Chapter 1

Introduction and overview

K Janssens and R. Van Grieken

1.1 INTRODUCTION

For the study, conservation and restoration of materials and artefacts of

culturo-historical value, there is a well-defined need for analytical methods
that are able to provide information on (see Fig. 1.1):
· the chemical nature/composition of selected parts of cultural heritage
artefacts and materials in order to elucidate their provenance;
· the state of alteration (on the surface and/or internally) of objects as a
result of short-, medium- and long-term exposure to particular environ-
mental conditions;
· the effect/effectiveness of conservation/restoration strategies during and
after application.
According to Lahanier et al. [1], the ideal method for analysing objects of
artistic, historic or archaeological nature should be:
(a) non-destructive, i.e., respecting the physical integrity of the material/
object. Often valuable objects can only be investigated when the analysis
does not result in any (visible) damage to the object. Usually this
completely eliminates sampling or limits it to very small amounts;
(b) fast, so that large numbers of similar objects may be analysed or a single
object investigated at various positions on its surface; this property is
very valuable since this is the only way of being able to discern between
general trends in the data and outlying objects or data points;
(c) universal, so that by means of a single instrument, many materials and
objects of various shapes and dimensions may be analysed with minimal
sample pre-treatment;
(d) versatile, allowing with the same technique to obtain average compo-
sitional information as well as local information of small areas (e.g.,
millimetre to micron-sized) from heterogeneous materials;
Comprehensive Analytical Chemistry XLII
Janssens and Van Grieken (Eds.)
C 2004 Elsevier B.V. All rights reserved ]
 K. Janssens and R. Van Grieken

Provenance
Studies

,Iteration/
egradation
rocesses

Fig. 1.1. Interaction between cultural heritage materials, the use of analytical
techniques and environmental factors.

(e) sensitive, so that object grouping and other types of provenance analysis
can be done by means of not only major elements but also trace-element
fingerprints; and
(f) multi-elemental, so that in a single measurement, information on
many elements is obtained simultaneously and, more importantly,
information is also obtained on elements which were not initially
thought to be relevant to the investigation.
While most methods that are described in the chapters of this book fulfil
several, but usually not all, requirements described above, it is obvious that
in the cultural heritage field, the analytical techniques should preferably be
non-destructive or micro-destructive. Non-destructive techniques allow
analytical information to be obtained with no damage to the sample or (in
some cases) to the artefacts in question. When micro-destructive methods are
used, all visible damage is avoided and the objects under examination remain
aesthetically unimpaired [2]. The possibility of using these types of methods
is of enormous advantage when sampling is not feasible or when fragments
used for analysis need to be put back in their original location at the end of
the investigation. Among the truly non-destructive methods are the
spectroscopies based on ultraviolet, visual and infrared (IR) radiations, as
well as the X-ray-based methods.

2
 Introduction and overview

Objects and monuments of culturo-historical significance comprise a wide

variety of materials (metals, ceramics, glass, various igneous and sedimen-
tary rocks, textile, leather, wood, horn, parchment, paper, etc.) and usually
exhibit a fairly complex three-dimensional structure and a heterogeneous
chemical composition. Especially in the case of artefacts of precious nature
(e.g., jewellery, weaponry, religious objects), cultural heritage objects often:
· are composed of various materials (e.g., Au/Ag alloy artefacts adorned
with gemstones),
· consist of a base material covered with one or more layers of pigmentation
(e.g., polychrome wooden statues, easel paintings, illuminated manu-
scripts) or
· show significant (surface) alteration due to burial or atmospheric
exposure (e.g., bronze statues, silver coins, etc.) [3].
In addition to the requirement that the method(s) of analysis that are
employed to assess the material state of such objects/materials are as
non-destructive as realistically possible, in most cases, preference is then
given to methods that are able to yield information on well-defined areas
of the artefacts in question [4]. Sometimes, these areas are microscopi-
cally small; in other cases, a lateral resolution of 1 mm2 suffices.
Techniques having a high spatial resolution are considered by some to
take an intermediate place between destructive and non-destructive
methods.
In recent years, partially driven by the increasing importance of high-
tech materials of a complex micro-structural nature and mainly as a result
of miniaturization of components (radiation sources, radiation guide tubes,
detectors), a number of portable and/or microscopic versions of established
analytical methods have come into existence. Such methods are well suited
for inspection and/or analysis of objects of great cultural value as
measurements can be made on site (e.g., pigment identification in frescoes)
thus eliminating the need to sample or even move the objects out of their
normal surroundings (e.g., a museum or an archaeological site). Thus, most
of today's major museums have at their disposal one or more (trans)port-
able instruments for high spatial resolution examination of the artefacts in
their collection.
As well as to being useful for analysing the cultural heritage artefacts
themselves, such techniques are also employed in support studies, where
under controlled laboratory circumstances, e.g., the deterioration of building
materials (mortar, sandstone, etc.) under the influence of rain, exposure to
solar radiation, pollution gases, etc., is examined.

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 K. Janssens and R. Van Grieken

Although such methods have been described in the specialized literature

of the field or sub-field to which they belong (e.g., portable and microscopic
X-ray fluorescence analysis (XRF) in the atomic spectrometry literature,
fibre-optic IR reflectography in the molecular spectroscopy literature), the
flow of information towards the larger field of potential users has been
limited because:
· the technical literature that pertains to each of the sub-fields from which
the techniques have emerged (physics, analytical chemistry, atomic/
molecular spectroscopy) is quite fragmented;
· the potential users (archaeologists, art-historians, conservators, archi-
tects, museum conservators) are not sufficiently trained in the technical/
scientific aspects to allow them to absorb/monitor the above-mentioned
state-of-the-art innovations.
In view of the above, we have gathered together a group of authors who
combine (a) a number of concise descriptions of non-destructive micro-
analytical techniques that have shown their effectiveness in the cultural
heritage field with (b) a number of case studies where one or a series of
artefacts of particular, generic nature (e.g., bronze statues, illuminated
manuscripts, glass artefacts, etc.) are studied from the provenance or
conservation point of view, preferably using an interdisciplinary, multi-
technique approach.
Among the chapters in the first section of this volume, the methods based
on the use of energetic radiation belonging to the X-ray or Rontgen part of
the electromagnetic spectrum are well represented. X-ray-based methods of
non-destructive analysis are very frequently employed in the cultural
heritage area for various purposes. Starting in earnest in the 1950s by
judicious use of the available means then, this is still very much the case
today where many technological advances increase the applicability of the
methods, resulting in an extensive literature.
This was also apparent during the seventh edition of the international
conference on "Non-destructive Investigations and Micro-analysis for the
Diagnostics and Conservation of the Cultural and Environmental Heritage"
(Art 2002) that was organized in Antwerp (Belgium) by the editors of this
book [5]. Of the ca. 200 papers presented at this conference, 115 included the
use of analytical techniques for characterization of cultural heritage
artefacts or materials. Among these contributions, 63 employed one or
more X-ray-based or related technique (such as XRF analysis, scanning
electron microscopy (SEM), transmission electron microscopy (TEM), proton-
induced X-ray emission (PIXE), X-ray diffraction (XRD), X-ray absorption

4
 Introduction and overview

spectroscopy (XAS), total-reflection X-ray fluorescence (TXRF) and X-ray

microtomography) while 28 made use of IR spectroscopy, 14 used Raman
microscopy, 12 used visible light spectrometry or reflectometry and six
employed gas chromatography coupled to mass spectrometry (GC-MS).
Thus, the first part of this volume can be considered to be the analytical
reference section of the book, introducing and bringing together all technical
information, library spectra (if any) and literature references of various
methods. Each description consists of an explanation of the basic principles
of the technique (keeping a cultural heritage user profile in mind),
information on the availability of equipment, skills required, etc., and is
illustrated with a few concrete examples of applications in the cultural
heritage field.
The second part of the book is intended to show the reader how these
methods can be employed, either separately or in combination with each
other, to solve concrete, real-world problems and provide overviews of the
literature in specific application areas. Among these case studies, both
investigations that aim to extract provenance information from cultural
artefacts as well as studies that seek to evaluate and monitor preservation/
restoration treatments have been included.

1.2 OVERVIEW OF THE ANALYTICAL REFERENCE SECTION

The first section of the book starts with a overview (Chapter 2) of imaging
and photographic techniques in the IR, visual, ultraviolet and X-ray part of
the electromagnetic spectrum. Strictly speaking, the techniques discussed
here are not microscopic in nature, but in practice will be very frequently
employed prior to or in combination with some of the micro-beam methods
that are discussed in later chapters.
Chapter 3 is intended to introduce the reader to various forms of
electron microscopy that are currently used to study cultural heritage
materials. It outlines the principles underlying the technique and continues
to discuss the role of electron microscopy in the field under study. The
instrumentation, analytical possibilities and limitations of both SEM and
TEM are discussed. An overview of recently published work involving the
application of SEM and/or TEM analyses in the cultural heritage field
concludes this chapter.
In addition to X-ray radiography and tomography, discussed in Chapter 2,
X-ray emission techniques are very frequently employed for non-destructive
analysis of cultural heritage materials and artifacts. Most X-ray emission
techniques involve irradiation of a material with a beam of X-ray photons

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 K. Janssens and R. Van Grieken

(or other particles), followed by detection of element-specific fluorescent

radiation. In Chapter 4, besides a brief outline of the theoretical background
of interactions between X-rays, and matter, the systematics of X-ray line
spectra, instrumentation of X-ray spectrometry, the principles of quantitat-
ive analysis by means of XRF, and various specialized forms of this method
that are of use in the cultural heritage sector are described, including total-
reflection XRF, microscopic XRF and portable XRF for in situ investigations.
Illustrative examples of their use are given. In addition, the use of more
exotic X-ray techniques based on synchrotron radiation such as (microscopic)
X-ray absorption near edge structure spectroscopy (-XANES) and (micro-
scopic) X-ray diffraction analysis (-XRD) in combination with (-)XRF are
also mentioned.
In Chapter 5, ion-beam methods of analysis (IBA) are discussed in detail.
After a description of the fundamentals of the interaction of heavy charged
particles with matter, attention is focused on the PIXE method and its
companion techniques, particle-induced gamma emission (PIGE), Ruther-
ford backscattering spectrometry (RBS) and elastic recoil detection analysis
(ERDA). Specific attention is given to instrumentation devoted to the
analysis of artistic and archaeological artifacts in so-called "external beam"
facilities. Examples of the application of IBA techniques for surface and/or
for bulk analysis of different materials are included in this chapter.
In Chapter 6, the topic of surface analysis of materials by means of
electron spectroscopy is discussed with a description of the theoretical
background and the instrumentation for X-ray photo-electron spectroscopy
(XPS) and (scanning) Auger spectrometry (SAM). The current state-of-the-
art of the method is described, with special attention to the lateral resolution
currently achievable with both methods. This chapter also discusses sample
preparation procedures and provides a review of SAM and XPS applications
in the cultural heritage domain.
Chapter 7 looks at the relatively new technique of laser ablation
inductively coupled plasma mass spectrometry (LA-ICP-MS). The chapter
begins with a short background showing the major steps leading to the
development of both lasers and ICP mass spectrometers. This is followed by a
more detailed technical discussion of a "generic instrument," dealing
separately with the ICP-MS and the laser. A section concerning the
analytical technique describes how the two components work together. The
reader is guided through appropriate sample preparation techniques
towards taking the right choice in setting instrument parameters and
dealing with the date produced. This chapter also concludes with a brief
review of the relevant literature.

6
 Introduction and overview

In the next chapter (Chapter 8) on IR and Raman microscopy (including

fiber-optics Raman spectroscopy, FORS), first a resume of the requirements
of IR, Raman spectroscopy and fiber-optic coupling in dealing with
archaeological and art specimens is presented; this is followed by some
case-type studies to illustrate the advantages and problems encountered in
the experimental use of these techniques. Studies involving the combined
use of XRD, SEM and GC-MS along with Raman microscopy are now
becoming more frequent and some of these are discussed as examples.
A description of secondary ion mass spectrometry or -microscopy (SIMS)
can be found at the end of the reference section in Chapter 9. After some
introductory considerations on the non-destructive nature of SIMS, and a
description of the basic principles, the instrumentation for SIMS measure-
ments is discussed together with an outline of the analytical procedures
employed here. The quantitative, imaging and in-depth modes of operation
are described and the chapter ends with a review of current applications in
the cultural heritage sector, including the measurement of lead isotopes,
determining the origin of gems and metal ingots and interface studies
of coatings.

1.3 OVERVIEW OF THE CASE STUDIES SECTION

The second part of the book starts with Chapter 10, which is devoted to the
analysis of corroded Cu-alloy materials, a very frequently encountered type
of artistic or archaeological artefact. The combined use of methods of non-
destructive analysis such as SEM, in situ XRD (with imaging system) and
optical examination by bench microscopic methods for characterization of the
alteration layers found at the surface of Cu-alloy objects is described. In situ
examination of such artefacts by means of XRF in point-analysis and/or
scanning mode is also discussed. The application of these types of methods is
discussed for the examination of a gilded bronze Osiris from ancient Egypt,
an important Greek-inscribed copper plaque of the 7th century BC, and small
fragments of corroded copper alloy Phiale from the Southern Italian site of
Francavilla Marittima, dated to the 5-6th century BC; the contribution of
analytical methods to the understanding of the development of patinas and
their authenticity is evaluated. The use of bulk in situ XRD to study the
corrosion of test coupons in assessing the museum environment is
exemplified by examples of copper alloy coupons exposed to fixed amounts
of formic and acetic acid pollutants.
Chapter 11 extensively discusses the characterization of gold artifacts of
various nature and the materials employed in various historical periods to

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 K. Janssens and R. Van Grieken

manufacture these items. The role of nuclear and atomic methods of non-
destructive analysis of noble metals is described with emphasis on the ability
of these methods to provide information on the bulk composition of the
materials. The complementary use of RBS-PIXE and nuclear reaction
analysis (NRA) for the compositional study of silver and gold artifacts is
outlined, including the investigation of thick objects by means of gamma-ray
transmission. Next, the study of the procedures of soldering on gold jewelry
objects of different origin (Achemenide, Roman, Greek, Artesic and Etruscan
artifacts) is treated, including the reproduction in laboratory circumstances
of ancient soldering and brazing procedures. The discussion includes a
comparison of modern analytical results with the description of ancient
recipes listed in the Natural History of Pliny (1st century AD). In this chapter,
a study on the gilding of Mesoamerican tumbaga (a copper-gold alloy)
artifacts is also presented.
Through the application of diagnostic analytical methods for studying
Byzantine iconography, the current state of preservation of works and the
associated creative process of both wall-painting ensembles and portable
icons may be revealed. In Chapter 12, the usefulness of this approach in the
detailed evaluation of the aesthetic and historic value of the artworks is
discussed. The use of stratigraphic data concerning structural painting
materials and techniques as applied to two major works of art is described in
detail: (a) the frescoes of the Protaton Church (end of the 13th century),
attributed to Manuel Panselinos, who is considered to be the chief exponent
and a legendary icon painter of the Macedonian School and (b) the icon of the
Mother of God Hodegetria, Church of St Modestos, Kalamitsi, Chalkidiki,
Greece, a representative portable icon of the 16th century Cretan style of
Byzantine art. The artworks were examined through the application of both
non-destructive and micro-analytical methods including, on the one hand,
digital photography and macrophotography, stereomicroscopic photography,
ultraviolet fluorescent photography, IR reflectography, X-radiography, image
processing and colorimetry (measurement and representation) and, on the
other hand, sampling of small fragments followed by optical microscopic
observation and digital capture of cross-sections, under polarized white light
and UV light, selective staining and micro-Raman and microscopic Fourier-
transform IR (p-FTIR) spectroscopies of polished sections.
Chapter 13 focuses on the advantages and disadvantages of analysing
corroded silver coins by means of energy-dispersive (ED) XRF compared to
SEM/EDX and PIXE, for the identification of the coin's mint by its chemical
composition. The objects of investigation are Austrian silver coins of the 12th
and 15th centuries. As most of the coins were found in soil, where they have

8
 Introduction and overview

been buried for hundreds of years, corrosion effects influence the qualitative
as well as the quantitative results that can be obtained. The different
information depths of all three techniques mentioned above are a main point
of discussion. Comparison of the Ag-K/Ag-L count ratios of the EDXRF
intensities with SEM/EDX measurements on cross-sections outlines the
inefficiency of quantitative non-destructive analysis for the investigation of
corroded objects.
In Chapter 14, the identification and trace analysis of pigments
encountered in illuminated manuscripts is described by means of a
combination of micro-Raman spectroscopy and total-reflection XRF. First,
the analysis of the various components of an illuminated manuscript, such as
the inorganic pigments, the dyes and inks, the binding material and the
parchment substrate, is discussed in general. In the second part, the analysis
of manuscripts from the collection of Raphael de Mercatellis and of the
"Brevarium Mayer van de Bergh," an illuminated 16th century prayer book,
is described. In the latter description, attention is given to a procedure that
allows us to differentiate between the different workshops that were involved
in the manufacture of this manuscript.
In Chapter 15, different examples chosen from various historical contexts
(from Protohistory to the Post-Medieval period) and from various geographi-
cal areas (mainly Europe and the Indian world) are used to illustrate the
information provided by the chemical analysis of historical glasses for trade
and provenance studies on one hand, and for understanding the development
and the history of sciences and techniques on the other hand. A long time
before artificial glass was invented, pre-historic populations were using
obsidian, a natural glass, to make tools. The importance of trace analysis to
understand and reconstruct the trade and exchange patterns of this material
during Neolithic times is briefly illustrated. During the Bronze Age, artificial
glass, as glass beads, was the object of long-distance trade. Relationships
between the chemical composition of these objects, their chronology and the
production area of the raw material can be used to build a distribution model
of glass. In a similar manner, the Indian glass trade and manufacture at the
beginning of our era is studied, with emphasis on the trade between India
and the Mediterranean world. In order to investigate the European recipes
used for glass making in Carolingian times, lead isotopes ratio analysis has
been used to identify the birthplace of these recipes and follow the
distribution of glass products through Europe. In the Post-Medieval period,
the Venetian and facon-de-Venice glass became very popular in various parts
of Europe. By means of information on the major to trace composition,
transfer of technology and recipes in 15-17th century Europe in various

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 K. Janssens and R. Van Grieken

stages can be followed, and the influence of the economic and political
changes in the Low Countries on the local glass technology and workshop
traditions is described.
During the exposure of medieval stained glass used in window panes of
cathedrals, churches and other historic buildings, weathering crusts
consisting of gypsum (Ca 2SO 4 -2H 2 0) and syngenite (K 2 SO 4 CaSO4H 2 0)
are formed as crystalline corrosion products and mainly hydrated silica as
amorphous material on the external surface of such glass objects. Chapter 16
discusses the manner in which these alternation layers can be characterized
by means of several methods. After a discussion of the chemical exchange
reactions that cause the weathering phenomena, analytical results obtained
from specimens of medieval glass objects by SEM as well as SIMS and NRA
are presented. Similar investigations were carried out on specimens from
medieval enamel of the Burgundian Treasure of the Vienna Kunsthistor-
isches Museum. Additionally, the monitoring of in situ weathering tests,
carried out on sample glass similar in chemical composition to medieval glass
and enamel by means of atomic force microscopy (AFM), is described.
In the final chapter (Chapter 17), the use of several analytical methods
(together with their advantages and limitations) for the investigation and
conservation of 16th century manuscripts endangered by iron-gall ink
corrosion will be described. After a discussion of the fundamental chemical
interaction that causes the mechanical strength of cellulosic materials to
decrease dramatically due to the presence of Fe2 + in the ink, the results
obtained by means of various analytical methods are described. This includes
destructive and non-destructive investigations performed by SEM and
electron probe micro-analysis, XRF spectrometry, inductively coupled
plasma mass spectrometry, atomic absorption spectrometry, Mossbauer
spectrometry and -XANES. Also, the use of these techniques for
optimization of a suitable conservation treatment for documents suffering
from damage induced by iron-gall ink is described.

REFERENCES

1 Ch. Lahanier, G. Amsel, Ch. Heitz, M. Menu and H.H. Andersen, Proceedings
of the International Workshop on Ion-Beam Analysis in the Arts and
Archaeology, Pont-A-Mousson, Abbaye des Premontr6s, France, February
18-20, 1985-Editorial, Nucl. Instr. Meth. Phys. Res., B14 (1986) 1.
2 E. Ciliberto and G. Spoto (Eds.), Modern Analytical Methods in Art and
Archaeology, Chemical Analysis Series, Vol. 155. Wiley, Chichester, 2000.

10
 Introduction and overview

3 A.M. Pollard and C. Heron, Archaeological Chemistry. Royal Society of

Chemistry, London, UK, 1996.
4 D.C. Creagh and D.A. Bradley (Eds.), Radiation in Art and Archaeometry.
Elsevier, Amsterdam, The Netherlands, 2000.
5 R. Van Grieken, K. Janssens, L. Van 't Dack and G. Meersman (Eds.), Proceedings
of Art 2002: Seventh International Conference on Non-destructive Testing and
Microanalysis for the Diagnostics and Conservation of the Cultural and
Environmental Heritage, 2-6 June 2002, Congress Centre Elzenveld, Antwerp,
Belgium, University of Antwerp (UIA), Antwerp, Belgium, 2002, 780 pp.

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