin, DDE, DDD, and DDT, alpha -Endosulfan, carbofuran, pirimicarb)
by gas chromatography coupled with electron capture and to determine the source of
contamination, whether is from environment and/or beekeeping practices.
The maximum allowed level for pesticides such as alpha HCH, beta HCH, HCH range,
Aldrin, Alpha Endosulfan, Dieldrin, Endrin is 0.01 mg/kg is and the maximum level for
DDD, DDT, DDE, Carbofuran and Pirimicarb is 0.05 mg/kg [Commission Regulation, 2015].
The honey samples were collected from 5 areas of Romania (from private
production) in the period July-September 2020. All 18 polyflora honey samples
belong to the conventional type of production and they are stationed on the
territory of Sibiu, Valcea, Olt, Constanta, Dolj (Fig.1).

Figure 1. Romanian regions from where the analyzed honey was collected

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Table 1. Pesticides concentration identified and quantified in the polyflora honey samples from
Sibiu, Vâlcea, Olt, Constanța and Dolj (mg/kg)
Alfa
Sample alpha HCH beta HCH gama HCH Aldrin Endosulfa pp DDE Dieldrin Endrin pp DDD pp DDT Carbofuran Pirimicarb
n
S1 nd nd 0,0367 nd nd nd nd nd nd nd nd 0,074
S2 nd 0,0215 nd nd nd 0,33 nd nd nd nd nd nd
S3 nd nd nd nd nd nd nd nd 0,018 nd nd 0,059
S4 nd nd nd nd nd nd nd nd nd nd 0,0169 nd
V1 nd nd 0,0157 nd 0,0171 nd nd nd nd nd nd nd
V2 0,0278 0,0221 nd 0,0642 nd nd 0,0606 nd nd nd 0,0209 nd
O1 0,0206 nd nd nd 0,0573 nd nd nd nd 0.0096 nd nd
O2 nd nd nd 0,0174 nd nd nd nd nd nd 0,0211 nd
O3 nd nd 0,0371 nd nd 0,328 nd nd nd nd nd nd
O4 nd 0,0215 0,038 nd nd nd nd nd nd nd nd 0,0215
C1 nd nd 0,0354 nd nd nd nd nd nd nd nd nd
C2 nd nd 0,0362 nd 0,0188 nd 0,0211 nd nd nd 0,0351 nd
C3 0,0284 0,0222 nd nd nd nd nd nd nd nd nd 0,0176
C5 0,0298 nd nd nd nd nd nd nd 0,0177 nd nd nd
D1 0,0302 nd nd nd nd 0,0327 nd nd nd nd nd nd
D2 nd nd nd 0,0173 nd nd 0,0199 nd nd nd nd nd
D3 nd nd 0,0759 0,0205 0,069 nd nd nd nd nd 0,0185 nd
D4 nd 0,0319 nd nd nd nd nd nd nd nd nd 0,0163

Following the performed determinations, one concludes that bee honey may
present an accumulation of metals, these lying within the limits approved by the
applicable standards. The reason for fact that the resulted values are low can be
that the honey was harvested from areas with a low pollution level, or from less
industrialized areas. The pesticides generally presented oscillating values. The
situations in which these exceeded the maximum admissible limits can be explained
by the improper use thereof, and a more attentive rationalization and a correct
information of land farmers are mandatory. The areas with the best quality results
out of this point of view were Sibiu and Vâlcea, and the most significant pesticide
concentrations were identified in the area of Constanța. The established values are
but not dangerous for the human body, as the limits were generally only exceeded
by four decimal places.

Key words: pesticides, honey, GC/ECD, contamination

Acknowledgments: Project PN 19110302 “Research on the variation trends

specific to stable isotopes in different tree species: deepening the fractionation
mechanisms and the chemical processes interconnected on the soil–water–plant
chain”.

References
Commission Regulation, 2015. (EU) 2015/1005 of 25 June 2015 amending Regulation (EC) No 1881/2006 as
regards maximum levels of lead in certain foodstuffs. https://eur-lex.europa.eu/eli/reg/2015/1005/oj.
Calatayud-Vernich P., Calatayud F., Simó E., Suarez-Varela M.M., Picó Y., 2016. Influence of pesticide
use in fruit orchards during blooming on honey bee mortality in 4 experimental apiaries. Sci
Total Environ. 541: 33-41.
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CHEMICAL PROFILE, ANTIMICROBIAL ACTIVITY OF ESSENTIAL OIL AND ELEMENTAL

COMPOSITION OF DILL (ANETHUM GRAVEOLENS L.) PLANTS GROWING IN
MOLDOVA

Violeta Popescu

Moldova State University, A. Mateevici str. 60, MD-2009, Chisinau, Republic of Moldova
Corresponding author: [email protected]

In recent years, the cultivation sector of hetero-oleaginous, medicinal and

aromatic plants in the Republic of Moldova is developing intensively. Especially,
lavender (Lavender angustifolia L.), sage (Salvia sclarea L.), coriander (Coriandrum
sativum L.), dill (Anethum graveolens L.) and lovage (Levisticum officinale WDJ
Koch) are cultivated and subjected to industrial processing. To date, several
scientific papers were published on the mentioned species, cultivated in the
Republic of Moldova, less about dill [Popescu, 2018-2021].
The specie belongs to fam. Umbelliferae and is native to the Mediterranean
and Western Asia, and is used as a spice and medicinal plant. GC-MS analysis of
industrially obtained dill volatile oil samples showed the presence of twenty-six
components, representing 99.40% of its total composition. The terpenic fraction
(99.40%) includes monoterpene hydrocarbons (51.28%), among which -
phellandrene (21.47%) and D-limonene (26.86%) are highlighted. Their oxygenated
derivatives constitute (47.80%), the main components being dill ether (12.16%) and
S-(+)-carvone (31.72%). The least numerous are sesquiterpenoids (0.32%), the most
abundant being germacrene D (0.13%).
The antimicrobial assessment of dill essential oil on Bacillus subtilis,
Pseudomonas fluorescens and Candida utilis showed its moderate activity.
The concentration of 36 major and trace elements was determined using
neutron activation analysis (NAA) in all morphological parts of A. graveolens L.
plants. The roots are highlighted by a higher mineral content, listed in descending
order: Al> Fe> Ti> Cr> V> Ce> La> As> Co> Th> Hf> Sc> Sm> Cs> Yb> Sb> Ta> Tb> Eu.
The elemental composition of the leaves is as follows: Ca> Na> Mg> Cl> Sr> Mn> Ba.
The Se content is comparative in leaves and inflorescences (0.33 mg/kg and 0.35
mg/kg, respectively). By comparing the concentrations of As, Br, Fe, Hf, Na, Sc, Se,
Ta, Th, Ti and V in roots and reference plant (RP), it was found that it is at least five
times higher. The content of Br, Na, Se and Th is also higher in all studied organs of
dill plants, as follow: for Br – inflorescences> leaves> stems> roots; Na – leaves>
stem> roots> inflorescences; Se – leaves = inflorescences> roots> stem; Th – roots>

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leaves> inflorescences> stem. In addition, it was observed that in the leaves of A.

graveolens, the Hf and Ta content was eight times and twenty times higher than in
the RP.

References
Ciocarlan A., Dragalin I., Aricu A., Lupascu L., Ciocarlan N., Popescu V. Chemical composition and
antimicrobial activity of the Levisticum officinale W.D.J. KOCH Essential Oil. Chemistry Journal of
Moldova, 2018, 13(2), 63-68.
Popescu V. Compoziţia chimică şi activitatea antimicrobiană a uleiului volatil de Salvie tămâioasă
(Salvia sclarea L.) produs în Republica Moldova. Conferinţa ştiinţifică a doctoranzilor. Tendinţe
contemporane ale dezvoltării ştiinţei: viziuni ale tinerilor cercetători. Ediţia a IX-a, 10 iunie,
2020, 87-91.
Popescu V. Compoziţia chimică şi activitatea antimicrobiană a uleiului volatil de Coriandru
(Coriandrum sativum L). Conferinţa ştiinţifică a doctoranzilor. Metodologii contemporane de
cercetare şi evaluare. 22 – 23 aprilie, 2021, 1-6.
Ciocarlan A., Hristozova G., Aricu A., Dragalin I., Zinicovscaia I., Yushin N., Grozdov D., Popescu V.
Determination of the elemental composition of aromatic plants cultivated industrially in the
Republic of Moldova using neutron activation analysis. Agronomy, 2021, 11, 1011-1030.
Ciocarlan A., Lupascu L., Aricu A., Dragalin I., Popescu V., Geana E.-I., Ionete R.E., Vornicu N., Duliu
O.G. Hristozova G., Zinicovscaia I. Chemical composition and assessment of antimicrobial
activity of Lavender essential oil and some by-products. Plants 2021, 10, 1829-1843.

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BIOACCUMULATION OF HEAVY METALS IN DIFFERENT FISH

SPECIES FROM OLT RIVER, ROMANIA

Claudia Sandru, Mihaela Iordache, Andreea Iordache, Ramona Zgavarogea,

Roxana Ionete

National Research and Development Institute for Cryogenics and Isotopes Technologies - ICSI
Ramnicu Valcea, 240050 Rm. Valcea, Romania
Corresponding author: [email protected]

Heavy metals pollution in aquatic environment has a significant adverse effect

for biota especially in vertebrates, fishes. This study was carried out to provide
information on heavy metal concentrations in the muscles of four fish species
available in Olt River, Romania and to evaluate the possible risk associated with
their consumption. The concentrations of Cd, Pb, Cu, Ni, Zn, Hg, Cr, Al and As were
determined in the muscles of Rutilus rutilus, Perca fluviatilis, Carasius gibelio and
Silurus glanis.
The heavy metal concentrations found in muscles varied for Cd: 0.0002-0.0139,
Pb: 0.0027-12.8706, Cu: 0.047-0.881, Ni: 0.0014-0.0585, Zn: 0.673-18.566, Hg:
0.002-0.174, Cr: 0.174-0.891, Al: 0.108-1.782 and As: 0.0007-0.5548 mg/kg wet
weight.
Estimated daily intake (EDI) and target hazard quotient (THQ), assessed for
potential human health risk implications, suggest that the values were within the
acceptable threshold for adults. Target hazard quotient for children was greater
than 1 for mercury in muscle of Silurus glanis and arsenic in muscles of Carasius
gibelio and Rutilus rutilus. Bioconcentration factors (BCFs) were significantly
different for different metals. The BCF study revealed the ability of fishes to
accumulate Cu, Cr, As, Hg and Pb.

Key words: heavy metals, bioconcentration factor, estimated daily intake,

accumulation, fish

Acknowledgments: This work is part of the project PN 19110303 “Advanced

techniques for identifying sources of contamination and biochemical reactions in
aquatic ecosystems” financed by the Romanian Ministry of Research and Innovation.

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RED & BLUE – COMPUTATIONAL INSIGHTS ON ECOTOXICOLOGY AND POTENTIAL

TREATS AGAINST AQUATIC ECOSYSTEMS

Radu Tamaian1, Violeta-Carolina Niculescu1

National Research and Development Institute for Cryogenic and Isotopic Technologies—
ICSI Rm. Valcea, Uzinei Street, No. 4, P.O. Box 7 Raureni, 240050 Valcea, Romania
Corresponding author: [email protected]

Basic Red 5 (BR5), also known as neutral red, and Nile Blue A (NBA) are two
dyes widely used worldwide since past century. BR5 is mainly used as dye in textile
and leather industries and analytic chemistry [Ghica and Brett, 2008; Gürkan et al.,
2015; Mikaelyan et al., 2001]. Moreover, BR5 is one of the most used (vital) steins
in bio-medical and environmental sciences [Mehlhorn, 2016; Repetto et al., 2008],
being also used in applied sciences, such us nanotechnology [Carvalho et al., 2010;
Wang et al., 2009] and (bio)sensor technology [Carvalho et al., 2010; Ericson et al.,
2021; Ghica and Brett, 2008; Stepanova et al., 2017]. NBA is traditionally used as
fluorophore for sensing application in biology and medicine [Bobo et al., 2021; Ju et
al., 2005; Terpetschnig and Wolfbeis, 1998] and, more recently, started to be used
in materials science [Duan et al., 2015; Martinez and Henary, 2016] and forensic
science (Alsolmy et al., 2020). Both compounds are registered at European
Chemicals Agency (ECHA) and, under the Classification and Labelling Inventory
(CLI), BR5 is already classified as a dangerous compound (GHS08: Serious health
hazard, GHS07: Health hazard, and GHS06: Acute toxicity) [ECHA, 2021a],
meanwhile for NBA no hazards have been yet officially registered [ECHA, 2021b].
However, a quick study of literature data indicates more (eco)toxicological concerns
and environmental risks than those registered in CLI, both for BR5 (Kastury et al.,
2015) and NBA [Gattuso et al., 2016; Hirakawa et al., 2014], therefore further
studies are required to have a more comprehensive global image concerning those
aspects.
In this respect, it was performed an ecotoxicology computational screening of
the two dyes with the help of OECD (Organisation for Economic Co-operation and
Development) QSAR Toolbox 4.3 [Dimitrov et al., 2016; Mombelli and Pandard,
2021; Schultz et al., 2018; Yordanova et al., 2019a, 2019b] – “a software application
intended to the use of governments, chemical industry and other stakeholders in

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filling gaps in (eco)toxicity data”1 to identify more potential risks/hazards of those

two dyes – especially in the aquatic ecosystem.
The computational screening of BR5 and NBA predicted a series of risk and
hazards issues, which can be grouped as following: (1) toxic hazard, (2) DNA,
protein and estrogen receptors (ERs) binding, and (3) aquatic toxicity.
In concordance with literature data [Kastury et al., 2015] and CLI (ECHA,
2021a), BR5 was identified as a compound with a high toxicity (Class III) using both
the classic decision tree approach [Cramer et al., 1976] and an extended
implementation toxicity scheme implemented in QSAR Toolbox 4.3. Moreover, NBA
was also classified as a compound with a high toxic hazard (Class III) using the same
scenarios used for BR5, despite the fact NBA isn’t yet classified as a dangerous
compound in CLI (ECHA, 2021b) – the predictions being in consent with literature
data [Gattuso et al., 2016].
Both dyes were classified a DNA binders – prediction being in concordance
with literature data in case of NBA [Hirakawa et al., 2014] and a new finding in the
case of BR5 (based on the QSAR approach implemented in software). Similarly,
based on the specific QSAR approaches implemented in databases of QSAR Toolbox
4.3, NBA and BR5 were classified as protein binders (dangerous compounds for all
aquatic lifeforms with proteome).
Moreover, NBA and BR5 were classified as strong ERs binders using a complex
set of predictive scenarios (Table 1).

Table 1. Predictions for binding of the estrogen receptors

Estrogen Receptor Binding
BR5 NBA
Predictive Tool
ERs binding (standard evaluation) Strong binder, –NH2 group Strong binder, –NH2 group
ERs binding, with tautomerism Strong binder, – NH2 group Strong binder, –NH2 group
ERs binding, with autoxidation
Strong binder, – NH2 group Strong binder, –NH2 group
simulator (alkaline medium)
ERs binding, with hydrolysis
Strong binder, – NH2 group Strong binder, –NH2 group
simulator (acidic)
ERs binding, with observed
Strong binder, – NH2 group Strong binder, –NH2 group
microbial metabolism
ERs binding, with autoxidation
Strong binder, – NH2 group Strong binder, –NH2 group
simulator
ERs binding, with observed
Strong binder, – NH2 group Strong binder, –NH2 group
mammalian metabolism

Binding of ERs may have a tremendous detrimental impact because they not
only regulate the activity of different genes (e.g.: DNA-binding transcription factor),
but also can affect the endocrine system and plays a critical role in sexual

1
https://www.oecd.org/chemicalsafety/risk-assessment/oecd-qsar-toolbox.htm (last accessed on 30/09/2021)
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maturation and gestation – therefore a massive decrease of specimens from a

particular species can have a negative impact over an entire aquatic ecosystem.
Additional aquatic toxicity risks were identified using QSAR models based on
structural alerts and problematic moieties contained by BR5 (more risks and
hazards) and NBA (less risks and hazards) (Table 2).
Table 2. Predictions for aquatic toxicity (AqT)
AqT Classification Schemes BR5 NBA
AqT classification by ECOSAR Anilines (Hindered) Vinyl/Allyl Ethers
AqT classification by ECOSAR, with Anilines (Hindered);
Vinyl/Allyl Ethers
tautomerism Aliphatic Amines;
Reactive unspecified
Acute AqT MOA by OASIS Reactive unspecified
Phenols and Anilines
Phenols and Anilines;
Acute AqT MOA by OASIS, with
Basesurface narcotics; Reactive unspecified
tautomerism
Narcotic Amine
Acute AqT classification by Verhaar Class 5 (not possible to classify
Class 2 (less inert compounds)
(modified) according to these rules)
Class 2 (less inert compounds);
Acute AqT classification by Verhaar Class 5 (not possible to classify
Class 1 (narcosis or baseline
(modified), with tautomerism according to these rules)
toxicity)
ECOSAR = Ecological Structure Activity Relationships Predictive Model developed by U.S. EPA
[https://www.epa.gov/]; MOA = Mode of Action; OASIS = classification scheme developed by LMC-
OASIS [https://oasis-lmc.org]; “Verhaar (modified)” = modified classification scheme [Enoch et al.,
2008] based on the Verhaar classification framework [Verhaar et al., 1992].

In conclusion, more wet-lab test and environmental sampling of living

specimens form aquatic ecosystems affected by pollution with those two dyes are
required to update the InfoCards of BR5 and NBA from CLI.

Key words: computational ecotoxicology, dyes, Neutral Red, Nile Blue, pollutants.

Acknowledgments: The work has been funded by the Romanian Ministry of

Research Innovation and Digitalization, NUCLEU Program-Financing Contract no.
9N/2019, under Project PN 19 11 03 01 “Studies on the obtaining and improvement
of the acido-basic properties of the nanoporous catalytic materials for application in
wastes valorization”.

References
Alsolmy, E., Abdelwahab, W.M., Martinez, V., Henary, M., Patonay, G., 2020. Investigation of
benzophenoxazine derivatives for the detection of latent fingerprints on porous surfaces. J.
Photochem. Photobiol. A Chem. 392, 112416.
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Repetto, G., del Peso, A., Zurita, J.L., 2008. Neutral red uptake assay for the estimation of cell
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ADAPTING DIRECT CO2 ABSORPTION METHOD FOR RADIOCARBON

MEASUREMENT OF THE ENVIRONMENTAL SAMPLES

Irina Vagner, Carmen Varlam, Denisa Faurescu, Diana Bogdan, Ionut Faurescu
1
National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Corresponding author: [email protected]

The CO2 direct absorption method and liquid scintillation counting (LSC) are
methods used in radioactivity monitoring programs of nuclear facilities for 14C
measurements due to high number of samples and relatively high expected level of 14C
concentration, more than 226 Bq/kg C [IRSN, 2012]. The paper describes the chemical
sample preparation applied to a quality control material (IAEA-C3 cellulose), in order to
adjust CO2 absorption method for radiocarbon measurements of the environmental
samples [Vagner et al., 2017].
The preparation steps involved: combustion of the material in a combustion Parr
bomb type 1121, bubbling of the combustion gasses directly through the scintillation
cocktail for CO2 absorption, and bubbling of the combustion gases through a sodium
hydroxide aqueous solution, followed by solution acidification, collection of the CO2 in
a gas bag and CO2 bubbling in scintillation cocktails. The liquid scintillation cocktail is
essential in a reliable 14C measurement, already existing on the market different types
with different CO2 absorption compound [Canducci et al., 2013; Horvatinčić et al.,
2004; Singleton et al., 2002]. In the experiments we used two home-made scintillation
cocktails, containing two amines [L'Annunziata, 2003], which detained CO2 forming
carbamates: methoxypropylamine (MPA), provided by Meridian Biotechnologies as
CarbonTrap, and methoxyethylamine (MEA), provided by Merck.
The reproducibility of the applied preparation method, involved the comparison of
the obtained results from both combustion gas mixture bubbling and pure CO2
bubbling obtained from acidification, and for both scintillation cocktails used, with the
14
C recommended value for IAEA-C3 cellulose. The amount of CO2 absorbed was
evaluated by the differences between initial and final scintillation cocktail masses, using
Ohaus Explorer Pro analytical balance.
Radiocarbon measurements using LSC were performed with a Quantulus 1220.
The counting efficiency was 57.77 % for samples prepared with MPA and 59,39 % for
samples prepared with MEA.
Two amines which enter in scintillation cocktails compositions were tested for CO2
absorption and 14C measurement using LSC method.

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The sample used in the experiments was chosen to be similar to some vegetable
environmental samples, considering that the method was mostly developed for
environmental monitoring. The chosen sample was cellulose from IAEA (Vienna,
Austria) and it can be used as a quality control material - IAEA-C3 (IAEA, 2014). The
IAEA recommended value for the 14C activity of this material is 129.41±0.06 pMC
(0.2925±0.0001 Bq/g C). The IAEA recommendation is also to use cellulose as a quality
control material, since the preparation steps carried out before are similar to the steps
for other types of biological or vegetable samples.
The masses of CO2 detained in the scintillation cocktails were lower for bubbling of
the combustion mixture (around 1.5g for MPA and 1.8 g for MEA) comparing with the
CO2 detained after acidification (around 2,2 g for MPA and 2.5 g for MEA), due to the
fact that CO2 capture is impeded by the existence of other gasses, like the excess of O2
used in combustion.
The 14C activity measured in the studied sample and the values obtained for the
two scintillation cocktails, and for each set of experiments are given in Figure 1.
The 14C specific activity values obtained using the cocktail with MPA had an
average of 0.295±0.007 Bq/g C for bubbling of the combustion mixture directly from
the combustion bomb and of 0.296±0.005 Bq/g C respectively, for bubbling of pure CO2
after absorption in NaOH solution, acidification and collection in a gas bag. Also 14C
specific activity values obtained using the cocktail with MEA had an average of
0.296±0.006 Bq/g C for bubbling of the combustion mixture directly from the bomb
and of 0.287±0.005 Bq/g C respectively, for bubbling pure CO2 from the gas bag.

0.32
0.32
0.31
0.31
A, [Bq/gC]

0.3
A, [Bq/gC]

0.3
0.29 0.29
0.28 0.28
0.27 0.27
0.26 0.26
1 2 3 4 5 1 2 3 4 5
MEA Combustion number MEA Combustion number
(a) (b)
14
Figure 1. C specific activity values obtained for IAEA-C3 Cellulose (quality control material)
combustion, following the two sets of experiments: (a) bubbling of the combustion gas mixture
directly through scintillation cocktails; (b) bubbling of the pure CO2 in scintillation cocktails.

In conclusion both amines can be used in our cocktail composition for 14C
measurements from cellulose using a combustion bomb and LSC, but the method
involving pure CO2 bubbling conducted to higher values for the mass of CO2
absorbed into the scintillation cocktail comparing with the bubbling directly from
the combustion bomb, which in fact conducts to a lower detection limit for pure
CO2 bubbling.
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Due to the fact that the reference material used in the experiments described
is cellulose (contained in the most of the vegetable materials), the method can be
considered as appropriate for 14C determination from environmental samples.

Key words: combustion Parr bomb, cellulose, CO2 direct absorption method

Acknowledgments: This paper was prepared in connection with the work done
for the monitoring program of Tritium Removal Facility PESTD from I.C.S.I. Rm.
Valcea, Romania

References
1. Institute de Radioprotection et de Surete Nucleaire IRSN, 2010. Radionuclide fact sheet—Carbon-
14 and the environment
2. International Atomic Energy Agency IAEA. 2014. Reference Sheet for Quality Control Materials.
RS_IAEA-C1 to IAEA-C9.Rev01/2014-03-24
3. L'Annunziata M F. 2003. Handbook of Radioactivity Analysis, 2nd Edition, ISBN: 978-0-12-436603-9
14
4. Vagner I., Varlam C., Faurescu I., Faurescu D., Bucura F. 2017. Comparison of two methods for C
analysis from essential oils using LSC. Journal of Radioanalytical and Nuclear Chemistry
314:709–713
5. Canducci C, Bartolomei P, Magnani G, Rizzo A, Piccoli A, Tositti L, Esposito M. 2013. Upgrade of
14
the CO2 direct absorption method for low-level C liquid scintillation counting. Radiocarbon
55(2-3):260–267
14
6. Horvatinčić N, Barešic J, Krajcar Bronić I, Obelić B. 2004. Measurement of low C activities in a
liquid scintillation counter in the Zagreb Radiocarbon laboratory, Proceedings of the 18th
International Radiocarbon Conference, edited by N Beavan Athfield and R J Sparks,
Radiocarbon 46(1):105–116
7. Singleton DL, Sanchez AL, Woods C. 2002. A comparison of two techniques to determine carbon-
14 in environmental samples. Journal of Radioanalytical and Nuclear Chemistry 251(3):353–
357

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TRITIUM R&D AND TECHNOLOGICAL TRANSFER FOR FUSION AND

FISSION

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CERNAVODA TRITIUM REMOVAL FACILITY PROJECT STATUS AND OBJECTIVES

Andrew Roberts1, Nicolae Trantea2, Laura Moscu Thijov2, Adrian Cojanu2

1
Kinectrics UK Ltd
2
CNE Cernavoda, Romania
Corresponding author: [email protected]

INTRODUCTION
The Cernavoda Tritium Removal Facility (CTRF) will be built on the CNE
Cernavoda site and is planned to be operational in late 2025.
The CTRF will handle tritiated heavy water from CNE Cernavoda Units 1 and 2,
with low tritium content heavy water being returned for reuse in the Units. The
Project will thereby contribute to improving the working conditions for the
operating personnel, reducing the tritium releases to the public and environment,
avoiding storage and eventual disposal of tritiated heavy water at the end of
reactors’ lifecycle. Separated tritium will be stabilized and placed into long term
storage.

DESCRIPTION
The technology used will be the Liquid Phase Catalytic Exchange (LPCE) process
followed by a Cryogenic Distillation (CD) step. In this process, tritium will be
transferred from the heavy water feed to the vapour phase and then to a
deuterium gas stream in the LPCE columns and subsequently separated from
deuterium in the CD system. High tritium content gas will then be collected and
absorbed onto titanium sponge within secure steel containers as titanium hydride.
The absorbed tritium shall be in a very stable, isolated form where it can be stored
indefinitely. Recovery of the tritium from the container is possible using a future
facility.
The Conceptual Design of the CTRF was completed in 2015 by a joint ICSI-
Kinectrics team. That same team was awarded the contract in 2020 for providing
Owner’s Engineer services to SNN/CNE Cernavoda over the lifetime of the Project.
Stage 1 of the CTRF Project is expected to end in late 2021 with the
appointment of an Engineering, Procurement and Construction (EPC) Contractor
who will detail the design of the CTRF and then follow this with procurement,
construction and commissioning/trial running. The tender process for the EPC
Contractor is underway and follows the procedures specified by the European Bank
of Reconstruction and Development (EBRD) who will be providing financing for the
project.
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The Project team are also in the process of preparing the environmental impact
assessments of the CTRF according to both the EBRD’s and National Romanian
environmental impact requirements. For the EBRD, an Environmental and Social
Impact Assessment has been prepared which is currently open for a public
disclosure period until mid-December. For the National Romanian assessment
process, an Environmental Impact Assessment (EIA) is in preparation. Once the EIA
is complete, a series of public meetings will be held, also involving neighbouring
countries, to invite public participation. A decision on the Environmental Permit for
the Project is due from mid-2022.

OTHER CONSIDERATIONS
The CTRF does not employ new or experimental technology. The separation
process used has been used elsewhere successfully in commercial sized operating
units. When operational, similar facilities have been shown to be very effective in
reducing the risks of tritium release to the environment, of radiation doses to the
workforce of a nuclear station and of radioactive releases to the public and
environment.
The CTRF, when completed, will play a vital role in reducing environmental
discharges and improving worker safety, ensuring the continuing safe operation of
Cernavoda’s operational CANDU reactors.

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A NEW METHOD TO GENERATE VERY LOW GAS FLOWS FOR

CALIBRATION OF HYDROGEN PERMEATION MEASUREMENT.
PART 1: CONCEPT AND FEASIBILITY TESTING

Nicolae Bidica1, Narcisa Ghimis1

National Research and Development Institute for Cryogenic and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street, No. 4, P.O. Box 7 Raureni, 240050 Valcea, Romania
Corresponding author: [email protected]

Generating of very low (and well-known) gas flows meets a wide variety of
needs in industry and research (especially in vacuum science and technology), but
also among consumers and society (e.g: calibrations of vacuum gauges and leak
detectors, leak testing to verify the tightness of many industrial products, assurance
of product reliability and performance, environmental and other safety issues, and
so on).
The simplest approach would be by using a single leak element (capillary type
preferably), with suitable calibrated conductance, through which the gas flows at
rates adjusted by varying its inlet pressure. However, this has a main drawback
when wide range of flows are needed: changing the inlet pressure by orders of
magnitude will cause changing of the flow regimes, so the conductance of the leak
element will need to be measured as a function of pressure, which is a difficult task
in practice.
Over time, but even recently, a multitude of methods have been proposed and
devices have been built, with increasing efforts to reduce the lower limit of flow-
rates, but also to improve the measurement accuracy of these ultra-low flows.
Thus, more and more complex and costly solutions have resulted.
However, most methods and devices have been developed to set flow
standards for metrology, while in certain particular research applications, new or
adapted methods and devices appear to be more suitable. Such particular case is
when the injection of very low flows of hydrogen and/or deuterium directly into the
permeation cell is the option for calibration of the measurements of hydrogen
isotopes permeation fluxes, in permeation experiments performed in very different
modes. An important aspect in this case is that, depending on how the experiment
is conducted, very different conditions may occur in the permeation cell, as for
example high vacuum - in the case of permeation to vacuum, or a wide range of
pressures - in the case of permeation to another gas. Thus, the simplest way of
using a single leak (of calibrated conductance) is not appropriate; besides the

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disadvantage due to change of the flow regimes as the inlet pressure is increased
(which leads to pressure dependent conductance), also wide ranges of pressure
(instead of high vacuum) at the outlet of the leak would make the task even more
difficult. Therefore, a new method has been proposed to accomplish this purpose,
and this work presents the concept of this method but also the results of the
experiments performed to test its feasibility.
The concept is based on two leaks of constant conductance through which a
so-called reference flow is generated, with two stages of pressure reduction, as well
as on a variable leak valve through which well-controlled flows (and over a wide
range) are generated to be injected into the permeation cell. The first leak with
constant conductance is connected with one end to a reservoir, where the test gas
(hydrogen/deuterium) is supplied at a constant pressure, while the other end is
connected to an (extremely) small volume chamber. The second leak with constant
conductance is connected with one end to the small volume chamber, while the
other end is connected to a high vacuum chamber. The variable leak valve - through
which the flows of interest are generated - has the inlet connected to the small
volume chamber, while the outlet will be connected to the permeation cell. The
test gas flows through the first fixed leak into the small volume chamber, then
forward through the second fixed leak to the vacuum chamber. With the variable
leak valve kept closed (so no flow of interest is generated), the pressure into the
small volume chamber will rise-up to a steady-state value, when the flow-rates
through both fixed leaks are equal. This steady-state pressure is called "reference
pressure", and so the flow through both fixed leaks is called "reference flow". By
opening the variable leak valve in order to generate the flow of interest, a new
equilibrium will be established among the three flows, leading to another steady-
state pressure level into the small volume chamber. The pressure drop from the
"reference" level to the new one is a measure of the generated flow of interest. The
largest flow that can be generated will conform to the lowest possible level of
pressure into the small volume chamber, as dictated by the pressure level into the
permeation cell. In our particular case, this level is about 100 Pa. On the other
hand, the lowest flow that can be generated will conform to the lowest measurable
drop of pressure into the small volume chamber (which is usually about 1-2 Pa for a
capacitance vacuum transducer for this range). Also, the needed flow-rates range
for the calibration of the permeation flux measurement is in the range of about E-
13 to about E-09 mol/sec..
The best performance of this method is achieved when the flow through both
fixed leaks is molecular, because linear relations will correlate the reference flow
with the driving pressures, and thus the generated flow of interest will be directly
proportional to the pressure drop from the reference level to the corresponding
level. Therefore, for our particular task, the conductances of the two fixed leaks will
be selected so that to allow molecular flow regime for supply pressures of the order
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of thousands of pascals. The ratio between the two conductances will also be
selected so that, for the desired reference flow, the stationary pressure in the small
volume chamber is as close as possible to the supply pressure of the first fixed leak.
Thus, the pressure drop into the small volume chamber – and consequently the
generated flow of interest – can cover more than three orders of magnitude: from
1-2 Pa (corresponding to the lowest flow) up to thousands of pascals
(corresponding to the highest flow).
The feasibility of this method has been experimentally tested. For these tests,
instead of the two leaks with constant conductances, other two variable leak valves
have been used. Their openings have been adjusted to the appropriate
conductances for the flow-rates introduced, with the aim of a thermal mass flow
controller, directly at the inlet of the first leak, and for pressures in the range of
thousands of pascals. Then, the pressure at the inlet of the first leak was
maintained at a given constant level and a corresponding steady-state pressure (the
“reference” pressure) was obtained into the small volume chamber, this showing
that the resulted flows through both fixed conductances became equal (the
“reference” flow-rate). Finally, the variable leak valve for generating the flows of
interest have been progressively opened to vacuum chamber, so that several new
stationary levels of pressure have been obtained into the small volume chamber.
Both the reference flow and the generated flows (of interest) were assessed
(separately) by measuring the pressure rise of the accumulated gas in a closed,
attached volume. The results indicate a very good linearity between the generated
flows and the pressure drop, but also almost three orders of magnitude between
the lowest and highest flow.
The results obtained in these tests encourage us to further advance in creating
an experimental rig where leaks with constant and properly sized conductances will
be used.
This method could also be used with other gases and in other applications
where it is necessary to generate very low and known gas flows.

Key words: leak, conductance, micro-flows, calibration, permeation, hydrogen.

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STUDY ON HYDROGEN ISOTOPE PERMEATION BEHAVIOR AND SURFACE

MODIFICATION TECHNOLOGY OF FeCrAl

Huang Hongtao

IFCEN, SYSYU, China

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EXPERIMENTAL SETUP FOR THE STUDY OF A HYDROPHOBIC PLATINUM CATALYST

IN A DIRECT-FLOW REACTOR

Ivan Alekseev, Alena Bryk, Dmitry Kuzmin, Oleg Fedorchenko

NRC «Kurchatov Institute» - PNPI, 188300, Russia,

Leningradskaya oblast, Gatchina 1, mkr. Orlova roshcha
Corresponding author: [email protected]

The liquid phase catalytic exchange (LPCE) of hydrogen isotopes between

hydrogen and water has proven itself well as an excellent process for detritiation
and deprotiation of heavy water. For example, the LPCE process is used to maintain
the required isotopic composition in reactors such as PIK or CANDU. To carry out
the isotopic exchange process, it is necessary to use hydrophobic catalysts for the
molecular activation of hydrogen. Currently, catalysts for this process are produced
in Canada, Belgium, Romania, India, Korea and Japan. In Russia the hydrophobic
catalyst RCTU-3SM is used, in which the platinum is supported on a hydrophobic
styrene divinylbenzene copolymer (SDBC). This catalyst has been successfully
operated for more than 25 years in the EVIO pilot plant located on the territory of
the National Research Center "Kurchatov Institute" - PNPI. This served as the basis
for the use of this catalyst in the tritium removal facility (TRF) under construction
for isotopic water purification in the heavy water loop of the PIK reactor. In order to
optimize the process, the study of the catalyst is essential. At the Laboratory for the
Separation of Hydrogen Isotopes, an experimental setup was assembled to study
the catalytic activity of RCTU-3SM catalyst samples, which makes it possible to carry
out experiments under various conditions.
This article presents a description of the experimental setup, as well as the data
obtained during the experiments: dependence on temperature, relative humidity,
isotopic composition.

Key words: hydrophobic catalyst, liquid phase catalytic exchange, direct-flow

reactor, hydrogen isotope

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EFFECTS OF Fe/Cr/Ni/Mn ON HYDROGEN ADSORPTION, DISSOCIATION AND

DIFFUSION IN HYDROGEN PERMEATION BARRIER OF alfa-Al2O3

Jiang Man

HUST, China

TRITIUM TRANSPORT BEHAVIOR IN FUSION REACTOR AND THE ENVIRONMENTAL

EFFECT

Ni Muy

IFCEN, SYSYU, China

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26–29 October 2021, Băile Govora, Romania

MICRO-CHANNEL REACTOR FOR LOW LEVEL H2 OXIDATION WITHIN AN O2

STREAM: PRELIMINARY TESTS IN VIEW OF INTEGRATION IN A H2 GENERATOR
WITHIN CECE PROCESS

Alina Niculescu, George Ana, George Bulubasa, Iulia Stefan,

Ciprian Bucur, Anisia Bornea

National Research and Development Institute for Cryogenic and Isotopic Technologies - ICSI Rm.
Valcea, Uzinei Street, No. 4, P.O. Box 7 Raureni, 240050 Valcea, Romania
Corresponding author: [email protected]

CECE process is the candidate for low level tritiated water detritiation within
any application. The process consists mainly of a H2 generator, a LPCE column and
an O2 striping column. During operation, tritium is being accumulated within the H 2
generator in the form of tritiated water and the effluent streams (hydrogen and
oxygen) show in time an increase concentration in tritium in the form of both
tritiated water vapors and gas, which needs to be recovered.
The tritium in the H2 stream is recovered in a LPCE column, while the tritium in
the O2 stream is recovered in a striping column. In view of lowering the load onto
the striping column and to recover the tritium in gas form, a micro-channel reactor
is proposed to be included for H2 oxidation followed by vapor recovery.
The design of the equipment together with the preliminary results of the tests
done with H2 and air will be shown, prior to integration in the CECE process.

Key words: CECE process, micro-channel reactor, LPCE column, mass spectrometry

Acknowledgments: This work was performed in the framework of Core

Program, conducted with the support of the Romanian Ministry of Research and
Innovation, project PN 19 11 01 04.

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“New Cryogenic and Isotope Technologies for Energy and Environment” – EnergEn 2021
26–29 October 2021, Băile Govora, Romania

ADVANTAGES AND CONSTRAINTS OF SPECIFIC AUTOCAD PLANT 3D FUNCTIONS

FOR DYNAMIC MANAGEMENT - CASE STUDY FOR THE CERNAVODA N.P.P. PLANT -
DETRITIATION INSTALLATION

I. Niţă, A. R. Olteanu, Camelia Coman, Hortensia Beznila

1
RATEN CITON, 409 Atomistilor Street, Magurele, Romania
Corresponding author: [email protected]

The advantages and constraints of the specific Autocad Plant 3D functions

for dynamic management - production of technological diagrams, isometrics,
orthogonal views, bills of materials and piping system erection projects for the
future detritiation plant at the Cernavodă NPP are presented in a case study.
In last decades 3D modelling of the plant has been increasing used in design
of new projects in NPP both in design period but also in design changes required
during life time and extended life time of a plant.
In the proposed cased we developed a model to make an engineering design
application for plant design incorporating disciplines such as piping, piping support,
equipment, civil and steel structure. Using 3D Plant capabilities we can improve
design process, interdisciplinary check-out as well as project execution. The project
could be updated after as built revision of isometric drawings in order to obtain a
training model of the system to prepare plant operators to make scheduled and
unscheduled maintenance and time estimation of different maintenance
procedures that could be required during plant operation in order to reduce as low
as reasonable possible dose received during detritiation installation maintenance.

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“New Cryogenic and Isotope Technologies for Energy and Environment” – EnergEn 2021
26–29 October 2021, Băile Govora, Romania

INVOLVEMENT OF MAGURELE PROFESSIONAL COMUNITY IN TRANSAT PROJECT

ACTIVITIES AND FUTURE R&D DEVELOPMENTS

Niţă Iulian1, Fako Raluca1, Meglea Sorin1, Cristian Postolache2

1
RATEN CITON, 409 Atomistilor Street, Magurele, Romania
2
“Horia Hulubei”, National Institute for Physics and Nuclear Engineering Reactorului Street no. 30,
Magurele, Romania
Corresponding author: [email protected]

Activities developed by Magurele R&D community in the TRANSAT project are

briefly described in this paper with stress on outcomes to be used in future national
major investments in the nuclear field.
Also, considering the analyse of overall results up to date on each work
package the other R&D team is proposing new R&D activities to be considered for
development in a new project proposal after the completion of the current
TRANSAT activities.
The paper will show the Magurele community results within TRANSAT project
mainly in the field of the tritium permeation in stainless steels and evaluating the
permeation barrier effect of thin copper films [Brad, 2008; Ioan, 2020; Postolache,
2020; Raty, 2019].
The role of design & engineering team for input data mining and for potential
further implementation of experimental activities within TRANSAT (TRANSversal
Actions for Tritium) project is described

Key words: Tritium, stainless steel, permeation barrier, nuclear safety.

References
S. Brad, et al. (2008) Experimental Stand for studies of hydrogen isotopes permeation, Fusion Sci .
Technol., 54, 2008, 530, DOI: 10.13182/FST08-A1870
M. R. Ioan, G. Bubueanu & C. S. Tuta, (2020)The Area Measurements in the Tritium Laboratory
Within NIPNE Magurele, Fus .Sci .Technol., 2020, DOI:
https://doi.org/10.1080/15361055.2020.1711850
C. Postolache, et al. (2020) Hydrides with Controlled H/T Ratio for AMS Facility Calibration, Fusion
Sci. Technol, 2020, DOI: https://doi.org/10.1080/15361055.2019.1704109, in press
A.Raty, et al.(2019), Characterization measurements of fluental and graphite in FiR1 TRIGA research
reactor decommissioning waste, Nucl. Eng. Des., 353, 2019, 110198,
DOI:10.1016/j.nucengdes.2019.110198

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26–29 October 2021, Băile Govora, Romania

TRITIUM EFFECTS IN POLYMERS

Cristian Postolache1, Irene Popovici2, George Bubueanu1,

Viorel Fugaru1, Catalin Stelian Tuta1
1
National Institute for Physics and Nuclear Engineering “Horia Hulubei”, Reactorului Street no. 30,
Magurele, Romania,
2
Romanian National Commission for Nuclear Activities Control (CNCAN)
Corresponding author: [email protected]

Different polymer structures are used in designing and achieved of nuclear

facilities like: catalyst supports, membranes, seals gaskets, tubes, matrix for liquid
solidification, etc.
Tritium is the radioactive isotope of hydrogen. The low energy of beta radiation
can lead to the idea of minimal effects in polymeric materials. But this nuclidic
characteristic is associated with a total energy transfer from ionizing radiation to
the macromolecular structures. Also, high specific activity of tritium can be
associated with high damages radio-induced in materials.
In this paper, the degradative effects induced by the presence of tritium in the
polymeric materials most often used in the realization of nuclear facilities are
analysed, respectively: PTFE, styrene-divinylbenzene copolymers [Matei, 2007],
Nafion [Matei, 2008], Viton [Bubueanu, 2015], methyl and phenyl siloxanes
(Postolache 2009), polystyrene, polyacrylic acid [Postolache, 2005],
At first, the fundamental radiolytically effects was analysed by quantum-
chemical simulations using HYPERCHEM software [Postolache, 2007]. In the next
step, the radiolytically effects was experimentally determined using gamma radiation
fields emitted by 60-Co sources and determination of chemical changes by ESR, IR
spectrometry, sol: gel and small molecules emission using radiometric methods.
The study was completed by determining of the self-radiolytically effects by
exposing of the samples to tritiated water [Postolache, 2005; Postolache, 2009;
Bubueanu, 2015].
The quantum-chemical simulations indicate a high instability of macromolecular
structures which contain strong electronegative elements, such as F. The experimental
results suggest a high degradative effect induced by gamma radiation in all analysed
polymers. The magnitude of self-radiolytically damage are about ten times larger in
comparison with radiolytically effects induced by gamma radiations for identical
absorbed doses. This fact can be associated with low dose rate and secondary effects
developed in time in tritiated water.

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Key words: Tritium, polymers, radiolysis, self-radiolysis, fusion, fission.

Acknowledgments: Work was supported by the Romanian Research and
Innovation Ministry through the Core Project PN 19 06 02 04/2019.

References
G. Bubueanu, et al.(2015), Behaviour of Fluoropolymers in Presence of Tritiated Water, Acta Phys.
Pol. A 127, 2015, 1363, DOI: 10.12693/APhysPolA.127.1363
L Matei., C. Postolache (2007), Radiolysis of Polytetrafluoroethylene and Polystyrene Catalytic
Supports in Presence of Tritiated Water, Rad Phys Chem, 76, 2007, 1257,
10.1016/j.radphyschem.2007.02.015
L. Matei, C. Postolache, I. Cristescu, S. Brad (2008), Behaviour of Nafion perfluorosulfonate ionomer
membranes in presence of tritiated water, Fus Sci Technol, 54, 2008, 475, DOI:
https://doi.org/10.13182/FST08-A1857
L. Matei, C. Postolache, C Tuta, S Brad (2011), Facility for Endurance Testing of Hydrophobic Isotope
Exchange Catalysts, FUS SCI TECHNOL, 60, 2011, 1419, DOI: 10.13182/FST11-A12697
C Postolache, L.Matei, R. Georgescu, Gh Ionita (2005), Optimal parameter determination for tritiated
water storage in polyacrylic networks, Fus Sci Technol, 48, 2005, 220, DOI:
https://doi.org/10.13182/FST05-A916
C. Postolache, l. Matei (2007) Evaluation of Fundamental Processes in Macromolecular Structures
Radiolysis Using Quantum-Chemical Methods, Rad Phys Chem, 76, 2007, 1267,
https://doi.org/10.1016/j.radphyschem.2007.02.075
C. Postolache, L. Matei, R. Georgescu (2009), Self-radiolytical processes in ethyl-phenyl siloxanes
labelled with tritium, J. Radioanal Nucl Ch. Chemistry 280, 2009, 2, 251, DOI: 10.1007/s10967-
009-0507-7

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26–29 October 2021, Băile Govora, Romania

IN-SITU TEM INVESTIGATION ON THE EVOLUTION AND MECHANISM OF

DISLOCATION LOOPS IN BCC METAL MATERIALS DURING ION IRRADIATION

Guang Ran

Xiamen University, China

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“New Cryogenic and Isotope Technologies for Energy and Environment” – EnergEn 2021
26–29 October 2021, Băile Govora, Romania

EXTENSION OF TRITIUM REMOVAL FACILITY PESTD WITH R&D

CAPABILITIES – TRI-VALCEA

Liviu Stefan

National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
th
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Coresponding author: [email protected]

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26–29 October 2021, Băile Govora, Romania

OBTAINING OF TRITIATED POLYSTYRENE THIN LAYERS THROUGH RADIO-INDUCED

GRAFTING ONTO POLYETHYLENE TEREPHTHALATE FOILS

Diana Chiper, Cristian Postolache, George Bubueanu, Catalin Stelian Tuță

“Horia Hulubei” National Institute for Physics and Nuclear Engineering, Magurele, Romania
E-mail address of presenting author: [email protected]
Corresponding author: [email protected]

In this paper was analysed the obtaining of the reference surface sources with
tritium by radio-induced grafting of labelled styrene onto polyethylene
terephthalate (PET) thin foils.
The researches were started by analysis of radiolytically (PET support) and self-
radiolytically (tritium labelled styrene) phenomena using quantum-chemical
methods, ESR and IR spectrometry.
The qualitative analysis of radio-induced unlabelled styrene grafting has been
performed using Fourier Transform Infrared spectrometer with Attenuated Total
Reflection and Scanning Electron Microscopy.
The grafting yields was determined by radiometric methods using tritium
labelled styrene. We analysed the variation of grafting yields for dose rates in the
1.5 and 9.5 kGy/h range and absorbed dose from 50 kGy to 250 kGy.
The applied grafting protocol was:
- Obtaining of styrene labelled with tritium in para position using
organometallic intermediates
- Depositing of PET thin foils onto stainless steel support plates
- Free radical inducing in PET foils using a gamma 60Co source
- Exposing of irradiated PET foils/stainless steel at labelled monomer vapours
The obtained surface sources have been analysed by:
- Determination of the surface distribution uniformity of the tritiated polymer
using Beta TLC Scanner Gina Star type
- Samples combustion using a dedicated oxidizer (catalytic oxidation column
heated using a tubular furnace, coupled at an HTO collector) and determination of
the total activity at liquid scintillation counter.

References
M. Enachescu, et al., J. Anal. At. Spectrom., 2018, 33, 431
V. Fugaru, et al., Rad. Phys. Chem., 2012, 81, 1345
C. Postolache, L. Matei, Rad. Phys. Chem., 2014, 76, 1267
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26–29 October 2021, Băile Govora, Romania

RADIOLOGICAL CHARACTERIZATION OF METAL SAMPLES

Diana Chiper1, Viorel Fugaru1, Cristian Postolache1, George Bubueanu1,

Catalin Stelian Tuta1, Irene Popovici2
1
National Institute for Physics and Nuclear Engineering “Horia Hulubei”,
Reactorului Street no. 30, Magurele, Romania
2
Romanian National Commission for Nuclear Activities Control (CNCAN)
E-mail address of presenting author: [email protected]
Corresponding author: [email protected]

An apparatus based on Total Degassing/Full Combustion method [Raty, 2019]

was designed and built for determination of tritium content in metallic samples.
Equipment used in experiment is constituted from:
- Oxygen supply with pressure regulator and flow control meter
- 2 tube furnaces with temperature controller, one for Total Degassing (at
1100°C temperatures) and secondary for catalytic oxidation of resulted gases at
water and carbon dioxide (800°C in presence of CuO wires)
- HTO collector
The protocol consists of calcination of samples followed by catalytic oxidation
in oxygen atmosphere of emitted hydrogen, obtained HTO kept and determined of
T activities at Liquid Scintillation Counting.
The overall yield of the Full Combustion facility was determined using as
standard sintered composite materials made from virgin stainless steel and
Titanium tritide powders [Postolache, 2020[. The determined yield (94.3 + 3.2%)
was used for correction of the obtained experimental values.
The new equipment was used in the radiological characterization of stainless-
steel samples from JET Culham UK and the decommissioned materials within
TRITIULAB NIPNE Romania.

Key words: Tritium, metal, radioactive wastes, fusion.

Acknowledgments: Work was supported by the Romanian Research and

Innovation Ministry through the Core Project PN 19 06 02 04/2019

References
C. Postolache, et al. (2020), Hydrides with Controlled H/T Ratio for AMS Facility Calibration, Fusion Sci.
Technol, 2020, DOI: https://doi.org/10.1080/15361055.2019.1704109 in press
A.Raty, et al.(2019), Characterization measurements of fluental and graphite in FiR1 TRIGA research reactor
decommissioning waste, Nucl Eng Des, 353, 2019, 110198, DOI:10.1016/j.nucengdes.2019.110198
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“New Cryogenic and Isotope Technologies for Energy and Environment” – EnergEn 2021
26–29 October 2021, Băile Govora, Romania

ASSESSMENT OF THE TRITIUM AND GAMMA RAY EMITTERS ACTIVITIES IN LIQUID

RADIOACTIVE WASTE GENERATED BY TRIGA REACTOR

Cristina Diaconescu1, Liliana Bujoreanu1, Ionut Florea1, Ilie Prisecaru2

1
Institute for Nuclear Research Pitesti, Romania, Campului Street, nr.1, POB 7, 115400-Mioveni
2
Polytechnic University, Bucharest, Romania
Corresponding author: [email protected]

The radiological characterization process is one of the most important step in

the establishment of the main stages of waste radioactive management. Therefore
the identification and quantification of the relevant radionuclide must be
accomplished in a systematic manner using proved methodologies, technologies
and techniques.
One of the radioactive waste categories generated by TRIGA reactor operation
consists of low and intermediate level liquid waste resulted mainly from the
regeneration of the ion exchange resins used in the purification systems. This liquid
waste is transfer to the Radioactive Waste Treatment Department (STDR) for
treatment and conditioning in view of final disposal to the National Repository
DNDR Baita Bihor.
The purpose of this study is to establish the inventory of gamma emitters and
to obtain information on the tritium activity concentration in the representative
samples of liquid radioactive waste generated by TRIGA reactor operation.
The gamma ray emitters were identified and quantified by direct
measurements using gamma ray spectrometry, with a GeHP detector (15% relative
efficiency at 1.33 MeV 60Co).
As tritium is a pure beta emitter, a distillation technique was applied to
separate the tritium from other beta emitters and the fractions collected by
distillation that contain only tritium, were measured by Liquid Scintillation Counting
(LSC) using a TRICARB model. The distillation technique was validated with solutions
with known tritium activity and tritium recovery yield of around 88% was obtained.
The experimental results obtained in this study are used in optimizing and
improving the actual procedure applied in radiological characterization of liquid
radioactive waste.

Key words: distillation technique, tritium, gamma ray emitters, gamma ray
spectrometry.

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26–29 October 2021, Băile Govora, Romania

EXPERIMENTAL TESTS FOR THE IMPLEMENTATION OF A METHOD FOR

MEASURING TRITIUM ON METAL SURFACES

Valentina Neculae, Cristian Dulama, Relu Dobrin

Institute for Nuclear Research (RATEN ICN), Piteşti, Romania

Corresponding author: [email protected]

This paper presents the results of experimental activities carried out for the
implementation of a method used for determining the tritium contamination of
metal surfaces. The tests were aimed at developing and qualifying a simple,
efficient and interference-free method for sampling contamination.
Generally, tritium is a radionuclide difficult to analyze mainly because of its
type of decay (β-), low energy and its chemical and physical behaviour. It decays by
emitting a weak beta particle with a maximum energy of approximately 18.6 keV
and it can exist in various forms, such as gaseous tritium, tritiated water (HTO), and
organically bound tritium. To investigate tritium in-situ directly on radioactive
wastes coming from nuclear facilities, sensitive and cost-effective analytical
techniques are rather limited, especially for wastes with low tritium activity. An
easy way to obtain spots of radioactivity in the field of dismantling is to use smears
and proportional counters or liquid scintillation counting technique (LSC).
More than 90% cases of materials contamination with tritium is in form of
tritiated water. This can be free water, diffused into the pores of the material or
bound water, in the form of emulsions, or water for hydrating the oxide film on the
surface of the material.
From the point of view of radiation protection, the external exposure to tritium
is not a critical concern, but the tritium contamination of surfaces becomes a risk
when it is not fixed or when it can be easily mobilized, which happens especially in
the case of contamination with free tritiated water. In general sense, unfixed
radioactive contamination is that part of the contamination of an object, which can
be transferred as a result of direct contact with another object. In a broader sense,
in terms of tritium contamination, we can consider as unfixed contamination, that
part of tritium activity that can be lost by exposure to free atmosphere or by direct
contact, including the loss of contamination by degassing.
The most common method used to determine non-fixed contamination is
smear sampling and measuring the sampled activity by an appropriate method.
Typically, the surface on which the sample is taken is about 100 cm 2, and the
smears used are pieces of absorbent paper or textile material. Conservatively, a
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sampling factor of 10% is considered, which is taken into account when determining
the amount of contamination. The smear method is widespread, mainly due to its
simplicity, being a very useful screening method in detecting the presence of
unfixed contamination. When it comes to radiological characterization, however,
the method does not provide a sufficiently high level of accuracy, and in terms of
tritium contamination, it cannot highlight the degassing phenomenon. Therefore, it
was considered necessary to develop another methodology for assessing surface
contamination.
Thus, the method of sampling the contamination should allow the most efficient
"extraction" of water from the surface of the material to be characterized. This goal
could be achieved by using a device containing a material with high hygroscopic
properties, applied in such a way as to maintain a closed enclosure which includes a
part of the surface of the object to be characterized. Also, the hygroscopic material
must be chosen so as to allow the quantitative transfer of the water collected in the
scintillation vial and to be compatible with the scintillating liquid.
Starting from the air tritium contamination monitoring method, based on the
use of the passive collector with calcium chloride developed within the Radiation
Protection, Environmental Protection and Civil Protection Laboratory of Institute for
Nuclear Research - Pitesti and based on the same concept that served to develop
this passive collector, a sampling methodology was imagined for the tritium surface
contamination. The collector has been modified so that it can be used for the
purpose of testing tritium contamination of metal surfaces.
For the functional verification of this passive collector, a series of experimental
tests were performed in order to highlight the ability of the device to quantitatively
take a known tritium activity deposited on a non-porous surface, by gravimetric
dosing of a tritiated water solution. The solution used to perform the tests was
prepared by dilution from a standard source of tritiated water.
From the obtained results it can be concluded that the recovery rate of the
activity is over 80%, having an average value of 90%. It is expected that in a
situation of real contamination, the value of the activity recovery rate will be lower.
In order to evaluate the effectiveness of the method it was decided to perform
some experimental tests to compare the results obtained in determining
contamination by the sampling with passive collectors method and by the method
of smear sampling, on real samples. These tests resulted in three samples of
contamination taken with passive collectors and three samples taken by the smear
sampling method. After processing the samples, the tritium activity in them was
determined by LSC.
The contaminations corresponding to the sampled activities were calculated by
relating the activity to the sampling surface, which were 1.5 cm2 in the case of
passive collectors and 10 cm2 in the case of smears.

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The results obtained showed that the contaminations determined by using the
passive collectors are higher than those determined by the smear sampling
method. This is because the smear sampling method is not a quantitative one.
Using a conservative approach it has been estimated that the efficiencies of the
passive collectors sampling method varied in the range of 0.4 and 1.0, with an
average value of 0.8.

Key words: Tritium passive collectors, Smear sampling method, Surface

contamination.

References
P. Calmon, J. Garnier-Laplac, Radionuclide Fact Sheet - Tritium and the environment, Institut de
Radioprotection et de Sûreté Nucléaire, 29 June 2001
Cristian Dulama, Relu Dobrin, Valentina Neculae, Optimization of The Smear Sampling Method for
Evaluation of Tritium Contamination On Metallic Surfaces, Journal of Nuclear Research and
Development, No. 20, May. 2021
Frédérique Eyrolle, Loïc Ducros, Séverine Le Dizès, Karine Beaugelin-Seiller, Sabine Charmasson,
Patrick Boyer, Catherine Cossonnet, An updated review on tritium in the environment, Journal
of Environmental Radioactivity, Volume 181, 2018, Pages 128-137, ISSN: 0265-931X,
https://doi.org/10.1016/j.jenvrad.2017.11.001.
International Organization for Standardization (1988), Evaluation of surface contamination - Part 1:
Betaemitters (maximum beta energy greater than 0.15 MeV) and alpha-emitters, ISO 7503-
1:1988, revised by ISO 7503-1:2016, ISO, Geneva, Switzerland
Johnson J. R., Draper D. G., Foulke J. D., Hafner R. S., Jalbert R. A., Kennedy W. E. et al.,
Recommended tritium surface contamination release guides, U.S. Department of Energy, March
1, 1991

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26–29 October 2021, Băile Govora, Romania

RADIOLOGICAL CHARACTERISATION AND DECONTAMINATION OF VARIOUS

SURFACES FROM FORMER RADIOCHEMISTRY LABORATORIES

C. Cimpeanu, C. M. Barna, C. Postolache, A. Luca, and M-R Ioan

“Horia Hulubei” National Institute for Physics and Nuclear Engineering,

Reactorului Street no. 30, Magurele, Romania
Corresponding author: [email protected]

The Radioisotopes and Radiation Metrology Department (RRMD) within “Horia

Hulubei” National Institute for R&D in Physics and Nuclear Engineering (IFIN-HH),
Romania, is been in operation since 1976, and carries out production and research
activities in the fields of obtaining of labelled compounds, radiopharmaceuticals and
sealed radioactive sources. In the last 10 years DRMR is in the process of
development [L. Matei and C. Postolache, 2011].
The refurbishing activities in a nuclear units must begin with the development
and validation of specific methods for radiological characterization [V. Fugaru et al.,
2020] and decontamination [D. Chiper et al., 2020] of the surfaces and equipment
for inventory of resulted radioactive and non-radioactive wastes.
In this paper, the obtained results regarding the radiological characterization
and decontamination of work areas within the DRMR (in which long-lived isotopes
have been handled), are presented.
The surface activity determination has been carried out by wiping of the
analysed surfaces using:
a. Extruded polystyrene smears moisten with ethylic or isopropyl alcohol [C.
Postolache and L. Matei, 2005], and measuring of smears radioactivity at a Liquid
Scintillation Counter (LSC)
b. Wet cotton smears followed by the measurement of smear’s activity at a
gamma spectrometric systems with high resolution HPGe detectors
The decontamination factor was determined for existent surface types from
the selected areas: stainless steel, PMMA glass, PVC pavement, apparent ceiling
and wall.
Analysed surfaces with 100 cm2 (10 x 10 cm) area, were realized and controlled
contaminated with tritium labelled compound [Postolache and L. Matei, 2010], 60Co,
137
Cs and 241Am aqueous solutions provided by the National Radioactivity Standard–
Ionising Radiation Metrology Laboratory (LMRI) [M. Sahagia et al., 2016; A. C.
Razdolescu and Ph. Cassette, 2004].

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Five decontamination protocols have been tested using obtained controlled

contaminated surfaces. The residual activities after decontamination were
determined using:
a. Total combustion facility coupled with a LSC, for tritiated surfaces [M.
Enachescu et al., 2018] and
b. Gamma spectrometric systems, with high resolution HPGe detectors,
ISOXCAL characterization, with DSA 1000 analysers and GENIE 2000 and LabSOCS
software. The representative peaks of the radionuclides (60Co - 1332.5 keV, 137Cs -
661.7 keV and 241Am 59.5 keV, where keV = 1.602 E-16 J) were used in the
quantitative determinations.
Decontamination factor was determined by the ratio between removed activity
and initial one.

𝐴𝑟 𝐴𝑖 − 𝐴𝑝𝑑
𝐷𝐹 % 𝑥100 𝑥100
𝐴𝑖 𝐴𝑖

where DF is decontamination factor expressed in percent; Ar, Ai and Apd are

Removed activity; Initial Activity and Post-Decontamination activity respectively,
expressed in Bq.
In the case of surfaces contaminated with tritium the highest decontamination
factor was obtained in the case of Stainless Steel, followed by PVC walls and PMMA
plates. The smallest decontamination factors were identified in the case of PVC
pavement.
The best decontamination factors were obtained for all surfaces types using
the 2 gels (Decongel 1121 and 1128) followed by alcohol.
In the case of surfaces contaminated with 60Co and 137Cs radionuclides, the
highest decontamination factor was obtained in the case of PMMA plates, followed
by PVC walls and pavement. The smallest decontamination factors were identified
in the case of Stainless Steel.
In the specific case of 241Am radionuclide, the highest decontamination factor
was also obtained also in the case of PMMA plates, followed by PVC walls. The
smallest decontamination factors were obtained in the case of PVC pavement.
The highest decontamination factors were obtained for all gamma radioactive
contaminants and surfaces types using the 2 gels (Decongel 1121 and 1128)
followed by EDTA, alcohol and water.
The obtained results will be used in the elaboration of the decommissioning
plan of the selected areas and the start of the radiological characterization,
dismantling and decontamination activities.

Key words: Long live radionuclides, tritium, gamma spectrometry, decontamination.

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Acknowledgments: Work was supported by the Romanian Research and

Innovation Ministry through the Core Project PN 19 06 02 04/2019

References
1. L. Matei, C Postolache, Refurbishment of the Tritium Laboratory from NIPNE Romania,
Fusion Science and Technology, 60, (2011) 1021
2. V. Fugaru, G. Bubueanu, C. S. Tuta, M-R Ioan, Radiological Characterization of the Resulting
Solid Materials from the Refurbishment of the Tritium Laboratory Fusion Science and
Technology, 76 (2020) 347
3. D. Chiper, C. S. Tuta, S. E. Manea and G. Bubueanu, Decontamination of Tritium
Contaminated Surfaces Using Strippable Polymeric Gels, Revista de Chimie, 71 (2020) 269
4. C. Postolache, L Matei, Evaluation of unfixed tritium surface contamination, Fusion Science
and Technology, 48, (2005) 413
5. C. Postolache, L. Matei, C. Tanase, George Bubueanu, Synthesis of E-275 Class Nucleoside
Analogue by Isotope Exchange Technique, Journal of Labelled Compounds and
Radiopharmaceuticals. 53, (2010) 461
6. M. Sahagia, A. Luca, A. Antohe, M.-R. Ioan, C. Ivan, Romanian Reports in Physics, 68 (2016)
177
204
7. A C Razdolescu, Ph. Cassette “Standardization of Tritiated Water and Tl by TDCR Liquid
Scintillation Counting” Applied Radiation and Isotopes, 60, (2004) 493
3 14
8. M. Enachescu, C.Stan-Sion, Al. R. Petre, C. Postolache, V. Fugaru, H and C measurements
of the irradiated graphite from the decommissioned VVR-S reactor in NIPNE Bucharest,
Journal of Analytical Atomic Spectrometry, 33 (2018) 431

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SYNTHESIS OF TRITIUM LABELLED THYMIDINE AND URIDINE

Cristian Postolache, George Bubueanu, Catalin Stelian Tuta,

Andi Sebastian Cucoanes

National Institute for Physics and Nuclear Engineering “Horia Hulubei”,

Reactorului Street no. 30, Magurele, Romania
Corresponding author: [email protected]

The main objective of the IFA ELI 09/2020 project is to enlarge the portfolio of
advanced biological investigations addressing the interaction of cells with radiation,
relevant for astrobiology and FLASH radiotherapy studies at ELI-NP [Manda, 2020].
The post irradiation cellular functional investigations will be realized by: (a)
cellular proliferation (flow cytometry with CFDA-SE and cell cycle analysis with
Vybrant Dye Cycle Orange stain, the tritium-labelled thymidine assay) and (b) RNA
synthesis using 3H-labelled uridine.
In this paper, tritium labeling of thymidine and uridine, used in cellular
investigations, is described.
The synthesis of thymidine has been performed using two different wais:
catalytic hydrogenation [Matei, 2008] of the methyl brominated derivative and of
hydroxy methyl deoxy uridine, respectively (Fig. 1).
O O O O
CH3 CH3 CH2Br CH2T
HN HN HN HN
(CH 3CO) 2O NBS
O N OH OCOCH 3 O N OCOCH 3 T2 OCOCH 3
O N O N
H O H H O H H O H H O H
AIBN
Pd/C
H H H H H H H
H OH H H
H OCOCH 3 OCOCH 3 H OCOCH 3
N
aH
CO

O
3

CH 2T
HN
O O
O N
CH2OH OH
T2
HN HN O3 H O H
/ Al 2
CH 2O Rh
N OH N OH H H
H O H H O H H OH

H H H H
H OH H OH

Figure 1. Labelling methods for obtaining of Thymidine-Methyl-T

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The uridine has been labelled by catalytic hydrogenation [Postolache, 2007] of

5-I-uridine following the reaction showed in Figure 2.
O O
I T
HN HN
T2
O N O N
H OH OH
O H H O H
Pd/C

H H H
OH OH H
OH OH

Figure 2. Synthesis of Uridine 5-T

After purification, the labelled compounds with characteristics presented in

Table 1 have been obtained.

Table 1. Characteristics of obtained tritiated thymidine and uridine

Thymidine-Me-T
from Br from hydroxyl Uridine-5-T
derivative derivative
Raw product activity [MBq] 25086 10767 9805
Purified product activity [MBq] 13986 9472 7955
Raw product radiochemical purity [%] 59 92 85
Purified product radiochemical purity [%] >95 >95 >95
Radioactive concentration [MBq/mL) 35 37 34
Chemical conc. [mg/mL] 0.008 0.011 0.010
Specific activity [GBq/mmol] 999 814 851

Key words: Tritium, labelled compounds, catalytic hydrogenation, thymidine,

uridine.

Acknowledgments: Work was supported by the Romanian Research and

Innovation Ministry through the PNIII/P5/5.1/ELI-RO 09 project

References
G. Manda, C. Postolache, I. V. Neagoe, A. Csolti, E. Milanesi, M. Dobre, The expression profile of
redox genes in human monocytes exposed in vitro, to γ radiation, Rad Phys Chem, 170, 2020,
108634, DOI: https://doi.org/10.1016/j.radphyschem.2019.108634
L. Matei, C. Postolache, G. Bubueanu, C. Podina, Synthesis of Labeled Compounds using Recovered
Tritium from Expired Beta Light Sources, Fusiom Sci Technol, 54, (2008) 643, DOI:
10.13182/FST08-A1897
C. Postolache, C. Tanase, L. Matei, V. Serban, Synthesis of [5-3H] Uracil Nucleoside Analogue, J.
Labelled Comp Radiopharm, 50 (2007) 609, DOI: https://doi.org/10.1002/jlcr.1305

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CALCULATION PROGRAM FOR THE PROCESSING OF LOW-CONCENTRATED

TRITIUM AND DEUTERIUM WASTE THROUGH THE CECE ISOTOPIC
SEPARATION PROCESS

Anisia Mihaela Bornea, Marius Valentin Zamfirache

National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm.
Valcea, 4 Uzinei Street, P.O. Box Râureni 7, 240050, Rm. Valcea, Romania
Corresponding author: [email protected]

Within the research conducted at our Institute of Cryogenic and Isotopic

Technologies (ICSI), is developed a project entitled "Innovative CECE process
solution to promote a new technology for decontamination of liquid waste, tritium
low concentrated and deuterium recovery”.
The main objective of the project carried out within our team is to promote an
innovative solution of CECE isotopic separation process (Combined Electrolysis and
Catalytic Exchange), part of a new technology for decontamination of liquid waste,
poorly concentrated in tritium, generated by nuclear reactors, ensuring increased
recovery of the isotope deuterium and tritium.
This paper presents the current stage of an innovative CECE isotopic separation
process solution, and also the mathematical model developed for the simulation of
hydrogen isotope separation processes through the CECE process and a theoretical
analysis based on numerical data resulting from the simulation of two CECE plant
operating mode.

Key words: Detritiation, heavy water, waste management

Acknowledgments: The work was supported by the Romanian Ministry of

Research, Innovation and Digitization - grants number: PN 19110104 "Innovative
CECE process solution to promote a new technology for decontamination of liquid
waste, tritium low concentrated and deuterium recovery”

References
A. Bornea, M. Zamfirache, N. Bidica, 2018. Proposal for Combined Electrolysis and Catalytic
Exchange System (CECE) Development Within the Pilot Plant. Fusion Eng. Des., 136, 645 (2018).
https://doi.org/10.1016/j.fusengdes.2018.03.046.

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A. Bornea et al., 2017. Theoretical Analysis for Setting up a Ctalyst-Packing Mixture that Equips a
Ctalytic Isotopic Exchange Column. Fusion Sci. Technol., 71, 4, 532 (2017).
https://doi.org/10.1080/15361055.2017.1290973
A. Bornea et al., 2020. The Study of CECE Process for Low-Tritiated Liquid Waste Prior to Experimental
Phase. Fusion Sci. Technol., 76, 4, 384-391. https://doi.org/10.1080/15361055.2020.1712991.
A. Bornea et al., 2018. New catalytic packing performance: Theoretical and experimental characterization
for LPCE process. Fusion Eng. Des., 146, 2384 (2018). https://doi.org/10.1016/j.fusengdes.
2019.03.196.
A. Busigin, 2017. Rigorous Two-Fluid and Three-Fluid Phase Catalytic Exchange Models and Their
Application. Fusion Sci. Technol., 71, 438-443. https://dx.doi.org/10.1080/15361055.2017.1293411.
G. Ionita, I. Spiridon, C. Bucur, 2018. Hydrodinamic Characteristics of Mixed Catalytic Packing for Heavy
Water Detritiation. Fusion Eng. Des., 136, 1252 (2018). https://doi.org/10.1016/j.fusengdes.
2018.03.111.

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OPTIMAL SOLUTION FOR CUTTING DOWN CO2 EMISSIONS

IN FLOOR HEATING APPLIANCES (summary)

Badea Gheorghe, Mateescu Ovidiu, Mateescu Monica,

Pavel Dragos-Iulian, Mateescu Ioan
AEHRo
Coreespondin author: [email protected]

ABSTRACT: Among the solutions for reducing carbon dioxide emissions are the use of
unconventional energies (solar, wind, hydraulic, geothermal) with hydrogen or ethyl
alcohol as energy vectors, low temperature sources, heat pumps, etc. For building heating
systems, the energy reduction solution is to achieve a good thermal insulation of the
external closing elements of the construction, to recover the heat from the contaminated
air eliminated outside and the use of heating systems with low thermal parameters (below
0
50 C) such as the heating of the spaces through the floor or walls.

1. Overview
The floor heating system in Romania has been used since antiquity (in ancient
Dacia), to heat many houses of the dignitaries of the time or to the thermal baths
under the name of hypocaust-hot air heating, due to the comfort created by this
heating system.

Figure 1. Hypocaust-hot air heating houses – ancient city of Sarmisegetuza Ulpia Traiana (Hațeg) and
Roman Fortress, Jidava (Argeș county)

The floor heating system using thermal agent as hot water circulating through
embedded floor pipes in the rooms has started to be widely used since approx. 50
years ago with the use of plastic pipes that have a lifespan of over 70 years. The
authors have widely used this system to heat chicken coop - ground flooring,
residential buildings, sports grounds or cathedrals (over 100 ample buildings).

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Figure 2. Floor heating in cathedrals: Catedrala Mântuirii Neamului-București,

Catedrala Romano-Catolică Iași and Biserica Crestină Baptistă – Deva

Floor heating is possible in the form of three solutions: hot air heating, liquid
heating and electric heating. Electric heating is recommended to be done only in
spaces where the living, including people, stay a maximum of 10 minutes/day on
these electrically heated surfaces due to the negative effects on the blood of
electromagnetic fields that form around the heating cables.
In Romania, technical design data were provided by suppliers of materials and
equipment obtained from their own experience or taken from research institutes,
such as INCERC.
Currently, European standards are being finalized for the floor heating systems
to which the authors of this paper propose to add some ideas that can be included
in the new Romanian regulations.

2. Solutions proposal to be introduced in design, construction and operation

of floor heating/cooling systems Standards.

The draft European Standards for the floor heating / cooling system, water based
surface embedded heating and cooling systems is presented in EN1264 and has 5
parts:
1. Symbols and Definitions
2. Methods for the determination of the thermal output using calculation and
test methods
3. Dimensioning
4. Installation
5. Thermal output calculation for heating/cooling floors, ceilings and walls.
The authors proposed updates to the new 2021 standars as follow:
a) the minimum speed of the water circulating in the pipes mounted in the
floor/walls for the elimination of the air is not specified In Fpr EN1264-2, chapter 4,
Thermal boundary conditions, the value for turbulent pipe flow is given: mH/di>
4,000 kg/(h ∙ m);
In our opinion this value ranging from 4000 to infinity cannot be used for
design because the upper limit is not stipulated in any 1264 series standard;
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A simple calculation shows that, if we go with the value of 4000 to a pipe with
an inner diameter of 15 mm, a water velocity results through the conduction of
about 0.0945 m/s.
Knowing that for most pipes, when mounted on the floor, it is not possible to
ensure a continuous slope to eliminate the open air as in conventional heating and
to eliminate the air in the pipes in the counter-slope the water must have a speed
higher than the air entrainment speed (calculated or measured), other conditions
must be added to the above mentioned condition; in the draft standard there are
also economic calculation conditions for maximum energy consumption.
The adjacent sheet shows the diagrams for the minimum water velocities
through pipes, at different diameters, water temperatures and the angle of
inclination of the pipes (counter-slope), so that the air from the pipes is easily
eliminated and the installation works at the parameters.
Example, for a pipe with an inner diameter of 15 mm minimum water speed at
water temperature of 500C and a slope higher than 40 degrees (connections to
distributors, collectors, stairs, performance halls sloping floor, amphitheater-type
places of worship, etc.) the minimum water speed must be 0.30 m/s, so mH/di will
have a value of about 3 times than the minimum indicated.
We propose to complete the standard with this diagram as well.
b) early detection of damage in the heated floor field due the water drained,
from damaged pipes under the polystyrene insulation;
From our experience of over 40 years in the field, we believe that it is
necessary for the floor heating system to be accompanied by warning systems for
possible water leaks from damaged pipes mounted in the floor; the need arises
because, in general, the pipes are mounted on a thermal insulation layer through
which water flows gravitationally at the base of the layer and the signal may be
delayed with the appearance of signs in other parts than where the damage is
located (crack).
The installation and equipment are similar to those used for the ground
installation of pre-insulated pipes.
An example is given in the attached sheet.
c) the influence of the groundwater table under the building is not taken into
account in the sizing calculation (for floor heating mounted on the ground);
Heat flow through the floor is influenced by the depth of the groundwater. We
believe that, especially in large buildings, this influence must be addressed.
d) standards for the installation of the system pipes buried in the floor
serpentine, is more a school assemble, which misleads the designers and builders.
In all the figures from the 1264 standards, only the floor pipe serpentine
installation system is presented with a single serpentine; it is good to indicate other
systems, for example the snail one, with several serpentines; this system is more
difficult in design and installation but has multiple advantages in operation,
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especially in case of a circuit failure, the average temperature at the floor surface is
uniform and the temperature peaks are much flatter than the coil mounting.

Annexes:

3. Conclusions
The floor heating system requires thermal agent (water/antifreeze solution)
with temperatures below 50°C, which can be obtained by variouse carbon dioxide
low emissions methods such as: solar energy, geothermal with heat pumps , heat
recovery from technological processes, etc. In well-insulated buildings, the floor
heating system or in high-rise buildings such as religious buildings, the system can
be used alone without having other additional heating systems, such as radiators,
radiant tubes, hot air, etc.

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The floor heating system creates superior comfort conditions compared to

other heating solutions
The system has a high inertia which gives it another major advantage because it
is both a storage and a distributor of low temperature heat.
Considering that in the European standards the dimensioning of the minimum
water speed through the system of pipes embedded in the floor is not given, it is
necessary that in the national norms to be introduced the calculation formula
proposed above; a lower water speed than the speed of air entrainment through
the pipes, at different slopes of the mounted pipe, would lead to large hydraulic
imbalances, with consequences on the uniform distribution of heat on the heated
surface.
The solution proposed in the standard to use in the heating field only one coil
has several disadvantages in the current operation. It is proposed to make heating
fields with several coils mounted in parallel, in a "snail" system.

References:
* * * pr EN 1264 Water based surface embedded heating and cooling systems (part 1,2,3,4,5)
* * * EN15377 Design of embedded water based surface heating and cooling systems. (part 1-8)
Badea Gheorghe, Mateescu Ioan, Badea Florin, Felseghi Raluca Andreea, Aschilean Ioan, HUB-ul
energetic roman intre intentie si realitate faptica, Conferina Stiinta Moderna si Energa ed.39,
Cluj Napoca, 2020.
Mateescu Ioan, Reducerea consumurilor energetice in zootehnie Conferinta Instalatii, Sinaia 1974
Mateescu Ioan, Popescu Miron, Incalzirea prin pardoseala, metoda de reducere a consumului de
combustibil in cladirile agrozootehnice, Conferinta de Instalatii (a XV-a), Sinaia 5-7 nov. 1981
Mateescu Ioan, Incalzirea prin pardoseala, Conferinta de Instalatii, Sinaia, 3-5 octombrie 1990
Mateescu Ioan, Mateescu Ovidiu, Consideratii privind incalzirea lacasurilor de cult. Conferinta
Nationala de Instalatii, Sinaia, 15-17 octombrie 2014
Ilina Mihai, Lungu Catalin, Tratat de inginerie termica in cladiri, Ed. Matrix, 2019

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SPONSORS OF CONFERENCE

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