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- Herausgeber: John Wiley & Sons
- Kategorie: Fachliteratur
- Serie: ISTE Consignment
- Sprache: Englisch
Many areas of material science have been transformed by the use of synchrotron radiation X-rays, including the fields of cultural heritage materials and biomineralization. This book presents a selection of contributions that illustrate recent developments and applications of these tools, focused either on the main techniques used in the cultural heritage and biomineralization communities or on specific materials, studying their intrinsic properties or how they change with time.
Each chapter can be read alone, and each individually demonstrates the intimate links between materials and methods. The chapters explore the main principles of synchrotron radiation, as well as techniques based on X-ray absorption and diffraction, and give an overview of how these approaches have developed in recent decades in the field of cultural heritage, with specific examples such as ancient ceramics, corrosion of iron-based materials, concrete used in Roman monuments and the biomineralization process in sea urchin spines.
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Veröffentlichungsjahr: 2024
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Table of Contents
Cover
Table of Contents
Title Page
Copyright Page
Preface
1 Introduction to Synchrotron Radiation: Application to the Study of Cultural Heritage Materials and Biominerals
1.1. Introduction
1.2. What is synchrotron radiation?
1.3. Synchrotron radiation and Cultural Heritage
1.4. Conclusion
1.5. Acknowledgments
1.6. References
2 Development of the Use of Synchrotron Radiation for the Study of Cultural Heritage Materials
2.1. Introduction
2.2. Synchrotron techniques used in the study of cultural heritage materials
2.3. Study of specific pigments in ceramics, sculptures and murals
2.4. Study of paintings
2.5. Study of murals and rock art
2.6. Study of cosmetics
2.7. Study of parchments and manuscripts
2.8. Artwork restoration and preservation effort with synchrotron
2.9. Other cultural heritage studies
2.10. Study in paleontology
2.11. Conclusion
2.12. Acknowledgments
2.13. References
3 Application of Full-field X-ray Absorption Spectroscopy Imaging in Transmission Mode to Study Cultural Heritage Samples
3.1. Introduction
3.2. The worldwide context of tender and hard X-ray domain FF-XANES instruments
3.3. Typical acquisition, processing and sample preparation strategies for CH studies: the example of the FF-XANES set-up at beamline ID21 (ESRF)
3.4. Applications of FF-XANES to study CH samples
3.5. Conclusion
3.6. Acknowledgments
3.7. References
4 Structural Cartography and Tomography by Diffraction/Diffusion: A Local Selective Analysis of Cultural Heritage Materials
4.1. Introduction
4.2. 2D mapping using diffraction
4.3. 3D mapping by tomography
4.4. Diffraction/scattering computed tomography: DSCT
4.5. Conclusion
4.6. Acknowledgments
4.7. References
5 Contribution of Synchrotron Radiation to the Study of Glazed Ancient Ceramics
5.1. Introduction
5.2. The problem
5.3. Spectroscopic techniques
5.4. Diffraction techniques
5.5. Conclusion
5.6. References
6 Relevant Synchrotron X-rays Techniques to Study Corroded Iron Cultural Heritage Material
6.1. Introduction
6.2. Iron corrosion diagnosis in historical monuments
6.3. In situ experiments for a direct observation of corrosion processes
6.4. Archaeological objects corrosion and stabilization
6.5. Protection of ancient iron artifacts
6.6. Conclusion and outlook
6.7. Acknowledgments
6.8. References
7 Synchrotron X-Ray Microdiffraction Studies of the Mortars of Ancient Roman Concretes
7.1. Introduction
7.2. Standard powder X-ray diffraction studies of Roman mortars
7.3. Synchrotron μXRD and μXRF studies of ancient Roman mortars
7.4. Architectural mortars – Markets and Forum of Trajan
7.5. Marine harbor mortar –
Baianus Sinus
Bay of Pozzuoli
7.6. Roman principles of concrete longevity
7.7. Conclusion
7.8. Acknowledgments
7.9. References
8 Biomineralization in Sea Urchin Spines: A View on Amorphous Calcium Carbonate Occurrence, Stabilization and Crystallization
8.1. Introduction
8.2. Biomineralization in sea urchins
8.3. Occurrence of ACC precursors in regenerated sea urchin spines
8.4. ACC structure and stability: role of water and ion impurities
8.5. Induced crystallization of remnant ACC in sea urchin spines
8.6. Conclusion
8.7. Acknowledgments
8.8. References
List of Authors
Index
End User License Agreement
List of Tables
Chapter 3
Table 3.1. Experimental parameters used for TXM-XANES imaging systems. Values ...
List of Illustrations
Chapter 1
Figure 1.1. a) Crab nebula mosaic image, taken by NASA Hubble Space Telescope ...
Figure 1.2. a) Schematic representation of a synchrotron storage ring. Adapted...
Figure 1.3. a) Incident flux delivered by the Superbend source of the 12.3.2 b...
Chapter 2
Figure 2.1. Left: Jian war with “hare’s fur” glaze, Southern Song dynasty, 12t...
Figure 2.2. Left: Maya Blue was used in the background on this Mayan painting ...
Figure 2.3. Combining synchrotron high-resolution powder diffraction and Laue ...
Figure 2.4. Synchrotron has revealed a hidden portrait of a woman (b) undernea...
Figure 2.5. (a) Scanning electron micrograph of the cosmetic powder taken from...
Figure 2.6. Synchrotron was used to study the red and black ink used in Egypti...
Figure 2.7. Through synchrotron studies, it was revealed that the yellow color...
Figure 2.8. Using synchrotron Laue microdiffraction, researchers examined the ...
Figure 2.9. The enigmatic fossil, Tullimonstrum gregarium, at the Museo di Sto...
Figure 2.10. The analysis of the Berlin fossil feather (left, Credit: H. Raab,...
Chapter 3
Figure 3.1. FF-XANES application in the tender and hard X-ray domain for CH st...
Figure 3.2. Example of a) a dark image; b) a flat-field image (reference); (c)...
Figure 3.3. a) Scheme and optical image of a 30 μm thick section of the binary...
Figure 3.4. Top: comparison of the acquisition conditions in focused mode (zon...
Figure 3.5. a) Photomicrograph of 7914Cd(OH)Cl thin section after thermal agin...
Figure 3.6. Photomicrographs of thin sections obtained from a naturally aged a...
Figure 3.7. FF-XANES of the thin section of a fragment from the Campanian samp...
Chapter 4
Figure 4.1. Experimental device and analysis steps to make 2D structural maps ...
Figure 4.2. 2D structural maps by diffraction of a fresco-type Roman wall pain...
Figure 4.3. Example of statues originating from the Duchy of Savoy, dating bac...
Figure 4.4. XRD and XRF analyses of the ID22 beamline of the ESRF, from micros...
Figure 4.5. One of the first observations of diffraction/scattering computed t...
Figure 4.6. The DSCT method: reconstruction by direct analysis. For a color ve...
Figure 4.7. The DSCT method: reconstruction by reverse analysis. For a color v...
Figure 4.8. Multimodal DSCT diffraction–tomography experimental device: a) an ...
Figure 4.9. Example of structural and chemical mapping of a sample of papyrus ...
Figure 4.10. Example showing the mapping of an applied brocade sample taken fr...
Chapter 5
Figure 5.1. 18th century bowl base (Cox, Haute-Garonne, France) with an indica...
Figure 5.2. Example of an analysis of a South Gaul sigillata glaze from the 1s...
Figure 5.3. Fragment of South Gaul pre-sigillata (1st century BCE) with black ...
Figure 5.4. Two-color mapping of the Fe(II)/Fe(III) distribution of the pre-si...
Figure 5.5. Maps of the Fe(II)/Fe(III) distribution for different types of pre...
Figure 5.6. SEM images corresponding to the red and black sides of the pre-sig...
Figure 5.7. Study of a fragment of porcelain from the Ming dynasty (1368–1644)...
Figure 5.8. Main steps in sample preparation. Cutting (cross-section 1 to 3) o...
Figure 5.9. Radiographs of the Attic vase sample before (7,070 eV) and after t...
Figure 5.10. Mappings of the energy position (left) and jump height (right) of...
Figure 5.11. Spatial distributions of the different phases obtained from the r...
Figure 5.12. Study of the blue pigmented zone of porcelain from the Ming dynas...
Figure 5.13. Fragment of marbled La Graufesenque sigillata from the 1st centur...
Figure 5.14. Study of a transverse section of sigillata with marbled glaze (AL...
Figure 5.15. a) 3-color mapping of the elemental composition allowing visualiz...
Figure 5.16. Diffraction pattern of a red zone of glaze collected with a monoc...
Figure 5.17. Polychromatic and monochromatic beam diffraction patterns collect...
Figure 5.18. Indexing of the Laue diffraction pattern using the X-ray Microdif...
Figure 5.19. Mapping the distribution of iron and quartz grains obtained after...
Figure 5.20. Example of a study coupling monochromatic and polychromatic diffr...
Chapter 6
Figure 6.1. Photographs of some historical and archaeological sites, where the...
Figure 6.2. Phases in presence in the case of atmospheric corrosion of iron. E...
Figure 6.3. Micrography of Deogarh (India) sample, where the main phases const...
Figure 6.4. Photographs of the set-up (top left) in transmission mode for XRD ...
Figure 6.5. Crystallographic structure of β-FeOOH akaganeite and β-Fe2(OH)3Cl ...
Chapter 7
Figure 7.1. Photographs of drill cores of ancient Roman concrete. A) Markets o...
Figure 7.2. SEM-BSE images of typical Roman mortar fabrics. (A) Markets of Tra...
Figure 7.3. Theater of Marcellus (44–11 BCE), Rome, standard X-ray diffraction...
Figure 7.4. Beamline 12.3.2 at the Advanced Light Source. (A). A polychromatic...
Figure 7.5. Markets of Trajan (100–110 CE), Rome, strätlingite mineral cements...
Figure 7.6. Markets of Trajan, Rome, scoria vesicle, drill core from the concr...
Figure 7.7. Forum of Trajan (dedicated 112 CE), Rome, pumice aggregate, fallen...
Figure 7.8. Baianus Sinus breakwater (ca. 55 BCE), Bay of Pozzuoli, 1.3 m belo...
Figure 7.9. Baianus Sinus breakwater, Bay of Pozzuoli, spherical microstructur...
Chapter 8
Figure 8.1. A) Test of sea urchin Paracentrotus lividus; B) 3D rendering of a ...
Figure 8.2. A) X-ray diffraction pattern of an intact spine with its c-axis or...
Figure 8.3. A) Growing tip of a spine composed of microspines at the very tip ...
Figure 8.4. A) SEM micrograph of the tip of regenerated spine; B) Ca component...
Figure 8.5. A) WAXS pattern of ACC obtained at ID11 with a large q-range and i...
Figure 8.6. Reduced pair distribution function G(r) of additive free ACC in bl...
Figure 8.7. A) PDF of additive free ACC and calcite, the WAXS signal of both p...
Figure 8.8. Differential maps (dPDF/dT) of A) additive free ACC and B) Mg-ACC ...
Figure 8.9. Part of the HR-XRD profiles of sea urchin spines (in purple) and t...
Figure 8.10. A) (006) XRD reflection peaks of the native, 200°C and 400°C anne...
Figure 8.11. A) Sea urchin spine SAXS intensity profiles for selected temperat...
Guide
Cover Page
Table of Contents
Title Page
Copyright Page
Preface
Begin Reading
List of Authors
Index
WILEY END USER LICENSE AGREEMENT
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SCIENCES
Physics of Condensed Matter,Field Directors – Roland Pellenq and Pierre Levitz
Cultural and Industrial Heritage Materials,Subject Head – Philippe Sciau
Synchrotron Radiation, Cultural Heritage, Biomineralization
Coordinated by
Catherine Dejoie
Pauline Martinetto
Nobumichi Tamura
First published 2024 in Great Britain and the United States by ISTE Ltd and John Wiley & Sons, Inc.
Apart from any fair dealing for the purposes of research or private study, or criticism or review, as permitted under the Copyright, Designs and Patents Act 1988, this publication may only be reproduced, stored or transmitted, in any form or by any means, with the prior permission in writing of the publishers, or in the case of reprographic reproduction in accordance with the terms and licenses issued by the CLA. Enquiries concerning reproduction outside these terms should be sent to the publishers at the undermentioned address:
ISTE Ltd27-37 St George’s RoadLondon SW19 4EUUKwww.iste.co.uk
John Wiley & Sons, Inc.111 River StreetHoboken, NJ 07030USAwww.wiley.com
© ISTE Ltd 2024The rights of Catherine Dejoie, Pauline Martinetto and Nobumichi Tamura to be identified as the authors of this work have been asserted by them in accordance with the Copyright, Designs and Patents Act 1988.
Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s), contributor(s) or editor(s) and do not necessarily reflect the views of ISTE Group.
Library of Congress Control Number: 2024943302
British Library Cataloguing-in-Publication DataA CIP record for this book is available from the British LibraryISBN 978-1-78945-199-3
ERC code:PE4 Physical and Analytical Chemical SciencesPE4_14 Radiation and Nuclear chemistrySH5 Cultures and Cultural ProductionSH5_8 Cultural studies, cultural identities and memories, cultural heritage
Preface
Catherine DEJOIE1, Pauline MARTINETTO2 and Nobumichi TAMURA3
1European Synchrotron Radiation Facility, Grenoble, France
2Institut Néel CNRS/UGA, Grenoble, France
3Advanced Light Source, Lawrence Berkeley National Lab, USA
The last significant book focusing substantially on the use of synchrotron radiation to study cultural heritage materials was published more than two decades ago1. Therefore, we strongly believe that the time is ripe for a new publication, considering the remarkable progress made in synchrotron techniques since then. These advancements have greatly broadened the range of applications, encompassing diverse materials. Hence, we have decided to curate contributions from several experts in the field to create a fresh and updated volume on the utilization of synchrotron radiation in studying cultural heritage materials, fossils and biominerals. Divided into three parts, this volume covers various contributions that showcase the impact of synchrotron-based techniques in these fields.
The first part begins with an introduction to synchrotron radiation and facilities, highlighting their increasing importance in cultural heritage and related research. The second part delves into the application of synchrotron radiation in examining cultural and paleontological artifacts. Techniques such as full-field X-ray absorption spectroscopy imaging and X-ray diffraction-computed tomography are explored, shedding light on various materials and offering valuable insights.
The third part focuses on specific materials significant to Cultural Heritage. Ceramics, which played a crucial role in ancient civilizations, are studied to understand glaze and slip compositions using synchrotron techniques. Iron-based materials are also investigated, revealing insights into their corrosion and long-term evolution. The study of Roman concrete using synchrotron-based techniques showcases the material’s exceptional resilience and provides inspiration for modern, sustainable materials.
Finally, the book explores biomineralization, where living organisms produce minerals, impacting materials like bones and ivory artifacts. Synchrotron methods aid in understanding the mineralization process and contribute to preservation and conservation strategies.
We hope this book captivates readers, offering insights into the diverse scientific studies at synchrotron facilities worldwide. It showcases significant contributions in cultural heritage, fossils and biominerals, highlighting the significant contributions made by synchrotron-based investigations in these fields. By exploring the pages of this book, we aim to provide readers with a glimpse of the vast array of applications and breakthroughs made possible by synchrotron technology. Our aspiration is to inspire future researchers, encouraging them to explore the endless possibilities of synchrotron technology and contribute to knowledge in these fields. May this book serve as a catalyst for transformative research ahead.
September 2024
Note
1
Creagh, D.C. and Bradley, D.A. (2000).
Radiation in Art and Archeometry
. Elsevier, Amsterdam.
1Introduction to Synchrotron Radiation: Application to the Study of Cultural Heritage Materials and Biominerals
Catherine DEJOIE1, Pauline MARTINETTO2 and Nobumichi TAMURA3
1 European Synchrotron Radiation Facility, Grenoble, France
2 Institut Néel CNRS/UGA, Grenoble, France
3 Advanced Light Source, Lawrence Berkeley National Lab, USA
1.1. Introduction
Cultural Heritage materials are often complex and heterogeneous with a hierarchical architecture spanning from the nanometer range to the macroscopic. An ancient ceramic is usually made of a clay body, on which a surface decoration is apposed (clay patterning, slip, glaze, etc.). The chemical and structural composition of the raw materials and the firing technique (temperature and atmosphere control) affect the end quality and intrinsic properties of the product for its everyday use. An ancient iron axe preserves traces of the manufacturing process in its inner structure, hinting at the knowhow of the craftsman who manufactured it. The passing of time, storage conditions and conservation intervention are assessed by the presence of corrosion products and/or passivation layers at the surface of the axe. Cultural Heritage does not only refer to manufactured objects, but also encompasses the tools and techniques developed by ancient societies. In such a context, Roman concrete has shown exceptional resilience over time, as evidenced by Roman monuments still standing today after two millennia. Finally, preservation and conservation of our Cultural Heritage is of societal concern, a legacy from the past to be transmitted to future generations.
Cultural Heritage is at the junction of several disciplines, such as history, art, archaeology, materials science, chemistry, physics, geology and biology. The reasons for studying Cultural Heritage materials are diverse: knowledge of ancient societies, evolution of practices, development of trading exchanges, material properties, artifact dating, artwork preservation and restoration, etc. Today, the study of Cultural Heritage materials often requires scientific collaborations across multiple disciplines, necessitating combined approaches and promoting interactions between different scientific communities. The rarity, fragility and complexity of Cultural Heritage materials makes them challenging to study, justifying the use of the most advanced scientific tools such as synchrotron radiation facilities to decipher the secrets hidden in their structure.
Synchrotron radiation is the electromagnetic radiation emitted when charge particles travelling at relativistic velocities are radially accelerated. One of the most spectacular manifestations of synchrotron radiation is the Crab Nebula (and associated pulsar, a 30.2 Hz spinning neutron star), remnant of a supernova observed in 1054 by Chinese and Japanese astronomers (Figure 1.1a) (Burbidge 1957; Caroff and Scargle 1969; Bychkov 1973). The strong magnetic field produced by the pulsar bends the electron path, thus generating synchrotron radiation.
Figure 1.1.a) Crab nebula mosaic image, taken by NASA Hubble Space Telescope (credit: NASA, ESA). b) View of the European Synchrotron Radiation Facility (ESRF), Grenoble, France (credit: ESRF/D. Morel).
Part of the theory around synchrotron radiation was formulated at the end of the 19th century (Liénard 1898). The first particle accelerators emerged in the first half of the 20th century, and synchrotron radiation was observed for the first time at General Electric in 1947 (Goward and Barnes 1946; Elder et al. 1947). In the beginning, such radiation, causing the particles to lose energy, was mainly seen as a nuisance in high-energy electron accelerators (Blewett 1998). Nevertheless, the possibility to produce X-rays of unprecedented brilliance was soon recognized. Synchrotron beams were first used in a parasitic way by scientists at particle accelerators. Today, more than 50 fully dedicated synchrotron sources exist, distributed all over the world (Figure 1.1b)1.
Pioneering work using synchrotron radiation for the study of Cultural Heritage materials was performed in the 1990s at both the Synchrotron Radiation Source (SRS) at the Daresbury Laboratory in the UK (Pantos 2005) and at the European Synchrotron Radiation Facility (ESRF) in France (Walter et al. 1999). The use of synchrotron radiation for the study of Cultural Heritage materials is today more common. Over the last 20 years, the potential of such an approach, the main relevant synchrotron methods and their applications to Cultural Heritage material studies have been extensively reviewed (for example, Bertrand et al. 2012; Dejoie et al. 2018b; Cotte et al. 2019; Janssens and Cotte 2020). The same synchrotron tools used in Cultural Heritage materials are also relevant to other fields such as paleontology and biomineralization. Like in Cultural Heritage, seashells and other biominerals have a complex and multiscale hierarchical structure, the properties of which we have only started to understand. Millions of years of evolution have led nature to create materials that are unique in their properties and a new branch of science, biomimetics, which seeks to understand how nature does it and how we can create new materials with that knowledge.
The objective of this book is to show some recent applications of synchrotron radiation in the field of Heritage Science through a series of contributions about ancient ceramics, the corrosion of iron-based materials, the concrete used in Roman monuments and in the related field of biomineralization. In this introductory chapter, a few elements concerning synchrotron radiation will be briefly described, before introducing the contents of the book in more detail.
1.2. What is synchrotron radiation?
Synchrotron radiation is emitted when charged particles travelling at relativistic speed are accelerated in a curved trajectory. In a synchrotron facility, electrons are circulated in a storage ring near the speed of light. They are guided by magnetic fields coming from bending magnets that cause deflection of their trajectory in the horizontal plane, generating synchrotron radiation tangentially to the electron orbit. The storage ring has a polygonal shape, made of a series of cells, alternating bending magnets and straight sections, with insertion devices (wigglers or undulators) sources occupying the straight sections (Figure 1.2a). Bending magnets generate a continuous polychromatic X-ray spectrum with maximum intensity at a bending magnet critical energy. Insertion devices are made of arrays of magnets that provide a sinusoidal magnetic field, thus causing the trajectory of the electrons to oscillate, and, in so doing, to emit synchrotron radiation at each trajectory bend. In an insertion device, each emission of synchrotron radiation either adds up to produce a photon energy spectrum similar to a bending magnet but brighter (wiggler) or interfere constructively at certain energies, resulting in a series of radiation peaks (called harmonics) an order of magnitude brighter than a bending magnet or wiggler (undulators). On each turn in the storage ring, radio frequency (RF) cavities, which contain electromagnetic fields oscillating at radio frequencies, restore the energy lost by the electrons as they circulate and emit synchrotron radiation (Figure 1.2a). Beamlines where synchrotron radiation is used (mainly X-ray photons, and also IR and gamma rays) are constructed tangentially from both bending magnets and straight sections. Additional information on synchrotron radiation can be found in Margaritondo (1988), Als-Nielsen and McMorrow (2001), Kim (2001), Fitch (2019) or Hwu and Margaritondo (2021).
The principle attributes of synchrotron radiation can be defined as follows:
high brightness, so a highly collimated and intense beam emitted from a small source size, delivering high flux of photons to the sample. This brightness parameter will be discussed further in the next paragraphs;
a tunable range of wavelengths, extending from infrared, to soft and hard X-ray regimes, depending on the synchrotron facility. A specific wavelength can be chosen, or variable energy used, for example, for spectroscopy;
an X-ray beam with a certain degree of coherence that can be exploited for specific experiments, for example, ptychography;
a polarized source, as the synchrotron radiation is normally linearly polarized in the plane of the synchrotron orbit;
a pulsed source, as the electrons do not circulate individually in the storage ring but are confined in bunches. The distribution of the bunches allows the time structure to be exploited for specific experiments.
Figure 1.2.a) Schematic representation of a synchrotron storage ring. Adapted from Fitch 2019. b) X-ray beam profile obtained at the ID22 beamline (ESRF) on September 2020. As a result of the EBS (Extremely Brilliant Source, see below) upgrade, the beam is quasi-symmetric.
Two parameters are often highlighted when discussing storage rings and beamline performance: the energy of the electrons in the storage ring and the spectral brightness (or brilliance). These two parameters will be discussed further in the next few paragraphs.
The energy Ee of the electrons circulating at a speed v is given by:
where me is the mass of the electron at rest (me = 9.10938356 × 10−31 kg), and γ is the factor by which the mass of an electron increases because of its relativistic speed. After conversion of me in eV, the electron rest mass becomes 5.10998946 × 105 eV, and then the y factor can be expressed as a function of the energy (in GeV), with
Thus, for a 1.9-GeV (e.g. the Advanced Light Source (ALS), Berkeley, USA, optimized for the use of soft to medium energy X-rays) and a 6-GeV machine (e.g. the ESRF, Grenoble, France, optimized to access harder energy X-rays), γ takes a value of 3,718 and 11,742 respectively. The mass of an electron with an energy of 6 GeV is then roughly 10,000 times heavier than at rest. Expressed in atomic mass units, the mass of a 1.9-GeV electron and a 6-GeV electron is then 2.04 (comparable to the atomic mass of deuterium!) and 6.44 (almost a lithium atom!) respectively. Knowing the circumference and beam current of the synchrotron facility, the electron lap time, the number of laps per second or the expected number of electrons in the storage ring can also be calculated.
The second parameter, the brightness of a beamline, is defined as the number of X-ray photons per second, per 0.1% bandpass, per mrad2, per mm2, where 0.1% bandpass corresponds to a δλ/λ of 0.001, mrad2 is the solid-angle emission of the X-rays from the source and mm2 is the cross-sectional area of the source. As a result, a high-brightness source produces (at a given energy) a lot of photons per second, into a narrow solid angle, with a small source size. The source size plays an important role and is strongly influenced by the electron beam properties, in particular its emittance. The lower the emittance, the smaller the source size, and thus the higher the resulting brightness. Lowering the horizontal emittance of the electron beam is the main challenge today, and a number of synchrotron facilities are currently undergoing or planning an upgrade to tackle this (e.g. Raimondi 2016; Sajaev 2019). In order to achieve this, the ESRF, the first among the third-generation facilities to achieve such an upgrade, has implemented a new ring lattice, the Hybrid Multi-bend Achromat (HMBA), based on an increase and a new arrangement of magnets within a cell. As a result, the horizontal divergence of the beam was reduced, and a more symmetric X-ray beam, of increased brightness, was obtained (Figure 1.2b). The new source, called EBS (Extremely Brilliant Source) became available to users in August 2020.
The X-ray source and the optical elements used to condition the X-ray beam differ from beamline to beamline and are chosen and tuned to best fit specific types of techniques and experiments (e.g. diffraction, spectroscopy, imaging, etc.). Bending magnet and wiggler sources provide a broad spectral range of X-ray photons and are more suited for polychromatic applications and techniques, where energy tunability is desirable (spectroscopy). An undulator source provides a sinusoidal magnetic field, so by choosing the period of the magnetic array and by varying the strength of the field, both wavelength distribution and X-ray beam divergence can be controlled. As well as its bending magnet or insertion device source, a beamline will incorporate a number of optical elements such as beam-size defining slits, a monochromator to select the wavelength, and focusing elements such as Kirkpatrick–Baez (KB) mirrors and compound refractive lenses (CRL). To illustrate this, the layout of two X-ray diffraction beamlines will be described in the next two paragraphs. The first beamline is dedicated to microdiffraction, thus providing high-spatial resolution for structural studies, while the second one is dedicated to high-angular resolution powder diffraction, for which the use of a larger beam of low divergence is favored.
Beamline 12.3.2 (ALS, Berkeley) is built on a superconducting magnet (or superbend) source, thus providing a continuous range of energy in the 5–24 keV range (Figure 1.3a). A grazing incidence toroidal mirror relays the source to the entrance of the experimental hutch. Two operation modes for single-crystal or powder diffraction measurements are provided, using either the full polychromatic (white) beam delivered by the superconducting magnet source or a monochromatic beam. A four-bounce monochromator allows for fast-switching between the two modes, while accurately maintaining the beam position on the sample. The X-ray beam is focused down to 0.5μm×0.5μm in polychromatic mode and 5μm×2μm in monochromatic mode using a pair of KB mirrors. Laue (white beam) microdiffraction has proven to be a successful approach to map at the micron scale crystal orientation and crystal distortion in polycrystalline and composite materials, including Cultural Heritage materials (Tamura et al. 2003; Kunz et al. 2009; Chen et al. 2016).
The ID22 beamline of the ESRF is built on an in-vacuum undulator source with a 26 mm magnetic period. The corresponding spectrum is shown in Figure 1.3b. The polychromatic beam delivered by the undulator source arrives untouched onto a cryogenically cooled channel-cut Si 111 monochromator, and, after passing a series of slits, a 1 mm × 1 mm highly monochromatic beam (Δλ/λ≈10-4), of low divergence, is delivered to the sample. Aluminum-CRL can be inserted in the monochromatic beam as desired, for a resulting focusing down to 50 μm × 50 μm. The high-angular resolution of the powder pattern is ensured by the presence of analyzer crystals (e.g. perfect Si 111 crystals) intercepting the diffracted beam (Hodeau et al. 1998). As a result, the instrumental contribution to the full width at half maximum of a diffraction peak, measured on the NIST standard 640c Si 111 peak, is very small (< 0.0025° (2θ) at 31 keV); and this is exploited for a wide range of powder diffraction experiments (Fitch 2004; Dejoie et al. 2018a; Fitch et al. 2023).
Figure 1.3.a) Incident flux delivered by the Superbend source of the 12.3.2 beamline at ALS (extracted using the reverse method, Dejoie et al. 2011). b) Spectrum delivered by the U26 undulator of the ID22 beamline, ESRF (70 keV incident energy).
Synchrotron radiation facilities are user facilities, usually publicly funded. To gain access to a particular beamline and instrument, scientists from external academic or industrial laboratories submit scientific proposals. Proposals are peer-reviewed and accepted on the basis of their scientific merit. Users do not need to be experts in synchrotron radiation methods, as support is provided by the facility and the scientific and technical staff of the beamlines. Access to carry out proprietary research can also be arranged. Users can also form consortia around similar scientific interest and techniques and apply for beam time as is. This procedure is currently under implementation at the ESRF for Materials Science users (Streamline project) and will also benefit to the Cultural Heritage community through a dedicated BAG (Block Allocation Group) (Cotte et al. 2022).
1.3. Synchrotron radiation and Cultural Heritage
Owing to their non-standard shapes, their unique nature, their heterogeneity and sometimes multiscale and composite architecture, Cultural Heritage materials present some analytical challenges that synchrotron-based techniques may help to overcome. The intense beams provided by synchrotron facilities allow the study of samples via a series of X-ray based techniques, such as X-ray diffraction and scattering, X-ray absorption and emission spectroscopy, tomography and other imaging methods. The reasons to study Cultural Heritage materials can be diverse, but, most of the time, four main types of information are exploited:
the chemical composition of the sample, using X-ray fluorescence (XRF);
the oxidation state of the relevant chemical elements, using X-ray absorption spectroscopy (XAS);
the structural composition of the sample using X-ray powder diffraction scattering (XRD) techniques, to retrieve information about the crystalline phases, and, in some cases, about the non-crystalline content;
the general organization of the sample using two-dimensional and/or threedimensional chemical (XRF, XAS) and structural (XRD) mapping. Most of the time, the spatial resolution that can be achieved is intrinsically linked to the size of the incident X-ray beam, so micro- to nano-size beams are favored.
Most of the examples described in this book will exploit one, or several of these four types of information, also combined with results obtained from lab-based techniques. In some cases, average information about the material is favored and macroprobes are used; while in others, information at a more local scale is necessary, thus requiring the use of micro- or nano-probes. It is often necessary to combine several approaches and results obtained from independent and complementary probes when materials related to Cultural Heritage are studied.
This book dedicated to Cultural Heritage and synchrotron radiation is divided into three parts. The first part is composed of a single contribution, covering the development of the use of synchrotron radiation for the study of Cultural Heritage materials, with the description of a few pertinent examples in the field of ancient ceramics, mural and oil paintings, rock art, cosmetics, manuscripts and paleontology.
The second, composed of two contributions, is oriented toward synchrotron method developments and the applications of synchrotron mapping techniques to Cultural Heritage materials and biomineralization. One unique feature provided by synchrotron facilities is the ability to generate high-brilliance micro- to nano-beams. These beams enable rapid chemical and structural mapping of relatively large regions within just a few minutes. This capability sets synchrotron facilities apart, offering researchers a powerful tool to explore and analyze materials with exceptional precision and efficiency. We choose to focus on two main techniques exploiting absorption and diffraction respectively, both of which show increasing interest in all areas of materials science. First, the full-field X-ray absorption spectroscopy imaging technique will be described, and a few applications in relation to Cultural Heritage will be presented, in the first contribution. The second technique we choose to highlight is X-ray diffraction – computed tomography (XRD-CT). The basic principle will be explained, before showing its potential for Cultural Heritage studies, in the second contribution.
The third part of the book is composed of four contributions, oriented toward the study of four different types of material for which synchrotron-based techniques have had significant impact. The first type of material is ceramics. Ceramics are among the first examples in history of a large-scale development of crafted objects, for everyday use, decoration or trading. The manufacturing process involves a series of steps, sometimes approaching the industrial scale, as in the case of Terra Sigillata ceramics (Sciau et al. 2006) produced by the thousands in Roman times, or the Chinese Jian ceramics, fired in giant dragon kilns during the Song dynasty (Dejoie et al. 2014a). Ancient ceramics are found on mostly all continents, each civilization having developed its own specificities in terms of shape, decoration or firing technique. Ceramics can be seen as cultural markers, and, owing to their resilience toward underground storage and time, a lot of sherds are available today for analytical studies. In this context, a review on the studies carried out on the glaze and slips of ancient ceramics, for which synchrotron radiation was used, is presented.
A different kind of material is the topic of the second contribution, also widely used in ancient times: iron-based materials. Metallic objects have been widely manufactured by ancient societies, to be used as tools, jewelry or weapons. Metallic objects have also been used as support materials, for example, as reinforcement in monuments. Iron-based materials are subject to corrosion, and through this contribution, the concept of long-term evolution of a material through the ages will be introduced. The study of corrosion involves knowledge of electrochemistry, and synchrotron radiation can be used to follow specific reactions, in situ. This illustrates how the study of Cultural Heritage materials is not simply limited to an ancient artifact, but can also lead to interesting research on a specific topic such as corrosion.
The concept of “support material” with great Cultural Heritage significance will be at the center of the third contribution, through a study of Roman concrete. Due to its specific properties, this material allowed quite complex monuments to be built and to survive over two millennia. In this contribution, a set of synchrotron-based techniques including X-ray fluorescence, X-ray powder microdiffraction and X-ray Laue microdiffraction was applied to the study of ancient concrete from Imperial Rome. The close examination of chemical and structural compositions of these concretes using synchrotron microprobe techniques allowed us to understand the chemical mechanisms behind the extraordinary resilience and longevity of these materials. Cultural Heritage materials can provide information about the long-lasting resistance of a material, something that cannot be reproduced easily in a laboratory. As a result, a material such as Roman concrete can also be attractive for modern applications, and this is an example showing how our past can be a source of inspiration to design new, long-lasting materials, following an archaeomimetic approach (Dejoie et al. 2014b). Specifically, roman concrete is currently actively studied by several researchers because of their durability and low carbon footprint, when compared to modern technologies based on Portland cement.
The last contribution opens the path toward a different field: biomineralization. Biomineralization, at the frontier of biology and materials science, refers to the process by which living organisms produce minerals. In the field of Cultural Heritage, materials obtained from a biomineralization process involve, among others, bones or ivory-based artefacts. The 3D structure of these materials is related to their origin and can serve as fingerprint of a particular species (e.g. mammoth tusk vs. modern elephant tusk), and their properties can be influenced by external factors, such as heating, weathering or burial conditions (Reiche and Chalmin 2008; Albéric et al. 2017). Biomineralization can sometimes lead to the long-term degradation of the artifact, but it can also be used as a strategy for conservation, for example, to preserve and reinforce stone-based materials (Marjadi 2016; Marvasi et al. 2020). Biomineralization leads to the formation of complex mineral architectures, with properties resulting from a multiscale organization. Understanding the mineralization process requires this organization to be probed from the nanoscale to the macroscale, and synchrotron-based techniques can be used to provide such multiscale information. The contribution will focus on the biomineralization process in sea urchins’ spines, and how synchrotron techniques can help in deciphering calcium carbonate formation and stabilization.
1.4. Conclusion
The use of synchrotron radiation X-rays has strongly influenced many areas in materials science, including the field of Cultural Heritage materials and biominerals. Today, some efforts are still required to make synchrotron facilities a more routine solution for Culture Heritage and related fields communities. The first problem is practical: to access a synchrotron facility, a researcher has to submit a proposal which will be peer-reviewed. Not all proposals get funded and many beamlines are oversubscribed, so beamtime is not guaranteed. On the contrary, new access procedures such as the one mentioned earlier (BAG proposal at the ESRF) should ease and guarantee more regular access to beamtime to the Cultural Heritage community. There is also a lag time of up to six months or more between a proposal being submitted/accepted and the measurements being done, which may create some logistic problems (will the specimen be available for the beamtime? Are the measurements time sensitive?). Moreover, cultural heritage specimens are often unique and precious. Would the results justify the insurance cost of travelling the artifacts to the synchrotron radiation facility? Beam damage to the sample resulting from even short exposure to very intense X-rays is also a concern that needs to be carefully weighted in. Progress in lab-based X-ray technologies also made synchrotron radiation facilities not always the necessary tool for cultural heritage samples. Sometimes, long measurements in a readily accessible lab machine is preferable to very short measurements which may (or may not) happen in six months’ time, especially when spatial or temporal resolution is not a critical issue! Cheap tabletop bright coherent X-ray source provided by a new generation of laser-driven plasma accelerators (Kneip et al. 2010) may also one day be a good alternative to synchrotron radiation facilities. For many researchers, in-situ measurements at the museum or directly on the excavation site may be preferred, and it is expected that portable X-ray fluorescence imaging or X-ray diffraction devices (Cuevas and Gravie 2011; Nakai and Abe 2012; Cuevas et al. 2015; Castaing et al. 2016) is becoming more commonplace. For the time being, however, synchrotron radiation continues to offer some sizeable advantages when it comes to spatial resolution and elemental sensitivity, compared to even the most efficient lab sources.
In this book, after an overview on the development of the use of synchrotron radiation for Cultural Heritage studies, we focus on two mapping strategies, through either X-ray absorption or X-ray diffraction and illustrate the enhanced capabilities provided by synchrotron radiation, surpassing what is generally possible with conventional lab-based techniques. Then, an overview of different studies carried out on a series of specific materials is presented, with a final chapter on the close-related field of biomineralization, highlighting how diverse the applications of synchrotron radiation for such complex and heterogeneous materials can be.
1.5. Acknowledgments
The Advanced Light Source at the Lawrence Berkeley National Laboratory is supported by the Office of Science, Office of Basic Energy Sciences, Scientific User Facilities Division of the US Department of Energy under contract No. DE-AC02-05CH11231. The project Streamline has received funding from the European Union’s Horizon 2020 research and innovation program under the INFRADEV grant agreement No. 870313. The authors also thank A. N. Fitch for his advice.
1.6. References
Albéric, M., Dean, M.N., Gourrier, A., Wagermaier, W., Dunlop, J.W.C., Staude, A., Fratzl, P., Reiche, I. (2017). Relation between the macroscopic pattern of elephant ivory and its three-dimensional micro-tubular network.
PLoS ONE, Public Library of Science
, 12(1), 0166671.
Als-Nielsen, J. and McMorrow, D. (2001).
Elements of Modern X-ray Physics
. Wiley, New York.
Bertrand, L., Robinet, L., Thoury, M., Janssens, K., Cohen, S.X., Schoder, S. (2012). Cultural heritage and archaeology materials studied by synchrotron spectroscopy and imaging.
Applied Physics A
, 106, 377–396.
Blewett, J.P. (1998). Synchrotron radiation – early history.
Journal of Synchrotron Radiation
, 5, 135–139.
Burbidge, G. (1957).
The Crab Nebula a Cosmic Synchrotron
. Astronomical Society of the Pacific, San Francisco.
Bychkov, K.V. (1973). Synchrotron radiation of the Crab Nebula.
Soviet Astronomy
, 17, 163–168.
Caroff, L.J. and Scargle, J.D. (1969). Coherent synchrotron emission in the Crab Nebula.
Nature
, 225, 168.
Castaing, J., Dubus, M., Gianoncelli, A., Moignard, B., Walter, P. (2016). Development of a portable X-ray diffraction/X-ray fluorescence device for non-destructive analysis of works of art.
Technè
, 43, 79–83.
Chen, X., Dejoie, C., Jiang, T., Ku, C.S., Tamura, N. (2016). Quantitative microstructural imaging by scanning Laue X-ray micro- and nano-diffraction.
MRS Bulletin
, 41, 445–453.
Cotte, M., Autran, P.O., Berruyer, C., Dejoie, C., Susini, J., Tafforeau, P. (2019). Cultural and natural heritage at the ESRF looking back and to the future.
Synchrotron Radiation News
, 32, 34–40.
Cotte, M., Gonzalez, V., Vanmeert, F., Monico, L., Dejoie, C., Burghammer, M., Huder, L., de Nolf, W., Fisher, S., Fazlic I. et al. (2022). The “historical materials BAG”: A new facilitated access to synchrotron X-ray diffraction analyses for cultural heritage materials at the European synchrotron radiation facility.
Molecules
, 27, 1997.
Cuevas, A.M. and Gravie, H.P. (2011). Portable energy dispersive X-ray fluorescence and X-ray diffraction and radiography system for archaeometry.
Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment
, 633(1), 72–78.
Cuevas, A.M., Bernardini, F., Gianoncelli, A., Tuniz, C. (2015). Energy dispersive X-ray diffraction and fluorescence portable system for cultural heritage applications.
X-Ray Spectrometry
, 44, 105–115.
Dejoie, C., Kunz, M., Tamura, N., Bousige, C., Chen, K., Teat, S., Beavers, C., Baerlocher, C. (2011). Determining the energy-dependent X-ray flux variation of a synchrotron beamline using Laue diffraction pattern.
Journal of Applied Crystallography
, 44, 177–183.
Dejoie, C., Sciau, P., Li, W., Noe, L., Mehta, A., Chen, K., Luo, H., Kunz, M., Tamura, N., Liu, Z. (2014a). Learning from the past: Rare e-Fe2O3 in the ancient black-glazed Jian (Tenmoku) wares.
Scientific Reports
, 4, 4941.
Dejoie, C., Martinetto, P., Tamura, N., Kunz, M., Porcher, F., Bordat, P., Brown, R., Dooryhee, E., Anne, M., McCusker, L.B. (2014b). Crystal structure of an indigo@silicalite hybrid related to the ancient Maya Blue pigment.
Journal of Physical Chemistry C
, 118(48), 28032–28042.
Dejoie, C., Coduri, M., Petitdemange, S., Giacobbe, C., Covacci, E., Grimaldi, O., Autran, P.O., Mogodi, M.W., Sisak-Jung, D., Fitch, A.N. (2018a). Combining a nine-crystal multi-analyser X-ray diffraction stage with a two-dimensional detector for high-resolution powder.
Journal of Applied Crystallography
, 51(6), 1721–1733.
Dejoie, C., Autran, P.O., Bordet, P., Fitch, A.N., Martinetto, P., Sciau, P., Tamura, N., Wright, J. (2018b). X-ray diffraction and heterogeneous materials: An adaptive crystallography approach.
Comptes Rendus Physiques
, 19, 553–560.
Elder, F.R., Gurewitsch, A.M., Langmuir, R.V., Pollock, H.C. (1947). Radiation from electrons in a synchrotron.
Physical Review
, 71, 829–830.
Fitch, A.N. (2004). The high-resolution powder diffraction beam line at ESRF.
Journal of Research of the National Institute of Standards and Technology
, 109, 133–142.
Fitch, A.N. (2019). Synchrotron radiation and powder diffraction. In
International Tables for Crystallography, Volume H
, Gilmore, C.J., Kaduk, J.A., Schenk, H. (eds). Wiley, New York.
Fitch, A.N, Dejoie, C., Covacci, E., Confalonieri, G., Grendal, O., Claustre, L., Guillou, P., Kieffer, J., de Nolf, W., Petitdemange, S. et al. (2023). ID22 – The high-resolution powder diffraction beamline at ESRF.
Journal of Synchrotron Radiation
, 30, 1003–1012.
Goward, F.K. and Barnes, D.E. (1946). Experimental 8 MeV. Synchrotron for electron acceleration.
Nature
, 4012, 413.
Hodeau, J.L., Bordet, P., Anne, M., Prat, A., Fitch, A.N., Dooryhee, E., Vaughan, G., Freund, A. (1998). Nine crystal multianalyser stage for high-resolution powder diffraction between 6 and 40 keV.
Conference Proceedings of SPIE
, 3448, 353–361.
Hwu, Y. and Margaritondo, G. (2021). Synchrotron radiation and X-ray free-electron lasers (X-FELs) explained to all users, active and potential
. Journal of Synchrotron Radiation
, 28, 1014–1029.
Janssens, K. and Cotte, M. (2020). Using synchrotron radiation for characterization of Cultural Heritage materials. In
Synchrotron Light Sources and Free-Electron Lasers
, 2nd edition, Jaeschke, E.J., Khan, S., Schneider, J.R., Hastings, J.B. (eds). Springer, Cham.
Kim, K.J. (2001). Characteristics of synchrotron radiation. In
X-Ray Data Booklet
, Thompson, A.C. and Vaughan, D. (eds). Lawrence Berkeley National Laboratory, California.
Kneip, S., McGuffey, C., Martins, J.L., Martins, S.F., Bellei, C., Chvykov, V., Dollar, F., Fonseca, R., Huntington, C., Kalintchenko, G. et al. (2010). Bright spatially coherent synchrotron X-rays from a table-top source.
Nature Physics
, 6, 980–983.
Kunz, M., Tamura, N., Chen, K., MacDowell, A.A., Celestre, R.S., Church, M.M., Fakra, S., Domning, E.E., Glossinger, J.M., Kirschman, J.L. et al. (2009). A dedicated superbend x-ray microdiffraction beamline for materials, geo-, and environmental sciences at the advanced light source.
Review of Scientific Instrument
, 80, 035108.
Liénard, A. (1898). Champ électrique et magnétique produit par une charge électrique concentrée en un point et animée d’un mouvement quelconque.
L’Eclairage Electrique
, 16, 5.
Margaritondo, G. (1988).
Introduction to Synchrotron Radiation
. Oxford University Press, Oxford.
Marjadi, D.S. (2016). Conservation and restoration of cultural heritage: A biotechnological approach.
Advances in Applied Science Research
, 7(4), 159–167.
Marvasi, M., Mastromei, G., Perito, B. (2020). Bacterial calcium carbonate mineralization in situ strategies for conservation of stone artworks: From cell components to microbial community.
Frontiers in Microbiology
, 11, 1386.
Nakai, I. and Abe, Y. (2012). Portable X-ray powder diffractometer for the analysis of art and archaeological materials.
Applied Physics A
, 106, 279–293.
Pantos, E. (2005). Synchrotron radiation in archaeological and cultural heritage science. In
X-Rays for Archaeology
, Uda, M., Demortier, G., Nakai, I. (eds). Springer, Dordrecht.
Raimondi, P. (2016). ESRF-EBS: The extremely brilliant source project
. Synchrotron Radiation News
, 29, 8–15.
Reiche, I. and Chalmin, E. (2008). Synchrotron radiation and cultural heritage: Combined XANES/XRF study at Mn K-edge of blue, grey or black coloured palaeontological and archaeological bone material.
Journal of Analytical Atomic Spectrometry
, 23, 799–806.
Sajaev, V. (2019). Commissioning simulations for the Argonne Advanced Photon Source upgrade lattice.
Physical Review Accelerators and Beams
, 22, 040102.
Sciau, P., Relaix, S., Roucau, C., Kihn, Y., Chabanne, D. (2006). Microstructural and microchemical characterization of Roman period Terra Sigillata slips from archeological sites in southern France.
Journal of the American Ceramic Society
, 89(3), 1053–1058.
Tamura, N., McDowell, A.A., Spolenak, R., Valek, B.C., Bravman, J.C., Brown, W.L., Celestre, R.S., Padmore, H.A., Batterman, B.W., Patel, J.R. (2003). Scanning X-ray microdiffraction with submicrometer white beam for strain/stress and orientation mapping in thin films.
Journal of Synchrotron Radiation
, 10, 137–143.
Walter, P., Martinetto, P., Tsoucaris, G., Brniaux R., Lefebvre, M.A., Richard, G., Talabot, J., Dooryhee, E. (1999). Making make-up in ancient Egypt.
Nature
, 397, 483–484.
Note
1
See:
https://lightsources.org/lightsources-of-the-world/
.
2Development of the Use of Synchrotron Radiation for the Study of Cultural Heritage Materials
Nobumichi TAMURA1, Catherine DEJOIE2 and Pauline MARTINETTO3
1 Advanced Light Source, Lawrence Berkeley National Lab, USA
2 European Synchrotron Radiation Facility, Grenoble, France
3 Institut Néel CNRS/UGA, Grenoble, France
The late 2000s saw an explosion in the use of synchrotron radiation to investigate cultural heritage materials. High brightness, collimation and energy tunability are some of the main features that made synchrotron appealing to the community of archeologists, historians and paleontologists. They enable researchers to examine small amounts of material with unprecedented chemical and structural details. From paint samples, to fabrics, metalwork to pigments and cosmetics, a vast array of artifacts have been analyzed using synchrotron radiation, providing insights into ancient cultures and know-how, as well as guidance for artwork preservation for future generations. This chapter provides an overview of the application of synchrotron radiation to the study of cultural heritage materials.
2.1. Introduction
The potential of using synchrotron radiation for studying cultural heritage materials was recognized as early as 1986 in the now seminal paper by Harbottle et al. (1986). Very high intensities that are orders of magnitude higher than in laboratory sources and energy tunability are the two main characteristics of synchrotron beams that make them attractive for such applications, as they provide high detection sensitivity, fast data collection and access to spectroscopic techniques such as X-ray absorption Near-Edge Spectroscopy (XANES) and Extended X-ray Absorption Fine Structure (EXAFS), not possible with laboratory sources. High beam collimation and coherence also result in a small probe size and allow for high spatial resolution imaging. Mapping the distribution of trace elements by synchrotron X-ray fluorescence (SXRF) and of minerals by synchrotron X-ray diffraction (SXRD) are the two main techniques that come to mind for cultural heritage materials, with applications for fast analysis of ceramics, paintings and other artifacts for determining their provenance, method of fabrication or age.
The very first published account on the use of synchrotron radiation in archeometry was the measurement of elemental composition in Gaulish coins (Brissaud et al. 1990) using a combination of surface/near surface analysis by Particle-Induced X-ray Emission (PIXE) (ISTN, Saclay), SXRF (LURE, Orsay) and bulk analysis by Neutron Activation Analysis (Orphee reactor, Saclay). The Photon Factory then reported the analysis of Chinese clay dolls and Tenmoku pottery using SXRF for elemental mapping and XANES for determining degree of oxidation (Nakai and Iida 1991; Nakai et al. 1991).
Until the early 2000s, there were very few synchrotron applications in cultural heritage materials, all of them exploratory in nature. These include the use of X-ray fluorescence at the National Synchrotron Light Source (NSLS) on beamline X26 to examine trace element concentrations in dental calculi (precipitates in teeth from bacterial plaques) with potential applications in paleonutrition research (Capasso et al. 1995). X26A has also been used to measure the chemical composition of ancient bronze mirrors from the Han dynasty of China. Specifically, no mercury has been detected, a result consistent with the dealloying hypothesis of the copper from the alpha phase to explain the surface microstructure (Taube et al. 1995). SXRD was furthermore used to get more information about the phase composition in the dealloyed microstructure (Taube et al. 1996).
Before synchrotrons became more widely accessible, the main alternative techniques to map elemental distribution were Particle-Induced X-ray Emission (PIXE), in which a cooled target is hit with MeV particles like protons and alpha particles to generate characteristic X-rays (Johansson 1989) and scanning electron microscopy energy dispersive spectroscopy (SEM-EDS). These techniques had the advantage of lateral resolution and speed, making them more suitable for small samples or archeological materials than laboratory-based XRF (Malmqvist 1986; Carmona et al. 2010; Leon et al. 2012). However, with synchrotron radiation, especially with the advent of third-generation storage rings, these advantages tend to be outweighed by the most glaring disadvantages of these techniques, such as the need for the sample to be in a vacuum, making the use of synchrotron more appealing (Janssens et al. 2000). However, one unique facility worth mentioning is the AGLAE (Accélérateur Grand Louvre d’analyse élémentaire) particle accelerator, housed within the Louvre museum in Paris, and managed by the Center for Research and Restoration of Museums of France. It was completed in 1987 and became operational in 1989, thanks to the collaboration with the National Electrostatics Corporation, which powers the accelerator. AGLAE uses two ion sources to produce hydrogen and helium ions, reaching energies of up to 4 MeV and 6 MeV respectively. Its primary purpose is to analyze cultural artifacts, determining their atomic composition and trace elements. Various methods like PIXE, Rutherford backscattering spectrometry (RBS) and gamma-ray emission spectrometry are employed for this purpose (Menu et al. 1990; Calligaro et al. 1998). To further enhance its capabilities and enable safer examination of paintings, an upgrade known as NEW AGLAE was completed in 2017 (Pacheco et al. 2016). While SEM-EDS remains widely used thanks to its high availability, better spatial resolution, low element sensitivity and complementary to synchrotron techniques, the general use of PIXE in archeology and other fields never gained traction, mainly due to the low accessibility and lack of experimental flexibility; its use today remains marginal at most (Lucarelli et al. 2011; Calligaro et al. 2015). The use of synchrotron radiation, on the contrary, is another story.
SXRF measurements clearly dominated the early synchrotron studies of cultural heritage materials. Both NSLS beamline X26A and the Doris III beamline at Hasylab were used to investigate the chemical composition and corrosion of Roman glass from Qumran, Jordan (Janssens et al. 1996; Adams et al. 1997; Aerts et al. 1999, 2000) as well as 15th to 17th century Venetian glass vessels excavated in Antwerp, Belgium (Janssens et al. 1998; De Raedt et al. 2000
