X-ray Spectrometry activities in 2019

Andreas KarydasHead of the XRF laboratory

http://www.inp.demokritos.gr/xrf/INPP, NCSR “Demokritos”karydas@inp.demokritos.gr

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http://www.inp.demokritos.gr/xrf/mailto:karydas@inp.demokritos.gr

• Andreas Karydas, Head of XRF-LabCollaborators:Vasiliki Kantarelou, Maria Kaparou, Georgios Mastrotheodoros, Eleni Kokiasmenou, Manos Manousakas

Students:• Nelly Kladouri, PhD, University of Peloponnese, in progress • Kalliopi Tsampa, MSc thesis, NTUA, in progress• Sotiria Symeonidi, Diploma, NTUA, Completed November 2019• Savvina Fotiou, MSc thesis, CultTech, Completed July 2019

XRF group 2019

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Research Activities

Development of XRF Spectrometers for tailored applications

Development of X-ray spectrometry

methodologies & applications

XRF-LabElettra (2 beamtime)AGLAE (1 beamtime)

KnowledgeTechnologyTransfer Services

Improvement/ Developmentof quantification models/approaches

X-ray Spectrometry

Elettra(2 beamtime)

Cultural Heritage

Environmentalresearch

Biomedicine

Advanced Materials

Resonant RamanScattering

Cascade X-rayEmission

X-ray FundamentalParameters Spin-off

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Services• ATC - TSAMPAS BROS S.A., • MagnisiaEphorate of

Antiquities• Finnish Institute at Athens• Benaki Museum

MSc studentsFive (5) - University of West AtticaOne (1) - University of Peloponnese

4/1

1/7

1/0

1/1

Geochemistry1/0

Peer Review/Abstracts

Three (3)Technical Reports

1/1

Scientific outcome (2019)

Education (2019)

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9 publications in peer–review journals1 invited plenary talk + 3 oral8 poster presentations

1 MSc thesis completed1 Diploma work completed6 MSc theses supported

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Elettra Sincrotrone Trieste, Trieste, Italy1) “Study of deep-implanted multilayered structures in silicon wafers with IBA (Ion Beam

Analysis) and Grazing Incidence X-ray Fluorescence Spectroscopy”, E. Ntemou

2) “A systematic study of the inelastic LM Resonant Raman scattering process on Au and

of the cascade Au-M emission to improve the non-invasive XRF characterization of

ancient/historical gold artefacts and of gilding layers”, K. Tsampa

3) “Measurements of different physical parameters for Sb at energies across its Li edge

energies using synchrotron radiation.”, S. Symeonidou

4) “Study of low probability atomic processes by Resonant Inelastic X-ray Scattering”

Accélérateur Grand Louvre d'Analyses Elémentaires – AGLAE, Paris, France1) “Provenance study of Mycenaean Gold”, M. Kaparou, K. Tsampa, N. Kladouri

Experiments at large scale facilities - 2019

Fundamental interactions/X ray parameters

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R. Kaur, A. Kumar, M. Czyzycki, (...), A.G. Karydas, S. Puri, “A study of the influence of chemical environment on the Li (i = 1–3) subshell X-ray intensity ratios and the L3 absorption-edge energy for some compounds of 66 Dy using synchrotron radiation”, X-Ray Spectrometry, (2019), 1-12

Deviations from theoretical estimations due to the combined influence of the many‐body and chemical environment effects, overall error in the present measured intensity ratios is estimated to be ~3–5%

Advanced materials characterization-Deep Implanted ions

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M. Kokkoris, E.G. Androulakaki, M. Czyzycki, M. Erich, A.G. Karydas, (...), V. Paneta, S. Petrović, “Argonions deeply implanted in silicon studied by Rutherford/Elastic Backscattering and Grazing Incidence X-rayFluorescence spectroscopy”, NIM B’, 450 (2019) 144–148

6 degrees incidence

Collaboration with TU of Athens

μ-XRF QC of periodic ZnO nanostructures fabrication

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P. Papageorgiou, A. G. Karydas, V. Kantarelou, G. Papageorgiou, E. Makarona, Combining bottom-up and top-down approaches with micro X-ray fluorescence spectroscopy for controllable fabrication of periodic ZnO nanostructures, presented at 45th International Conference on Micro & Nano Engineering, Rhodes Greece, September 23rd - 26th, 2019

3-step Fabrication Process combining bottom-up (sol-gel + hydrothermal growth of nanostructures) with top-down fabrication methods (e-beam lithography

Results of μ-XRF can ne used to evaluate non-destructively the uniformity and homogeneity of seeding layer’s nanotopography and can be used to reveal possible correlations to the subsequent lithographic steps and hydrothermal growth of nanostructures

Micro-XRF as non-destructive and enabling nanometrology technique that can leverage the development of novel nanofabrication processes

Zn-K signal variability

bare Si

Si with SiO2

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P. M. Wróbel, Ł. Chmur, M.M. Grzelak, Z. Stęgowski, M. Lankosz, D. Adamek, R. Jach, A. Migliori, A. G. Karydas,“Towards histopathological analysis based on X-ray fluorescence elemental imaging supported by multivariateanalysis - Case study of ovarian cancers”, Spectrochimica Acta Part B 155 (2019) 4–11

Biomedicine

K-means clustering and non-negative matrix factorization were applied for image segmentation of acquired elemental distribution maps into three sub-regions corresponding to stromal area, tumour area and unclassified area. Great potential in the investigation on the role of micro and trace elements in tumour biology

S: stromal area, T: tumour area

AGH University of Science and Technology. Poland

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A. Kavčič, K. Mikuš, M. Debeljak, J. Teun van Elteren, I. Arčon, A. Kodre, P. Kump, A. G. Karydas, A. Migliori, M.Czyzycki, K. Vogel-Mikuš, “Localization, ligand environment, bioavailability and toxicity of mercury in Boletusspp. and Scutiger pes-caprae mushrooms”, Ecotoxicology and Environmental Safety 184 (2019) 109623

Environmental safety - Ecotoxicology

University of Ljubljana, Józef Stefan Institute

Scutiger pes-caprae

Hg in examined mushrooms from non-polluted environments ismainly bound to di-thiolate (43-82%) and di-selenol (13-35%) ligands and less to tetra-thiols (12-20%), while at Hgpolluted sites the proportion of di-selenoland tetra-thiol ligandsincreases

S1: di-thiolate - Hg(S-R)2S2: tetra-thiolate - Hg(S-R)4EXAFS spectrum

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I. Tzifas, A. Papadopoulos, P. Misaelides, A. Godelitsas, J. Göttlicher, H. Tsikos, P.N. Gamaletsos, G. Luvizotto,A.G. Karydas, M. Petrelli, F. Noli, V. Kantarelou, A. Kontofakas, A. Hatzidimitriou, “New insights into mineralogyand geochemistry of allanite-bearing Mediterranean coastal sands from Northern Greece”, Geochemistry,Volume 79(2) (2019) 247-267

Geochemistry: Th-REE associations in black sands N. Greece

Knowledge of the REE-, Th-and U-bearing phases has key implications for the economic viability of the said placer deposits and the potential environmental impact of their beneficiation.

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E. Kokiasmenou, C. Caliri, V. Kantarelou, A. G. Karydas, F. P. Romano and H. Brecoulaki, “Macroscopic XRFimaging in unravelling polychromy on Mycenaean wall-paintings from the Palace of Nestor at Pylos”, To bepublished in Journal of Archaeological Sciences: Reports

MA-XRF imaging of Bronze Age Wall-paintings

MSc Diploma thesis: Eleni Kokiasmenou

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Analysis of paintingblue material used tocover the surface of aZoetrope, a pre-cinemaoptical toy from theGreek Film Archivecollection © T. Vazelaki,MSc thesis

Analysis of inks and deteriorations the working drawing (anthivolo), "The Holy Trinity" from the Chioniadespainters' workshop. © A. Papacharalambous - Kritzali, MSc thesis

Investigation of pigments on printed silk fabric of the collection of the National Historical Museum, © N. Tasiouli, MSc thesis

Analysis of pigments onRussian icons from the BenakiMuseum collection, 16th - 20thc. © A. Kalliga, MSc thesis,Benaki museum

In-situ XRF measurements at the “Bema of Phaidros” within the Dionysos Theatre located at the south slopes of the Acropolis hill. © K. Kallinteraki, MSc thesis © Ministry of Culture and Sports /Athens Ephorate of Antiquities

Training of MSc students

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The Challenge (2019-2023)The main aims and objectives of the Action is to coordinate the efforts made at national and transnational level to establish total reflection X-ray fluorescence (TXRF) as a reference technique for reliable elemental analysis of solid and liquid matrices, for the purposes of both fast screening and accurate quantitative determination. These objectives will be achieved via the development of a strong TXRF network, building capacity by training, connecting and involving stakeholders.

StructureThe Managing Committee (MC) decided on the following Working Group (WG) structure for the Action:•WG1 - Instrumentation, modelling, data evaluation and software •WG2 - Metrology and standardization •WG3 - Sample preparation and analytical procedures •WG4 - Performance Assessment and Data Analysis Thematic Sub Groups (SG) are also established:•SG Environment •SG Surfaces and Thin Films •SG Bio-medical Diagnostics

https://www.cost.eu/actions/CA18130/#tabs|Name:management-committeehttps://enforcetxrf.eu/working-groups/wg1/https://enforcetxrf.eu/working-groups/wg2/https://enforcetxrf.eu/working-groups/wg3/https://enforcetxrf.eu/working-groups/wg4/https://enforcetxrf.eu/subgroups/sg-environment/https://enforcetxrf.eu/subgroups/sg-surfaces-and-thin-films/https://enforcetxrf.eu/subgroups/sg-bio-medical-diagnostics/

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Outlook – Future perspectives ➢ Awaiting evaluation for 4 “Research + Innovation” projects + 1 “ELIDEK PostDoc” +

1 infrastructure EU project H2020-INFRADEV-2019-3 “GEOANT-Labnet”

• Continuation of basic and applied research activities at Elettra Sinctrotrone TriesteStudy of X-ray FPs of key elements: Ge, Sb, Re, Hf, AuSystematic Resonant Raman Scattering studies on Ge, Au

• Continuation of “Myc-GoldPro” project in all “fronts”: Beamtime @AGLAE, XRF-lab measurements, in-situ campaigns at Greek sitesGoal: XRF-Lab to be connected with the European Research Infrastructure Cultural Heritage (ERICH) as infrastructure within the National Greek node (ERIHS.gr)

• Further strengthening of the strategic partnership with LANDIS group at INFN-LNS, Italy to be equipped next year with state of the art X-ray instrumentation (3ME) but also with: INN at NCSR-D, University of Ioannina, University of Thessaloniki and University of Peloponnese

Acknowledgements

Dr Maria KaparouΑrchaeologist/Archaeometry

specialist

Dr GeorgiosMastrotheodoros

Conservator/Archaeometry

specialist

Ms Nelly Kladouri,Conservator/ PhD Candidate

Ms Kalliopi TsampaPhysicist, MSc NTUAErasmus at AGLAE

➢ Dr. Paolo Romano, LNS- INFN Laboratori Nazionali del Sud & CNR, Istituto per i Beni Archeologici e Monumentali (IBAM)➢ Dr. Claudia Caliri, LNS- INFN Laboratori Nazionali del Sud

Dr Vicky Kantarelou

Physicist